6 International Discussion Meeting on Relaxations in ... - Sapienza

6 th <strong>International</strong> <strong>Discussion</strong> <strong>Meeting</strong> on
Relaxations in Complex Systems
New results, Directions and Opportunities
“Sapienza” Università di Roma
Rome, Italy
August 30 - September 4, 2009
List of Abstracts

MEMORY OF MULTIPLE AGING STAGES IN AN ELECTRIC DIPOLAR GLASS ALSO
ABOVE THE FREEZING TEMPERATURE
F. Cordero (1), F. Craciun (1), C. Galassi (2)
(1) CNR-ISC, Istituto dei Sistemi Complessi, Area della Ricerca di Roma-Tor Vergata, Via del Fosso
del Cavaliere, 100, I-00133 Roma, Italy
(2) CNR-ISTEC, Via Granarolo 64, I-48018 Faenza, Italy
Correspondant author: francesco.cordero@isc.cnr.it
The memory of an aging stage at a temperature Ta while heating through Ta after having cooled well
below that temperature is considered to occur in a frozen glassy state or to be caused by imprinting of
a domain structure in the distribution of defects that are marginally mobile around Ta.
We show that in the relaxor ferroelectric the memory of multiple aging stages can be recovered also
above the temperature of polar freezing, and that this is an intrinsic feature of the polar glassy state
rather than due to mobile defects. Relaxor ferroelectrics are materials where chemical disorder
prevents the formation of a long range ferroelectric state and may be considered as realizations of spin
glasses with electric instead of magnetic dipoles. In fact, the electric polarization and dielectric
susceptibility of relaxors may present all the features of the magnetic counterparts of spin glasses,
including the frequency dispersion of the maximum of susceptibility near freezing, aging, rejuvenation
and memory.
We measured the dynamic dielectric susceptibility and elastic compliance of a (Pb/La)(Zr/Ti)O3
(PLZT) sample whose polar state is frozen below Tg < 340 K, as deduced from the frequency
dispersive maximum of the dielectric susceptibility and the splitting of ZFC and FC polarizations. On
the other hand, both the electric and elastic susceptibilities during heating exhibit dips at multiple
aging stages at temperatures up to 374 K, well above freezing. We also verified that mobile defects are
not the source of memory above freezing. In fact, after introduction of O vacancies, H and the
accompanying ionized charge carriers, the phenomena were depressed rather than enhanced. In
addition, at La contents slightly outside the relaxor regime, memory is drastically reduced and is
observed only after aging for months at room temperature, in this case possibly due to migration of
defects.
It appears therefore that PLZT presents a peculiar glassy state of polarization, exhibiting memory also
above freezing.
EFFECT OF CLAY PLATELETS ON α-TRANSITION IN AMORPHOUS OR
CRYSTALLINE POLYMER
L. A. Utracki,
NRCC/IMI, 75 de Mortagne, Boucherville, QC, Canada, J4B 6Y4; Leszek.utracki@nrc.ca
The Pressure-Volume-Temperature (PVT) of clay-containing nanocomposites with polystyrene or
polyamide-6 matrix were studied within T = 300 – 600 K and P = 0.1 – 190 MPa [1]. The
compressibility, κ, and thermal expansion coefficient, α, were computed as functions of T, P and clay
content, w. In the PS systems the isobaric κ and α vs. T functions showed the secondary transitions,
Tβ/Tg ≈ 0.9 ± 0.1 and Tc/Tg = 1.2 ± 0.1. The plots of α = α(T) and κ = κ(T) were nearly T-independent
in the glassy and molten phase, connected by a large transitory region stretching from the ambient
pressure values of Tg to that of Tc. In the PA-6 based nanocomposites the isobaric κ = κ(T) followed
the same dependence on both sides of the melting zone, while the isobaric α = α(T) dependencies
were dramatically different for the solid and molten phase. The effect of clay addition on α and κ
depended on the polymer type and T-range, viz. in molten PS it was small, but large in molten PA-6.

The behavior in the molten and vitreous state followed the Simha-Somcynsky (S-S) cell-hole theory
while that of the semicrystalline state the Midha-Nanda-Simha-Jain (MNSJ) cell model [2].
[1] LA Utracki, J. Polym. Sci. Part B: Polym. Phys., 46, 2504 (2008), ibid. 47, 299; 966 (2009)
[2] LA Utracki, Europ Polym J (2009), in press
A MULTISCALE MOLECULAR MODELING APPROACH TO POLYMER-CLAY
NANOCOMPOSITES
Sabrina Pricl (1), Giulio Scocchi (1,2), Paola Posocco (1), and Maurizio Fermeglia (1)
(1) MOSE Laboratory, Department of Chemical Engineering, University of Trieste, Piazzale Europa 1,
34127 Trieste, Italy
(2) ICIMSI, University School of Southern Switzerland, Galleria 2, Manno, CH-6928, Switzerland
Corresponding author: sabrina.pricl@dicamp.units.it
In order to develop new materials and composites with designed original properties, it is essential for
these properties to be predicted before preparation, processing, and experimental characterization.
Computer-assisted molecular simulations can then play a major role in this context. Given these
concepts, however, it is necessary to carry out calculations for realistic time scales fast enough to be
useful in design. This requires developing techniques useful to design engineers, by incorporating the
methods and results of classical, low scales quantum mechanics/molecular dynamics (QM/MD)
simulations to mesoscale modeling (MS) to finite element (FE) calculations [1-3].
Here, we report the results of our efforts in developing a hierarchical procedure for bridging the gap
between atomistic and MS/FE simulations for PCN design. According to the computational recipe, all
necessary parameters of the mesoscopic models are estimated by an ad hoc, step-by-step procedure
involving different QM/MD calculations. Finally, the mesoscopic simulated structures are passed on to
the FEM calculations, to estimate the macroscopic properties of the PCN (e.g., Young modulus,
diffusivity, etc.).
The global perspective of our work is the complete integration of all available simulation scales, in a
hierarchical procedure to provide an efficient and robust simulation protocol for the successful design
of PCNs of industrial interest and the prediction of their final performance.
[1] S. Pricl et al., J. Phys. Chem. B, 111, 2143, 2007.
[2] S. Pricl et al., Fluid Phase Eq, 261, 366, 2007.
[3] S. Pricl et al., Micropor. Mesopor. Mat., 107, 169, 2008.
FORMATION OF HELICES IN ISOTACTIC POLYPROPYLENE IN THE PRESENCE OF
NANOFILLERS
X. Chen (1), S. K. Kumar (2), R. Ozisik (1)
(1) Rensselaer Polytechnic Institute, Troy, NY 12180, U.S.A.
(2) Columbia University, New York, NY 10027, U.S.A.
ozisik@rpi.edu
Formation of helices in isotactic polypropylene (iPP) was studied using on-lattice, coarse-grained,
Metropolis Monte Carlo simulations [1,2]. Influences of polymer-filler interaction and filler size on
formation of helices during early stages of crystallization were studied by placing iPP chains on flat
surfaces and by inserting isotropic (spherical) fillers into neat iPP melt. Results indicated that
attractive interaction between polymer and filler plays a dominant role in the formation of early helical
structures. Repulsive interaction excludes polymer chains from the neighbourhood of the flat surface
and triggers coil-helix transition earlier (at higher temperatures). Irrespective of the energy potential
used, flat surface always influences the orientation of the helices to be parallel to the surface. In
addition, presence of isotropic filler leads to a length scale effect on the formation of long helical
structures at low temperatures, i.e., below melting temperature. Confinement effect was also
investigated by changing the gallery spacing between two flat surfaces. Confinement significantly
prohibits the growth of long helical structures but has no effect on the overall helicity as well as the
ordering of helices.

[1] X. Chen, S. K. Kumar, R. Ozisik, J. Polym. Sci., Part B: Polym. Phys. 44, 3453, 2006.
[2] X. Chen, R. Ozisik, S. K. Kumar, P. Choi, J. Polym. Sci., Part B: Polym. Phys. 45, 3349, 2007.
COMPETITION OF TIME SCALES IN SHORT-TIME RESPONSE OF DEFORMED
POLYMER GLASSES: MOLECULAR MODELLING
Alexey V. Lyulin and M.A.J. Michels
Group Polymer Physics, Eindhoven Polymer Laboratories, Technische Universiteit Eindhoven, P.O.
Box 513, 5600 MB Eindhoven, The Netherlands, and Dutch Polymer Institute, P.O. Box 902, 5600
AX Eindhoven, The Netherlands
a.v.lyulin@tue.nl
We use molecular-dynamics simulations to explore the influence of thermal and mechanical history of
typical glassy polymers in a bulk, atactic polystyrene and (bis)phenol A polycarbonate on their
deformation. Stress-strain and energy-strain developments have been followed for different
deformation velocities, also in closed extension-recompression loops. The latter simulate for the first
time the experimentally observed mechanical rejuvenation and overaging of polymers. Energy
partitioning reveals essential differences between mechanical and thermal rejuvenation. The main
message is that differences in stress-strain and energy-strain curves between the polymers could be
interpreted [1] in terms of ratios between three time scales: for cooling down from the hightemperature
melts, for deformation up to the yield point (forced out-of-cage motion), and the
segmental in-cage relaxation times. For confined polymers it has been speculated [2] that additional
relaxational processes exist due to the presence of a free interface. We present our first findings on the
thickness- and substrate-dependence of the glass-transition temperature for thin polystyrene films, also
under the influence of shear.
[1] A.V. Lyulin and M.A.J. Michels, Phys. Rev. Lett., 99, 085504, 2007
[2] V Lupaşcu, S. J. Picken and M. Wübbenhorst, J. Non-Cryst. Solids, 352, 5594, 2002
PHYSICAL AGING OF GLASSES: THE VFT APPROACH
Jacques. Rault * Laboratoire de Physique des Solides, UMR 8502 Université de Paris-Sud, Bât. 510,
91405 Orsay (France)
e-mail rault@lps.u-psud.fr
The aging properties (volume, enthalpy and mechanical properties) of fragile glasses are reviewed and
interpreted in the framework of the Vogel-Fulcher-Tamann-Hess (VFT) law which is a consequence
of the coupling of the cooperative and individual motions, α and β. In the equilibrium melt state the
relaxation times of these motions verify the relation τα ~ (τβ) 1/n where n ~ T-T0 is the Kohlrausch
exponent (inverse of the number of individual motions participating to a cooperative motion) which
extrapolates to ∝ at the Vogel temperature T0 . In the non equilibrium glassy state we show that the
same relation applies but the Kohlrausch exponent n(T’) is now a function of the equivalent
temperature T’, temperature of the equilibrium melt which would have the same specific volume. The
relaxation time τα (T,T’) is then dependent on the aging time in the glassy state, on the heating and
cooling rates, on the pressurization and depressurization rates. The differential VFT relaxation
equations (VFT-RE) giving the evolution of V and H of glasses under atmospheric and high pressures
are given. The experimental non linear and non exponential relaxation curves during isothermal and
non isothermal aging (cooling and heating) are explained by this generalized VFT equation. The glass
properties (V, H) during aging and/or during temperature scans (or/and pressurization) depend only on
the parameters of the liquid state (WLF parameter; C1, C2, the Vogel and merging temperatures T0 and
T*) and the thermal expansion (or/and compressibility) coefficients. The solutions of the VFT-RE are
compared to the KWW functions (stretched and compressed exponentials). The relation between the
parameters (nk, τk) of the KWW function and the relaxation time τα (T,T’) of the VFT-RE is given. It is
shown that the KWW function does not give good agreement with the experimental relaxation curves
of Kovacs, and that the KWW parameters have no straightforward meaning. The memory effects

(amplitude and memory time) observed by Kovacs, Struik and Adachi et al are explained by this
model, without any adjustable parameters; relaxation of glass formers materials, after an up T-jump
(and during heating), involves the two processes: β at small time and α at long time. The various glass
temperatures (always defined arbitrarily) in these non equilibrium systems and deduced from the VFT-
RE are compared to the Deborah glass temperature. We emphasize that the relation between the
volume and enthalpy relaxations in these non equilibrium systems can be deduced from the Grüneisen
relation, and that the effects of pressure can be deduced from the linear variation of the temperatures
T0 and T* with P and from the “fan structure” of the isotherms and isobars. Finally the mechanical
properties, modulus, yield stress, creep and stress relaxation, are interpreted in the framework of this
generalized VFT model. The evolution of the mechanical properties can be fitted with the KWW
function or the Struik-Andrade law. It is shown that the relaxation time τ and the Kohrausch exponent
n describing these evolutions vary inversely with the aging time, temperature and stress. The observed
correlation law, n log τ ~ Constant, is a consequence of the generalized VFT law.
CRYSTALLIZATION AND MELTING BEHAVIORS OF ALKYLAMMONIUNIONS IN
NANOCONFINED SPACE
M. Okamoto (1), M. Kajino (1), H. Sato (2) and Y. Ozaki(2)
(1) Advanced Polymeric Nanostructured Materials Engineering, Graduate School of Engineering,
Toyota Technological Institute, Hisakata 2-12-1, Tempaku, Nagoya 468-8511, Japan
(2) Department of Chemistry, School of Science and Technology, Kwansei-Gakuin University,
Research Center for Environment Friendly Polymers, Sanda 669-1337, Japan
okamoto@toyota-ti.ac.jp
To understand the effect of one-dimensional confined space (nano-gallery space in montmorillonite
(MMT)) on the nonisothermal crystallization kinetics and melting behaviors including the
conformational changes of the chain segment of the intercalants, we have characterized the MMT
modified with di-octadecyl di-methylammonium (DC18DM) cations (MMT-DC18DM) by using
temperature-modulated differential scanning calorimeter (TMDSC), wide-angle x-ray diffraction
(WAXD) and Fourier transform infrared spectroscopy (FTIR) technique. For MMT-DC18DM, the
crystallization peak was much broader and it appeared at lower themperature (Tc). In addition, the
formation of gauche conformer was enhanced and the poor chain packing took place for the
crystallized alkyl chains in MMT-DC18DM as compared with those of the crystallized di-octadecyl dimethylammonium
bromide (DC18DM-Br), as a reference, in bulk. Upon heating, however, the
mobility of the alkyl chains was obviously reduced during heating and finally up to the melting owing
to the one-dimensional confined space. For the nonisothermal crystallization of DC18DM-Br, the
normal crystallization took place in the bulk, like polymer melt crystallization. On the other hand, the
confinement had significant contribution to enhance the nonisothermal crystallization at higher
cooling rate (~ 5.0-20.0 °C/min). The promoted crystallization in one-dimensional confined space at
different Tc ranges (cooling rate > 5.0 °C/min) was successfully interpreted by much lower energy
barrier.

Analysis of overlapped dielectric relaxations by means of retardation time spectra.
R. Díaz-Calleja (1), M. J. Sanchis (2), E. Riande (3)
(1) Instituto de Tecnología Electrica, ETSII. Universidad Politecnica de Valencia (Spain).
(2 Instituto de Tecnología Electrica, ETSII. Universidad Politecnica de Valencia (Spain).
(3) Instituto de Ciencia y Tecnología de Polímeros C.S.I.C. Madrid (Spain).
Corresponding author: rdiazc@ter.upv.es
In the moderate supercooled regime, the response of liquids to external force fields is a single
absorption. In cooling, this absorption splits into two relaxations in the loss spectra. The fast relaxation
is named the β process and the other one, which is slow, is called the α or glass-liquid absorption [1].
An important issue in the study of chain dynamics is to perform a good deconvolution of overlapping
peaks in the loss spectra. Usually, relaxations in the frequency domain are described in terms of the
Havriliak-Negami (HN)-type equations [2]. Because many relaxations are poorly defined, it is often
difficult to discriminate between different values of fitting HN parameters describing the loss spectra
in a wide frequency window. Due to the fact that a Debye-type relaxation covers about 2.29 decades in
the frequency domain, but it becomes a Dirac delta function in the retardation time spectra,
compliance relaxation processes are better defined in the time domain [3]. In the present work some
results of this strategy of analysis are presented when applied to several polymers systems. Dipole
correlation function is calculated from the retardation spectra and subsequently, the Williams ansatz is
analyzed [4]. A discussion of the molecular origin of the secondary absorptions is carried out
assuming that the dipoles associated to polar groups librate around the bonds of the main chain, or
more frequently, the side-chains.
[1] F.S. Stillinger, Science 267 (1995) 1935
[2] S. Havriliak, S. Negami Polym. 8 (1967) 161–210; J Polym Sci, Polym Symp 14 (1966) 99
[3] G. Domínguez-Espinosa, D.Ginestar, M.J. Sanchis, R.Díaz-Calleja, E. Riande, J. Chem. Phys. 129
(2008) 104513
[4] G. Williams, Adv. Polym. Sci. 33 (1979) 60,; G. Williams, in Keynote Lectures in Selected Topics
of Polymer Science, edited by E. Riande CSIC, Madrid, 1995, Chap. 1
DIELECTRIC SPECTROCOPY S OF THE DYNAMICS IN NATURAL RUBBER-
CELLULOSE II NANOCOMPOSITES
P. Ortiz-Serna (1), R. Díaz-Calleja (1), M.J. Sanchis (1), G. Floudas (2), E. Riande (3), A. Martins (4),
L. Visconte (4), R. Nunes (4)
(1) Inst. de Tecnología Eléctrica Univ. Politécnica Valencia, 46022 Valencia, Spain
(2) Univ. of Ioannina, Dep. of Physics, P. O. Box 1186, 451 10 Ioannina, Greece
(3) Inst. de Ciencia y Tecnología de Polímeros (CSIC), 28006 Madrid, Spain
(4) Inst. de Macromoleculas Prof. Eloisa Mano, Univ. Federal do Rio de Janeiro, Brazil
Corresponding author: portiz@ter.upv.es
Nanocomposites materials obtained from natural rubber (NR) reinforced with different amounts of
cellulose II nanoparticles [1] (in the range of 0 to 30 phr) are studied by both dielectric spectroscopy
(DS) [2] and high pressure dielectric spectroscopy (HPDS) [3]. For comparative purpose pure
materials, NR and cellulose, are also investigated. The dielectric spectra of the nanocomposites exhibit:
(a) two overlapped α-relaxations associated with the dynamic glass transitions of NR and to a lipid

present in the NR as an impurity [4]; (b) a β-relaxation associated with local chain dynamics of
cellulose and (c) a relaxation process due to presence of water. The spectra exhibit conductivity
phenomena at low frequencies and high temperatures. The samples were also studied in the dry state.
An explanation of the reinforcement effect in the dielectric properties of the dry and wet
nanocomposites analyzed is offered.
[1] A.F. Martins,. L.L.Y. Visconte, R.C. Nunes, Kautschuk Gummi Kunststoffe, 55 (12) (2002) 637
[2] , N.G. McCrum, B.E Read, W. Williams, Anelastic and Dielectric Effects in Polymeric Solids,
Dover Publications, Inc., New York, (1991) 118
[3] G. Floudas in Broadband Dielectric Spectroscopy, F Kremer, A. Schönhals (Eds) Springer-Verlag
Berlin Heidelberg New York, (2003) Chap. 8
[4] S. Kawahara, T. Kakubo, J. T. Sakdapipanich, Polymer, 41 (2000) 7483
DYNAMICS OF GLASS-FORMING SYSTEMS UNDER PRESSURE
G. Floudas
University of Ioannina, Dept. of Physics and FORTH/BRI, Ioannina, Greece
gfloudas@cc.uoi.gr
We report on the origin of the dynamic arrest associated with the liquid-to-glass temperature in glassforming
liquids, amorphous polymers [1], biopolymers [2,3] and columnar discotic liquid crystals
[4,5]. Pressure together with the other thermodynamic parameters is essential for understanding the
dynamics in such systems. With respect to glass-forming liquids and polymers we show that monomer
volume and local packing play a key in controlling the dynamic arrest at Tg [1]. In the case of
polypeptides glass-formation originates from a network of broken hydrogen bonds and is independent
from the presence or absence of side chains, solvent molecules and type of peptide secondary structure
[2,3]. Lastly, the presence of multiple glass temperatures in columnar discotic liquid crystals ba`sed on
graphenes is discussed in the light of recent concerted efforts by dielectric spectroscopy and NMR
[4,5].
[1] G. Floudas, K. Mpoukouvalas, P. Papadopopulos, J. Chem. Phys. 124, 074905, 2006
[2] G. Floudas, H.W. Spiess, Macromol. Rapid Commun. 30, 278, 2009.
[3] P. Papadopoulos, G. Floudas, I. Schnell, T. Aliferis, H. Iatrou, N. Hadjichristidis, J. Chem. Phys.
122, 224906, 2005.
[4] M. Elmahdy, G. Floudas, M. Mondeshki, H.W. Spiess, X. Dou, K. Muellen, Phys. Rev. Lett. 100,
107801, 2008.
[5] M. Elmahdy, X. Dou, M. Mondeshki, G. Floudas, H.-J. Butt, H.W. Spiess, K. Muellen, J. Am.
Chem. Soc. 130, 5311, 2008.
INELASTIC NEUTRON SCATTERING OF ULTRATHIN POLYMER FILMS
T. Kanaya (1), R. Inoue (2), K. Kawashima (1), K. Nishida (1), G. Matsuba (1)
(1) Institute for Chemical Research, Kyoto University, Uji, Kyoto-fu 611-0011
(2) IFF, Forschungszentrum Jülich, D-52425 Jülich, Germany
Confined glass-forming polymers in thin films show very interesting but unusual properties different
from bulk. In order to understand the glassy dynamics and the glass transition mechanism in thin
films, we studied dynamics of polystyrene (PS) thin films (20–100 nm) by inelastic neutron scattering
(INS). In the meV region we found that mean square displacement as well as the density of
phonon states G(w) decreased with the film thickness below about 100 nm. In the meV region, we
evaluated the apparent glass transition temperature Tg from the mean square displacement . The
evaluated Tg increased as the film thickness decreased. This observation completely contradicts the
results revealed by X-ray and neutron reflectivity, where Tg decreased with film thickness. In the
conference we will discuss the molecular origin of these anomalous properties of PS thin films in
terms of dynamic heterogeneity of polymer thin films.

MOBILITY OF CHAIN MOLECULES IN NANOPORES
G. Yu (1), K. Lee (1), W. Cho (1), E. Woo (1), J. Huh (2), S. Obukhov (3), Y. G. Jeong (4), and K.
Shin (1)
(1) School of Chemical and Biological Engineering, Seoul National University, Seoul 151-744 South
Korea
(2) Active Polymer Center for Pattern Integration (APCPI), Yonsei University, 134 Shinchon-dong,
Seodaemun-gu, Seoul 120-749, South Korea
(3) Department of Physics, University of Florida, Gainesville, FL 32611 USA
(4) School of Advanced Materials and Systems Engineering, Kumoh National Institute of Technology,
Gumi 730-701, South Korea
Corresponding author: shin@snu.ac.kr
Polymer science under nanoscopic confinement has been focused on flat planar thin and ultrathin films.
But, quite recently, another geometry, other than thin film, is started being investigated. We could find
several instances where the behaviors of materials are not traditional any more due to non-flat
geometrical confinement. When the mobility of polymeric melt, crystallization kinetics of chain
molecules, or structure-formation of materials were taken as examples, it was easy to find that
nanoscopic cylindrical confinement renders the breakdown of bulk behaviors. The measured mobility
of polymers in the confined geometry is much higher than the mobility of the unconfined chains, and
the kinetics and structure was strongly dependent on the degree and shape of confinement. Those
unexpected physical behaviors are of significant importance in the design and processing engineering
on nanoscale.
COLLECTIVE DYNAMICS IN MOLECULAR LIQUIDS: NEUTRON SCATTERING AND
COMPUTER SIMULATIONS
Ubaldo Bafile (1), Fabrizio Barocchi (2,4), Eleonora Guarini (2,4) and Marco Sampoli (3,4)
(1) Consiglio Nazionale delle Ricerche, Istituto dei Sistemi Complessi, I-50019 Sesto Fiorentino
(Firenze), Italy
(2) Dipartimento di Fisica, Università di Firenze, I-50019 Sesto Fiorentino (Firenze), Italy
(3) Dipartimento di Energetica, Università di Firenze, I-50139 Firenze, Italy
(4) CNR-INFM, CRS-Soft, c/o Dipartimento di Fisica, Università di Roma "La Sapienza", I-00185
Roma, Italy
ubaldo.bafile@isc.cnr.it
Molecular dynamics calculations of the dynamic structure factor of simple molecular liquids (methane
and carbon dioxide) have been performed with intermolecular anisotropic potentials selectively
validated by neutron Brillouin scattering data [1] in the whole experimental Q range up to the main
peak position of the static structure S(Q). Accurate S(Q,ω) data can then be obtained by extending the
simulation study to a much wider Q range, also for quantities not directly derivable from
measurements, such as the centre-of-mass correlation spectra. We exploit this possibility for a detailed
study of the translational dynamics of molecules, by applying the concepts described in a recent work
[2]. S(Q,ω) spectra are accurately described by a viscoelastic modelling of the second-order memory
function for the time evolution of the intermediate scattering function. The Q dependence of the
various parameters provides valuable insight into the relaxation processes that rule the propagation
and damping of acoustic waves with varying wavevector.
[1] E. Guarini et al., Phys. Rev. Lett. 99, 167801, 2007; Chem. Phys. Lett. 464, 177, 2008
[2] U. Bafile et al., Phys. Rev. E 73, 061203, 2006
DYNAMICS AND ORDER WITHIN THE NANOPARTICLE CORONA
R.A. Vaia, P. Mirau, J. Busbee, D. Jacobs, M. Jespersen, M. Tchoul, H. Koerner, F. Oyerokun

NanoStructured and Biological Materials Branch, Air Force Research Laboratory, Wright-Patterson
AFB, OH
richard.vaia@wpafb.af.mil
Notwithstanding the substantial commercial success of blends of nanoparticles and polymers, a
succinct articulation of the ultimate performance afforded by these concepts is limited by an
incomplete fundamental understanding of the perturbations to polymer properties resulting from the
structural and chemical details of the nanoparticle and its coupling with the matrix. Potential
aerospace applications are pushing focus beyond the impact of low volume fractions of nanoparticles
on thermomechanical properties towards the role of high volume fraction of nanoparticles on dielectric
and mechanically responsive attributes. Carrier transport, leakage current, local field distribution as
well as mechanical energy transduction and dissipation motivate our attention on high-inorganic
fraction systems where granular and chain dynamics are coupled and display comparable time scales.
We will discuss current efforts combining in-situ scattering, dielectric spectroscopy, NMR and
simulations to understand the structure and dynamics within the “corona” surrounding these
nanoparticles. To maximize inorganic fraction, we are investigating nanocomposites in which all of
the organic phase is pre-associated with the nanoparticle (in contrast to dispersing a nanoparticle with
surface modifier into a matrix phase). The corona architecture spans ionic liquid and ionomer motifs
to low and intermediate graft densities of linear polymers with multi-modal distributions.
Multiscale simulation of polymer melt viscoelasticity: expanded-ensemble end-bridging Monte
Carlo coupled with atomistic nonequilibrium molecular dynamics
Vlasis G. Mavrantzas
Department of Chemical Engineering, University of Patras & FORTH-ICE/HT, Patras, GR 26504,
Greece
Abstract
We present a powerful framework for computing the viscoelastic properties of polymer melts
based on an efficient coupling of two different atomistic models: the first is represented by the Non-
Equilibrium Molecular Dynamics (NEMD) method and is considered as the micro-scale model. The
second is represented by a Monte Carlo (MC) method in an expanded statistical ensemble and is free
from any long time scale constraints. Guided by recent developments in nonequilibrium
thermodynamics, the expanded ensemble incorporates appropriately defined “field” variables driving
the corresponding structural variables to beyond equilibrium steady states. The expanded MC is
considered as the macro-scale solver for the family of all viscoelastic models built on the given
structural variable(s). The explicit form of the macroscopic model is not needed; only its structure in
the context of the GENERIC (General Equation for the Non-Equilibrium Reversible Irreversible
Coupling) or generalized bracket formalisms of nonequilibrium thermodynamics is required. We
illustrate the method here for the case of unentangled linear polymer melts, for which the appropriate
structural variable to consider is the conformation tensor c% . The corresponding Lagrange multiplier is
a tensorial field α . We have been able to compute model-independent values of the tensor α , which
for a wide range of strain rates (covering both the linear and the nonlinear viscoelastic regimes) bring
results for the overall polymer conformation from the two models (microscale and macroscale) on top
of each other. In a second step, by comparing the computed values of α with those suggested by the
macroscopic model addressed by the chosen structural variable(s), we can identify shortcomings in the
building blocks of the model. How to modify the macroscopic model in order to be consistent with the
results of the coupled micro-macro simulations is also discussed. From a theoretical point of view, the

proposed multiscale modeling approach provides a solid framework for the design of improved, more
accurate macroscopic models for polymer melts.
References
H.C. Öttinger, Beyond Equilibrium Thermodynamics (Wiley-Interscience, Hoboken, New Jersey,
2004).
V.G. Mavrantzas and D.N. Theodorou, Macromolecules 31, 6310 (1998).
V.G. Mavrantzas and H.C. Öttinger, Macromolecules 35, 960 (2002).
C. Baig and V.G. Mavrantzas, Phys. Rev. Lett. 99, 257801 (2007).
C. Baig and V.G. Mavrantzas, Phys. Rev. B., in press (2009).
TRANSPORT PROPERTIES FOR A FLUID SYSTEM WITH PENETRABLE PARTICLES
Helge-Otmar May (1) and Peter Mausbach (2)
(1) University of Applied Sciences Darmstadt, Schöfferstr. 3, D-64295 Darmstadt, Germany,
helge.may@h-da.de
(2) Cologne University of Applied Sciences, Betzdorferstr. 2, D-50679 Cologne, Germany
The aim of this study is to analyze the self-diffusion coefficient, the shear viscosity and the thermal
conductivity of the Gaussian core model (GCM). Because the potential is bounded, overlapping of
particles is possible, and the GCM shows many thermodynamic peculiarities [1]. Transport
coefficients were studied by means of the Green-Kubo formulas calculated from molecular dynamics
simulations for a very large density and temperature range. We show that anomalous behaviour occurs
for the self-diffusion coefficient and the shear viscosity resulting in a surprising Stokes-Einstein
behaviour [2]. In recent studies, kinetic scaling relationships have been employed to connect transport
coefficients to the excess entropy. It was shown how entropy scaling can be used to predict state
conditions for which kinetic anomalies might be found. Therefore, we calculated the excess entropy
from an equation of state for the GCM. We constructed scaling laws for the transport properties which
are different from that proposed for “normal” fluids.
[1] P. Mausbach, H.-O. May, Fluid Phase Equilib. 249, 17-23 (2006)
[2] H.-O. May, P. Mausbach, Phys. Rev. E 76, 031201 (2007)
DIELECTRIC RELAXATION OF EPOXY MATRIX NANOCOMPOSITES WITH CARBON
NANOTUBES
Filippo Scarponi (1), Marco Leonardi (1,2), Daniele Fioretto (1), Luca Valentini (2) and José M.
Kenny (2)
(1) Department of Physics, University of Perugia, 06100 Perugia, Italy
(2) Laboratory of Materials Science and Technology, University of Perugia, 05100 Terni, Italy
kenny@unipg.it
The dielectric relaxation behavior of reactive epoxy systems and their nanocomposites with carbon
nanotubes have been analyzed and are reported here. The frequency dependent dielectric permittivity
of a typical epoxy resin (DGEBA) reacting isothermally with an aromatic amine hardener (MDEA)
has been measured by means of dielectric spectroscopy in the range 10 Hz - 10 6 Hz. Dielectric spectra
were taken at regular intervals during curing reaction, in the pure epoxy-amine reactive system and in
the nanocomposites obtained by adding 0.1 % and 1.0 % weight fractions of purified multiwall carbon
nanotubes. The dielectric response in the pure reactive system appears to be dominated by ionic
conductivity and by structural relaxation with the characteristic time strongly increasing with curing
time. In the carbon nanotube loaded samples the presence of the nanofiller originates a new and strong
relaxation, which overcomes and hides the structural contribution. The characteristic parameters of the
dielectric relaxation in the loaded samples are compatible with hopping dominated conduction

mechanisms. An increase of DC conductivity in the final part of the reaction is also observed, which
can be ascribed to dielectrophoretic migration of carbon nanotubes.
MOLECULAR RELAXATION IN GREEN COMPOSITES, USING WHEAT FLOUR BASED
THERMOPLASTIC MATRIX REINFORCED BY NATURAL FIBRES
N. Leblanc (1), P.A. Sreekumar (1, 2), L. Dobircau (1, 2), A.Galandon (1, 2), R. Saiah (1, 2) and J. M.
Saiter (2)
(1) LGMA – Esitpa, 3 rue du Tronquet, BP 40 118, 76 134 Mont Saint Aignan cedex, France
(2) LECAP – PBS FRE 3101 Université de Rouen - Avenue de l’Université, B.P. 12, 76801
Saint Etienne du Rouvray Cedex
nleblanc@esitpa.org
A biodegradable thermoplastic material based on wheat flour by-product was fabricated by using
extrusion technique. It was shown that this material displays after extrusion similar properties as
thermoplastic starches [1]. By means of DSC and DMA measurements, we show that this new
generation of biodegradable thermoplastic exhibit two glass transition, one at low temperature (-40°C)
which is characteristic of a glycerol rich phase and the second one at high temperature (40°C) which is
characteristic of the starch rich phase. The characteristic time of relaxation of each glass transition and
the relaxation map of this complex system have been determined. We also show that the molecular
relaxation dynamics at the glass transition of each vitreous phase are very sensitive to the existence of
fillers as SiO2 or the incorporation of natural fibres as cotton, flax or sisal. Finally we show that
incorporation of natural fibers (flax, sisal, cotton) improve the mechanical properties, leads to the
realisation of 100% green composites [2].
[1] N. Leblanc, R. Saiah, E. Beucher, R. Gattin, M. Castandet, J-M. Saiter, Carbohydrate Polymers, 73,
548, 2008.
[2] R. Saiah, P.A. Sreekumar, P. Gopalakrishnan, N. Leblanc, R. Gattin, J.M. Saiter, Polymer
Composites, in press, 2008.
Keywords: Wheat flour, Biodegradable thermoplastics, natural composite, mechanical properties,
DMA.
COMPUTER SIMULATION ON ERGODICITY OF SILICA GLASS
Akira TAKADA, a) Pascal RICHET b) and Tooru ATAKE c)
a) Research Center, Asahi Glass Co. Ltd, 1150 Hazawa-cho, kanagawa-ku, Yokohama, 221-8755
Japan
b) Institut de Physique du Globe, 4 Place Jussieu, 757252 Paris Cedex 05, France

c) Materials and Structures Laboratory, Tokyo Institute of Technology, 4259 Nagatsuta-cho, Midoriku,
Yokohama, 226-8503 Japan
A new method called ‘atomistic energy distribution analysis’ has been recently developed. Thermally
activated structural transformations in silica glass were successfully explained by employing this
method. This method is applied to investigate ergodicity of silica glass. Ensemble-averaged and timeaveraged
atomistic energies are compared. The calculated results show that the ergodic-to-nonerdogic
transition occurs when the system temperature is decreased, that is, when the liquid-to-glass transition
occurs.
ORDER AND DISORDER IN POLYMER NETWORKS
Jens-Uwe Sommer (1,2)
(1) Leibniz-Institute of Polymer Research Dresden, D-01069 Dresden, Germany
(2) Technische Universität Dresden, Institute of Theoretical Physics, D-01069 Dresden, Germany
email: sommer@ipfdd.de
Polymer networks are structurally and topologically disordered soft solids. Their applications are
ranging from tires over polymer surface design to biological and medical applications. We consider
orientational order of chain segments in polymer networks both theoretically and using large scale
Monte Carlo simulations with the bond fluctuation method [1-3]. In particular we focus on the
properties of the tensor order parameter which is directly related to the dynamic (residual) coupling
constant in multi-quantum NMR experiments, during swelling of networks. The goal is to relate
NMR-experiments to molecular models of polymer networks [4]. We show that good solvent
conditions in the swollen state play a crucial role for the tensor order parameter which has been
disregarded in the literature so far. In particular, we show that the tensor order parameter decreases
due to excluded volume interactions. Using analytical results and scaling arguments we derive a
universal behavior for the observable order parameter (residual spin-spin coupling in NMR
experiments) with respect to the equilibrium degree of swelling which has been experimentally
verified [3]. In the light of these observation we discuss several microscopic models of network
swelling. Using a general relation between local forces on chain bonds and the tensor order parameter
we further discuss possible observations on structurally regular networks such as obtained recently in
experiments [5].
[1] J.-U. Sommer and K. Saalwächter, European Phys. J. E 18 (2005) 167-182
[2] Z. Usatenko and J.-U. Sommer, Macrom. Theory Simul. 17, 39 (2008)
[3] J.-U. Sommer, Walter Chassé, Juan López Valentín, and Kay Saalwächter, Phys. Rev. E 78,
051803 (2008)
[4] K. Saalwächter, F. Kleinschmidt and J.-U. Sommer, Macromolecules 37, 8556 (2004)
[5] T. Matsunaga, T. Sakai, Y. Akagi, U. Chung, and M. Shibayama, Macromolecules 42, 1344 (2009)
WHAT MAKES INORGANIC SOLIDS MELT AND FORM GLASSES?
H. J. Hoffmann
Institute of Materials Science and Technology, University of Technology, Englische Strasse 20, 10587
Berlin, Germany
hoffmann.glas@tu-berlin.de

To understand melting, the enthalpy and the specific heat capacities of solids have been analysed. In
many cases the specific heat of the electrons cannot be neglected near the melting transition. Thus,
electrons make transitions from low to high energy levels with increasing temperature. The charge
distribution changes according to the random time series of electronic transitions into different states
and drives the core ions to new positions. If the core ions relax to their new positions within the
lifetime of the excited states we have a changing arrangement of the core ions or a melt. The
distribution of the electronic energy levels in the molten state differs from that of the crystalline solid
with respect to both energy and space. With decreasing temperature the electrons relax to lower states
of the disordered arrangement. If the forces are too weak to attract the core ions to new and regular
positions the transformation into a glass takes place. Thus, electronic transitions to higher energy
states with a sufficiently large deviation of the charge distribution freeze out near the glass
transformation temperature and the disorder becomes fixed. This is supported by sufficiently strong
directional bonds between neighbouring ions and a low melting entropy per atom.
A PLAUSIBLE INTERPRETATION OF THE DENSITY SCALING OF THE DIFFUSIVITY
AT VARIOUS PRESSURES IN VISCOUS LIQUIDS
Anthony N. Papathanassiou
University of Athens, Physics Department, Solid State Physics Section, Panepistimiopolis, 15784
Zografos, Greece
antpapa@phys.uoa.gr
A preliminary attempt to understand why some dynamic properties of supercooled liquids scale with
density and temperature is made. Fundamental thermodynamics and an earlier elastic solid-state point
defect model [1, 2] are employed to formulate an analytical second-order polynomial function
describing the density scaling of the diffusion coefficient in viscous liquids [3]. The function
parameters are merely determined by the scaling exponent, which is directly connected with the
Grüneisen constant. Density scaling diffusion coefficient isotherms obtained at different pressures
collapse on a unique master curve, in agreement with recent computer simulation results of Lennard-
Jones viscous liquids [4]
[1] P. Varotsos and K. Alexopoulos, Phys. Rev. B 15, 4111, 1977
[2] P. Varotsos and W. Ludwig, 8, 2683, 1978
[3] A. N. Papathanassiou, Phys. Rev. E, 79, 032501, 2009
[4] D. Coslovich and C.M. Roland, J. Phys. Chem. B, 112, 1329, 2008
SALTY ICE VII UNDER PRESSURES
L.E. Bove (1), S. Klotz (1), Th. Strässle (2), T.C. Hansen (3), A.M. Saitta (1)
(1)Physique des Milieux Denses, IMPMC, CNRS-UMR 7590, Université P&M Curie, 75252 Paris,
France
(2)Laboratory for Neutron Scattering, ETH Zurich and Paul Scherrer Institut, Villigen, Switzerland
(3)Institut Laue Langevin, BP 156, F-38042 Grenoble, France
Correspondence author: bove@impmc.jussie.fr
It is widely accepted that ice, no matter what phase, is unable to incorporate large amount of salt into
its structure. This conclusion is based on the observation that upon freezing of salt water, ice expels
the salt almost entirely into brine, a fact which can be exploited to desalinate seawater. Here we show,

y neutron diffraction measurements under high pressure, that this behaviour is not an intrinsic
physico-chemical property of ice phases. We demonstrate that substantial amounts of dissolved LiCl
can be built homogeneously into the ice VII structure if it is produced by re-crystallization of its glassy
state under pressure [1]. Such ` alloyed` ice VII has significantly different structural properties
compared to pure ice VII, such as a 8% larger unit cell volume, 5 times larger displacement factors, an
absence of a transition to an ordered ice VIII structure, plasticity, and most likely ionic conductivity.
[1] S. Klotz, L.E. Bove, T. Strassle, T. Hansen, and M. Saitta, Nature Materials 2009, 8, 405.
THE BEHAVIOR OF ULTRATHIN POLYMER FILMS AT THE NANOMETER SIZE
SCALE: VISCOELASTIC AND ELASTIC RESPONSES
Shanhong Xu, Paul A. O’Connell and Gregory B. McKenna
Department of Chemical Engineering, Texas Tech University, Lubbock, TX 79409-3121 USA
Correspondence author: greg.mckenna@ttu.edu
We report on the viscoelastic and elastic responses of ultrathin polymer films obtained by a novel
bubble inflation method developed in our labs [1,2]. Of particular interest is the observation that the
reduction of the glass transition temperature of polymer films is non-universal, i.e., Tg decreases
dramatically for polystyrene and polycarbonate while it does not change for poly(vinyl acetate).
Furthermore, we find that the “rubbery plateau” regime is dramatically stiffened in all materials
investigated but that the amount of stiffening depends on the polymer. The polystyrene, polycarbonate
and poly(vinyl acetate) show stiffening of upwards of 1,000 fold while poly(n-butyl methacrylate)
shows stiffening of approximately 50-100 fold. Finally, surface tension effects are found to be more
important in the poly(n-butyl methacrylate) than in the other materials, suggesting that the stiffening is
due to both “molecular effects” and to surface tension effects.
[1] P. A. O’Connell and G.B. McKenna, Science, 307, 1760 2005.
[2] P.A. O’Connell and G.B. McKenna, Rev. Sci. Instr., 78, 013901 2007.
DISPERSION PROFILES OF ALPHA AND BETA DIELECTRIC RELAXATIONS IN GLASS
FORMING MOLECULAR LIQUIDS
Li-Min Wang (1) and Ranko Richert (2)
(1) State Key Lab of Metastable Materials Science and Tecnhology and Department of Materials
Sicence and Engineering, Yanshan University, Qinhuangdao, Hebei 066004, China
(2) Department of Chemistry and Biochemisty, Arizona State University, Tempe, AZ 85285, USA
Limin_Wang@ysu.edu.cn
At glass transition regime, two relaxation dynamics, alpha and beta, are usually observed in various
glassforming liquid. Alpha relaxations are referred as to the structural relaxations, whose dynamics
scales with viscosity and, are associated with the calorimetric glass transition, while beta relaxations
concern Johari-Goldstein (JG) relaxation and those generated from the intramolecular dynamics [1,2].
Here, we investigated the relaxation times and the dispersions of alpha and beta relaxations in a
number of glass forming molecular liquids by using dielectric technique within a broad dynamic range.
The compilation of the dynamic parameters found that the time-temperature-superposition (TTS)
liquids [3] usually show an appreciate beta relaxation. The width of alpha relaxation basically
decreases with liquid fragility, while that of JG-type beta relaxation increases, and a coincidence of the
two relaxation parameters is expected in the high fragility extreme, m ~ 170. The dynamic span of the
TTS regions largely depends on the fragility, and at the high fragility limit, the region is expected to
extend up to a dynamics of relaxation time 10 -7 s. The transition from non-Debye (non exponential) to
Debye type in alpha-relaxations is expected to complete before the approach to the dynamics of
relaxation time 10 -10 s. The dispersion width of the JG-type beta-relaxation dynamics holds a strong

dependence on relaxation dynamics, and rapidly decreases towrad that of alpha-relaxation with
increasing dynamics. The present studies emphasized the corrlelation between the alpha- and betarelaxation
dynamics in the molecular liquids.
[1] G. P. Johari and M. Goldstein, J. Phys. Chem. 74, 2034, 1970; J. Chem. Phys. 53, 2372, 1970
[2] K. L. Ngai and M. Paluch, J. Chem. Phys. 120, 857, 2004
[3] N. B. Olsen, T. Christensen, and J. C. Dyre, Phys. Rev. Lett. 86, 1271, 2001
SOLID NMR STUDIES OF LOCAL AND COLLECTIVE MOTION IN SEMI-
CRYSTALLINE POLYETHYLENE: THE INFLUENCE OF MORPHOLOGY AND CHAIN
BRANCHING
R. Graf (1), Y.-F. Yao (2), Y. Wei (3), K.B. Wagener (3), S. Rastogi (4), H.W. Spiess (3)
(1) Max-Planck Institute for Polymer Research, Ackermannweg 10, 55128 Mainz, Germany
(2) Department of Physics, East China Normal University, North Zhongshan Road 3663, 200062
Shanghai, China
(3) Chemistry Department, University of Florida, Gainesville, Florida 32611-7200, USA
(4) Eindhoven University of Technology, Chemical Engineering, PO Box 513, 5600 MB Eindhoven,
NL
graf@mpip-mainz.mpg.de
In linear semi-crystalline polyethylene, the crystallisation conditions determine the local morphology.
Solid state NMR results monitoring CH dipolar couplings, 13 C chemical shift anisotropy and 13 C
exchange processes are reported. Comparing chemically identical samples subjected to different
crystallisation procedures, the melt crystallized sample shows higher local molecular mobility in the
non-crystalline regions, but chain diffusion through the crystallites is substantially slower then in the
better ordered solution crystallized samples. The activation energies for chain diffusion in the two
samples match. Thus, the differences are attributed to entropic reasons [1]. Polyethylene with regular
spaced methyl branches exhibit in the crystalline regions pronounced rotational dynamics around the
chain axis at the methyl site emerging to a collective motion and ultimately to a rotator phase for
shorter spacing between the methyl branches [2]. These rotational modes, however, do not contribute
to translational diffusion of the polymer chain.
[1] Y.-F. Yao, R. Graf, H.W. Spiess, S. Rastogi, Phys. Rev. E, 76, 060801, 2007; Macromolecules, 41,
2514, 2008.
[2] Y. Wei, R. Graf, J.C. Sworen, C.-Y. Cheng, C.R. Bowers, K.B. Wagener, H.W. Spiess, Angew.
Chem. (Int. Ed.), in press.
ADAPTABILITY CONCEPT FOR CHEMICALLY-ORDERED COVALENT-BONDED
NETWORKS EXEMPLIFIED BY GLASSY As-S/Se
O. Shpotyuk (1,2), M. Hyla (2), V. Boyko (1), and R. Golovchak (1)
(1) Institute of Materials of SRC “Carat”, 202, Stryjska str., Lviv, 79031, Ukraine
(2) Institute of Physics of Jan Dlugosz University, 13/15, al. Armii Krajowej, Czestochowa, 42200,
Poland
shpotyuk@novas.lviv.ua
In respect to Phillips-Thorpe mean-field rigidity theory [1,2], the covalent-bonded networks possess an
intermediate phase having just 3 Lagrangian constrains per atom, which appears so as to avoid stress.
We shall try to examine this idea for binary As-S/Se glass-forming system within computational
cluster-modeling approach developed for different two-cation AsnSm clusters. Our approach, namely
CINCA – the cation-interlinking network cluster approach, – allows to simulate glass-forming
tendencies in covalent-bonded networks owing to HyperChem program package with RHF/6-311G *
basis set.

The performed calculations showed that self-adaptive phase in these glasses can be formed only by
corner-shared AsS(Se)3/2 pyramids having 3 Lagrangian constraints per atom, while the optimallyconstrained
quasi-tetrahedral S(Se)=AsS(Se)3 units are energetically impossible. To check the possible
upper limit in self-adaptive phase, we recalculate the numerical values of forming energies for some
three-cation network clusters. It is shown that this limit can be stretched over stoichiometric As2S3
composition, provided As3S3.5 structural blocks will appear. However, this process is partly
compensated by another one connected with over-constrained As2S4/2 clusters having one homopolar
As-As covalent bond.
[1] J.C. Phillips, J. Non-Cryst. Sol., 34, 153, 1979)
[2] M.F. Thorpe, J. Non-Cryst. Sol., 57, 355, 1983.
HIKING DOWN THE ENERGY LANDSCAPE: STABLE GLASSES BY PHYSICAL VAPOR
DEPOSITION.
M.D. Ediger (1), S.F. Swallen (1), K.L. Kearns (1), K.J. Dawson (1) , L. Yu (2).
(1) Department of Chemistry, University of Wisconsin-Madison, Madison, WI 53706 USA
(2) School of Pharmacy, University of Wisconsin-Madison, Madison, WI 53705 USA
ediger@chem.wisc.edu
The prevailing view in the literature is that vapor deposition produces unstable glasses. We show that
slow depositions onto substrates held near 0.85 Tg can produce exceedingly stable glasses, likely the
most stable glasses ever produced in a laboratory. Producing glasses of similar stability by slowly
cooling a liquid would require thousands of years. A mobile surface layer (~ 2 nm) at the glass
surface allows rapid equilibration of incoming molecules at a temperature where bulk relaxation is
very slow. We demonstrate that vapor-deposited glasses have low enthalpies, high densities, and a
high resistance to water uptake. More surprisingly, we show that transformation of the stable glass
into the supercooled liquid above Tg occurs via a growth front mechanism. For indomethacin, WAXS
measurements show that the most stable vapor-deposited glasses have a new amorphous packing
arrangement. Vapor deposition may ultimately produce samples that can test proposed resolutions of
the Kauzmann entropy crisis and we will review our progress towards this goal.
DIELECTRIC PROPERTIES OF BOUND WATER IN BIOLOGICAL SYSTEMS; THE
BEAUTY OF NATURE
Yu. Feldman, A. Puzenko, P. Ben Ishai
Department of Applied Physics, The Hebrew University of Jerusalem, Givat Ram, 91904 Jerusalem,
Israel
yurif@vms.huji.ac.il
The mediator of many biological reactions is the interaction of water with biological structures. This
paper reviews some of the most intriguing of these mechanisms. Consequently, the results presented
herein are expected to have a far reaching impact on disciplines such as biophysics, biochemistry,
pharmacology and medical physics. In many dielectric relaxation processes involving water in

iological systems, the mechanisms are governed by Cole-Cole (CC) behaviour. The paper will review
the nature of the CC model and the relationship between the stretch parameter, α, of the CC formula
and the relaxation time, τ, of the process. It will be shown that this links structural and dynamic
elements of the relaxation mechanism.
SELF-ASSEMBLY AND DYNAMICS OF SYNTHETIC POLYMERS AND POLYPEPTIDES
FROM NMR SPECTROSCOPY
H.W. Spiess (1), G. Floudas (2)
(1) Max-Planck Institute for Polymer Research, Ackermannweg 10, 55128 Mainz, Germany
(2) Department of Physics, University of Ioannina, P.O. Box 1186, GR-45110 Ioannina, Greece
spiess@mpip-mainz.mpg.de
This talk highlights the results of recent efforts on understanding the hierarchical self-assembly and
dynamics of polypeptides with the aid of different NMR techniques, X-ray scattering and dielectric
spectroscopy as recently reviewed in [1]. The concerted application of these techniques shed light on
the origin of the glass transition, the persistence of the α-helical peptide secondary motif and the
effects of topology and packing on the type and persistence of secondary structures. With respect to
the freezing of the dynamics at the liquid-to-glass temperature it was found that the origin of this
effect is a network of broken hydrogen bonds. The presence of defected hydrogen bonded regions
reduces the persistence length of α-helices. Block copolypeptides provide means of manipulating both
the type and persistence of peptide secondary structures.
[1] G. Floudas and H. W. Spiess, Macromol. Rapid Commun. 30, 278, 2009
Slow dynamics on a complex lattice of water molecules:
KOH doped tetrahydrofuran clathrate hydrate
A. Nowaczyk (1), S. Schildmann (1), B. Geil (1,2), C. Gainaru (1), R. Böhmer (1)
(1) Technische Universität Dortmund, 44221 Dortmund, Germany
(2) Institut fuer Physikalische Chemie, Tammanstr. 6, 37077 Goettingen
andre@e3.physik.uni-dortmund.de
Depending on the interaction strength of dipolar molecules located on crystalline lattices, such
molecules may show an orientational glass transition. On the other hand, for some small, molecules,
e.g., CO or N2O, the dipolar interactions are insufficient to establish an ordered low-temperature state.
During the slow-down of the motion in these compounds electrical order is approached without
establishing it on accessible time scales. Also phases with ice-like structures show such slow dynamics
and clathrate hydrates provide examples. Here the requirement to fulfill the Bernal-Fowler ice rules, in
conjunction with the presence of defects, leads to complex freezing dynamics. An interesting
observation made here is that minute amounts of ionic dopants, e.g., KOH, can alter the ordering
tendencies significantly. Some aspects of adding ionic impurities were studied previously [1]. To
monitor the establishment of order on the water lattice on a microscopic level we carried out 2 H-NMR
employing deuterated THF guest molecules as probes. The presence or absence of a low-temperature
ordered state is revealed via measurements of spin-lattice relaxation times and absorption spectra.
[1] see O. Yamamuro, T. Matsuo, H. Suga, W.I.F. David, .M. Ibberson, A.J. Leadbetter Physica B
213&214, 405 (1995); T, Madhusudan, S. S. N. Murthy, J. Chem. Phys. A 106, 5072 (2002) and
references cited therein.

Glass transition in thin atactic polystyrene films:
Molecular modelling approach
Dmytro V. Hudzinskyy, Alexey V. Lyulin and M.A.J. Michels
Group Theory of Polymers and Soft Matter, Technische Universiteit Eindhoven,
P.O. Box 513, 5600 MB Eindhoven, The Netherlands,
Dutch Polymer Institute, P.O. Box 902, 5600 AX Eindhoven, The Netherlands
Polymers near or at solid surfaces are confined because the presence of the surfaces strongly reduces
the number of possible configurations of a polymer and hence its entropy. It means that properties of
polymers – both structure and segmental relaxations -close to the support and free surface are
principally different from those in a bulk. A molecular understanding of polymer segmental dynamics
and structure in thin films in the vicinity of the glass transition is still missing. The main goal of our
study is to investigate the influence of free interface as well as the strength of attraction to the
substrate for supported thin films on a reduction of glass-transition temperature. We perform
molecular-dynamics simulations to explore the influence of confinement on a glass transition
temperature for free-standing and supported atactic polystyrene (aPS) thin films of different thickness
and strength of attraction to the substrate. It was found that for thin supported films (less than 100Å
thickness) the glass-transition temperature dramatically decreases. We prove that for such thin films
both free interface and a substrate plays an important role as compared to bulk. Therefore, the Tg
values in three different layers - close to the free interface, the core layer in the middle of the film, and
substrate layer - have been simulated separately. We studied the corresponding dependences of Tg on
thickness and adsorption strength. For these layers the segmental order parameter has been calculated
as well. The substrate is shown to orient the aPS segments significantly. Computational annealing of
aPS melts at different temperatures does not influence the final results.
EXPOSING THE DIELECTRIC BEHAVIOR OF ‘EXOTIC’ GELS
P. Ben Ishai (1) , D. Libster (2), A. Aserin (2), N. Garti (2) and Yu. Feldman (1)
(1) Dept. of Appl. Physics, The Hebrew University of Jerusalem, Givat Ram, Jerusalem 91904, Israel.
(2) Casali Inst. of Appl. Chemistry, The Hebrew University of Jerusalem, Givat Ram, Jerusalem
91904, Israel.
paulb@vms.huji.ac.il
In the search for tailorable drug delivery systems “exotic” gels offer inviting possibilities. One avenue
is structures, such as reverse hexagonal mesophases (HII) that can be tuned to drug release under
specific biological conditions. We present a dielectric study of ternary glycerol monooleate
(GMO)/tricaprylin (TAG)/ phosphatidylcholine (PC) /water hexagonal systems that form long “pipes”
encasing water. The results reveal an intriguing percolation of the heavy TAG molecule, intercalated
between the GMO tails. Adding an even heavier macromolecule, such as the drug Cyclosporin A,
disrupts the percolation of TAG. The power and stretch parameters of the correlation functions of this
process reveal a critical temperature, T0=307 °K, at which the breakdown of interfacial water can
“release” the drug. Additionally the study reveals further complex molecular behavior in and around
the interfaces of the mesoscopic structures of the gel. Once again the critical temperature is revealed
in the behavior of the Cole-Cole parameter α of these processes. The implications towards drug
delivery are explored.
SOLVENT-INDUCED MORPHOLOGY EVOLUTION AND ORDERING IN DIBLOCK
COPOLYMER FILMS
Irina V. Neratova (1, 2) and Pavel G. Khalatur (1)
(1) Department of Polymer Science, Ulm University, Albert-Einstein-Allee 47, 89081, Ulm, Germany

(2) Department of Physical Chemistry, Tver State University, Sadovy per., 35, 170002, Tver, Russia
irina.neratova@googlemail.com
The well-defined nanostructures with long-range order are technologically and industrially important.
Because of the self-assembly into periodic arrays block copolymers form polymer films with different
patterns. If one could achieve defect-free ordering over macroscopic areas these materials would find
applications in semiconductor industry or as filtration devices. The coating process is one of the key
elements of many modern technologies to produce nanostructured polymer films. Coating is the
complicated process, which leads to the formation of different morphologies within the films. During
this process the transport properties, such as the interdiffusion of a solvent in a polymer matrix, are
necessary to control. The solvent evaporation is an interesting non-equilibrium phenomenon taking
place in painting, printing, creation of templates and high-resolution patterns for fabricating functional
nanostructures. However, many aspects of the film formation induced by the solvent evaporation,
including the polymer segment relaxation and microdomain orientation, are still not clear. In the
present study, we use the Dissipative Particle Dynamics (DPD) simulation to explore the influence of
solvent on the phase behavior in ultrathin AB-copolymer films. We propose a new approach to
generate target morphologies by controlling the solvent evaporation. The main idea is to vary the
solvent concentration, solvent selectivity, and evaporation rate to reach the long-range order of
microdomain arrays with tunable orientation. We compare the phase behavior of confined block
copolymer systems to that observed for the unconfined bulk. Using the solvent evaporation based
approach, it is possible to reach the equilibrium target structures within much smaller time as
compared to that necessary for the structure formation without solvent effects.
The financial support SFB 569 «Hierarchische Strukturbildung und Funktion Organisch-
Anorganischer Nanosysteme», Ulm, Germany is highly appreciated.
TWINKLING FRACTAL THEORY OF THE GLASS TRANSITION: EXPERIMENTAL
PROOF
R.P. Wool (1), J. F. Stanzione III (2), and K.E Strawhecker (3)
(1) (2) Department of Chemical Engineering, University of Delaware, Newark DE, 19716 USA
(3) Army Research Lab, Aberdeen, MD USA
wool@udel.edu
The Twinkling Fractal Theory (TFT) is a new approach to the glass
transition in amorphous solids [1]. The development of dynamic
percolating fractal structures near Tg is the main element of the TFT. The
key concept of the TFT derives from the Boltzmann population of excited
states in the anharmonic intermolecular potential between atoms in the
energy landscape, coupled with percolating solid fractal structures near Tg
The percolating solid fractal twinkles with a frequency spectrum F(ω) ~
ω df-1 exp -|∆E|/kT as solid and liquid clusters interchange with
frequency ω. The Orbach vibrational density of states for a fractal is
g(ω) ~ ω df-1 , where df = 4/3 and the temperature dependent
activation energy behaves as ∆E ~ (T 2 – Tc 2 ). The twinkling fractal
spectrum F(ω) at Tg predicts that the spatio-temporal
autocorrelation relaxation function [1]:
C
ω=
1
t
2
2 ⎛ β T −T
⎜ kT
⎝
df −1
g
( t,
T ) = ω exp −ωt
exp⎜−
⎟ dω
∫
ω
o
⎪
⎧
⎨
⎪⎩
⎞
⎪
⎫
⎟
⎬
⎠⎪⎭
Log(C(t))
0.0
-0.5
-1.0
-1.5
-2.0
Experimental
Experimental Fit
Theoretical Fit (a.u.)
-2.5
0.0 0.4 0.8 1.2
Log(t/s)
1.6

C(t) behave as C(t) ~ t -1/3 (short times), C(t) ~ t -4/3 (long times) and C(t) ~ t -2 (ω

2500 California Plaza
Omaha, NE 68178
Abstract
The viscoelastic relaxation of glass forming (Na2O)x(P2O5)1-x liquids was measured by photon
correlation spectroscopy at temperatures near the glass transition for compositions extending from
pure phosphorus pentoxide to the metaphosphate (x = 0.5). Over this compositional range, alkali
addition produces a continuous depolymerization of the covalently-bonded structure from one of a 3-
dimensional network to that of polymer chains. Substantial increases in the fragility accompany the
depolymerization and are shown to be identical to those seen in certain ion-free chalcogenide glass
formers suggesting the time scale for viscoelastic relaxation in network-forming liquids is controlled
only by the topology of the covalent structure. The relaxation is non-exponential and the stretching
exponent shows a complex variation with regards to both composition and temperature that is believed
to arise from a decoupling of ionic motions from those of the network occurring as the glass transition
is approached.
WATER AND FLUCTUATIONS CONTROL PROTEIN FUNCTIONS
H. Frauenfelder (1), G. Chen (1), J. Berendzen (1), P. W. Fenimore (1), H. Jansson (2), B. H.
McMahon (1), I. R. Stroe (3), J. Swensson (4), and R. D. Young (5)
(1) Los Alamos National Laboratory, Los Alamos, NM 87545, USA
(2) The Swedish NMR Center, Göteborg University, SE 40530, Göteborg, Sweden
(3) Department of Physics, Worcester Polytechnic Institute, Worcester, MA 01609, USA
(4) Department of Applied Physics, Chalmers University of Technology, SE 41296 Göteborg Sweden
(5) Department of Physics and Astronomy, Northern Arizona University, Flagstaff, AZ 86011, USA
frauenfelder@lanl.gov
Proteins are the workhorses of life. X-ray structures and most biology texts depict them as static,
bereft of a hydration shell and a surrounding solvent. It turns out, however, that proteins are complex
dynamic systems and that the fluctuations in the hydration shell and the enveloping solvent are crucial
for their function [1]. In particular the role of the hydration shell, usually discussed in vague terms, has
now been clarified. Help in understanding the effect of the fluctuations has been the analogy between
proteins, supercooled liquids, and glasses. These systems show two major types of fluctuations, the
primary or α fluctuations and the secondary or β fluctuations. The present model [1] can be crudely
described as follows. The protein proper has a viscosity similar to water; it can therefore easily be
moved. The shape of the protein and large-scale conformational motions are controlled by the α
fluctuations in the bulk solvent [2] [3]. Folding and unfolding involve also large-scale conformational

changes and are also affected by the α fluctuations in the solvent [4]. The α fluctuations are inversely
proportional to the viscosity of the bulk environment and hence extremely slow in a solid environment.
Internal protein motions, in contrast, are controlled by the β fluctuations in the hydration shell. These
fluctuations depend on the degree of hydration; a dehydrated protein has no (or limited) internal
motions. These results have been obtained with experiments over a broad range temperatures, but
always with myoglobin as test protein. Extension to other proteins and a broad range of solvents will
be necessary to obtain a broader picture. Incidentally, the experiments show conclusively that there is
no dynamic transition.
[1] H. Frauenfelder, G. Chen, J. Berendzen, P. W. Fenimore, H. Jansson, B. H. McMahon, I. R. Stroe,
J. Swensson, and R. D. Young, Proc. Nat. Acad. Sci. USA 106, 5129, 2009
[2] P. W. Fenimore, H. Frauenfelder, B. H. McMahon, and F. G. Parak, Proc. Nat. Acad. Sci. USA, 99,
16047, 2002
[3] V. Lubchenko, P. G. Wolynes, and H. Frauenfelder, J. Phys. Chem. B 109, 7488, 2005
[4] H. Frauenfelder, P. W. Fenimore, G. Chen, and B. H. McMahon, Proc. Nat. Aca. Sci. USA 103,
15469, 2006
TEMPERATURE INDUCED BREAKAGE OF HYDRATION WATER NETWORK AT
BIOSURFACES
A. Oleinikova and I. Brovchenko
Physikalische Chemie, Technische Universität Dortmund, D-44227 Dortmund, Germany,
alla@pc2a.chemie.uni-dortmund.de
Hydrogen bonded network of hydration water enveloping a biomolecule in aqueous solution
transforms into an ensemble of small clusters upon heating via a quasi 2D percolation transition. This
transition occurs at biologically relevant temperatures (from 310 to 330 K) at various biosurfaces and
may be related to the unfolding transitions of proteins [1,2]. A rapid change in thermodynamics of
hydration water due to the percolation transition is observed: contribution of water-water interaction
within hydration shell to the partial specific heat of hydration water sharply decreases, whereas the
contribution of interactions between hydration and bulk water sharply increases. The improving
connectivity between hydration and bulk water makes the surface of biomolecule effectively more
hydrophobic that may cause a conformational changes of biomolecules and eventually their
aggregation. Effect of a possible increase of the entropy due to the cluster diversity at the percolation
threshold for the protein folding is discussed in a line of Schrödinger´s idea [3].
[1] I.Brovchenko, A.Krukau, N.Smolin, A.Oleinikova, A.Geiger and R.Winter, J.Chem.Phys., 123,
224905, 2005.
[2] I. Brovchenko and A. Oleinikova, ChemPhysChem, 9, 2695, 2008.
[3] E. Schrödinger, What is Life? The Physical Aspect of the Living Cell, University Press,
Cambridge, 1944.
WHAT IS KNOWN ABOUT THE LOCATION OF THE FIRST LIQUID-LIQUID
TRANSITION OF BULK AND CONFINED WATER?
I. Brovchenko and A.Oleinikova
Physical Chemistry, Dortmund University of Technology, D-44227, Dortmund, Germany
ivan.brovchenko@tu-dortmund.de
Knowledge of the location of the first (lowest density) liquid-liquid transition of water is crucial for
the understanding of its anomalous properties at low pressures and along the liquid-vapor coexistence,
in particular. Simulations studies of the phase diagram of various water models evidence that the
critical point of the first liquid-liquid transition of water is located at negative pressures. The most
adequate model exhibit a triple point, wher the liquid-liquid transition crosses the liquid-vapor
transition. The temperature of the liquid-liquid-vapor triple point can be attributed to the temperature
(~235 K) of the homogeneous nucleation of liquid water. Accordingly, the apparent singularity of

water at ~228 K should be attributed to the spinodal of the liquid-liquid transition [1,2]. Simulation
studies show that the temperatures of the triple point and of the liquid density maximum shift to lower
temperatures due to confinement in hydrophobic pore.Confinement in hydrophilic pore causes the
shift of the liquid-liquid critical point from negative to positive pressures, whereas it practically does
not affect the temperature of the liquid density maximum [3,4].
[1] A. Oleinikova and I.Brovchenko, J. Phys.: Condens. Matt. 18, S2247, 2006
[2] I. Brovchenko and A. Oleinikova, ChemPhysChem. 9, 2660, 2008
[3] I. Brovchenko and A.Oleinikova, J. Chem. Phys. 126, 214701, 2007
[4] I. Brovchenko and A.Oleinikova, Interfacial and Confined Water, Elsevier, Amsterdam, 2008
Complex formation of DNA and polycations of various chain topologies
D. Störkle, S. Duschner, F. Kühn, K. Fischer, M. Maskos, M.Schmidt*
Institute of Physical Chemistry, University of Mainz
Abstract: The complex formation between DNA (pUC19-supercoiled DNA, 2686 base pairs) and
some polycations of different chain topologies in aqueous solution was studied by light scattering, gel
electrophoresis and AFM. The investigated polycations comprised cylindrical brush polymers with
quaternized polyvinylpyridine and polyethylene imine side chains as well as a 5 th generation
dendrimer thus covering a broad molar mass regime of 3 10 4 g mol -1 < Mw < 1 10 7 g mol -1 and very
different chemical charges/molecule, Z + , of 127 < Z + < 5500. Irrespective of the polycation the
complexes formed in dilute solution exhibited a similar size in terms of the mean square radius of
gyration, , i.e. 30 nm < Rg < 40 nm (excess of DNA) and 40 nm < Rg < 55 nm (excess of
polycation). At a large excess of either DNA or polycation the complexes were shown to coexist with
the uncomplexed molecules of the excess component and did not vary in size with increasing weight
fraction of the minority component. Only if the number of complexes became comparable to the
number of uncomplexed molecules inter complex bridging was observed to occur which eventually
led to phase separation. The extremely large charge density mismatch between the DNA and the
polycations caused strongly “overcharged” cationic complexes to be formed at excess polycation
whereas at excess DNA a small anionic charge of the complexes was found. The results are explained
qualitatively in terms of kinetically controlled complexation. Some preliminary results on the kinetics
of complex formation investigated by light scattering in combination with a stopped flow device
reveal up to three processes in the observable time regime of a few milliseconds up to hundreds of
seconds.

SEGMENTAL AND GLOBAL CHAIN MOBILITY IN INTERCALATED POLY
(PROPYLENE OXIDE) AMINES / LAYERED SILICATE NANOCOMPOSITES
A. Kyritsis (1), S. Kripotou, A. Panagopoulou (1), P.I. Xidas (2) and K.S. Triantafyllidis (2)
(1) Department of Physics, National Technical University of Athens, 15780 Athens, Greece
(2) Department of Chemistry, Aristotle University of Thessaloniki, 54124 Thessaloniki, Greece
akyrits@central.ntua.gr
The dynamics of poly (propylene oxide) amines (known as Jeffamine D-series) with constant length
(MW of 2000) direct incorporated in the galleries of montmorillonite clays via ion-exchange process
[1], have been investigated by means of Differential Scanning Calorimetry (DCS), Thermally
Stimulated Depolarization Currents (TSDC) and broadband Dielectric Relaxation Spectroscopy (DRS)
methods. In this work we study comparatively the dynamics of intercalated chains hosted in galleries
with variable heights (different geometrical restrictions) and/or exhibiting different interfacial
interactions (both, one or none chain ends are electro statically bound to the clay platelets). Dielectric
spectroscopy allows us to monitor both, segmental (α process) and global chain relaxations (normal
mode, nm, process). Our experimental results show that all the intercalated systems exhibit a new
global chain process, which is slower than the segmental but faster than the nm process in the bulk.
Surprisingly, our results indicate that only for the systems with both chain ends attached to the walls
the segmental dynamics becomes faster compared to that of net chains by decreasing temperature and
approaching Tg. The effect becomes more pronounced with decreasing gallery height. Effects of
adsorbed water on the dynamics of the intercalated chains are also investigated.
[1] C.S. Triantafillidis, P.C. LeBaron, T.J. Pinnavaia, Journal of Solid State Chemistry 167 (2002) 354
TOPOLOGICAL CONTROVERSIES IN THE ADAPTABILITY CONCEPT APPLIED TO
GLASSY GERMANIUM SULPHOSELENIDES
O. Shpotyuk (1,2), R. Golovchak (1), V. Boyko (1), and M. Hyla (2)
(1) Institute of Materials of SRC “Carat”, 202, Stryjska str., Lviv, 79031, Ukraine
(2) Institute of Physics of Jan Dlugosz University, 13/15, al. Armii Krajowej, Czestochowa, 42200,
Poland
shpotyuk@novas.lviv.ua
The adaptability concept was examined for germanium-based glassy chalcogenide networks using
computational cluster-modeling approach to justify the validity of previously reported boundaries of
the reversibility window. The quantum mechanical calculations were performed with HyperChem
program, ab initio calculations with RHF/6-311G * basis set being used to determine the total energies
of GemS(Se)n clusters.
The performed calculations showed that directly linked edge- and corner-shared GeS(Se)4/2
tetrahedrons are basic glass-forming blocks in the studied glasses, the former being more energetically
preferential. These overconstrained tetrahedrons are specifically interconnected in a space within more
extended structural blocks forming a so-called outrigger raft structural motive [1]. Despite
overconstrained nature of constituting blocks, they are specifically distributed in a glassy network via
optimally-constrained intercation linking elements. In such a way, the pseudo-reversibility window
appears in the glass compositions between average coordination numbers from 2.4 to approximately
2.5. This conclusion well agreed with last results on chemical ordering in these glasses tested with
high-resolution photoelectron spectroscopy.

[1] J.C. Phillips, J. Non-Cryst. Sol., 34, 153, 1979.
POST-IRRADIATION RELAXATION IN VITREOUS ARSENC/ANTIMONY
TRISULPHIDES
V. Balitska (1,2), Ya. Shpotyuk (1,3), J. Filipecki (4), and O. Shpotyuk (1,4),
(1) Institute of Materials of SRC “Carat”, 202, Stryjska str., Lviv, 79031, Ukraine
(2) Lviv State University of Vital Function Safety, 35, Kleparivska str., Lviv, 79023, Ukraine
(3) Faculty of Electronics of the Ivan Franko National University of Lviv, 50, Dragomanova str., Lviv,
79005, Ukraine
(4) Institute of Physics of Jan Dlugosz University, 13/15, al. Armii Krajowej, Czestochowa, 42200,
Poland
shpotyuk@novas.lviv.ua
Post-irradiation instability was studied in gamma-irradiated (As2S3)1-x(Sb2S3)x glasses (x = 0, 0.1, 0.2
and 0.3).
It was shown that gamma-irradiation caused low-energetic shift in fundamental optical absorption
edge of the studied glasses, this effect being unstable with time after irradiation. Within singleexponential
fitting, the typical values of time constants for this process are close to 2 days decaying
monotonically with x. The kinetics of the observed process was satisfactorily described within
suppressed-exponential relaxation function, tending towards monomolecular one. This result
contradicts to previous study on Ge-based glasses [1], where bimolecular relaxation kinetics proper to
annihilation of coordination topological defects was dominant. It means that non-defect relaxation
processes at the level of medium-range order are more essential in the glasses under consideration.
The above conclusion well agrees with results of positron annihilation lifetime spectroscopy. Low
deviations in average positron lifetimes testify rather in a favour of slight structural changes observed
in post-irradiation period. This dynamic behaviour can be explained well by compositional
dependence of atomic compactness in the studied glasses.
[1] V. Balitska, O. Shpotyuk, H. Altenburg, J. Non-Cryst. Sol., 352, 4809, 2006.
NEW EFFECTS IN THE THERMAL CONDUCTIVITY OF MOLECULAR GLASSES
A.I. Krivchikov (1), O.A. Korolyuk (1), I.V. Sharapova (1), О.О. Romantsova (1), F. J. Bermejo (2),
C. Cabrillo (2), R. Fernandez-Perea (2), and I. Bustinduy (2)
(1) B. Verkin Institute for Low Temperature Physics and Engineering of NAS Ukraine, 47 Lenin Ave.,
Kharkov 61103, Ukraine
(2) Instituto de Estructura de la Materia, CSIC, and Departamento Electricidad y Electrónica-Unidad
Asociada CSIC, Facultad de Ciencia y Tecnología, Universidad del País Vasco/EHU, P.O. Box 644,
E-48080 Bilbao, Spain
Krivchikov@ilt.kharkov.ua
New results and generalized data of low temperature investigations of heat transfer in molecular
glasses are presented and illustrated by the example of a homologous series of monoatomic alcohols
and their isomers. The thermal conductivity κ(T) of amorphous alcohols (methanol [1], ethanol [2],
isomers of propanol [3] and butanol) was measured in the interval from 2 K to the glass-formation
temperature by the steady-state heat flow technique under equilibrium vapor pressure. The results
obtained are analyzed within current models of heat transfer in glasses. It is found that κ(T) of the

investigated alcohols increases as the molecule masses increase. The effect is most evident in the low
temperature region, where the heat is transferred by ballistic phonons. The temperature dependences
κ(T) of orientational and structural glasses of ethanol appear to be very close despite the
fundamentally different molecular disorder in these glasses. The shift of the hydroxyl OH group from
the extreme position to the middle of the carbon skeleton of propanol and butanol molecules affects
the thermal conductivity significantly.
[1] O.A. Korolyuk et al., Low Temp. Phys., 35, 380 (2009)
[2] A.I. Krivchikov et al., Phys. Rev. B 74, 060201 (2006)
[3] A.I. Krivchikov et al., Phys. Rev. B 77, 024202 (2008)
HYDRATION WATER IN CARBOHYDRATES AND PROTEIN AQUEOUS SOLUTIONS
REVEALED BY DEPOLARIZED LIGHT SCATTERING
Lucia Comez (1,2), Daniele Fioretto (1,2), Maria Elena Gallina (3), Laura Lupi (1), Assunta Morresi
(3), Marco Paolantoni (3), Stefania Perticaroli (3), Paola Sassi (3), Filippo Scarponi (1)
(1) CNISM, Unità di Perugia - Dipartimento di Fisica, Via A.Pascoli, I-06123 Perugia, Italy
(2) CRS SOFT-INFM-CNR, c/o Università di Roma La Sapienza, 00185 Roma, Italy
(3) Dipartimento di Chimica, Università di Perugia, Via Elce di Sotto, 8, I-06123 Perugia, Italy
daniele.fioretto@fisica.unipg.it
A depolarized light scattering study has been performed on glucose [1,2], trehalose [3] and lysozyme
[4] aqueous solutions in the spectral range between 0.4 and 36000 GHz through the coupled use of
interferometric and dispersive devices. The quasi-elastic scattering region gives evidence for the
existence of two distinct relaxation processes at picosecond timescales. The fast process (fractions of
picosecond), is related to the dynamics of bulk water, while the slow one (few picoseconds) is
attributed to the rearrangement of water molecules directly interacting with the solute (hydration
water). The retardation factor undergone by the latter with respect to the bulk has been evaluated to be
~5-6 in carbohydrates aqueous solutions and ~9 in the presence of lysozime. The rotational diffusion
of the solute molecules and the origin of local specific vibrational contributions, including the boson
peak, are also discussed.
[1] D. Fioretto, L. Comez, M.E. Gallina, A. Morresi, L. Palmieri, M. Paolantoni, P. Sassi, F. Scarponi,
Chem. Phys. Letters, 441, 232 (2007).
[2] M. Paolantoni, L. Comez, D. Fioretto, M.E. Gallina, A. Morresi, P. Sassi, F. Scarponi, J. Raman
Spectroscopy 39, 238 (2008).
[3] M. Paolantoni, L. Comez, M.E. Gallina, P. Sassi, F. Scarponi, D. Fioretto, and A. Morresi, J. Phys.
Chem. B, in press.
[4] S. Perticaroli, L. Comez, M. Paolantoni, P. Sassi, L. Lupi, D. Fioretto, A. Paciaroni , A. Morresi,
submitted for publication.

RESEARCHES OF NONGAUSSIAN KUHN SEGMENT LENGTH FLUCTUATIONS USING
MONTE CARLO SIMULATON FRAENKEL CHAINS DYNAMIC.
N. Fatkullin (1), N. Balakirev (1) and T. Shakirov (1)
(1) Department of molecular physics, Kazan State University, 420008, Kremlevskaya Str.,18, Kazan,
Russia nikitana1987@mail.ru
The phenomenological Rouse model [1] was formulated originally for highly course grained
description of polymer chain dynamics, when macromolecule considered as consisting from sub
chains any of which contains enough number of Kuhn segments to obey for Gaussian statistics.
Actually the Rouse model is used for relatively short chains, or for relatively short times in cases of
long chains, when entanglement effects can be ignored. For that conditions deviations from Gaussian
statistics certainly can not be ignored. We argue, that the Rouse model can be reformulated without
using Gaussian statistic for minimal unite of course grained description of polymer chain, i.e. for
example up to Kuhn segment length. Only difference with original Rouse modell to be captured in
numerical coefficient of effectively itramolecular entropic term. Instead the usual numerical multiplier
−1
2
, where k B –Boltzman constance, T -absolute temperature, we get
kT B r
s
− . It has been
2
3kT B r
s
shown that the initial binary correlation function decay to be equal to Rouse one. The resulting
nonlinear equations describing chain dynamics couldn’t be treat analytically. Monte Carlo simulation
of the Langevin equation [2] gives an additonal information about chain dynamic on times to be
inaccessible for direct description . On account of relatively simplicity and the rigidity on the
segment Fraenkel chain model has been used for detailed investigations in the field of nongaussian
Kuhn segment length fluctuations.
[1] E.P. Rouse , J. Chem Phys. 21,1272,1953
[2] Y.-H. Lin and A. K. , J. Chem. Phys. 126,074902,2007.
DIELECTRIC RELAXATIONS AND GLASS TRANSITIONS IN PARTIALLY
CRYSTALLIZED AQUEOUS SOLUTIONS OF PROTEIN
N. Shinyashiki (1), T. Yoshinari (1), W. Yamamoto (1), A. Yokoyama (1), Y. Hikita (1), S. Yagihara
(1), R. Kita (1), K. L. Ngai (2), and S. Capaccioli (3)
(1) Department of Physics, Tokai University, Hiratsuka, Kanagawa 259-1292, Japan
(2) Naval Research Laboratory, Washington, DC, 20375-5320, USA
(3) Dipartimento di Fisica, Uneversita di Pisa, Largo B Pontecorvo 3, I-56127, Pisa, Italy, and
polyLab, CNR-INFM, Largo B Pontecorvo 3, I-56127, Pisa, Italy
naoki-ko@keyaki.cc.u-tokai.ac.jp
To compare relaxation processes and glass transitions observed by the adiabatic calorimetry and other
dynamical properties by neutron scattering and NMR techniques in protein water mixtures, broadband
dielectric measurements of aqueous solutions of bovine serum albumin (BSA), lysozyme and
ovalbumin were performed in a frequency range of 2 mHz - 20 GHz and temperatures in a range
between 300K and 80K. Three relaxation processes were observed. The glass transition temperatures,
Tgs, at which the relaxation times of the three processes are 100 s, are approximately 110K, 130K, and
200K. These Tgs agree well with those observed by adiabatic calorimetry [1]. The relaxation
processes can be interpreted to be due to a local chain fluctuation of protein, relaxation of ice, and
molecular motion of uncrystallized water. Moreover, our dielectric data can enhance the interpretation
of the neutron and NMR data of hydrated proteins as well as linking the dynamics of hydration water
to experimental data of aqueous mixtures of hydrophilic glassformers.
[1] K. Kawai, T. Suzuki, and M. Oguni, Biophys. J., 90, 3732, 2006
OVERVIEW OF ENTROPY AND ENTROPY PRODUCTION IN RELAXATION:
A FIRST PRINCIPLES STUDY
James Baker-Jarvis
NIST, Boulder, CO 80305

jjarvis@boulder.nist.gov
It is shown that many electromagnetic-spectroscopy nanoscale metrology areas can be formulated
using entropy production[1,2]. Many high-frequency electromagnetic measurements are based on the
relationships between dissipation and fluctuations. In nanotechnology an understanding of fluctuations
of thermal and electromagnetic energy and the effects of nonequilibrium are particularly important. In
this presentation I will show that direct small-scale measurements of entropy production are
advantageous for characterizing systems on a nanoscale. The approach used here is based on my
derivation of an entropy evolution equation using an exact, reversible Liouville-based statisticalmechanical
theory. I develop an exact equation for entropy rate in terms of time correlations of the
microscopic entropy production. This equation is an exact fluctuation-dissipation relation. I then
define the entropy and its production in
electromagnetic driving, both in the time and frequency domains, and apply this equation to dielectric
and magnetic material measurements, cavity resonance, noise, and power. I apply this equation to
study entropy fluctuation-dissipation equations for dielectric and magnetic susceptibilities, impedance
and resonant systems, and Johnson-Nyquist noise. I relate entropy production to cavity resonance and
relaxation loss peaks and derive a relation for the positivity of the permittivity loss factor.
[1] J. Baker-Jarvis, Entropy, 10 (2008) 411
[2] J. Baker-Jarvis, Phys. Rev. E 72 (2005) 066613
GLASS TRANSITIONON IN MICRO-PHASE SEPARATED STRUCTURE FORMED BY
AMPHIPHILIC LIQIUD CRYSTALLINE DI-BLOCK COPOLYMERS HAVING VERIOUS
MESOGENIC GROUPS
T. Yamada, S. Nishikawa, S. Boyer and H. Yoshida
Department of Applied Chemistry, Graduated Shcool of Urban Embironmental Science, Tokyo
Metropolitan University, Hachiouji, Tokyo, 191-0397, Japan
yoshida-hirohisa@tmu.ac.jp
We have reported the phase transitions and the nano-scale order structure of amphiphilic di-block
copolymers, PEO114-b-PMA(R)n, consisted of hydrophilic poly(ethylene oxide) (PEO) and
hydrophobic poly(methacrylate) derivatives PMA(R) containing liquid crystalline mesogenic unit (R)
[1-3]. Two types of R unit, azobenzene (Az) and stilbene (Stb) were used to compare the glass
transition of PEO114-b-PMA(Az)n and PEO114-b-PMA(Stb)n. Glass transition temperature of PEO114-b-
PMA(Az)n observed at around 50 o C on heating (10 Kmin -1 ) accompanying with endothermic peak
caused by rapid enthalpy relaxation occurred during cooling. That of PEO114-b-PMA(Stb)n observed at
temperature range between 60 and 80 o C without endothermic peak due to slow enthalpy relaxation
process. The isotropic transition temperature from Smectic A phase of PEO114-b-PMA(Stb)n was 40 o C
higher than that of PEO114-b-PMA(Az)n, which was indicated the high aggregation energy of Stb unit.
The aggregation energy difference between Az and Stb units induced the difference of glass transition
behavior.
[1] H. Yoshida, K. Watanabe, R. Watanabe and T. Iyoda, Trans. Mat. Res. Soc. Japan, 29, 861, 2004
[2] S. Y. Jung and H. Yoshida, Colloids & Surface A, 284-285, 305, 2006
[3] T. Yamada, J. Li, C. Koyanagi, T. Iyoda and H. Yoshida, J. Appl. Cryst., 40, s585, 2007
PARAMETERS CONTROLLING VISCOSITY EQUATIONS
I. AVRAMOV
Institute of Physical Chemistry, 1113 Sofia, Bulgaria
avramov@ipc.bas.bg
This study analyzes the parameters controlling viscosity equations. It is demonstrated that by means of
the glass transition temperature Tg (at which viscosity is 10 13.5 [dPa.s]) the number of free parameters
of viscosity equations can be reduced. In this way the Avramov & Milchev, AM, equation becomes

α
⎛
⎞
⎜
⎛ Tg ⎞
η = η ( − ) ⎟
⎜
⎜
⎟
A exp 2.
3 13.
5 lgη
A . Also the classical form of the VFT equation can be
⎟
⎝
⎝ T ⎠ ⎠
Tg
−To
transformed to: lg η = lgηV
+ ( 13.
5 − lgηV
) . Although the accuracy of the AM equation is
T −To
always superior, both AM and VFT expressions are capable to describe the literature experimental
data with sufficient precision. There are correlations between the corresponding parameters of the two
equations. Thus the preexponential constants are allied as follows: lg ηV = −1.
9 + 1.
2lgη
A . There is
relationship 1/a=0.82-0.74 To/Tg between the fragility parameter a and the temperature To. The AM
equation permits to predict also the dependence of fragility parameter a on composition. It is
demonstrated that, within the frameworks of the activation energy theory, the only possibility to
interpret properly the experimentally observed break in the viscosity curves, that appear in the glass
transition region, is to assume that at least several independent processes are taking place. Single
process cannot explain the break. This assumption was already developed in details in the jump
frequency model of AM. According to it, the ratio of the slopes of equilibrium viscosity curve to nonequilibrium
viscosity curve is equal to the ratio of the heat capacity of melt to that of the glass.
Acknowledgment: The support of the EU Project INTERCONY, Contract no
NMP3-CT-2006-033200 is appreciated
LARGE SCALE DYNAMICS OF PROTEINS
Ralf Biehl (1), Rintaro Inoue (1),Bernd Hoffmann (2) Tobias Rosenkrantz (3) and Dieter Richter (1)
(1) Institut für Festkörperforschung, Forschungszentrum Jülich, 52425 Jülich, Germany
(2) Institut für Bio- und Nanosysteme, Forschungszentrum Jülich, 52425 Jülich, Germany
(3) Institut für Strukturbiologie und Biophysik, Forschungszentrum Jülich, 52425 Jülich, Germany
Correspondence author: ra.biehl@fz-juelich.de
The dynamics of proteins is a keystone to understand their function as vital important nanomachines.
The length scale of these processes is comparable to the size of the protein and its subdomains.
Neutron spin echo spectroscopy is used to determine the protein dynamics on nanometer scale and a
timescale from ps up to several 100 ns. The protein can be studied in a D2O buffer similar to the
physiological conditions. We show that aside of the observation of translational and rotational
diffusion, NSE directly observes the correlated domain dynamics on its proper length and time scales.
We examine here the protein alcohol dehydrogenase (ADH), responsible for the interconversion
between alcohol and ketone and the protein phosphoglycerate kinase (PGK), which is involved in
glycolysis to recharge adenindiphosphate. ADH is a compact tetramer with a cleft between binding
and catalytic domain in each monomer. PGK is a monomer with 2 domains connected by a hinge.
Large scale dynamics seems to enable and promote the function of the proteins.
DISORDERED EFFECTS IN HEAT TRANSPORT OF A MOLECULAR GLASSY CRYSTAL
I.V. Sharapova (1), A.I. Krivchikov (1), O.A. Korolyuk (1), A. Jezowski (2), L.C. Pardo (3), M.
Rovira-Esteva (3), J.Ll. Tamarit (3) and F.J. Bermejo (4)
(1) B. Verkin Institute for Low Temperature Physics and Engineering of NAS Ukraine, 47 Lenin Ave.,
Kharkov 61103, Ukraine
(2) Institute for Low Temperature and Structure Research, Polish Academy of Sciences, PN 1410, 50-
950 Wroclaw, Poland
(3) Grup de Caracterització de Materials, Departament de Física i Enginyieria Nuclear, ETSEIB,
Universitat Politècnica de Catalunya, Diagonal 647, 08028 Barcelona, Catalonia, Spain

(4) CSIC - Department of Electricity and Electronics, University of the Basque Country, P.O. Box 664,
48080 Bilbao, Spain
Sharapova@ilt.kharkov.ua
The thermal conductivity κ(T) of the orientationally disordered and orientational glass phases of 1,2difluorotetrachloroethane
has been measured under equilibrium vapor pressure from the melting
temperature down to 2 K by the steady-state method. The temperature dependence of κ(T) in the
orientational glass state is remarkably close to that of structural glasses, especially at low temperatures.
The measurements show a glass-like behavior up to 60 K and an anomaly in κ(T) around the transition
concerning the trans-gauche conformational disorder. Such results emphasize the role played by
internal molecular degrees of freedom as sources of strong resonant phonon scattering and will be
discussed together with neutron scattering measurements. The glass-like behavior of κ(T) is
phenomenological described using the model of soft potentials. The thermal transport is then
understood in terms of a competition between phonon-assisted and diffusive transport effects.
EXPERIMENTAL EVIDENCE FOR THE SIMILARITY OF THE BOSON PEAK IN
GLASSES TO THE TRANSVERSE ACOUSTIC VAN HOVE SINGULARITY IN CRYSTALS
A. I. Chumakov (1), A. Monaco (1), G. Monaco (1), W. Crichton (1), A. Bosak (1), R. Rüffer (1), A.
Meyer (2), L. Comez (3,4), D. Fioretto (3,4), H. Giefers (5), S. Roitsch (5), G. Wortmann (5), M. H.
Manghnani (6), A. Wushur Hushur (6),
Q. Williams (7), J. Balogh (6), K. Parliński (8,9), P. T. Jochym (8), and P. Piekarz (8).
(1) European Synchrotron Radiation Facility, BP 220, F-38043 Grenoble, France
(2) Physics Department E13, Technische Universität München, D-85747 Garching, Germany.
Presently at the Institut für Materialphysik im Weltraum, Deutsches Zentrum für Luft- und Raumfahrt,
D-51170, Köln, Germany
(3) INFM CRS-SOFT, c/o Universitá di Roma "la Sapienza", I-00185 Roma, Italy
(4) Dipartimento di Fisica, Universitá di Perugia, I-06123 Perugia, Italy
(5) Department of Physics, University of Paderborn, D-33095 Paderborn, Germany
(6) School of Ocean and Earth Science and Technology University of Hawaii, Honolulu, Hawaii
96822, USA
(7) University of California at Santa Cruz, Department of Earth Sciences, Santa Cruz, CA 95064, USA
(8) Institute of Nuclear Physics, Polish Academy of Science, Kraków, Poland
(9) Institute of Techniques, Pedagogical University, Kraków, Poland
chumakov@esrf.fr
We studied the pressure dependence of vibrational dynamics of an iron-containing sodium silicate
glass by nuclear inelastic scattering. The density of vibrational states (DOS) was measured up to 11
GPa using a diamond anvil cell. In addition, the DOS of a crystalline counterpart of the glass was
measured at ambient conditions.
The increase of pressure causes a shift of the boson peak to higher energy and a decrease of its height.
The reduced DOS of the crystalline phase shows a peak at yet higher energy and with still lower
height. Ab-initio calculations of atomic vibrations of the crystalline phase show that this peak arises
from the van Hove singularity of a transverse acoustic (TA) branch.
The changes in elastic medium of the glass with pressure were characterized by the pressure
dependence of Debye energy, calculated from the measured density and sound velocities. In order to
correct the data for the variable elastic medium, the DOS data were re-calculated in Debye energy
units.
After the correction, the boson peak of the glass for various pressures looks almost identical. More
important, it matches the energy and the height of the TA singularity of the crystalline phase.
Furthermore, the estimated wave vector of the TA mode at the energy of the boson peak in the glass
coincides with the wave vector of the TA van Hove singularity in the crystal. Thus, the results suggest
a similar origin of the boson peak in glasses and the TA van Hove singularity in crystals.

DIELECTRIC MATERIAL PROPERTIES USING TIME DOMAIN REFLECTOMETRY
Soualmia Achour(1), Abdelguerfi Mériem (2), Allouane Ouiza (3),Bendahah Abla (4)
(1),(2),(3),(4): Laboratoire Physique des Matériaux Equipe Spectroscopie Diélectrique Faculté de
Physique USTHB Alger
a_soualmia@yahoo.fr
Abstract
Molecular motions and dielectric relaxation process can be studied over a wide frequency range when
an electromagnetic field is applied to dielectric materials leading to observed responses which can be
related to molecular events caused by dipole orientation and charge migration
Migration of charges gives rise to dielectric losses by conductivity and dipole orientation produced as
a result of the dipole alignment in the applied field direction gives rise to dielectric losses by
relaxation process
The most attractive of dielectric spectroscopy lies in its applicability to the study of direct correlations
between the response of real system that is a dielectric sample and an idealized equivalent model
circuit ready to describe dielectric losses process
Basically, behaviour of polar and conductive molecules is experimentally described by the
conductivity and dielectric permittivity over the necessary frequency range
But because the whole field of dielectric spectroscopy covers an unusually wide frequency range, a
large number of tools and laborious frequency domain techniques may then be required.
This is why, for some decades Time Domain Reflectometry methods have seemed to be the alternative
to the point by point approach in the Frequency Domain
The objective of our proposed study is to understand the characteristic parameters which describe the
dielectric losses model; in the other hand an approach of models ready to describe the dielectric
relaxation and the electrical conductivity, in the other hand the polarisation mechanisms
For that TDR is proposed as useful method requiring some theoretical basis allowing correct
interpretation TDR measurements and then predictions and interpretations about dielectric matter
behaviour
Basically TDR methods are described in terms of reflection coefficient that is the ration of the
reflected waveform amplitude to the input wave form amplitude. Waveforms are acquired with
Tektronix 11802 digital sampling oscilloscope
Examples of studied samples are obtained with ionic mixtures of soil/water, salt/water and
alcohols/water; results from time domain to frequency domain and from frequency domain to time
domain are obtained by using Direct Fourier Transform and Inverse Fourier Transform
Keywords: Time Domain Spectroscopy, permittivity, conductivity, relaxation.
COMPUTER SIMULATION OF DYNAMICAL PROPERTIES POLYMER MELT
CONFINED IN CYLINDRICAL PORE
T. Shakirov (1), N. Fatkullin (1), P. Khalatur (2) and R. Kimmich (3)
(1) Department of molecular physics, Kazan State University, 420008, Kremlevskaya Str.,18, Kazan,
Russia
(2) Department of Polymer Science, the University of Ulm, Albert-Einstein-Allee 11, Ulm, 89069,
Germany
(3) Sektion Kernresonanzspektroskopie, the University of Ulm, Albert-Einstein-Allee 11, Ulm, 89069,
Germany

timur.m.shakirov@gmail.com
We report results of molecular dynamics simulation of polymer melt confined in cylindrical pore. Melt
consists of identical 20-segment chains (density approximately 0.6). Neighbour beads interact with
rigid potential that is segment length is constant, interaction with other beads in the melt is Lennard-
Jones interaction. Pore diameter equals approximately 11.6 segment length.
We calculated dynamical (coherent and incoherent) structure factor for both transfer momentum
vector directions: longitudinal and transverse to pore axis. Results of our simulation demonstrate
difference in time dependence of structure factor for transverse and longitudinal directed momentum
transfer. This difference appears at short times when typical displacements of polymer segments are
about segment size and much shorter than pore diameter. Slowing down of “transverse” structure
factor can be concerned with reptation behaviour induced over corset-effect recently found in NMRexperiments
[1, 2].
Acknowledgement
This work was supported by Russian Foundation for Basic Research, project # 07-03-00222-a.
[1] C. Mattea at al, The “Corset Effect” of Spin-Lattice Relaxation in Polymer Melts Confined in
Nanoporous Media, Applied Magnetic Resonance, 2004, vol. 27.
[2] N.Fatkullin, E.Fisher, C.Mattea, U.Beginn and R.Kimmich, Polymer Dynamics under Nanoscopic
Constraints: The Corset effect as Revealed by NMR Relaxometry. ChemPhysChem,2004, v.5,p884
MECHANICAL RELAXATION NEAR GLASS TRANSITION STUDIED BY VARIOUS
EXPERIMENTAL METHODS
Y. Hiki
Faculty of Science, Tokyo Institute of Technology, 39-3-303 Motoyoyogi, Shibuya-ku, Tokyo 151-
0062, Japan
hiki.tit@nifty.com
We are interested in relaxations in glassy materials, especially near the glass transition temperature Tg
[1,2]. We have extensively studied the mechanical relaxations using various experimental methods. A
wide range of probe frequency f is adopted for the experiments: shear viscosity, f ~ 0 Hz; internal
friction, f = 0.001-25 Hz; ultrasound, f = 5 MHz; Brillouin scattering, f = 10 GHz. The measurement
temperature is from the room temperature up to and above Tg. The materials used are ionic, metallic
and polymer glasses. Viscosity of inorganic glasses such as metaphosphate (MP) and polymer glasses
such as polystyrene (PS) was studied. Viscosity in pure shear deformation mode is measured. The
viscosity is of the hydrodynamic (Vogel-Tammann-Fulcher) type and of the hopping (Arrhenius) type
at high and low temperatures, respectively. Double Arrhenius dependence is seen in glasses containing
molecular chains. Internal friction was measured near Tg in metallic glasses such as Johnson alloy and
a polymer glass PS. The viscoelastic relaxation is observed and is explained by adopting the Maxwell
model and the Maxwell relation. Correlation between the pre-exponential factor and the activation
energy (compensation effect) is seen in the relaxation. Ultrasound and Brillouin scattering experiments
were performed for a polymer glass PS. Relaxation is seen near Tg in the sound velocity and sound
attenuation. The activation energy values for the relaxation obtained by various experimental methods
are compared and discussed by adopting the idea of the potential energy landscape in glasses.
[3] Y. Hiki, Y. Kogure, Recent Res. Devel. Non-Cryst. Solids 3 (2003) 199.
[4] Y. Hiki, Mat. Sci. Eng. A 370 (2004) 253.

MOLECULAR DYNAMICS FOR As-Se GLASSES DURING LONG-TERM NATURAL
PHYSICAL AGEING : EVOLUTION OF COOPERATIVE REARRANGING REGION SIZE
R. Golovchak (2), A. Saiter (1), O. Shpotyuk (2,3), J.-M. Saiter (1).
(1) LECAP-PBS, FRE3101, Institut des Matériaux de Rouen. Université de Rouen, Faculté des
Sciences, Avenue de l'Université BP 12, 76801 Saint Etienne du Rouvray, France
(2) Institute of Materials of SRC “Carat”, 202, Stryjska str., Lviv, 79031, Ukraine
(3) Institute of Physics of Jan Dlugosz University, 13/15, al. Armii Krajowej, Czestochowa, 42200,
Poland
The influence of two-decade natural storage on the size of cooperative rearranging region (CRR) in
As-Se glasses is studied by temperature-modulated differential scanning calorimetry (TMDSC). The
glasses of different compositions covering the whole glass-forming region of As-Se system are
examined. It is shown that compositional dependence of CRR volume size for as-prepared glasses
exhibits peculiarities near the average coordination numbers Z = 2.1 and Z = 2.4 depicting a general
connectivity of glass backbone. Size of CRR volume increases drastically for Se-rich glasses (Z < 2.4)
after two-decade natural physical ageing. This effect is explained by the decrease in size of open
volume defects due to the alignment of Se polymeric chains, which is considered as a main
microstructural mechanism of physical ageing effect in these materials [1]. On the basis of these
results and using data of positron annihilation lifetime spectroscopy, the hypothesis has been put
forward that the influence of individual open-volume defects size has greater impact on the average
CRR size, than the connectivity of glass backbone.
[1] Golovchak R, Jain H, Shpotyuk O, Kozdras A, Saiter A, Saiter J M, Phys. Rev. B 78 (2008)
014202(6).
CLEAR EVIDENCE OF CONFINEMENT EFFECTS IN FREELY-STANDING AND
CAPPED ULTRATHIN FILMS BY MEANS OF DIELECTRIC SPECTROSCOPY
S Napolitano, C Rotella, M Wübbenhorst
Laboratory of Acoustic and Thermal Physics, Katholieke Universiteit Leuven, Leuven, B3001,
Belgium
simone.napolitano@fys.kuleuven.be
We present clear evidence of confinement effects on the molecular relaxations of polymers by means
of dielectric relaxation spectroscopy. Ultrathin polymer layers (thickness < 200 nm) of several polar
and nonpolars were prepared in restricted geometries, having two (freely-standing films) or no free
surfaces (capped films or model nanocomposites). The experimental trends, rationalized by means of a
careful modeling of the dielectric properties of nanolayers, are in line with observations derived from
ellipsometry and fluorescence measurements. In particular, we observe that: 1) in capped films, the
dielectric strength scales with the inverse of film thickness already at hundreds of nanometers; the
relaxation time (similarly as the glass transition, Tg) sharply changes only below 20 nm; 2) for
extremely thin films of nonpolar polymers, the capacitance continuously increase with temperature,
implying an apparent negative expansion coefficient also in well equilibrated samples; 3) in freelystanding
films, the Tg-shifts towards lower temperatures are accompanied by an asymmetric
broadening of the structural relaxation peak towards shorter relaxation times; 4) the relative variation
of the relaxation time vanishes at sufficiently high temperatures. We bring strong experimental proofs
that the processes observed in extremely thin films only originates from a mere polymer response.
Napolitano, S.; Wübbenhorst, M. Macromolecules 2006, 39, 5967-5970
Napolitano, S.; Wübbenhorst, M. Journal of Physical Chemistry B 2007, 111, 5775-5780
Napolitano, S.; Wübbenhorst, M. Journal of Physical Chemistry B 2007, 111, 9197-9199
Napolitano, S.; Lupascu, V.; Wübbenhorst, M. Macromolecules 2008, 41, 1061-1063
Peter, S.; Napolitano, S.; Meyer, H.; Wübbenhorst, M.; Baschnagel, J. Macromolecules 2008, 41,
7729-7743

Rotella, C.; Napolitano, S.; Wübbenhorst, M. Macromolecules 2009, 42, 1415-1417
PROTON NMR INVESTIGATIONS OF POLYMER CHAIN DYNAMICS IN MELTS,
BRUSHES AND NANOSCOPIC CONFINEMENT
K. Saalwächter (1), F. Vaca Chávez (1), P. Hübsch (1), S. Ok (2), and M. Steinhart (2)
(1) Institut für Physik – NMR, Martin-Luther-Univ. Halle-Wittenberg, Betty-Heimann-Str. 7, D-06120
Halle, Germany
(2) Max-Planck-Institut für Mikrostrukturphysik, Weinberg 2, D-06120 Halle, Germany
kay.saalwaechter@physik.uni-halle.de
Proton multiple-quantum (MQ) NMR, possibly performed on simple low-field instruments, has
recently evolved as the most powerful method for the study of the microstructure of polymer networks
[1,2]. We here extent the use of this method to the study of the dynamics of linear polymer chains in
melts, grafted to surfaces, and confined to cylindrical pores. A quantitative understanding of linear
chain dynamics is essential for the understanding of the complex mechanical behavior of polymer
melts, and the most useful methods that deliver rich molecular-scale information are NMR and
inelastic neutron scattering, the latter being a prohibitively expensive technique, being further limited
to sub-microsecond dynamics. In this contribution, it is shown that low-field proton MQ NMR is
sensitive to polymer dynamic timescales over the relevant range covering the tube-model regimes II-
IV of Doi and Edwards. We are able for the first time to extract characteristic timescales τe and τd, and
thus confirm the validity of the tube model, as well as delineate its limitations and necessary
extensions. Our experiments further show directly the change in dynamics associated with grafting
chain ends to a surface or confining a melt to cylindrical pores in the 10-100 nm diameter range,
where in the latter case, layer-specific dynamics is indicated.
[1] K. Saalwächter, Progr. NMR Spectrosc. 51, 1-35, 2007.
[2] K. Saalwächter, J.-U. Sommer. Macromol. Rapid Commun. 28, 1455–1465, 2007.
MOLECULAR DYNAMICS OF POLYMERIC NANOCOMPOSITES WITH LAYERED
NONOFILLERS – INTERPLAY BETWEEN MATRIX AND INTERFACIAL EFFECTS
A. Schoenhals
BAM Federal Institute for Materials Research and Testing, D-12205 Berlin, Germany
Andreas.Schoenhals@BAM.de
Two sets of different types polymerbased nanocomposites with layered nanofillers are prepared:
polypropylene-graft-maleic anhydride with modified clays and polyethylene with layered double
hydroxide. The concentration of the nanofiller is varied. TEM images show an exfoliated morphology.
Both systems are studied in detail by dielectric spectroscopy (DS) but also complementary methods
like gas transport measurements, calorimetry, and Raman spectroscopy are employed. Besides the
dispersion, the interfacial area between the nanoparticles and the polymer matrix is crucial for the
properties of the nanocomposites. Therefore attention is paid to investigate this interfacial area by DS
because the polar groups of both the surfactant and compatibilizer are located close to the layers. For
both systems it is found that the molecular mobility in the interfacial area is essentially higher than in
the matrix. In addition a Maxwell/Wagner/Sillars polarization is found due to the blocking of charges
at the layers. The time constant of this MWS-process can be correlated with characteristic length
scales in the nanocomposites and provides information about the dispersion of the nanofiller.
Femtosecond Optical Kerr Effect Study of Ionic Liquids: Comparison to Concentrated
Electrolyte Solutions.
T. Fujisawa (1), K. Nishikawa (1) and H. Shirota (1)

(1) Graduate School of Advanced Integration Science, Chiba University, 1-33 Yayoi, Inage-ku, Chiba
263-8522, Japan
fujisawa@restaff.chiba-u.jp
In this study, we have employed femtosecond optically heterodyne-detected optical Kerr effect
spectroscopy [1] to investigate the interionic dynamics in ionic liquids (ILs) with a hydrophobic
bis(trifluoromethanesulfonyl)amide anion ([NTf2] - ). Our main focus has been on the comparison
between interionic interactions involving [NTf2] - in ILs and electrolyte solutions with a high
concentration. Four ionic liquids, 1-butyl-3-methylimidazolium, N-butylpyridinium, N-butyl-N,N,Ntriethylammonium,
N-butyl-N-methylpyrrolidinium with [NTf2] - , and four Li[NTf2] solutions (3.3 M)
of water, methanol, propylene carbonate, and poly(ethylene glycol) were used. From the Fourier
transform OKE spectra, we found a general difference between the relative intensities of
intramolecular vibrational bands of [NTf2] - in ILs and the electrolyte solutions. The origin could be
the difference of the equilibrium of two conformers of [NTf2] - : cisoid and transoid forms. In the lowfrequency
intermolecular vibrational region, the intermolecular band shape exhibited a bimodal
distribution in ILs due to the interionic motions of the cation and anion. The characteristic component
of [NTf2] - was seen about ~30 cm -1 . In the presentation, we will compare the details of interionic
interactions found between the ILs and electrolyte solutions on the basis of the OKE spectra.
[1] Castner, E. W. Jr.; Wishart, J. F. ;Shirota, H. Acc. Chem. Res. 2007, 40, 1217.
Extracting Information regarding molecular interaction in hydrogen bonded binary liquid
through dielectric parameters.
A.C. Kumbharkhane* and S.C. Mehrotra**
*SCHOOL OF PHYSICAL SCIENCES, SWAMI RAMANAND TEERTH MARATHWADA
UNIVERSITY, NANDED 431606, INDIA.
**DEPARTMENT OF COMPUTER SCIENCE & INFORMATION TECHNOLOGY, DR.B.A.
MARATHWADA UNIVERSITY, AURANGABAD 431 004, INDIA.
ABSTRACT — The values of complex permittivity for hydrogen bonded binary liquid mixtures have
been determined in the frequency range of 10 MHz – 20 GHz using time domain reflectometry
(TDR) method. TDR method involves the generation of step pulse with rise time of 25 pico-second in
a coaxial line system and monitoring the change in pulse shape after reflection from the sample placed
at the end of the coaxial line. There is a great interest to study the dielectric relaxation behaviour in
binary mixtures to understand the role of hydrogen bond in liquid system. The dielectric constant for
the mixtures can be explained using hydrogen bonded model by assuming the formation of hydrogen
bonds between solute-solute and solute-solvent pairs. The orientation correlation between neighboring
molecules due to hydrogen bonding interactions is determined in terms of Kirkwood factors. The
number of hydrogen bonds of solute-solute and solute-solvent molecules is computed. The theoretical
model to explain the experimental results has been discussed.

VARIATION OF THE DILATOMETRIC GLASS-TRANSITION TEMPERATURE
WITH THE CRYSTALLINITY IN AN IRON-RICH GLASS-CERAMIC
Alexander Karamanov and Emilia Karamanova
Institute of Physical Chemistry, Bulgarian Academy of Sciences,
G. Bonchev Str. Block 11, Sofia, 1113, Bulgaria
Abstract
The glass-transition, Tg, temperatures of an iron-rich composition, forming different percentages of
crystal phase, were studied by differential dilatometer. The obtained experimental results were
compared with the values for the viscosities of residual glasses, calculated by the method of Fluegel.
The Tg values of the parent glass and of the final glass ceramic were also evaluated by precise density
measurements.
The glass-transition temperatures of the parent glass and glass-ceramic samples with low crystallinity
are in acceptable agreement with the calculated values, while the samples with 50-60 wt %
crystallinity highlight Tg values, which are with 100-150 °C higher than the expected and ones,
estimated by the density measurements. These differences might be explained, assuming the formation
of crystallization induced porosity in the materials.
DIELECTRIC AND VISCOELASTIC INVESTIGATION OF POLYISOPRENE UNDER
PRESSURIZED CARBON DIOXIDE
Y. Matsumiya, A. Uno and H. Watanabe
Institute for Chemical Research, Kyoto University, Uji, Kyoto 611-0011 Japan
matsmiya@scl.kyoto-u.ac.jp
Dielectric and viscoelastic measurements were conducted for cis-polyisoprene (PI) under pressurized
carbon dioxide, CO2, to test the effect of CO2 on the chain dynamics. The PI chain has the type-A
dipole parallel along its backbone to exhibit the slow dielectric response reflecting the global chain
motion (end-to-end vector fluctuation). For a PI sample with Mw = 20K (Mw /Mn =1.1), the dielectric
data at 65C indicated that CO2 at various pressures (= 0-10 MPa) behaved as a simple diluent to
accelerate the global chain motion. For the other PI sample with Mw = 260K (Mw/Mn =1.7), the
dielectric as well as viscoelastic tests were made at 25C, with the latter being conducted with a
magnetic driven rheometer. The dielectric and viscoelastic data at various CO2 pressures (= 0-10 MPa)

satisfied a relation deduced for the dynamic tube dilation mechanism. This result further confirmed
the simple diluent nature of pressurized CO2 for the global dynamics of the PI chains.
Relaxation modes in complex metallic glasses studied by local and global mechanical
spectroscopy
Konrad Samwer 1 , A. Kahl, H.Wagner, J.Hachenberg, D. Bedorf, T. Koeppe,
,S.Küchemann, W.Arnold, S.M. Chathoth, M. Demetriou 2 W.L. Johnson 2
1 I.Physikalisches Institut, Universit G ngen, Germany
2 Keck Lab. Caltech, Pasadena, USA
A microscopic model for the macroscopic properties of complex metallic glasses was recently
developed. The alpha- and beta-relaxation of the systems can be explained within the potential energy
landscape picture.
Combining these ideas with computer simulations developed by S.G. Mayr et al. give an insight into
the microscopic origin of the cooperative atomic motion, which is quite different compared to
crystalline materials. Using these results, we can predict the rheology of metallic liquids including the
strain-rate dependence and compare the model with the latest ultrasound measurements of the shear
modulus which is the most important material parameter. Using a newly developed atomic force
acoustic microscope we are now able to determine the local elastic modulus and compare the results
with predictions from the potential energy landscape.
Molecular dynamics in pharmaceutically important hydrochloride salts studied by Dielectric
Spectroscopy
K. Adrjanowicz, Z. Wojnarowska, P. Wlodarczyk, K. Grzybowska, K. Kaminski, M. Paluch
Institute of Physics, Silesian University, ul. Uniwersytecka 4, 40-007 Katowice, Poland
Recently the amorphous drugs have received considerable attention, especially because of the
advantages given in terms of their solubility and bioavailability. Active Pharmaceutical Ingredients
(API) prepared in the amorphous state are markedly more soluble, have higher dissolution rate and in
a consequence greater bioavailability compared to that prepared in the crystalline form. However,
because of instability reasons preparation of amorphous drugs for commercial use is very limited.
During storage amorphous drug will tend to revert to more stable crystalline form. It seems that the
key factor responsible for stability of amorphous phase is molecular mobility. In this presentation we
will investigate relaxation properties of selected pharmaceuticals (painkillers and calcium channel
blocker) especially being hydrochloride salts. Since the latter are typical ionically conducting glassformers
to gain information about structural relaxation in supercooled liquid state we employed
electric modulus representation. We will show that chemical transition of drug from monohydrate into
hydrochloride salt results in significant increase of its glass transition. As a consequence it is possible
to prepare its oral dosage form completely amorphous in the room temperature and even human body
temperature. We will focus on molecular dynamics in glassy as well as liquid states. Since in
examined APIs secondary relaxation JG type occurred we linked up an
opposite tendencies to crystallization of investigated drugs with different local molecular mobility
involved in their β-relaxations. As a final point we will present results of solubility measurements and
intrinsic dissolution tests of examined APIs to show what are the potential benefits given by
amorphous state.

Dynamics in Confined Spaces: Looking at Polymers in Nanopores with Solid State NMR
David B. Zax
Department of Chemistry & Chemical Biology, Baker Laboratory, Cornell University, Ithaca, NY
14853-1301 USA
dbz1@cornell.edu
We report on the implications of a wide variety of solid-state NMR experiments to the understanding
of dynamical properties of systems in nanometer-sized pores. Such systems are ubiquitous in the
modern scientific endeavor; both in the nanocomposite materials which are the subject of this
symposium and in nature’s nanocomposites. As the intimate coexistence of the two phases is essential
where we wish to achieve properties not obviously similar to those of the two bulk constituents, in situ
tools capable of assessing both the structural and dynamical properties of these disordered phases are
essential. Our NMR studies demonstrate, and are confirmed in some cases by simulations, that the
dynamical properties near the interface vary widely from that observed in bulk and more interestingly
that there is a significant dynamical gradient observed with widely varying timescales found on length
scales as short as 1 nm. That these dynamical changes are relevant to bulk properties can be easily
demonstrated, suggesting that significant modification of the macroscopic can be achieved with what
appear to be small changes in chemistry. A remaining question of some importance is the range over
which dynamical properties relax from those imposed by the interface to that of the bulk.
[1] E. Manias, V. Kuppa, D.-K. Yang and D. B. Zax, Coll. Surf. A: Phys. Eng. Aspects, 187-188, 509,
2001.
[2] D.-K. Yang and D. B. Zax, Sol. State. Nucl. Magn. Reson. 29, 153, 2006.
[3] D. B. Zax, D. E. Armanios, S. Horak, C. Malowniak and Z. Yang, Biomacromolecules, 5, 732,
2006.
ON THE REALITY OF RESIDUAL ENTROPIES OF GLASSES AND DISORDERED CRYSTA.LS:
THE ENTROPY OF MIXING
M. Goldstein (1)
(1) 299 Riverside Drive, #7A, New York, NY 10025, USA ifg2@columbia.edu
We have previously shown that the vanishing of the configurational entropy of a glass or disordered crystal on
kinetic arrest would imply a non-trivial violation of the second law of thermodynamics [1]. We consider here
the specific case of the entropy of mixing, and show that not only would the second law be violated, but also
that the chemical potentials of the components of a solution would become independent of concentration, a
clearly counter-intuitive result. While this prediction is readily testable on a polymer-diluent system, a search
of the literature has failed to turn up the necessary data.
M. Goldstein, J. Chem. Phys. 128, 154510 (2008)
PHOTOINDUCED PHYSICAL AGEING IN GLASSY ARSENIC SELENIDES
A. Kozdras (1) , R. Golovchak (2,3) , O. Shpotyuk (2,3)
(1)
Institute of Mathematics and Physics of Opole University of Technology, 75, Ozimska str., Opole,
45370, Poland
(2)
Institute of Materials of SRC “Carat”, 202, Stryjska str., Lviv, 79031, Ukraine
(3)
Institute of Physics of Jan Dlugosz University, 13/15, al. Armii Krajowej, Czestochowa, 42200,
Poland
shpotyuk@novas.lviv.ua
Physical ageing effects induced by above-bandgap phoexposure at normal conditions (far below
corresponded glass transition temperature) are comprehensively studied in glassy As-Se using
conventional differential scanning calorimetry (DSC). It is shown that the kinetics of enthalpy losses
under illumination conditions in bulk Se-rich As-Se glasses is much faster, than during isochronal

natural storage of these glasses in the dark. It means that above-bandgap photoexposure accelerates
physical ageing in these materials during natural storage at room temperature.
The mechanism of the observed phenomenon is assumed to be connected with dissipation into bulk of
elastic strains produced at the surface of the glass by light excitations. This process facilitates the
elementary relaxation acts like twisting of inner Se atoms of Se-Se-Se units within double-well
potential, which are shown to be responsible for the conventional short-term natural physical ageing
[1]. In such a way the changes produced by above-bandgap photoexposure near the surface of the
samples propagate into their depth producing a measurable effect for DSC technique.
[1] R. Golovchak, O. Shpotyuk, A. Kozdras, B. Bureau, M. Vlcek, A. Ganjoo, H. Jain, Phil. Mag. 87
(2007) 4323.
INTERIONIC VIBRATIONAL DYNAMICS AND INTERACTION IN ROOM
TEMPERATURE IONIC LIQUIDS: HEAVY ATOM SUBSTITUTION EFFECTS
Hideaki Shirota (1), Hiroki Fukazawa (1), Tomotsumi Fujisawa (1), Keiko Nishikawa (1), Tateki
Ishida (2), James F. Wishart (3)
(1) Department of Nanomaterial Science, Chiba University, 1-33, Yayoi, Inage-ku, Chiba 263-8522,
Japan
(2) Department of Theoretical and Computational Molecular Science, Institute for Molecular Science,
38 Nishigo-Naka, Myodaiji, Okazaki 444-8585, Japan
(3) Chemistry Department, Brookhaven National Laboratory, Upton, NY 11973, USA
(4) Department of Chemistry and Chemical Biology, Rutgers University, 610 Taylor Road,
Piscataway, NJ 08854, USA
shirota@faculty.chiba-u.jp
We have reported the heavy atom substitution effects on the shear viscosity and intermolecular
vibrational dynamics of some aromatic cation-based ionic liquids (ILs) [1-4]. Currently, we are
investigating these effects further by focusing primarily on non-aromatic ILs, [N222(2O2O2)][PF6],
[N222(2O2O2)][AsF6], [P222(2O2O2)][PF6], and [P222(2O2O2)][AsF6], to see if the heavy atom substitution
effects of both the cation and anion are simply additive, synergistic, or compensating. In this talk, we
will also show the effects of heavy atom substitution on the interionic vibrational dynamics in the nonaromatic
ILs studied by femtosecond optical Kerr effect spectroscopy, and comparing them with our
earlier results of aromatic ILs to see the larger picture of heavy atom substitution effects on the shear
viscosity and interionic interaction in room temperature ILs. (This work is supported in part by the
Ministry of Education, Culture, Sports, Science and Technology (MEXT) of Japan (199559001 and
21685001 (HS), 17073002 (KN), 20031027 (TI)), Izumi Science and Technology Foundation (HS)
and the U.S. Department of Energy (DE-AC02-98CH10886 (JFW)).)
[1] E. W. Castner, Jr., J. F. Wishart, H. Shirota, Acc. Chem. Res. 40, 1217, 2007.
[2] H. Shirota and E. W. Castner, Jr. J. Phys. Chem. B 109, 21576, 2005.
[3] H. Shirota, K. Nishikawa, T. Ishida, J. Phys. Chem. B in press.
[4] T. Ishida, K. Nishikawa, H. Shirota, J. Phys. Chem. B in press.
DEFORMATION CALORIMETRY STUDY OF THE EFFECTS OF TEMPERATURE ON
THERMODYNAMIC BEHAVIOR OF EPOXY GLASS UNDER LARGE DEFORMATION
H. Kawakami, K. Futaduka
Graduate School of Osaka City University, Sumiyoshi, Osaka 558-8585, Japan
hkawakam@mech.eng.osaka-cu.ac.jp
Epoxy glass was subjected to large deformation at different temperatures, and during the course of
deformation the amount of heat flowing into a specimen was measured by a laboratory made
calorimetry. The amount of heat flowing into a specimen per unit strain increment, dq/dε, was
calculated from data obtained. In addition to dq/dε, the amount of external work per unit strain

increment, dw/dε, was calculated from a stress-strain relationship, and then the change in internal
energy with unit strain increment, du/dε = dw/dε+dq/dε, was also calculated. From these
thermodynamic values, we calculated the proportion of entropic force, which resulted from rubber
elasticity of polymer chains, to total force. The proportion was higher at higher temperature in a strain
range below the lower yielding range, while the order in the proportion reversed in the lower yielding
range. The effects of temperature on the thermodynamic behavior of large deformation of epoxy glass
are discussed.
MOLECULAR LEVEL INTERACTIONS IN IONIC LIQUIDS
Patricia Hunt (1)
Imperial College London, SW7-2AU, United Kingdom
p.hunt@imperial.ac.uk
The study of ionic liquids (IL) has emerged as an exciting new field.[1] As a class room temperature
ILs exhibit some unusual physical properties; vanishing vapour pressure, large liquidous range, high
thermal stability, high ionic conductivity, high electrochemical stability, and favourable solvation
behaviour. However, they are more viscous than aqueous solvents/electrolytes.
Network forming interactions, such as hydrogen-bonding and alkyl association occur in addition to the
basic ionic interactions; all play a key role influencing the IL's properties. Rotational freedom of the
alkyl chains in the cation and conformational variability of both the cation and anion all generate
disorder, increasing the entropy.
We have used quantum chemical methods to investigate the molecular level structure and electronic
properties of ion-pairs formed from imidazolium (alkyl and alcohol R groups) and ammonium cations
with Cl- and [F3CSO3]- anions. We have obtained insight into the alkyl chain rotations, functional
group hydrogen-bonding and variable cation-anion association motifs. Water molecules, an almost
ubiquitous contaminant of ILs, have been introduced and their effect on the cation-anion associations
examined.
From this study we have built up an understanding of the molecular level (close range) interactions
within the IL, and we have used this knowledge to rationalise a number of the physical and chemical
properties of these ILs
[1] “Ionic Liquids in Synthesis” 2 nd Ed, P. Wasserschied and T. Welton (eds.), VCH Wiley, Weinheim,
2007
(a) one possible structure for [HO-pmim][OTf][H2O], (b)
HOMO showing a dominant interaction between the
anion and OH group of the cation

GLASS TRANSITION OF POLYMERS AT SOLID INTERFACES
K. Tanaka (1), T. Nagamura (1), M. Doi (2) and H. Morita (3)
(1) Department of Applied Chemistry, Kyushu University, Fukuoka 819-0395, Japan
(2) Department of Applied Physics, The University of Tokyo, Tokyo 113-8656, Japan
(3) National Institute of Advanced Industrial Science and Technology, Ibaraki 305-8568, Japan
k-tanaka@cstf.kyushu-u.ac.jp
The segmental mobility of a typical amorphous polymer, polystyrene, at the interfaces with solid
substrates was noninvasively examined by fluorescence lifetime measurements using evanescent wave
excitation [1] in conjunction with coarse-grained molecular dynamics simulation [2]. The glass
transition temperature (Tg) was higher at the interface than in the internal region. Measurements at
different incident angles of excitation pulses revealed that Tg became higher closer to the interface.
The gradient became more marked with an increasing difference in the free energy at the interface
between the polymer and solid substrate. The Tg value at the interface decreased with decreasing
molecular weight. However, the decrement for the interfacial Tg was not as much as that for the bulk
Tg, due to the restriction of chain end portions by the substrate. Finally, it was observed that when a
film became thinner than 50 nm, the depressed mobility at the interface coupled with the enhanced
mobility induced by the presence of the surface.
[1] (a) Tanaka et al., Appl. Phys. Lett. 89(6), 061919-1-2, 2006, (b) Tanaka et al., J. Phys. Chem. B.
113(14), 4571-4577, 2009
[2] Morita et al., Macromolecules 39(18), 6233-6237, 2006
COMPARISON OF ACOUSTIC BEHAVIORS BETWEEN THE CRYSTALLINE AND
VITREOUS STATES OF ASPIRIN STUDIED BY MICRO-BRILLOUIN SCATTERING
Jae-Hyeon Ko (1), Kwang-Sei Lee (2), and Seiji Kojima (3)
(1) Department of Physics, Hallym University, 39 Hallymdaehakgil, Chuncheon, Gangwondo 200-702,
Republic of Korea
(2) Department of Nano Systems Engineering, Center for Nano Manufacturing, Inje University,
Gimhae 621-749, Gyeongnam, Republic of Korea
(3) Institute of Materials Science, University of Tsukuba, Tsukuba city, Ibaraki 305-8573, Japan
hwangko@hallym.ac.kr
We report micro-Brillouin scattering measurements on crystalline and vitreous states of aspirin, which
is one of the most representative pharmaceutical materials and whose glassy state has recently been
studied extensively [1]. The temperature dependence of the Brillouin frequency shift (νB) proportional
to the sound velocity is obtained in both crystalline and glassy phases of aspirin. The temperature
dependence of νB of the longitudinal acoustic waves in aspirin crystal is explained by the normal
lattice anharmonicity, from which the Debye temperature is estimated to be 357 K. The temperature
dependence of νB of glassy aspirin monotonically decreases upon heating and then exhibits a clear
change in slope at the glass transition temperature. The acoustic damping in the glassy phase is larger
than that in the crystal phase indicating stronger coupling between the longitudinal acoustic waves and
some internal degrees of freedom remnant in the vitreous state of aspirin. These acoustic properties of
aspirin [2] will be compared to those of other pharmaceutical materials.
[1] G. P. Johari, S. Kim and R. M. Shanker, J. Pharm. Sci., 96, 1159 (2007).
[2] J.-H. Ko, K.-S. Lee, Y. Ike and S. Kojima, Chem. Phys. Lett., 465, 36 (2008).

Dynamics of reversibly associating magnetic colloids
Albert Philipse, Van’t Hoff Laboratory for Physical and Colloid Chemistry, Utrecht University,
Padaualaan 8, 3584 CH Utrecht, TheeNetherlands.
a.p.philipse@u.nl
Any association in solution of dipolar colloids due to their dipole moments affects both
thermodynamic and transport phenomena. It has been claimed that the thermodynamics of weakly
associating ferromagnetic colloids can be simply modeled via an effective isotropic attraction. The
present work is motivated by the insight that this isotropic attraction would also determine transport
quantities such as sedimentation and diffusion. We have studied sedimentation of stable dispersions of
monodisperse magnetic iron-oxide (Fe3O4) colloids, with a dipolar coupling constant tuned by the
average particle size. The concentration-dependence of sedimentation rates abruptly changes sign,
going from pure hard spheres to even weakly dipolar particles. This marked transition does not follow
from predictions for isotropic attractions. Instead, the concentration dependence can be explained by
the mass action law for reversible colloid dimerization, without pre-averaging the anisotropy magnetic
attraction.
[1] K.Planken, M.. Klokkenburg, J.Groenewold and A.Philipse, J. Phys. Chem. B, 113, 3932, 2009.
GLASS TRANSITION AND POLYMER DYNAMICS IN RUBBER/SILICA AND
RUBBER/TITANIA NANOCOMPOSITES
Polycarpos Pissis (1), Anna Panagopoulou (1), Panagiotis Klonos (1), Daniel Fragiadakis (2) and
Liliane Bokobza (3)
(1) National Technical University of Athens, Department of Physics, Zografou Campus, 15780,
Athens, Greece
(2) Chemistry Division, Code 6120, Naval Research Laboratory, Washington, DC 20375-5342
(3) Laboratoire de Physico-Chimie Structurale et Macromoleculaire ESRCI, 10 rue Vauquelin, 75231
Paris cedex 05, France ppissis@central.ntua.gr
Differential scanning calorimetry (DSC), thermally stimulated depolarization currents (TSDC) and
dielectric relaxation spectroscopy (DRS) were used to study effects of polymer-filler interactions and
morphology on molecular dynamics in poly(dimethylsiloxane (PDMS)- and natural rubber (NR)-silica
nanocomposites. Nanocomposites with aggregated or finely dispersed nanoparticles were prepared by
in situ precipitation of tetraethoxysilane in the rubber matrix before or after crosslinking, respectively.
IR spectroscopy confirmed hydrogen bonding between oxygens in the backbone of PDMS and
hydroxyls on the surface of silica. No such interactions are present in NR-silica nanocomposites. In
dispersed samples, an interfacial polymer layer of modified dynamics is detected around silica
particles, estimated 2-3 nm thick, not contributing to the calorimetric glass transition. However, in
TSDC and DRS measurements this layer gives rise to a second, slower segmental relaxation. TSDC
thermal sampling measurements show a continuous distribution of relaxation times and glass transition
temperatures in this layer. Dynamics in the aggregated NR/silica samples is very similar to that of the
pure polymer showing a single segmental relaxation. Based on these results a methodology has been
developed for using DRS to check models which predict effects of solid surfaces on chain mobility. In
a next step of that work PDMS/silica and PDMS/titania with modified chain ends of PDMS are under
investigation.

THE 4ω METHOD: AN EXPERIMENTAL AND THEORITICAL STUDY OF THE LINEAR
RESPONSE IN DYNAMIC CALORIMETRY
J.-L. Garden (1), J. Richard (1), and H. Guillou (1)
(1) Institut Néel, CNRS et Université Joseph Fourier, BP 166, 38042 Grenoble cedex 9, France
jean-luc.garden@grenoble.cnrs.fr
In complex systems with slow phase transformations the dynamic aspect can be directly probed by the
ac-calorimetry method. The measurement of amplitude and phase of the oscillating temperature at the
frequency 2ω provides a frequency dependent complex heat capacity. If the departure from
equilibrium of the system is small during relaxation, then the linear response theory is applicable. In
this talk, based on physics of irreversible processes, I will derive a quantitative criterion defining the
range of applicability of the linear response theory. I will show that when this criterion is not fulfilled
there is an emergence of a non-negligible 4ω term (amplitude and phase) in the recorded temperature
oscillation. We have measured this 4ω contribution during slow phase transition in
polytetrafluoroethylene. I will give a possible physical meaning to this non linear contribution. Finally,
by means of this criterion I will argue that most of the calorimetric experiments on glass-formers occur
in the linear regime. Thus, the linear assumption is useful for describing the gradual freeze of the
configurational modes and a glass is not necessarily a far from equilibrium state of matter.
MUTAROTATION IN CARBOHYDRATES
P. Wlodarczyk (Silesian University)
Mutarotation is an isomerization process, which occurs in carbohydrates. After one century
from its discovery, we have used dielectric spectroscopy to study this phenomenon in undercooled
sugars. Dielectric spectroscopy proved to be very convenient and useful method in this research and,
in comparison to the standard polarimetry studies, it has many advantages. Mutarotation in
supercooled liquid phase proved to be very interesting. Unusual kinetic curves and two different
energy barriers for this complex process in D-fructose, as well as mutarotation analysis for D-ribose at
ambient and elevated pressure, will be presented.
THE NATURE OF AMORPHOUS ICES AND THEIR RELATION TO DEEPLY
SUPERCOOLED LIQUIDS
Thomas Loerting 1 , Katrin Winkel 2 , Michael S. Elsaesser 1 , Markus Seidl 1 , Philip Handle 1 , Erwin
Mayer 2
(1) Institute of Physical Chemisty, University of Innsbruck, Innrain 52a, A-6020 Innsbruck, Austria
(2) Institue of General, Inorganic&Theoretical Chemistry, University of Innsbruck, Innrain 52a, A-
6020 Innsbruck, Austria
Correspondence author: thomas.loerting@uibk.ac.at
It is still unresolved why water is such an anomalous liquid. Theories aiming at explaining the
increasingly anomalous behaviour as water is supercooled have proposed co-existence or at least a
sharp transition between two ultraviscous liquids differing in density. These liquids, denoted highdensity
liquid (HDL) and low-density liquid (LDL), are presumed to be the liquid counterpart to their
low-temperature amorphous ice proxies, high-density amorphous ice (HDA) and low-density
amorphous ice (LDA), respectively. On the other hand other theories presume HDA and LDA to be of
nanocrystalline nature and unrelated to a deeply supercooled liquid. We here show a study on the
volumetric glass-to-liquid transition in amorphous ices up to 0.3 GPa, which demonstrates that HDL

and HDA as well as LDL and LDA are indeed intimately related and that all amorphous ices can be
treated to produce a metastable equilbrium state. The onset temperature for the glass-to-liquid
transition is determined to be Tg, onset≈137 K for LDA→LDL and Tg, onset(0.1 GPa)≈125 K and Tg,
onset(0.2 GPa)≈134 K for HDA→HDL. By contrast, HDA directly crystallizes at p≈0.3 GPa without
showing signatures of a glass-to-liquid transition. Thus, at 140 K all amorphous states studied are
shown to relax on the time scale of minutes and to be in fact ultraviscous liquids for pressures p≤0.2
GPa. Furthermore macroscopic segregation and co-existence of LDL and HDL in the bulk state are
evidenced upon decompressing HDL at 140 K. This constitutes the first direct experimental evidence
for a first-order liquid-liquid transition in bulk liquid water at temperatures slightly below the noman’s
land, where crystallization can still be suppressed.
Computational Studies of the Thermodynamics, Structure and Dynamics of Water in Nano-scale
Confinement
Pablo G. Debenedetti
Department of Chemical Engineering
Princeton University
Princeton, NJ 08544
USA
The behavior of water in confining geometries with characteristic size in the nm range is of interest in
a wide range of scientific fields and technical applications, such as biological self-assembly and the
preservation of labile biochemicals. Recent computational work on water in nano-scale confinement
by inorganic and biological surfaces sheds new light on the roles of surface chemistry and geometry
on water structure [1], water phase behavior in hydrophobic confinement over broad ranges of
temperature and pressure [2-4], the evolution from surface-influenced to bulk-like dynamics [5], the
dependence of dynamics on surface polarity [6], the relationship between the mechanical properties of
glassy water thin films and surface polarity [7], water structure in confinement by heterogeneous
surfaces [8], and the control of surface hydrophobicity by coupling polarity and topography [9]. Such
studies help develop the physical understanding needed for the rational design of surfaces for practical
applications.
[1] N. Giovambattista, C.F. López, P.G. Debenedetti and P.J. Rossky. Proc. Nat'l. Acad. Sci. USA,
105, 2274, 2008.
[2] N. Giovambattista, P.J. Rossky and P.G. Debenedetti. Phys. Rev. E, 73, 041604, 2006.
[3] N. Giovambattista, P.J. Rossky and P.G. Debenedetti. Phys. Rev. Lett., 102, 050603, 2009.
[4] N. Giovambattista, P.G. Debenedetti and P.J. Rossky. J. Phys. Chem. B, DOI: 10.1021/jp9018266,
2009.
[5] S. Romero-Vargas Castrillón, N. Giovambattista, I.A. Aksay and P.G. Debenedett. J. Phys. Chem.
B, DOI: 10.1021/jp9025392, 2009.
[6] S. Romero-Vargas Castrillón, N. Giovambattista, I. A. Aksay and P. G. Debenedetti. J. Phys.
Chem. B, 113, 1438, 2009.
[7] T.G. Lombardo, N. Giovambattista and P.G. Debenedetti. Faraday Discuss., 141, 359, 2009.
[8] N. Giovambattista, P.G. Debenedetti and P.J. Rossky. J. Phys. Chem. C, 111, 1323, 2007.
[9] N. Giovambattista, P.G. Debenedetti and P.J. Rossky. In review, 2009.

The role of Eshelby backstress in the relaxation process of metallic glass-forming liquids
Marios D. Demetriou 1a , William L. Johnson 1 , and Konrad Samwer 2
1
Keck Engineering Laboratories, California Institute of Technology, Pasadena, CA 91125.
2
I. Physik Institute, University of Goettingen, Goettingen, Germany.
a
Author to whom correspondence should be addressed: marios@caltech.edu
Inspired by the deformation of soap bubble rafts, Argon proposed that flow of metallic glasses and
liquids is accommodated by plastic rearrangements of atomic regions involving tens of atoms, termed
shear transformation zones (STZs). Argon further recognized that these plastically rearranging
regions are not free but confined within an elastic medium, in conformity with the early insightful
theories of Eshelby. As proposed by Johari and Goldstein, the underlying relaxation mechanisms of
liquids and glasses are governed by two kinetic processes: a fast process, termed the β process, viewed
as a locally initiated and reversible process, and a slow process, termed the α process, viewed as a
large scale irreversible rearrangement of the material. From a potential energy landscape perspective,
Stillinger and co-workers have identified the β transitions with reversible hopping events across “subbasins”
confined within the inherent “metabasin”, and the α transition with an irreversible hopping
event that extends across metabasins. In this presentation, the relevance of the α and β relaxation
mechanisms to Argon’s concept of “dressed” STZs will be addressed. Specifically, it will be argued
that the faster β processes are associated with isolated STZ transitions confined within the elastic
matrix, while the slower α process is associated with the percolation of β events leading to the
collapse of the confining matrix and the breakdown of elasticity. Mechanical, calorimetric, ultrasonic,
and strain recovery experiments aimed to probe the instantaneous changes in stress, configurational
potential energy, isoconfigurational shear modulus, and anelastic strain recovery, will be presented.
The data gathered in these experiments support that the transition from anelastic to plastic response is
separable into reversible and irreversible activated hopping across the energy landscape, identified
with the β and α relaxation processes, respectively. More interestingly, a critical stress that arises
from this transition is recognized as an effective Eshelby “backstress” that confines the STZs to be
elastically coherent with the surrounding matrix, thereby supporting that the onset of α relaxation is
indeed associated with the collapse of the STZ elastic matrix confinement.

THE STRUCTURE OF IONIC LIQUID SOLUTIONS OF BENZENE DERIVATIVES:
AROMATIC SOLUTES AS MOLECULAR CHARGE TEMPLATES OF THE
IONIC LIQUID SOLVENT.
J. N. Canongia Lopes (1,2), K. Shimizu (1), M. F. Costa Gomes (3), A. A..H. Pádua (3), L. P. N.
Rebelo (2)
(1) Centro de Química Estrutural, IST/UTL, 1049-001 Lisboa, Portugal,
(2) Instituto de Tecnologia Química e Biológica, ITQB2/UNL, 2780-901 Oeiras, Portugal,
(3) Laboratoire Thermodynamique et Interactions Moléculaires, CNRS/UBP, Clermont-Ferrand,
France
jnlopes@ist.utl.pt
Mixtures of ionic liquids with aromatic compounds such as benzene and its fluorinated
derivatives have very interesting structural and fluid phase behavior. [1-3]. In this work the
diverse dipole and quadrupole moments of benzene and its twelve fluorinated derivatives (from
fluorobenzene to hexafluorobenzene) were correlated to their solubility in the ionic liquid 1-ethyl-
3-methyl-imidazolium bis(trifluoromethanesulfonyl)imide, [C2mim ][NTf2]. Albeit empirical,
the correlation was built taken into account molecular insights gained from ab-initio calculations
of the isolated aromatic solute molecules and Molecular Dynamics simulations of all thirteen
aromatic solute plus ionic liquid solvent binary mixtures. This type of molecular-assisted
approach unveiled a simple correlation between the dipole and quadrupole moments of the
solutes and the ionic liquid solvent. It also revealed the complex nature of the interactions
between aromatic compounds and ionic liquids, with the charge density functions of the former
(aromatic solute) acting as a sort of molecular template that promotes the segregation of the ions
of the latter (ionic liquid solvent) and define the fluid phase behaviour (liquid-liquid demixing) of
the corresponding binary mixtures. Such approach can be extended to other systems involving the
interactions of different types of solute with ionic liquid solvents.
[1] J. Lachwa, I. Bento, M. T. Duarte, J. N. Canongia Lopes and L. P. N. Rebelo, Chem.
Commun., 2445, 2006.
[2] M. Blesic, J. N. Canongia Lopes, A. A. H. Pádua, K. Shimizu, M. F. Costa Gomes, L. P. N.
Rebelo, L. P. N. J. Phys. Chem. B, available ASAP, 2009.
[3] M. B. Shiflett and A. Yokozeki, J.Chem. Eng. Data, 53, 2683, 2008.
Temperature and pressure dependence of structural relaxation time for ionic liquid
verapamil hydrochloride – analysis in terms of the entropic models
Z. Wojnarowska, K. Grzybowska, A. Grzybowski, M. Paluch
Relaxation dynamics of ionic liquid verapamil hydrochloride was studied in wide frequency,
temperature and pressure range using broadband dielectric spectroscopy. The tested sample has a
cardiological application. It is very useful to reduce several heart and blood pressure problems.
From isobaric and isothermal dielectric measurements, carried out at different thermodynamical
conditions, we determined the structural relaxation times τα, defined as the inverse frequency of
the α-peak maximum, . The obtained results were presented in the form of two relaxation
maps, first one as a dependence log10τ(P) and the second as a log10τ(T). Because, in many
respects, it is important to analyze the isobaric and isothermal data simultaneously, the main goal
of this work is to describe the experimental results by using models which connect both
temperature and pressure influence with the structural relaxation time in one equation. At present
there are two fundamental models, based on configurationally entropy, which are able to realize
this purpose. The first is Adam – Gibbs model and the second one is Avramov entropic model.

Herein, we present results obtained from fitting both entropic models into isothermal and isobaric
experimental data.
OPTICAL QUENCHING OF THE DYNAMICS IN A MOLECULAR LAYER OF
AZOPOLYMER FLOATING ON WATER
D. Orsi (1), L. Cristofolini (1), M. P. Fontana (1)
(1) Physics Dep.t and INFM- CRS SOFT, Parma University, Italy
Cristofolini@fis.unipr.it
We report on very recent results obtained by the surface
rheology technique ISR [1] on the dynamics of a side
chain azopolymer [2,3] confined in the 2D geometry of
a Langmuir monolayer: a floating needle is oscillated by
an alternated magnetic field gradient. From the
amplitude and phase of the oscillations the viscoelastic
parameters of the polymeric Langmuir film are deduced.
We use the photoinduced azobenzene isomerisation
mechanism to drive the polymeric layer from a state of high 2D viscosity into a state of low
viscosity, and then by illumination with appropriate wavelength, we drive the film back to the
high viscosity state.
In figure we show the evolution of oscillation amplitude under UV illumination (low viscosity
phase, large oscillations) and under visible illumination (high viscosity phase, oscillations
vanishing). We shall discuss the potentiality of this for the preparation of out-of-equilibrium
polymeric systems, also in conjunction with a recent x-ray photocorrelation experiment [4].
[1] CF. Brooks et al. Langmuir 15, 2450 (1999)
[2] A. Natansohn et al. Chem Rev., 102, 4139 (2002)
[3] L. Cristofolini, et al. Phys. Rev. Lett. 85 (2000) 4912.
[4] XPCS, this conference
BROADBAND DIELECTRIC AND CONDUCTIVITY SPECTRA (100 Hz - 2 THz) OF
STRAIN SENSITIVE POLYISOPRENE-CARBON NANOCOMPOSITES
V. Bovtun (1), D. Nuzhnyy (1), J. Petzelt (1), M. Knite (2), I. Aulika (3), A. Fuith (4)
(1) Institute of Physics ASCR, Na Slovance 2, 18221 Prague, Czech Republic
(2) Institute of Technical Physics, Riga Technical University, Latvia
(3) Institute of Solid State Physics, University of Latvia, Riga, Latvia
(4) Institute of Experimental Physics, University of Vienna, Austria
bovtun@fzu.cz
Polyisoprene-carbon nanoparticle composites possessing a giant electric resistance dependence
on mechanical strain near the percolation threshold [1,2] were studied by broadband dielectric
spectroscopy. Dielectric permittivity, loss and conductivity spectra were measured at room
temperature in a very broad frequency range: 100 Hz – 2 THz. Dielectric/conductivity dispersion
was observed. Three mechanisms contributing to the dielectric and conductivity responses were
revealed and attributed to: 1) dc carbon network conductivity in percolated clusters responsible
for the low-frequency conductivity plateau; 2) ac carbon conductivity in finite clusters; 3) intercluster
polarization of the insulating polymer matrix. The last two mechanisms are responsible for
the power-law dispersion observed above 1 MHz.

[1] M. Knite, V. Teteris, A. Kiploka, I. Klemenoks, Adv. Eng. Mater., 6, 742, 2004
[2] M. Knite, A. Hill, V. Bovtun et al., Latvian J. of Physics and Technical Sciences, N2, 15,
2006
PROPERTIES OF GLASS TRANSITION CAN BE UNDERSTOOD ON THE BASIS
OF
ELASTIC WAVES
Kostya Trachenko (University of Cambridge)
We propose that the properties of glass transition can be understood on the basis of
elastic waves. Elastic waves originating from atomic jumps in a liquid propagate local
expansion due to the anharmonicity of interatomic potential. This creates a dynamic
compressive stress, which increases the activation barrier for other events in the liquid.
The non‐trivial point is that the range of propagation of these high‐frequency elastic
waves, del, increases with liquid relaxation time τ, as del=cτ, where c is the speed of
sound. A self‐consistent calculation shows that this increase gives the Vogel‐Fulcher‐
Tammann law, with the VFT temperature T0 related to liquid thermal expansion and
compressibility without adjustable parameters.
As well as explaining the VFT law, the theory also explains the origin of two dynamic
crossovers: the crossover from non‐cooperative to cooperative relaxation at high
temperature and the crossover from the VFT to a more Arrhenius relaxation at low
temperature. The corresponding values of τ at the two crossovers are in quantitative
agreement with the experiments without using adjustable parameters. The origin of the
second crossover allows us to reconcile the ongoing controversy surrounding a possible
divergence of τ at T0. The crossover to Arrhenius relaxation universally takes place
when del reaches system size, thus avoiding the divergence and associated theoretical
complications such as identifying the nature of the phase transition and the second
phase.
The previously puzzling division between ʺfragileʺ and ʺstrongʺ liquids is explained by
asserting that there is no basic difference but the ʺfragileʺ region in the usual examples of
ʺstrongʺ liquids occurs at sufficiently high temperatures where usually no experimental
data exist.
NEARLY CONSTANT LOSS EFFECT STUDIED IN METAPHOSPHATE GLASSES
L. Badr (1) and K. Funke (2)
(1) Institut für Physikalische Chemie and Graduate School of Chemistry, Westfälische Wilhelms-
Universität Münster, Corrensstrasse 30, 48149 Münster, Germany
(2) Institut für Physikalische Chemie, Westfälische Wilhelms-Universität Münster, Corrensstrasse
30, 48149 Münster, Germany
lbadr_01@uni-muenster.de
The Nearly Constant Loss (NCL) effect, discovered by Nowick et. al. in 1991 [1], is one of the
most puzzling features in the field of solid state ionics. It is characterized by a dielectric loss

function which is constant over a wide frequency range. NCL behavior has been detected in a
huge number of structurally disordered ion-conducting materials, such as glasses. Models devised
to explain the NCL effect are based on localized movements of many interacting ions.
Information revealing essential features of the localized movements is obtained by measuring the
ionic conductivity in wide ranges of frequency and temperature. In this work, the scaling property
of the dispersive conductivity due to hopping processes [2] is used in log(conductivity) versus T
plots at fixed frequencies to remove the contribution due to hopping from the total measured
conductivity. Detectable temperature dependences are obtained for the conductivities caused by
the localized processes occurring at low temperatures. For some glasses, this effect could be
observed in a temperature range from 5 K to more than 100 K. The temperature dependences are
investigated in relation to the applied frequency and the structure of the glass. The crossover from
the hopping-type motion to the NCL behavior is examined for different glasses. The systems
employed in our study are the silver halide-silver metaphosphate glasses, AgX·AgPO3 (X = I, Br,
and Cl), and the pure metaphosphate glasses, YPO3 (Y = Ag, Na, and Li). Along with our
experimental findings we present a new model concept for the NCL effect.
[1] W.K. Lee, J.F. Liu and A.S. Nowick, Phys. Rev. Lett. 67, 1559, 1991
[2] D.M. Laughman, R.D. Banhatti and K. Funke, Phys. Chem. Chem. Phys., 11, 3158, 2009
STRUCTURE AND DIELECTRIC PROPERTIES OF PMMA-
ORGANOMONTMORILLONITE NANOCOMPOSITES
N. Suárez (1), N. Salazar Serge (2), J. L. Feijoo (3) and M. Hernandez (1)
(1) Departamento de Física, Universidad Simón Bolívar, Apartado 89000, Caracas 1080-A,
Venezuela
(2) Departamento de Química, Universidad Simón Bolívar, Apartado 89000, Caracas 1080-A,
Venezuela
(3) Departamento de Materiales, Universidad Simón Bolívar, Apartado 89000, Caracas 1080-A,
Venezuela
nsuarezr@usb.ve
This work is related to the preparation of polymer-clay nanocomposites (PCNs) by the
exfoliation-adsorption technique, from atactic poly(methyl methacrylate) (PMMA), using
Bentonite (B) as a layered-silicate natural clay. To optimize the intercalation of B with PMMA, it
has been organically modified (OB) with a quaternary ammonium salt. An investigation of the
morphology and molecular motions or dynamics of the net polymer as well as the PCNs final was
performed by X-ray diffraction (XRD), Transmission Electron Microscopy (TEM), Infra-Red
Spectroscopy (IR), Thermally Stimulated Depolarization Currents (TSDC), Differential Scanning
Calorimetry (DSC) techniques. XRD diffraction patterns, TEM microphotographs, TSDC low
temperature spectra, and FTIR spectra of the Si-O stretching region, as previously reported [1],
show an increasing overall degree of intercalation/exfoliation with OB content up to 5%. Two
segmental relaxations were detected by TSDC, the majority due to chains affected by the
exfoliation, and the minority, at lower temperatures, due to the intercalated chains. variations in
the temperature position of these relaxations with OB content has been rationalized assuming two
opposite effects: the reduction of the intermolecular (cooperative) domain size of layered silica,
which increases with the exfoliation; and the restrictions of segmental mobility of the layered
silicate/polymer interactions.
[1] Yi, H. L. Duan, Y. Chen, and J. Wang, Phys. Let., A 372, 68-71, 2007.

Scaling of the current-current time correlation function of a suspension of hard sphere-like
particles; Exposing when the motion of particles is Brownian.
W. van Megen, V.A. Martinez and G. Bryant
Department of Applied Physics, Royal Melbourne Institute of Technology, Melbourne, Victoria
3000, Australia.
ABSTRACT
The current-current correlation function, C(q,τ), is determined by dynamic light scattering for a
suspension of particles with hard sphere-like interactions. Factorization of space and time
variables provides direct support for the notion that the motion of suspended particles can be
described in terms of uncorrelated Brownian encounters, the assumption that underpins the
Smoluchowski equation. This applies to the suspension known to be in thermodynamic
equilibrium ie, for volume fractions less than φf=0.493, the known first order freezing point of the
hard-sphere system. In the metastable case, for φ>φf, non-monotonicity in C(q,τ) implies a loss of
space-time factorization. This signals the presence of another impediment to structural relaxation,
one that is incompatible with the loss of memory of the particles’ momenta.
Further evidence of such impediments is seen in previous studies of Newtonian [1] and colloidal
[2] hard spheres. These expose the emergence, at φf, of negative algebraic decays in the velocity
auto-correlation function—features reminiscent of flow in channels [3] and porous media [4]. In
these cases the fluid is presented with a structural obstacle to momentum diffusion. In response,
overdamped compression waves are excited in the suspending liquid, first, it would appear with
wavevectors around the location of the main structure factor peak and then, with increasing
volume fraction, spreading to other wavevectors [5].
1. S.R. Williams, G. Bryant, I.K. Snook and W. van Megen, Phys. Rev. Lett.
96, 087801 (2006).
2. W. van Megen, Phys. Rev. E 73, 020503(R) (2006).
3. I. Pagonabarraga, M.H.J. Hagen, C.P. Lowe and D. Frenkel, Phys. Rev. E 59,
4458 (1999).
4. D.O. Riese and G.H. Wegdam, Phys. Rev. Lett. 82, 1676 (1999).
5. W. van Megen, V.A. Martinez and G. Bryant, Phys. Rev. Lett. 102, 168301 (2009).
Mobile cation motion in superionic glasses.
M.Russina, E.Kartini, F.Mezei, M.Nakamura, M. Arai
Solid electrolytes (e.g. AgI, Ag2S) are materials where the cationic or anionic components are not
confined to specific lattice sites but able to move throughout the structure. Such systems exhibit
substantial electrical conductivity, however, only at quite high temperatures, when Ag + ions
become mobile. The electrical conductivity of the network glasses such as AgPO3 is quite low [1],
but the addition of AgI and Ag2S dopants to AgPO3 results in remarkable increase of their
electrical conductivity (up to 10 -2 Ω -1 cm -1 ) already at room temperature, i.e. well below the glass
transition point [1]. Besides the potentially high technological use of such materials, an important

fundamental aspect is the mechanism of the microscopic diffusion leading to the conductivity in
otherwise frozen disordered systems.
We investigated the microscopic behavior of three systems, the network glass AgPO3 and the
composite systems (AgI)0.5(AgPO3)0.5 and (AgI)0.33(Ag2S)0.33(AgPO3)0.34 by using cold neutron
scattering [2],[3]. The conductivity of the doped systems changes from 10 -7 S cm -1 for AgPO3 to
10 -2 Scm -1 for both (AgI)0.5(AgPO3)0.5 and (AgI)0.33(Ag2S)0.33 (AgPO3)0.34 glasses at room
temperature. Our inelastic scattering data show the onset of strong anharmonic dynamics on the
energy scale corresponding to the picoseconds (0.40 meV~ 15 ps) at temperatures far below the
glass transition temperature. Since such motion is not observed in the non-conducting glass
AgPO3 and the viscous flow at such temperatures is many orders of magnitude slower, only
motion of a mobile fraction of ions can cause such anharmonic quasielastic intensity. Furthermore,
the Q-dependence of this quasielastic scattering exhibit a clear pronounced peak at Q=2.5 Å -1
corresponding to the distance Ag-Ag correlation distance and indicating that nature of the
superionic conductivity is related to the back-and-forth oscillating short-range jumps within the
solid glass matrix.
[1] E. Kartini at el, Solid State Ionics 1 (2003) 157
[2] M.Russina, et al, Physica B, 385-386 (2006) 240
[3] E. Kartini at el, Solid State Ionics, Volume 180, Issues 6-8, 14 May 2009, Pages 506-509
Analysis of overlapped dielectric relaxations by means of retardation time spectra.
R. Díaz-Calleja (1), M. J. Sanchis (1), G.Dominguez-Espinosa (1),E. Riande (2)
(1) Instituto de Tecnología Electrica, ETSII. Universidad Politecnica de Valencia (Spain).
(2) Instituto de Ciencia y Tecnología de Polímeros C.S.I.C. Madrid (Spain).
Corresponding author: rdiazc@ter.upv.es
In the moderate supercooled regime, the response of liquids to external force fields is a single
absorption. In cooling, this absorption splits into two relaxations in the loss spectra. The fast
relaxation is named the β process and the other one, which is slow, is called the α or glassliquid
absorption [1]. An important issue in the study of chain dynamics is to perform a good
deconvolution of overlapping peaks in the loss spectra. Usually, relaxations in the frequency
domain are described in terms of the Havriliak-Negami (HN)-type equations [2]. Because many
relaxations are poorly defined, it is often difficult to discriminate between different values of
fitting HN parameters describing the loss spectra in a wide frequency window. Due to the fact
that a Debye-type relaxation covers about 2.29 decades in the frequency domain, but it becomes a
Dirac delta function in the retardation time spectra, compliance relaxation processes are better
defined in the time domain [3]. In the present work some results of this strategy of analysis are
presented when applied to several polymers systems. Dipole correlation function is calculated
from the retardation spectra and subsequently, the Williams ansatz is analyzed [4]. A discussion
of the molecular origin of the secondary absorptions is carried out assuming that the dipoles
associated to polar groups librate around the bonds of the main chain, or more frequently, the
side-chains.
[1] F.S. Stillinger, Science 267 (1995) 1935
[2] S. Havriliak, S. Negami Polym. 8 (1967) 161–210; J Polym Sci, Polym Symp 14 (1966) 99
[3] G. Domínguez-Espinosa, D.Ginestar, M.J. Sanchis, R.Díaz-Calleja, E. Riande, J. Chem. Phys.
129 (2008) 104513

[4] G. Williams, Adv. Polym. Sci. 33 (1979) 60,; G. Williams, in Keynote Lectures in Selected
Topics of Polymer Science, edited by E. Riande CSIC, Madrid, 1995, Chap. 1
HOW MANY MOLECULES ARE DYNAMICALLY CORRELATED ALONG THE
GLASS TRANSITION LINE?
C. DALLE-FERRIER, C. ALBA-SIMIONESCO
Laboratoire de Chimie Physique, CNRS-Université Paris Sud, Orsay, France
Laboratoire Léon Brillouin, CNRS-CEA UMR12, Saclay, France
cecile.dalle-ferrier@lcp.u-psud.fr
By cooling a liquid fast enough under its melting point, the crystallization can be avoided and a
glass obtained. The transition between an equilibrium liquid phase and an out-of-equilibrium
glass is characterized by a huge increase in the viscosity or relaxation time of the system. It is
tempting to ascribe the strong temperature dependence of the dynamics, irrespective of molecular
details, to a collective or cooperative behaviour characterized by a length scale that grows as one
approaches the glass transition. To access this length experimentally, we use the recently
introduced three-point dynamic susceptibility [1], from which can be extracted a number of
dynamically correlated molecules during the structural relaxation, Ncorr [2]. The three-point
functions are related to the sensitivity of the averaged two-time dynamics to external control
parameters, such as temperature and density. We studied Ncorr values on the whole pressure and
temperature range for an organic liquid called dibutylphtalate (DBP) thanks to extensive
dielectric spectroscopy measurements on a home built pressure setup and literature data [3]. We
obtained an increasing number of dynamically correlated molecules along the glass transition line
and explained it by identifying the density and temperature contributions to this number of
dynamically correlated molecules. We generalized this result to other liquids by using the scaling
law of relaxation time [4] with density and temperature.
[1] L. Berthier, G. Biroli, J.P. Bouchaud, L. Cipelletti, D. El Masri, D. L'Hôte, F. Ladieu, M.
Pierno, Science 310, 1797, 2005
[2] C. Dalle-Ferrier, C. Thibierge, C. Alba-Simionesco, L. Berthier, G. Biroli, J.-P. Bouchaud,
F. Ladieu, D. L'Hôte, G. Tarjus, Phys. Rev. E, 76, 041510, 2007
[3] M. Paluch, M. Sekula, S. Pawlus, S. J. Rzoska, J. Ziolo, C. M. Roland, Phys. Rev. Lett., 90,
175702, 2003
[4] C. Alba-Simionesco, A. Cailliaux, A. Alegria, G. Tarjus, Europhys. Lett., 68, 58, 2004
DYNAMICS OF LIQUIDS AND LIQUID CRYSTALS AT THEIR TRANSITIONS
C.M. Roland (1), R. Casalini (1), R. Bogoslovov (1), J. Czub (2), and S. Urban (2)
(1) Naval Research Laboratory, Code 6120, Washington DC 20375-5342, USA
(2) Institute of Physics, Jagiellonian University, Reymonta 4, 30-059 Krakow, Poland
mike.roland@nrl.navy.mil
The dynamics of molecular liquids and polymers exhibit various “transitions”, associated with
characteristic changes in properties at particular combinations of temperature or pressure. These
transitions include (i) the onset of non-Arrhenius and non-Debye behavior, (ii) the dynamic
crossover, (iii) vitrification, and (iv) for anisotropic molecules the development of liquid
crystallinity. At each of these transitions, the structural or reorientational relaxation time of the
liquid is constant, independent of thermodynamic conditions; that is, while the temperature of the
transition depends on pressure, the relaxation time does not. This constancy of τ for liquid crystals

at their clearing line and for transitions between different ordered phases means there is a
surprising connection between the thermodynamic conditions defining the stability limits
(reflecting competition between the anisotropic interaction energy and the orientational entropy)
of a liquid crystalline phase and the dynamic properties in the ordered state. This relationship is
unanticipated by any model of liquid crystals.
The construction of a reliable potential for GeO2 from first-principles
D. Marrocchelli *(1), M. Salanne (2,3), P.A. Madden (4), C. Simon (2,3) and P. Turq (2,3)
(1) School of Chemistry, University of Edinburgh, Edinburgh EH9 3JJ, UK
(2) UPMC Univ Paris 06, UMR 7612, LI2C, F-75005, Paris, France
(3) CNRS, UMR 7612, LI2C, F-75005, Paris, France
(4) Department of Materials, University of Oxford, Parks Road, Oxford OX1 3PH, UK
*D.Marrocchelli@sms.ed.ac.uk
In the vitreous and liquid states, at ambient pressure, germania (GeO2) (a close structural
analogue of silica (SiO2)) forms a tetrahedrally-coordinated three-dimensional network. GeO2 is
used in several fields, mainly related to optical technologies. For example, a mixture of SiO2 and
GeO2 allows precise control of the refractive index in optical fibres and waveguides. For this
reason, it is of interest to develop simulation methods to allow a detailed examination of the local
structure in such mixtures and to predict the infrared spectrum, since this determines the longwavelength
limit for their use as optical fibres.
In the past few years, a lot of effort has been done to study this material by means of both firstprinciples
molecular dynamics (FPMD) [1] and classical molecular dynamics (MD) simulations
[2], using pair-wise additive potentials. Although these techniques were successful in some cases,
they both present some important drawbacks. FPMD simulations, in fact, though successful at
reproducing the structural and optical properties of this system are computationally very
expensive and therefore unsuitable for the system sizes and timescales usually required for the
study of glassy materials. Classical molecular dynamics simulations, on the other hand, are much
faster and can be easily used to study systems with many hundreds of atoms on the nanosecond
scale but they usually lack accuracy and need different sets of parameters to represent different
properties.
In this work we describe the parameterization of a new classical MD interaction potential for
GeO2, using techniques we have developed for halides and oxides [3], which is entirely based on
first-principles, electronic structure calculations. In order to provide an accurate, transferable
description of the interactions, these potentials include dipole polarization effects and the ions
carry full valence charges. The obtained potential is able to reproduce all the studied properties
(structural, dynamical and vibrational) to a high degree of precision with a single set of
parameters. The agreement with the experimental data is comparable with the one obtained from
FPMD calculations, although our simulations are much faster. We are currently using these
potentials to study the effects of pressure on glassy GeO2, to evaluate the thermal conductivity of
this material and to study SiO2-GeO2 mixtures.
[1] L. Giacomazzi, P. Umari, and A. Pasquarello, Phys. Rev. Lett. 95 (7), 075505 (2005).

[2] M. Micoulaut, Y. Guissani, and B. Guillot, Phys. Rev. E 73, 031504 (2006).
[3] P.A. Madden, R. Heaton, A. Aguado and S. Jahn, Journal of Molecular Structure :
THEOCHEM 771, 9-18 (2006)
MOLECULAR MOBILITY AND LI + CONDUCTION IN POLYESTER COPOLYMER
SINGLE ION CONDUCTORS USING DIELECTRIC SPECTROSCOPY
J. Runt, D. Fragiadakis, S. Dou and R.H. Colby (1)
(1) Department of Materials Science and Engineering, Penn State University, University Park, PA
16802 USA
runt@matse.psu.edu
In this presentation we review the findings of our recent investigation of segmental and local
dynamics, as well as Li + transport, in a series of model poly(ethylene oxide)-based ionomers
using dielectric spectroscopy [1]. We observe a slowing down of segmental dynamics and an
increase in glass transition temperature above a critical ion content, as well as the appearance of
an additional relaxation process associated with rotation of ion pairs. Conductivity is strongly
coupled to segmental relaxation. For a fixed segmental relaxation frequency, molar conductivity
increases with increasing ion content. A physical model of electrode polarization is used to
separate ionic conductivity into the contributions of mobile ion concentration and ion mobility,
and a model for the conduction mechanism involving transient triple ions is proposed to
rationalize the behavior of these quantities as a function of ion content and the measured
dielectric constant.
[1] D. Fragiadakis, S. Dou, R.H. Colby and J. Runt, J. Chem. Phys., 130, 064907, 2009
We thank the U.S. Department of Energy, Office of Basic Energy Sciences, for support for this
research.
INFLUENCE OF CHAIN-GRAFTED NANOPARTICLES ON THE MACROSCOPIC
DYNAMICS AND THE GLASS TRANSITION OF POLYMER MELTS
Peter F. Green and Hyun Joon Oh
Materials Science and Engineering, Applied Physics
University of Michigan, Ann Arbor
The influence of polystyrene (PS) chain grafted gold nanoparticles on the glass transition, Tg, and
the dynamics of unentangled PS chains of degree of polymerization P was investigated. Through
careful control of the degree polymerization, N, of the grafted chains, the nanoparticle diameter,
D, and the grafting density, s, we show that the glass transition of the PS/gold-PS nanocomposites,
Tg, could be induced to increase or decrease, appreciably, at low nanoparticle concentrations.
More importantly, dielectric spectroscopy studies show that the longest relaxation time, t,
associated with translational dynamics of the host chains, exhibited changes commensurate with
the changes in Tg. The “fragilities” exhibited only minor changes with nanoparticle concentration.
The connection between the morphological structure of these PS/gold-PS mixtures and the
properties will be discussed. Additionally, we show how the changes in Tg and the dynamics may
be interpreted in light of various models.

Glassy dynamics beyond the α-relaxation investigated by broadband dielectric spectroscopy
and aging measurements
P. Lunkenheimer, M. Köhler, S. Kastner, and A. Loidl
Experimental Physics V, Center for Electronic Correlations and Magnetism, University of
Augsburg, 86135 Augsburg, Germany
Peter.Lunkenheimer@Physik.Uni-Augsburg.de
We report current results from broadband dielectric spectroscopy and aging measurements on a
variety of glassforming liquids, including propylene glycol (mono-, di-, tri-, and polymer), xylitol,
sorbitol, Salol, and benzophenone. We concentrate on the dynamic processes faster than the αrelaxation,
which are quite universally present in all types of glassy matter. Aside of the fast βrelaxation,
which occurs in the GHz-THz range, in this talk the slow β-relaxation observed in the
Hz-MHz range will be discussed in detail. Amongst others, the following questions will be
treated: Is the excess wing caused by a Johari-Goldstein β-relaxation or by another, additional
type of secondary relaxation? Can the Johari-Goldstein β-relaxation be identified with the Cole-
Cole relaxation predicted by the mode-coupling theory? What is the temperature dependence of
the β-relaxation time close to and above the glass temperature? Is aging at temperatures deep in
the glassy state dominated by the β-relaxation? While further work is necessary to arrive at
definite conclusion, the present results at least give some hints helping to enlighten the origin of
the so far mysterious slow β-relaxations.
DIELECTRIC RELAXATIONS IN ANHYDROUS TREAHLOSE AND MALTOSE
GLASSES
Hyun-Joung Kwon, Jeong-Ah Seo+, Hyung Kook Kim, and Yoon-Hwae Hwang*
Department of Nanomaterials Engineering & BK21 Nano Fusion Technology Division, Pusan
National University, Miryang 627-706, Korea
+Current address : USTL, UFR de Physique, Bat. P5 LDSMM, Université de Lille 1, 59650
Villeneuve d'Ascq Cédex. France.
yhwang@pusan.ac.kr
We studied dielectric relaxations in anhydrous trehalose and maltose glasses in the frequency
range from 10 mHz to 1 GHz. We found four relaxation processes in dielectric loss spectra and
those are α-relaxation, Johari-Goldstein(JG) β-relaxation [1], an extra relaxation, and γ-relaxation
as the frequency increased. The temperature dependence of α-relaxation times was changed from
non-Arrhenius to Arrhenius behavior at the glass transition temperature (Tg) as the temperature
increased. Also the temperature dependence of JG β-relaxation times showed a crossover at the
temperature near Tg. The ratio of the crossover temperature to Tg was 0.94 and this value is quite

universal [2-4]. The extra relaxation observed between JG β-relaxation and γ-relaxation seems to
originate from the intra-molecular relaxation and might be related to the flexible glycosidic bond
in disaccharides.
[1] S. Capaccioli, K. Kessairi, D. Prevosto, M. Lucchesi, K.L. Ngai, J. Non-Cryst. Solids 352
(2006) 4643.
[2] R. Casalini, C. M. Roland, Phys. Rev. Lett. 102 (2009) 035701.
[3] N. Shinyashiki, M. Shinohara, Y. Iwata, T. Goto, M. Oyama, S. Suzuki, W. Yamamoto, S.
Yagihara, T. Inoue, S. Oyaizu, S. Yamamoto, K. L. Ngai, S. Capaccioli, J. Phys. Chem. B 112
(2008) 15470.
[4] T. Blochowicz, E. A. Rossler, Phys. Rev. Lett. 92 (2004) 225701.
GLASS TRANSITION IN ULTRA THIN POLYMERIC FILMS MEASURED BY
DIFFERENTIAL AC-CHIP CALORIMETRY
H. Huth (1), DS. Zhou (1,2) , C. Schick (1)
(1) Institute of Physics, Rostock University, Rostock, 18055, Germany
(2) Department of Polymer Science and Engineering, Nanjing University, Nanjing, 210093,
China
huthheiko@googlemail.com
The film thickness dependency of glass transition in polymer films is still controversially
discussed. For different experimental probes different dependencies are observed and a generally
accepted link to molecular mobility is not yet established. Calorimetry has proven to provide
useful information about glass transition, because it establishes a direct link to energetic
characterization. In several cases a direct comparison with results from other dynamic methods
like dielectric spectroscopy is possible giving further insights. For thin films in the µm…nm
range standard calorimetric methods are mostly not applicable. We set up a differential AC-chip
calorimeter capable to measure the glass transition in nanometer thin films with pJ/K sensitivity
in a relative broad frequency range [1-3]. Changes in heat capacity can be measured for sample
masses below one nanogram as needed for the study of the glass transition in nanometer thin
polymeric films. The glass transition in thin films was determined at well defined experimental
time scales. No thickness dependency of the glass transition temperature was observed within the
error limits - neither at constant frequency nor for the traces in the activation diagrams.
[1] H. Huth, AA. Minakov, A. Serghei, F. Kremer, and C. Schick, The European Physical
Journal - Special Topics;141 153 (2007).
[2] AA. Minakov, J. Morikawa, T. Hashimoto, H. Huth, and C. Schick, Meas. Sci. Technol.;17
199 (2006).
[3] H. Huth, AA. Minakov, and C. Schick, J. Polym. Sci. B Polym. Phys. 44 2996 (2006).
THE LOW FREQUENCY PHONONS DYNAMICS IN SUPERCOOLED LICL, 6H2O
M. E. Gallina (1,2), L. Bove (2), C. Dreyfus (2), R. Cucini (3), A. Taschin(3),R. Torre (3) and R.
M. Pick (2)
(1) Dipartimento di Chimica, Università di Perugia, Perugia (Italy)

(2) IMPMC, Université P. et M. Curie et CNRS-UMR 7590, Paris (France)
(3) LENS and Dipartimento di Fisica, Università di Firenze, Sesto Fiorentino (Italy)
robert.pick@courriel.upmc.fr
LiCl, 6H20 can be supercooled down to its liquid-glass transition temperature, Tg~138 K. We
shall present and discuss results of a series of ultrasound, Brillouin scattering, and optical
Heterodyne Detected Transient Grating experiments performed from room temperature down to
the vicinity of Tg. Down to T~215 K, the supercooled liquid has behaviour similar to what is
expected for supercooled water (which always crystallizes above 247 K). The zero frequency
sound velocity, C 0 of the solution continuously decreases while the corresponding infinite
frequency velocity, C ∞ , sharply increases, reflecting the increasing importance of H bonding
when temperature is lowered. Below 215 K, specific aspects of the solution, presumably related
to the role of the Li + and Cl - ions, modify the thermal behaviour of C 0 . Upon further cooling,
C 0 exhibits an apparent increase while a β relaxation process also appears and couples to the
sound propagation. The origin of those two effects will be discussed, and compared with results
obtained on a LiBr, 6H20 solution. The latter has approximately the same Tg but has a different
behaviour in the strongly supercooled regime.
LIQUID-LIQUID TRANSITIONS AND BIZARRE VISCOSITY BEHAVIOR OF THE
MELTS UNDER HIGH PRESSURE
V.V. Brazhkin (1), M. Kanzaki (2), Ken-ichi Funakoshi (3), Y. Katayama (4), M.V. Kondrin (1),
A.G. Lyapin (1) and H. Saitoh (4)
(1) Institute for High Pressure Physics RAS, 142190 Troitsk Moscow region, Russia
(2) Institute for Study of the Earth Interior, Okayama University, Yamada 827, Misasa, Tottori
682-0193, Japan
(3) Japan Synchrotron Radiation Research Institute (JASRI), SPring-8, 1-1-1 Kuoto, Sayo-cho,
Sayo-gun, Hyogo, 679-5198, Japan
(4) Japan Atomic Energy Agency (JAEA), SPring-8, 1-1-1 Kuoto, Sayo-cho, Sayo-gun, Hyogo,
679-5143, Japan
brazhkin@hppi.troitsk.ru
We report several examples of anomalous behaviour of the viscosity vs pressure dependence
associated with structural phase transformations in elementary liquids (Se), chalcogenide liquids
(AsS) and oxide melts (B2O3). Phase transitions in liquids can lead to the drastic changes of the
viscosity. During polymerization of AsS melt under pressure large viscosity increase is observed
(from several Pa s to hundreds Pa s). During metallization of liquid Se and AsS the viscosities
drop by several orders of magnitude (up to 20 mPa s for AsS and up to 7 mPa s for Se). B2O3 melt
exhibits record viscosity decrease under pressure from 3000 Pa s to 0.3 Pa s at 5.5 GPa
simultaneously with the appearance of tetra-coordinated boron in the melt. Preliminary data for
liquid Se and liquid AsS were published in [1,2]. The importance of these viscosity changes for
the material science and geophysics is discussed.
[1] V.V. Brazhkin, K. Funakoshi, M. Kanzaki, and Y. Katayama, Phys. Rev. Lett., 99, 245901,
2007
[2] V.V. Brazhkin, K. Funakoshi, M. Kanzaki, and Y. Katayama, Phys. Rev. Lett., 102, 115901,
2009

PHYSICAL AGING IN POLY(METHYL METHACRYLATE)/SILICA
NANOCOMPOSITE
D. Cangialosi (1), V. Boucher (2), A. Alegrìa (1),(3), J. Colmenero (1),(2),(3), I. Pastoriza-Santos
(4), L. M. Liz-Marzan (4),
(1) Facultad de Química, Centro de Física de Materiales Centro Mixto (CSIC-UPV/EHU),
Apartado 1072, 20080 San Sebastián, Spain
(2) Donostia <strong>International</strong> Physics Center, Paseo Manuel de Lardizabal 4, 20018 San Sebastián,
Spain
(3) Departamento de Física de Materiales, Universidad del País Vasco (UPV/EHU),
Apartado 1072, 20080 San Sebastián, Spain
(4) Universidad de Vigo, Deptartamento de Química Física Unidad Asociada CSIC, 36310 Vigo,
Spain
swxcacad@sw.ehu.es
We monitored the physical aging process below the glass temperature (Tg) of poly(methyl
methacrylate) PMMA/silica nanocomposites by means of broadband dielectric spectroscopy
(BDS). To do so, we followed the evolution with time of the dielectric strength of PMMA
secondary relaxation process that dominates the dielectric response overall below Tg. The
employed silica particles are spherical and present a diameter of several hundreds nanometres.
We investigated nanocomposites with silica concentration up to 10% wt. This results in an
interparticle distance, i.e. a typical length scale for PMMA, of the order of 100 nm. Despite the
general similarity between the structural dynamics of the nanocomposites and that of pure
PMMA as evidenced by both differential scanning calorimetry (DSC) and BDS experiments, the
former systems display markedly accelerated physical aging in comparison to the pure polymer.
This striking result implies that the length scale imposed to the PMMA matrix by the presence of
the silica particles plays a crucial role in affecting the rate physical aging. As a natural
consequence of such evidence, the diffusion of free volume holes, annihilating at the “external
surface” of the polymer being aged, has been invoked to explain the strong mismatch between the
physical aging in the nanocomposite and that of pure PMMA [1]. Such an interpretation is
discussed in light of the present state of the art in the physical aging of polymer nanocomposites
[2].
[1] D. Cangialosi, M. Wübbenhorst, J. Groenewold, E. Mendes, H. Schut, A. van Veen, S.J.
Picken, Phys. Rev. B, 70, 224213, 2004.
[2] R.D. Priestley, Soft Matter, 5, 919, 2009.
Nuclear magnetic resonance investigations reveal a connectivity of primary relaxations and
high-frequency modes in supercooled liquids
Authors: Andre Nowaczyk (1), Burkhard Geil (1,2) and Roland Böhmer (1)
(1) Fakultät für Physik, Technische Universität Dortmund, 44221 Dortmund, Germany
(2) Institut für Physikalische Chemie, Universität Göttingen, 37077 Göttingen, Germany
andre@e3.physik.uni-dortmund.de
The question regarding a possible interrelation of primary and secondary relaxation has been
addressed long ago for a few polymeric systems in which the α-response is characterized by
anisotropic molecular motions [1, 2, 3]. In order to find out whether such effects are observable in

systems with a more typical, isotropic α-relaxation behavior we devised a spin-lattice relaxation
weighted stimulated-echo technique and applied it to various substances including D-sorbitol and
cresolphthalein-dimethylether somewhat above their calorimetric glass transition temperature [4].
Clear evidence for a positive connectivity of primary and secondary relaxation times in these
supercooled liquids is obtained using our deuteron NMR method. Applying the technique to
ortho-carborane, a substance with no secondary relaxation, no connectivity effect is seen in our
experiments. The experimental results are compared with numerical simulations of different
correlation scenarios. Finally, we discuss our findings in the context of various theoretical and
phenomenological approaches.
[1] G. Williams, Trans. Faraday Soc. 62, 2091 (1966)
[2] J. Leisen, K. Schmidt-Rohr and H.W. Spiess, Physica A 201, 79 (1993)
[3] A.S. Kulik, H. W. Beckham, K. Schmidt-Rohr, D. Radloff, U. Pawelzik, C. Boeffel and H. W.
Spiess, Macromolecules 27, 4746 (1994)
[4] R. Böhmer, G. Diezemann, B. Geil, G. Hinze, A. Nowaczyk and M. Winterlich, Phys. Rev.
Lett. 97, 135701 (2006); B. Geil, G. Diezemann and R. Böhmer, Phys. Rev. E 74, 041504 (2006);
A. Nowaczyk, B. Geil, G. Hinze and R. Böhmer, Phys. Rev. E 74, 041505 (2006)
A SIMPLE DESCRIPTION OF THE FULL RELAXATION RANGE OF MOLECULAR
GLASS FORMERS
C. Gainaru (1), R. Kahlau (2), E.A. Rössler (2), R. Böhmer (1)
(1) Fakultät für Physik, TU Dortmund, 44221 Dortmund, Germany
(2) Fakultät für Physik, Univ. Bayreuth, 95440 Bayreuth, Germany
The dielectric response of simple molecular glass formers reveals a multitude of relaxation
processes when investigated from the boiling point down to cryogenic temperatures. While a
general picture regarding the evolution of the overall dynamics is missing, some
phenomenological approaches indicate strong temperature changes of the individual spectral
contributions [1,2]. Here we introduce an alternative approach assuming that the spectral shape of
the α-process is temperature invariant, obeying frequency temperature superposition in the full
temperature range above the glass transition temperature Tg. As a result of this constraint, the
excess wing appears to have a different origin than the β-process. Based on our new aging
experiments it is argued that the latter is always present in the spectra of glass forming systems
close to Tg in addition to the excess wing and its time constants follow a common temperature
activated behavior on Tg/T scale.
In the glass (T < Tg) the interplay of both excess wing and β-process determines the relaxation
pattern. The β-process appears as the only non-universal feature in the evolution of the dielectric
response, since its relaxation strength does not correlate with the molecular dipole moment. This
process is discussed here in the frame of the Gilroy-Phillips model [3]. The distribution of the
activation barriers is directly accessed for several small-molecule glass formers by scaling their
spectra in accordance with this model.
[1] K.L. Ngai, P. Lunkenheimer, C. Leon, U. Schneider, R. Brand and A. Loidl, J. Chem. Phys.,
115, 1405, 2001
[2] T. Blochowicz, C. Tschirwitz, S. Benkhof and E. Rössler, J. Chem. Phys., 118, 7544, 2003
[3] K.S. Gilroy and W.A. Phillips, Philos. Mag. B, 43, 735, 1981.

SLOW DYNAMICS IN A MOLECULAR LAYER OF AZOPOLYMER STUDIED BY
XPCS
L. Cristofolini (1), D. Orsi (1),M. P. Fontana (1), E. Pontecorvo(2), A. Madsen(3), C. Caronna (3)
(1) Physics Dep.t and INFM- CRS SOFT, Parma University, Italy
(2) Physics Dep.t and INFM- CRS SOFT, Rome University, Italy
(3) ESRF, Grenoble, France
Cristofolini@fis.unipr.it
We report on a recent X ray Photocorrelation experiment on
Langmuir Blodgett multilayers of an azobenzene polymer [1]
deposited on a Si substrate, in total reflection geometry.
Density correlation functions were measured as a function
of Q, at different T’s and under different UV-vis
illumination conditions. We could measure the effect of UV
illumination, accelerating the relaxational dynamics, as
opposed to blue light illumination, which seems to hinder
the dynamics. As a control, we also measured the relaxation
in dark at two selected temperatures. In the figure we show
for comparison data measured at 62°C and 42°C, in dark (red symbols) and under UV light (blue
symbols). As the temperature is varied, the exponent n (the slope of the lines) remains constant,
while diffusion becomes faster at higher temperature.
These effects- confirmed by our independent ISR results [2]- seem to be related to azobenzene
isomerization, and are very relevant to the possible application of azobenzene polymers as alloptical
memories.
[1] A. Natansohn et al. Chem Rev., 102, 4139 (2002)
[2] D. Orsi et al., this conference.
DYNAMICS OF POLYMER MELTS STUDIED BY 1 H FIELD CYCLING NMR
A. Herrmann, A. Abou Elfadl , R. Meier , V. N. Novikov and E.A. Rössler
Experimentalphysik II, Universität Bayreuth, 95440 Bayreuth, Germany
axel.herrmann@uni-bayreuth.de
Segmental reorientation dynamics in melts of linear polymers (PB, PDMS, PI, PPO, PS) with
varying molecular weights M is studied by 1 H field cycling NMR. By transforming the dispersion
data of the spin-lattice relaxation time T1(ω) to the susceptibility representation χ’’(ω)=ω/T1(ω)
and employing frequency-temperature superposition master curves are constructed. This
facilitates comparisons with spectra obtained by, e.g., dielectric spectroscopy and allows to
separate spectral contributions from glassy and polymer specific dynamics. In order to extract the
latter for each M we subtract the glassy spectrum, which is identified with that of the lowest M
systems. Thereupon the polymer relaxation strength f(M) is obtained and the “polymer spectra”
are compared to spectra calculated from discrete Rouse theory. Measuring different partially
deuterated PB and PI in the high M limit we show that in contrast to previous reports the
relaxation behavior at low frequencies, for which polymer-specific contributions show up,
depends on the particular inter-nuclear vectors of the 1 H spin pairs in the monomer unit. Although
an anomalous glassy spectrum is found for PDMS as well as PPO, we demonstrate that only after
accounting for the glassy contribution, the extracted “polymer spectra” reveal a universal
behavior.

[1] S. Kariyo et al. Macromolecules, 41, 5313, 2008; dito 41, 5322, 2008
[2] A. Herrmann et al. Macromolecules, 42, 2063, 2009; dito 2009 accepted
COMMON FEATURES OF WATER DYNAMICS IN DIFFERENT ENVIRONMENTS
Silvina Cerveny (1), Fabienne Barroso-Bujans (1), Angel Alegría (1,2), and J. Colmenero (1,2,3)
(1) Unidad de Física de Materiales, Centro Mixto CSIC- UPV/EHU, Paseo Manuel de Lardizabal
4, 20018, San Sebastian, Spain
(2) Departamento de Física de Materiales, UPV/EHU, Facultad de Química, Apartado 1072,
20018, San Sebastian, Spain
(3) Donostia <strong>International</strong> Physics Center, Paseo Manuel de Lardizabal 4, 20018, San Sebastian,
Spain
Correspondence author: scerveny@ehu.es
We report broadband dielectric studies on water mixtures with very different hydrophilic
substances in a broad temperature range. Different hydration levels (from dry up to 50 wt% of
water) were explored with no observation of crystallization during cooling at a rate of 10K/min.
Typically, two dynamics are well distinguished in these solutions: a slower one, attributed to the
collective movements of the whole solution and a faster one, due to the reorientation of water
dipoles [1]. The temperature dependence of the relaxation times corresponding to the faster
process, exhibits a crossover from non-Arrhenius to Arrhenius behaviour at the Tg range of the
mixtures. This crossover will be discussed in terms of the confinement effects.
In addition, we will also present results of water confined in graphite oxide (GO). GO is a
hydrophilic layered material derived from the strong oxidation of bulk graphite. Due to the
hydrophilic nature of GO, it is possible to intercalate water molecules between the layers. As in
the case of the water solutions, a dielectric relaxation due to water molecules emerges. The Tdependence
of the relaxation times in this confinement system also present a crossover similar to
that observed in water-solution. In this talk, we will discuss and similarities and differences
between these two kinds of water-containing systems
[1] S. Cerveny, A. Alegria, J. Colmenero, Phys. Rev. E 77, 031803, 2008
[2] S. Cerveny, F. Barroso-Bujans, A. Alegria, J. Colmenero, submitted to J. Chem. Phys. B
Absence of fragile-to-strong transitions in hydrated connective tissue proteins
C. Gainaru (1), A. Fillmer (1), R. Böhmer (1)
(1) Fakultät für Physik, TU Dortmund, 44221 Dortmund, Germany
When confined to the hydration shell of proteins, water does not crystallize and therefore, unlike
bulk water, can be supercooled. With the motion of the hydration water freezing, also the
conformational changes of the protein cease. We studied the low-temperature dielectric relaxation
of collagen and elastin over a wide range of hydrations h. The hydration-shell response is shown
to increase weakly with temperature, to be thermally activated, and to conform to energy barrier
scaling. This demonstrates the existence of a secondary relaxation akin to that in structural glass
formers. Previously suggested fragile-to-strong transitions and other changes of mechanism [1,2]

are not indicated by our data for collagen and elastin. For low h the dielectric strength increases
superlinearly with h. It is argued that concomitantly the water molecules trigger significant
mobility of the protein surface. Comparison with other hydrated protein systems and with other
measuring techniques is made [3].
[1] M. Vogel, Phys. Rev. Lett., 101, 225701, 2008
[2] J. Swenson, H. Jansson and R. Bergman, Phys. Rev. Lett., 96, 247802, 2006
[3] S. Pawlus, S. Khodadadi, A. P. Sokolov, Phys. Rev. Lett. 100, 108103, 2008
UNIVERSAL POLYMER DYNAMICS REVEALED BY 1 H FIELD CYCLING NMR
A. Herrmann, A. Abou Elfadl , R. Meier , V. N. Novikov and E.A. Rössler
Experimentalphysik II, Universität Bayreuth, 95440 Bayreuth, Germany
ernst.roessler@uni-bayreuth.de
We apply field cycling NMR to study the crossover from glassy through Rouse to reptation
dynamics in series of different linear polymers with molecular weight M ranging from the low M
limit (simple liquid) to the high M limit. Dispersion data of the spin-lattice relaxation time T1(ω)
are transformed to the susceptibility representation χ’’(ω) = ω/T1(ω), and using frequency
temperature superposition master curves χ’’(ωτs) are constructed which reflect spectral
contributions from glassy as well as polymer specific dynamics. We are thus able to cover six
decades at ωτs < 1 allowing to monitor in detail the emergence of polymer specific relaxations.
Transforming the master curves into the time domain yields the segmental reorientational
correlation function which we follow over six decades in amplitude. From this the order
parameter as well as the bond vector correlation function is derived. Furthermore, the molecular
weight of the Rouse unit MR (≈ 10·Mmonomer) and Me (entanglement M) is obtained by this
technique. A comparison with theoretical predictions by the tube-reptation model as well as
renormalized Rouse theory reveals significant discrepancies whereas good agreement is found
with simulations. We conclude that the crossover to entanglement dynamics appears to be very
protracted.
[1] S. Kariyo et al. Macromolecules, 41, 5313, 2008; dito 41, 5322, 2008
[2] A. Herrmann et al. Macromolecules, 42, 2063, 2009; dito 2009 accepted
HIGH FREQUENCY ACOUSTIC ATTENUATION OF VITREOUS SILICA: NEW
INSIGHT FROM INELASTIC X-RAYS SCATTERING
G. Baldi (1), V. M. Giordano (2), B. Ruta (2) and G. Monaco (2)
(1) CNR-INFM CRS-SOFT Operative Group in Grenoble c/o E.S.R.F., BP220, 38043 Grenoble,
France
(2) European Synchrotron Radiation Facility, BP220, 38043 Grenoble, France
giacomo.baldi@esrf.fr
We present new experimental results on the propagation and damping of the high frequency
acoustic-like modes in vitreous silica. The new data are measured by means of the inelastic x-rays
scattering (IXS) technique down to an exchanged wavevector Q ~ 0.09 Å -1 , at the limit of the
instrument capabilities. Thanks to the continuous development of the IXS technique at the ESRF,
the new spectra are characterized by a very high signal to noise ratio when compared to previous
experiments. The higher data quality finally allows for a reliable determination of the position

and width of the inelastic excitations, unveiling a complex phenomenology previously masked by
the error bars.
Below the boson peak frequency, the mode damping is marked by a strong, more than quadratic,
frequency dependence. At higher frequencies the excitations get rapidly overdamped and the
apparent sound velocity presents a peculiar negative dispersion effect. This reduction of the sound
velocity and the fast growth of the damping can be directly related to the excess of modes at the
boson peak.
We will present a detailed analysis of these new findings and a comparison with existing
experimental data and models for the vibrations in glasses.
EFFECT OF DENSIFICATION ON THE DYNAMICS OF THE SECONDARY
RELAXATION
R. Casalini(1) and C.M. Roland(1)
(1)Naval research Laboratory, Chemistry Division, Washington DC, USA
Correspondence author: riccardo.casalini@nrl.navy.mil
Polymers vitrified by different chemical and thermodynamic pathways exhibit different densities
in the glassy state and very different mechanical properties. We find that the secondary relaxation
(the Johari-Goldstein process involving local motion of segments of the chain backbone) can be
used to probe the local structure in the glassy state. In fact, The rate and amplitude of the
secondary relaxation mode can either correlate or anti-correlate with the density depending on
local order in the glassy state. This implies that neither the unoccupied (free) volume nor the
configurational entropy governs the local dynamics in any general sense. Rather it is the
magnitude of the fluctuations in local density that underlie these nm-scale motions. We show how
properties of the dynamics and the density fluctuations can both be interpreted in terms of a
minimal asymmetric double well potential model.
Pressure and strain rate effects in equation of state determination for polymers
D. M. Dattelbaum, L. L. Stevens, S. A. Sheffield, D. L. Robbins (DE-9), Philip Rae (MST-8), E. B.
Orler (MST-7), B. Clements (T-1), M. Ahart and R. J. Hemley(Carnegie Institution of
Washington)
Understanding the response of polymers to the combined extreme conditions of high pressure and
high strain rate deformation is necessary for modeling and simulating their behaviors in materials
applications in which they are subjected to impact loading. We have applied a number of
experimental methods, ranging in strain rate and applied pressures from the quasi-static
(equilibrium) and ambient pressure, to >10 5 s -1 and > 10 GPa, to the interrogation of the behavior
of several classes of polymeric materials. Here, we will present an overview of experimental
techniques and modeling approaches applied to semi-crystalline fluoropolymers used as energetic
materials binders, as a relevant example. In particular, in the quest for static high pressure
methods to probe compressibility, we have applied Brillouin scattering in diamond anvil cells to
gain insight into elastic properties, material strength, and equation of state properties under
extreme conditions.

A NEW TYPE OF THE RELAXATION TIME CHARACTERIZING SLOW RESPONSE
OF THE GLASS DYNAMICS TO TEMPERTAURE CHANGE
A. Harada (1), H. Yao (1), K. Fukao (2) and Y. Saruyama (1)
(1) Macromolecular Science and Engineering, Kyoto Institute of Technology, Matsugasaki,
Sakyo, Kyoto 606-8585, Japan
(2) Deaprtment of Physics, Ritsumeikan University, Noji Higashi, Kusatsu, Shiga 525-8577,
Japan
saruyama@kit.ac.jp
Temperature dependence of the relaxation time of the α process, τα, has been studied extensively
by a large number of authors and successful empirical equations for the temperature dependence
have been proposed. Usually τα is considered to change with temperature according to an
equation with proper values of parameters for each sample. However, remembering that the glass
dynamics significantly depends on the structure which changes slowly after, for example, a
temperature jump, it may be considered that τα changes with non-negligible retardation to the
temperature change. In this work we carried out an experimental study to measure the retardation
of τα. We utilized a new technique called temperature modulated dielectric measurement
developed in our laboratory in which the dielectric measurement was made with periodic
temperature modulation with amplitude less than 1K. The time characterizing the retardation,
written as ττ below, was estimated at ca.1s around Tg of poly(vinyl acetate) and exhibited notable
temperature dependence. It is known that τα is related to the two-body correlation function. This
implies that ττ is related to the four-body correlation function since ττ is considered to be the
relaxation time of τα.
Secondary processes in orientationally disordered phases
S.S.N. Murthy,* L.P. Singh and Geeta Singh,
School of Physical Sciences,
Jawaharlal Nehru University,
New Delhi-110067, INDIA.
Abstract
The main aim of the present report is to see how various relaxation processes including the chairchair
transformation in cyclohexane derivatives, and secondary relaxations in orientationally
disordered crystals evolve as the temperature is lowered. For this purpose two-component solid
solutions that are orientationally disordered are investigated by means of dielectric spectroscopy
and differential scanning calorimetry (DSC). The cooresponding liquid-solid phase diagrams are
also determined. The two-component systems investigated are cyclohexanol + neopentanol/
cycloheptanol/ neopentylglycol, cyanocyclohexane + cyclohexylchloride, neopentanol +
neopentylglycol, cis 1,2 dimethylcyclohexane + fluorobenzene (at lower concentrations only)
where the liquid mixture on cooling forms an orientationally disordered phase which is a solid
solution of the corresponding pure phases. Depending upon the concentration, this phase reveals a
glass transition in the temperature range 135 - 150 K and associated with this is a pronounced
relaxation process identifiable with the so called α -process. The dielectric spectra of this process
is found to follow the Havriliak-Negami (HN) equation. The analysis of the various parameters
obtained show an isomorphic relationship between the pure components through a continuous
change of parameters. Another process of much smaller magnitude designated α׳ - process was

found in cyclohexane derivatives above the glass transition temperature Tg which kinetically
freezes around 170 K. This process interestingly, is also non-Arrhenius in nature, becomes
increasingly weaker with increase in the second component, and may be identified with (axial)
chair- (equatorial) chair transformation. In addition, a weak high frequency process which may be
identified with the Johari-Goldstein relaxation process based on the coupling model, and a clear
sub-Tg process designated as β- process, are found. The activation energy of β-process of various
non-hydrogen bonded solutes in glassy OTP matrix is found to be in the range 20-30kJ/mol. The
identification of the β- process with internal degrees of freedom is fraught with some problems in
the interpretation of the experimental data that are high-lighted.
-----------------------------------------------------------------------------------------------
Author for correspondence: e-mail: ssnm0700@mail.jnu.ac.in, ssnm0700@gmail.com
Conductivity in Mixed Alkali Ionic Solids with Fractal Description
Young-Hoon Rim * and Yong Suk Yang **
*
School of Liberal Arts, Semyung University, Chechon, Chungbuk 390-711, Korea
**
College of NanoScience and NanoTechnology, RCDAMP, Pusan National University, Pusan
609-735, Korea
**Corresponding author
E-mail: ysyang@pusan.ac.kr, Tel: +82-55-350-5837, Fax: +82-55-350-5837
Abstract:
The ionic conductivity can be decreased drastically by replacing a fraction of the mobile ions
with another type of mobile ion. This pronounced drop in conductivity with a non-linear way is
referred to as the mixed alkali effect (MAE). We report measurements of the conductivity of a
series of mixed alkali borate glasses (Li1−xAx)2B4O7 (A=Na, K, Rb, Cs) in the frequency range
100 Hz to 15 MHz and in the temperature range from 300K to above the glass transition
temperature T g . The power-law frequency dependence of the conductivity,
β
σ ω)
= σ [ 1+
( ω / ω ) ] + Bω
( 0 J , of the conducting materials including mixed alkali (MA) glass
has been used to explain a frequency-dependent ionic conductivity. In spite of the advances made,
the origin of universal behavior still provokes discussion among scientists. Using a scaleinvariant
model, we derive relevant power-law expression for σ (t)
and compare this with the
Kohlraush-Williams-Watts (KWW) description of the electrical modulus. We show that the
2
α
empirical expression of mean-square displacement of the mobile ions < r ( t)
> ~ t can be
obtained as an approximation of ions moving through the fractal pathway. We, also, reproduced
the expression of universal macroscopic conductivity by using the fractional Fokker-Planck

equation with repulsive Coulomb interaction in a disordered network structure of glasses. The
power law dispersion β in MA borate glasses indicates that the ions move through the different
branches of conduction pathway due to the blocking by randomly mixed alkali ions.
BIOLOGICAL BREATHERS
G. P. Tsironis (1)
(1) Department of Physics, University of Crete and IESL, FORTH, P.O. Box 2208, Heraklion
71003, Crete, Greece
Correspondence author: gts@physics.uoc.gr
We will review work on discrete breathers that are localized oscillations in nonlinear lattices
with characteristic frequencies non-resonant to the lattice band modes. They can be mobile and
are used for local energy deposition and transfer in polymer-like chains that model proteins [1].
In a fluctuating environments they may appear as a result of external energy injection and survive
for relatively long times [2]. Recent work has shown that breathers may be generated
stochastically in model proteins and their formation may be linked to functional properties and
enzymatic activity of proteins [3]. Absorption and pump-probe spectroscopy in peptide-bonded
crystals, such as acetanilide, show that quantum aspects of localization may be used for detection
[3,4]. Furthermore, heat transfer in proteins may be connected to these processes [5].
[1] M. Ibanes, J. M. Sancho and G. P. Tsironis, Phys. Rev. E 65, 041902 (2002).
[2] G. P. Tsironis and S. Aubry, Phys. Rev. Lett. 77, 5225 (1996).
[3] B. Juanico, Y.H. Sanejounad, F. Piazza and P. De Los Rios, Phys. Rev. Lett. 99, 238104
(2007).
[3] P. Hamm and G. P. Tsironis, Eur. Phys. J. Sp. Topics 147, 303-331 (2007).
[4] P. Hamm and G. P. Tsironis, Phys. Rev. B 78, 092301 (2008).
[5] V. Botan, et al. PNAS 104, 12749 (2007).
STRUCTURAL AND DYNAMIC COMPLEXITY IN ROOM TEMPERATURE IONIC
LIQUIDS
O. Russina (1) and A. Triolo (1)
(1) Istituto Processi Chimico-Fisici, Consiglio Nazionale delle Ricerche, Messina, Italy
triolo@me.cnr.it
Room temperature ionic liquids (RTILs) are a novel class of materials whose range of ecosustainable
applications is constantly expanding due to their smart performances. In order to
better exploit these compounds it is mandatory to gain a broad knowledge of their morphological
and relaxation behaviour. In fact, as structural and dynamic issues are explored, several novel and
unexpected features are found.

In this presentation we will describe new X-ray and neutron diffraction evidences of the existence
of spatial heterogeneities at the nm scale in these materials in their liquid state.
It will be then shown that this structural complexity has a direct dynamic counterpart, as observed
using neutron spin echo and other spectroscopic techniques.
An attempt to provide a rationalisation for this complex structural and dynamic scenario will be
made.
HYDROGEN BONDING PROPERTIES OF AMORPHOUS LOW-WATER PROTEIN-
SACCHARIDE MATRIXES AND BIOPROTECTION
L. Cordone
Dipartimento di Scienze Fisiche ed Astronomiche, Università di Palermo, Via Archirafi 36 I-
90123 Palermo, Italy
cordone@fisica.unipa.it
Glassy matrices of saccharides exhibit an outstanding ability to protect biological structures
against adverse environmental conditions, such as freezing, heating, and dehydration [1,2].
Saccharides are employed by several organisms that can long survive under extreme drought and
high temperature, entering a state of suspended metabolism (anhydrobiosis), which is preceded by
a massive synthesis of specific carbohydrates [1,2]. Among sugars, the disaccharide trehalose
appears to be the most effective protectant [1,3,4]. In this communication will be presented a set
of measurements, performed with different experimental techniques, which concur in suggesting
how a relevant role, in determining the difference in bioprotection among different saccharides, is
played by the hydrogen bonding properties of low water amorphous saccharide matrixes.
[1] J. H. Crowe, J. F Carpenter, and L. M. Crowe, Annu. ReV. Physiol., 60, 73, 1998
[2] L. M. Crowe, Comp. Biochem. Physiol. A., 132, 505, 2002
[3] J. H.; Crowe, L. M. Crowe, S. A., Jackson, Arch. Biochem. Biophys., 220, 477, 1983
[4] M. Uritani, M. Takai, K. Yoshinaga, J. Biochem., 117, 774, 1995,
MICROSCOPIC STRUCTURE AND INTRAMOLECULAR DYNAMICS IN AQUEOUS
SOLUTIONS: A RAMAN/NEUTRON DIFFRACTION STUDY
T. Corridoni (1), R. Mancinelli (1)
(1) Dipartimento di Fisica "E. Amaldi", Università degli Studi Roma Tre, Via della Vasca Navale
84, 00146 Roma, Italy
tcorridoni@libero.it, mancinelli@fis.uniroma3.it
Following previous studies [1, 2], we performed Raman and NDIS measures on alkaline
hydroxides (LiOH, NaOH, KOH) aqueous solutions over a large range of solute concentration, at
standard conditions. Our results show the existence of a relationship between the evolving
percolative properties of the HB net in concentration and the vibrational relaxation of the OH - ion
stretching mode: better defined the percolation is, less rapidly the stretching is modulated, and
viceversa. Moreover a number of peculiar thermodynamical properties seems to be related to the
evolution of microscopic structure in concentration and to the relative change from a slow
modulation regime (low concentrations) to a rapid one (high ones), showing that where it is
possible to study vibrational relaxation of intramolecular bonds, the comparison between NDIS,

Raman spectra and thermodynamic of solutions could be the key to give a possible microscopic
interpretation of their macroscopic behaviour.
[1] S.Imberti, A.Botti, F.Bruni, G.Cappa, M.A.Ricci, A.K.Soper, J. Chem. Phys. 122, 194509
(2005)
[2] T. Corridoni, A. Sodo, F. Bruni, M.A. Ricci, M. Nardone, Chem. Phys. 336, 183–187, (2007)
DIELECTRIC RELAXATION STUDIES OF IONIC LIQUID VERAPAMIL
HYDROCHLORIDE UNDER HIGH PRESSURE.
M. Paluch (1), Z. Wojnarowska (1), A. Grzybowski (1), K. Adrjanowicz (1), K. Grzybowska (1),
K. Kaminski (1), P. Wlodarczyk (1), J. Pionteck (2)
(1) Institute of Physics, Silesian University, ul. Uniwersytecka 4, 40-007 Katowice, Poland
(2) Leibniz Institute of Polymer Research Dresden, Hohe Str. 6, D-01069 Dresden, Germany
marian.paluch@us.edu.pl
Relaxation dynamics of verapamil hydrochloride (VH), which is a representative of ionic liquids,
was studied under isobaric and isothermal conditions by using dielectric spectroscopy. In addition
we also carried out pressure-temperature-volume (PVT) measurements. The obtained data enable
us to examine the structural α-relaxation time τα as a function of temperature, pressure, and
volume. Since the examined sample is a typical ionically conducting material, we employed the
dielectric modulus formalism to gain information about α-relaxation process. It was found that
application of pressure changes the shape of the modulus spectrum. The α-peak becomes
narrower with compression. Consequently, it was also shown that the stretching parameter βKWW
increases with pressure. Based on experimental data both the isobaric fragility (mp) at various
pressures and isothermal fragility (mT) at various temperatures were calculated. Analyzing the
effect of pressure on the dependences τα(T) as well as on the shape parameter of the α-peak it was
found that a phenomenological correlation between mp and βKWW established for glass forming
liquids is also valid for VH under condition of high compression. The pressure dependences of
glass transition temperature determined from dielectric and volumetric measurements have been
compared. Moreover, PVT data allow us to assess the relative contribution of thermal energy and
free volume fluctuation to the dramatic slowing down of the molecular dynamics in the vicinity
of Tg. It is established from the ratio of the isochronic and isobaric expansivities that the thermal
energy has a stronger effect on the relaxation times than the free volume, although the latter
contribution is significant. Moreover, we also discuss the validity of thermodynamic scaling in
the case of VH and examine the scaling exponent γ at various thermodynamic conditions. Finally,
we tested the entropic models proposed for description of the combined T and P dependence of
the structural relaxation times.
MELTING, RECRYSTALLIZATION AND SUPERHEATING OF POLYMER
CRYSTALS STUDIED BY FAST CALORIMETRY (1 MK/s)
E. Zhuravlev, A. Wurm, C. Schick
University of Rostock, Institute of Physics, 18051 Rostock, Germany
christoph.schick@uni-rostock.de
For polymers the origin of the multiple melting peaks observed in DSC curves is still
controversially discussed. This is due to the difficulty to investigate the melting of the originally
formed crystals exclusively. Recrystallization is a fast process and most experimental techniques
applied so far do not allow fast heating in order to prevent recrystallization totally. We developed

a thin-film (chip) calorimeter allowing scanning rates as high as one million Kelvin per second
[1]. The calorimeter was used to study the melting of isothermally crystallized polymers like
isotactic polystyrene (iPS), isotactic polypropylene (iPP), poly(ethylene therephthalate) (PET) [2,
3] and others. Our results on melting at rates as high as 1,000,000 K/s support the validity of a
melting-recrystallization-remelting process at low scanning rates (DSC) for all polymers studied
so far. At isothermal conditions they form crystals, which all melt within a few dozens of K
slightly above the isothermal crystallization temperature. There is no evidence for the formation
of different populations of crystals with significantly different stability (melting temperatures)
under isothermal conditions. Superheating of polymer crystals can not be neglected already at
medium rates [4].
[1] Minakov, A. A.; Schick, C., Ultrafast thermal processing and nanocalorimetry at heating and
cooling rates up to 1 MK/s. Rev. Sci. Instrum. 78 (2007) 073902
[2] Minakov, A. A.; Mordvintsev, D. A.; Schick, C., Melting and Reorganizationof Poly(ethylene
Terephthalate) on Fast Heating (1,000 K/s). Polymer 45 (2004) 3755 – 3763
[3] Minakov, A. A.; Mordvintsev, D. A.; Schick, C., Isothermal reorganization of poly(ethylene
terephthalate) revealed by fast calorimetry (1000 K s-1; 5 ms). Faraday
Discuss 128 (2005) 261 – 270
[4] Minakov, A. A.; Wurm, A.; Schick, C., Superheating in linear polymers studied by ultrafast
nanocalorimetry. Eur. Phys. J. E 23 (2007) 43 – 53
NUCLEI FORMATION IN POLY ε-CAPROLACTONE IN A WIDE RANGE OF TIME
AND TEMPERATURE STUDIED BY FAST CALORIMETRY
E. Zhuravlev, C. Schick
University of Rostock, Institute of Physics, 18051 Rostock, Germany
christoph.schick@uni-rostock.de
PCL solidification kinetics was studied in a wide range of scanning rates using a chip based fast
scanning calorimeter[1]. At a certain range of cooling rates a double crystallization peak, referred
to as homogeneous and heterogeneous (inc. surface) nucleation, was observed. Cooling rates
equal or above 400 K/s results in amorphous PCL. At even higher cooling rates the influence on
nucleation was studied. Following Mathot et al. [2] and Oguni et al. [3] heating curves at
1,000 K/s after different thermal histories were recorded to identify differences in nucleation
density. The heating after cooling faster than 400 K/s reveals decreasing cold crystallization and
melting peaks. That is indication that on previous cooling we not only avoid crystallization, but
also create fewer nuclei. Above 10,000 K/s cooling rate the cold crystallization peak reduction
saturates, but the peak is still visible due to the existence of a few heterogeneous nuclei. The
absence of homogeneous nuclei after fast cooling in the glassy state and the possibility to jump
fast enough to any temperature, again avoiding nuclei formation, allow us to measure time and
temperature dependency of nucleation. Annealing time was varied between 10 -4 s and 10 5 s. The
Tg at 1,000 K/s occurs at 200 K. The nucleation at 185 K (15 K below Tg) yields a time constant
of about 100,000 s. At temperatures above Tg, e.g. 220 K, nucleation saturates and eventually
superimposes with isothermal crystallization. Comparing the relaxation times of nucleation with
previously derived dielectric relaxation data [4] places the nuclei formation process intermediate
between α- and β- process, what is in first approximation in agreement with Oguni’s
observations on low molecular mass glass formers [3].
REFERENCES
[1] Gao, Y. L.; Zhuravlev, E.; Zou, C. D.; Yang, B.; Zhai, Q. J.; Schick, C., Calorimetric
measurements of undercooling in single micron sized SnAgCu particles in a wide range of
cooling rates. Thermochimica Acta 2009:482:1 - 7.

[2] SalmeronSanchez M, Mathot VBF, VandenPoel G, GomezRibelles JL. Effect of the Cooling
Rate on the Nucleation Kinetics of Poly(L-Lactic Acid) and Its Influence on Morphology.
Macromolecules 2007:40(22):7989-7997.
[3] Oguni M. Intra-Cluster Rearrangement Model for the Alpha-Process in Supercooled Liquids,
as Opposed to Cooperative Rearrangement of Whole Molecules Within a Cluster. J Non-Cryst
Solids 1997:210(2-3):171-177
[4] Wurm A, Soliman R, Schick C. Early Stages of Polymer Crystallization – A Dielectric Stud.
Polymer 2003:44(24):7467-7476.
RELAXATION, AGING AND NONLINEAR MECHANICAL RESPONSE OF
POLYMER GLASSES
Kang Chen (1) and Kenneth S. Schweizer (1)
(1) Department of Materials Science, University of Illinois, Urbana, IL 61801, USA
kschweiz@illinois.edu
A force-based statistical mechanical theory of segmental dynamics, barriers and vitrification in
deeply supercooled polymer melts based on nanometer scale density fluctuations, a
nonequilibrium free energy, and thermally driven activated hopping [1] has been generalized to
treat alpha relaxation [2], physical aging [3] and nonlinear mechanical response [4] in the glass
state. The relaxation time follows an effectively Arrenhius temperature dependence, and grows on
intermediate aging times scales as a power law with a temperature dependent exponent. Applied
stress weakens dynamical constraints thereby accelerating relaxation and softening the modulus.
A constitutive equation has been constructed under constant stress and strain rate conditions, and
rate-dependent yielding and local plastic flow is predicted. Quantitative comparisons with
experiments on PMMA reveal good agreement. A non-entropic theory based on conformational
distortion induced prolongation of the alpha relaxation has been developed for the post-yield high
deformation strain hardening response [5].
[1] E.J.Saltzman and K.S.Schweizer, J.Phys.Condens. Matter,19,205123,2007.
[2] K.Chen and K.S.Schweizer, J.Chem.Phys.,126,014904, 2007.
[3] K.Chen and K.S.Schweizer, Phys.Rev.Lett.,98,167802, 2007; Phys.Rev.E,78,031802,2008.
[4] K.Chen and K.S.Schweizer, Macromolecules,41,5908,2008; J.Chem.Phys.,129,184904,2008.
[5] K.Chen and K.S.Schweizer, Phys.Rev.Lett.,102,038301,2009.
ACTIVATED DYNAMICS IN GLASSY SUSPENSIONS AND FLUIDS OF SPHERICAL
AND NONSPHERICAL OBJECTS
E.J.Saltzman, M.Tripathy, J. Yang, G.Yatsenko, R.Zhang, and K.S.Schweizer (1)
(1) Department of Materials Science, University of Illinois, Urbana, IL 61801, USA
kschweiz@illinois.edu
We have developed microscopic theories for thermally activated glassy dynamics in suspensions
and fluids of spherical [1,2] and anisometric [3,4] hard objects. True solids emerge only as
jamming is approached with a divergent relaxation time of an essential singularity form.
Intermittent barrier hopping results in multiple dynamic heterogeneity effects. Kinetic
vitrification, relaxation, diffusion, and the elastic modulus of uniaxial objects are nonmonotonic

functions of aspect ratio in accord with experiments on dicolloids. A plastic glass state is
predicted, and multi-dimensional Kramers theory allows a mechanistic understanding of
cooperative translation-rotation hopping. The theory has been extended to treat families of rigid
objects of 1(rods), 2(disks), 3(e.g.,cube, tetrahedron), and mixed dimensional character. The role
of particle shape on relaxation and dynamic fragility in suspensions and molecular liquids is
established and understood in a unified manner based on interparticle collisions and local packing.
If repulsions are softened to treat many arm stars and microgels, qualitatively new elastic and
relaxational behavior emerges. Attractive interactions and nonlinear rheological response can also
be treated.
[1] K.S.Schweizer, Curr.Opin.Coll.Interface Sci.,12,297,2007.
[2] E.J.Saltzman and K.S.Schweizer, Phys.Rev.E,77,051504,2008.
[3] G.Yatsenko and K.S.Schweizer, Phys.Rev.E,76,041506,2007.
[4] M.Tripathy and K.S.Schweizer, J.Chem.Phys.,in press,2009.
ELECTRICAL CONDUCTIVITY STUDY OF POLYMER / METALLIC NANOWIRES
COMPOSITES
A. Lonjon (1), L. Laffont (2), Ph. Demont (1), E. Dantras (1), C. Lacabanne (1)
(1) Laboratoire de Physique des Polymères, CIRIMAT, Université de Toulouse France
(2) ENSIACET, CIRIMAT, Toulouse France
Corresponding authors: lonjon@cict.fr
A lot of work has been devoted to the introduction of CNTs in polymers for improving their
electrical conduction. Above the percolation threshold (

(1) Department of Applied Physics, Chalmers University of Technology, SE-412 96 Göteborg,
Sweden
(2) Swedish NMR Centre at Göteborg University, SE-405 30 Göteborg, Sweden
jan.swenson@chalmers.se
Dielectric relaxation, quasi-elastic neutron scattering, and DSC data on water containing systems,
such as hydrated proteins, MCM-41 and aqueous mixtures are presented with the aim to
understand how the water dynamics affect and/or is affected by the structural and dynamical
properties of the whole system. We show that the main relaxation of supercooled interfacial water
is rather universal [1], provided that smaller ice-free water clusters are formed. However, for very
low water contents, where the probability for a water molecule to interact with several other water
molecules is low, the water dynamics is strongly dependent on the chemical interactions with the
nearest surrounding and may therefore be severely slowed down [2]. The physical nature of this
water process and the reason for why it generally shows a dynamical crossover at 180±20 K from
a low temperature Arrhenius dependence to a high temperature non-Arrhenius behaviour is
further discussed [3]. The experimental data suggest that this crossover in temperature
dependence (and the corresponding change in physical nature of the water dynamics) is
responsible for the glass transition of hydrated proteins [4]. Likely, it is the onset of long-range
cooperative water motions at the crossover temperature that initiate the larger-scale protein
motions present above the glass transition temperature.
[1] S. Cerveny, G. A. Schwartz, R. Bergman, J. Swenson, Phys. Rev. Lett. 93 (2004) 245702.
[2] J. Sjöström et al., to be published.
[3] J. Swenson, H. Jansson and R. Bergman, Phys. Rev. Lett. 96 (2006) 247802.
[4] H. Jansson and J. Swenson, submitted to Biochimica Biophysica Acta (BBA – Proteins and
Proteomics).
RELAXATION PHENOMENA AND PHYSICAL STRUCTURE OF HYBRID
FERROELECTRIC NANOCOMPOSITES
J-F. Capsal (1), E. Dantras (1), L. Laffont (2), J. Dandurand (1), C. Lacabanne (1)
(1) Laboratoire de Physique des Polymères, CIRIMAT, Université de Toulouse,France
(2) ENSIACET, CIRIMAT, Université de Toulouse, France
Corresponding authors: dantras@cict.fr
The use of ferroelectric inorganic nanofillers dispersed into a thermoplastic polymer allows us to
realize hybrid nanocomposites with better mechanical and electroactive properties [1]. Polyamide
11 (PA 11) has been chosen as matrix and barium titanate (BT) nanoparticles ranging from 50 to
700 nm as fillers. PA 11/BaTiO3 0-3 nanocomposites with a volume fraction of BT ranging from
0.024 to 0.4 were elaborated. Due to the coercitive field of BT and PA 11, unpoled polymer/
poled BT composites were elaborated. Suitable piezoelectric and pyroelectric activity was
obtained close to the poled PA 11 with composite of 20% in volume of BT. The quality of the
dispersion at a nanometric scale has been checked by Scanning Electronic Microscopy. The
physical structure of the amorphous phase has been analysed by dynamic dielectric spectroscopy
and thermo stimulated current analysis. The influence on the dielectric properties of the filler
nanosize, the volume fraction on the one side and molecular mobility of PA 11 on the other side
was studied.
[1] Capsal, J-F; Dantras, E.; Dandurand, J.; Lacabanne, C. J of Non Crystalline Solids 2007, 353,
4437-4442.

THIN FILM AC CHIP CALORIMETRY FOR ULTRATHIN FILMS AND SMALL
SAMPLES
H. Huth , C. Schick
University Rostock, Institute of Physics, Universitätsplatz 3, 18051 Rostock, Germany;
huthheiko@googlemail.com
Calorimetry is known as a very powerful tool for the characterization of a wide variety of
materials and their transitions. The combination of silicon technology and calorimetry opens up
new possibilities in this research area as demonstrated recently [1]. Based on a differential AC
calorimeter we show an improved experimental setup combining the advantages of the different
methods. The measurements are done at slow scanning or at constant bath temperature. The
frequency chosen provides a well defined time scale of the experiment. In several cases, e.g. at
glass transition, a direct comparison with results from other dynamic methods like dielectric
spectroscopy is possible. Due to the differential setup we achieve a sensitive in the pico Joule per
Kelvin range allowing to measure samples below one nanogram and consequently films down to
1 nm thickness [2 − 5]. Because of the small total heat capacity (addenda + sample) not only a
high sensitivity is achieved but AC measurements at relative high frequencies are possible too.
[1] D. W. Denlinger; E. N. Abarra; K. Allen; P. W. Rooney; M. T. Messer; S. K. Watson; F.
Hellman, Rev. Sci. Instrum. 65 (1994) 946.
[2] H. Huth, A. Minakov, C. Schick, Netsu Sokutei 32 (2005) 69.
[3] Lupascu V., Huth H., Schick C. and Wübbenhorst M. Thermochim. Acta 432 (2005) 222.
[4] Serghei, H. Huth, M. Schellenberger, C. Schick, F. Kremer, Phys. Rev. E, 71 (2005) 061801-
1.
[5] Serghei, Y. Mikhailova, H. Huth, C. Schick, K.J. Eichhorn, B. Voit, F. Kremer, Eur. Phys. J.
E, 17 (2005) 199.
OXYGEN ION DYNAMICS AND NEARLY CONSTANT LOSS IN HIGHLY
DISORDERED
PYROCHLORE-TYPE IONIC CONDUCTORS
M.R. Díaz-Guillén (1), J.A. Díaz-Guillén(1), A.F. Fuentes(1), J. Santamaría(2), C. León(2)
(1) Cinvestav-Saltillo, Apartado Postal 663, 25000-Saltillo, Coahuila, Mexico.
(2) GFMC, Departamento de Física Aplicada III, Facultad de Física, Universidad Complutense de
Madrid, 28040 Madrid, Spain.
Correspondence author: carlos.leon@fis.ucm.es
We report on the effect of cation size on oxygen ion dynamics in highly disordered pyrochloretype
ionic conductors of general formula A2B2O7 (A= Y, Dy, Gd, Gd1-xLnx (Ln=Er, Y, Dy,
Sm ,Nd and La); B=Zr1-yTiy). Samples were prepared by mechanical milling and their electrical
properties measured by using impedance spectroscopy in the temperature range from 125 K to
1000 K. We investigate the effect of cation radii RA and RB on the activation energy for oxygen
ion dc conductivity, Edc, and find that for a fixed B-site cation radius RB, the dc activation energy
decreases with increasing A-site cation size, RA, as a consequence of the increment in the unit cell
volume. In contrast, and for a given RA size, the dc activation energy Edc of the Ln2Zr2-yTiyO7
series increases when the average RB size increases. The latter behavior is explained in terms of
the enhanced interactions among mobile oxygen ions as the structural disorder increases when RB

approaches RA. We present also the characteristic features of the nearly constant dielectric loss
found in these materials at low temperatures.
[1] K. J. Moreno, A. Fernández-Fuentes, M. Maczka, J. Hanuza, U. Amador, J. Santamaría and C.
León, Phys. Rev. B 75, 184303 (2007).
[2] M. R. Diaz-Guillen, K. J. Moreno, J. A. Diaz-Guillen, A. F. Fuentes, K. L. Ngai, J. García-
Barriocanal, J. Santamaria, and C. León, Physical Review B 78, 104304 (2008).
[3] J. A. Diaz-Guillen, A. F. Fuentes, M. R. Diaz-Guillen, J. M. Almanza, J. Santamaria, and C.
León , J. Power Sources 186, 349 (2009).
INTERFACE-CONTROLLED IONIC AND ELECTRONIC CONDUCTION IN THIN
FILM NANOSTRUCTURED OXIDES
S. Ramanathan, A. Karthikeyan, M. Tsuchiya
Harvard University, Cambridge, MA 2138
A fascinating problem in solid state ionics is the role of interfaces in mass and charge transport.
Of particular interest for pure oxides is the case where the grain size (or film thickness)
approaches lengthscales which could be comparable to the space charge region. In alio-valently
doped oxides, a further complication is cation segregation at interfaces or surfaces which can
affect both carrier concentration and mobility. Under such conditions, it may be possible to
observe conduction phenomena typically not seen in bulk. In this presentation, we will discuss
our on-going investigation on high temperature carrier transport in interface-controlled oxides
using thin films and superlattices as model systems. The effect of oxygen partial pressure on
electrochemical conduction as well as phase formation and stability boundaries will be
highlighted. Approaches to modulate point defect concentration in complex oxides controllably
using photons will be presented. Subsequently, relevance to energy conversion technologies such
as solid oxide fuel cells as well as synthesis of novel interfacial energy materials will be pointed
out.
ANALYTICAL COARSE-GRAINED THEORIES TO BRIDGE TIME SCALES IN THE
DYNAMICS OF MACROMOLECULAR SYSTEMS
J. McCarty, I. Y. Liubimov and M. G. Guenza
Department of Chemistry and Institute of Theoretical Science, University of Oregon, Eugene, OR
97403, USA
mguenza@uoregon.edu
Macromolecular liquids are complex fluids characterized by an extended range of time scales
where dynamical processes occur. Theoretical models and computer simulations are limited in the
range of time scales they can describe. Coarse-graining and multiscale modeling procedures can
alleviate this problem.

We present, first, an analytical coarse-grained approach and a multiscale procedure derived from
the solution of the Ornstein-Zernike equation, to describe the structure of polymer liquids and
their mixtures across the length scales of interest.[1,2] Second, an analytical rescaling approach
allows for the direct measurement of “real” dynamics from mesoscale simulations of a coarsegrained
polymer liquid. The rescaling procedure is obtained from the approximated solution of
the memory kernels, and friction coefficients. Finally, Generalized Langevin Equations (GLE)
for coarse-grained models of macromolecular structures can describe their dynamics across many
orders of magnitude in time. Specifically, using projection operator techniques a GLE is obtained
that describes the sub-diffusive regime in dynamically heterogeneous polymer liquids, in
quantitative agreement with Neutron Spin Echo experiments.[3] A new model for the
hydrodynamic interaction (Oseen tensor) is included in our GLE for the dynamics of a protein in
solution, which predicts internal relaxation of proteins in good agreement with NMR T1, T2, and
NOE measurements as well as with X-ray Debye-Waller factors.[4]
[1] M. G. Guenza J. Phys.: Cond. Matt. 20, 033101 (2008).
[2] E. J. Sambriski, M. G. Guenza Phys. Rev. E 76, 051801 (2007).
[3] M. Zamponi, A. Wischnewski, M. Monkenbusch, L. Willner, D. Richter, P. Falus, B. Farago,
and M. G. Guenza J. Phys. Chem. B 112, 16220 (2008).
[4] Esther Caballero-Manrique, Jenelly K. Brey, William A. Deutschman, Fredrick W. Dahlquist
M. G. Guenza Biophys. J. 93, 4128 (2007).
FROM β-RELAXATION TO SUB-Tg NUCLEATION BY MEANS OF CALORIMETRY
S. Vyazovkin
Department of Chemistry, University of Alabama at Birmingham, Birmingham, AL 35294, USA
Vyazovkin@uab.edu
Heating of glassy systems aged for short time at temperatures around 0.75Tg (50-70°C below Tg)
gives rise to endothermic recovery peaks observed in sub-Tg (pre-glass transition) region. The
peaks can be used to evaluate activation energy of the recovery process. The resulting values
obtained for a number of low and high molecular glassy systems are found to be in close
agreement with the activation energies of the β-relaxation measured by the standard dielectric and
mechanical methods. The results suggest that the molecular mobility present in the respective
temperature regions is similar to the β-relaxation process. Furthermore, the detected mobility is
demonstrated to be sufficient to cause intensive nucleation of crystallizable glasses such as glassy
indomethacin. Aged at 0 and -10°C for respective periods of 109 and 210 days, indomethacin
samples demonstrate the emergence of a small melting peak after aging for 69 days at 0°C and for
147 days at -10°C (i.e., ~55°C below Tg) that provides evidence of nucleation occurring in the
temperature region of the β-relaxation. The evolution of an endothermic recovery peak
temperature features a plateau at longer annealing times. Reaching the plateau appears to
correlate with the emergence of the melting peaks. The results highlight the importance of
studying physical aging in the temperature region of the β-relaxation as a means of evaluating the
physical stability of amorphous pharmaceutical materials.
______________________________________________________________________
___

NANOMECHANICAL THERMAL ANALYSIS OF THE GLASS TRANSITION OF
POLYSTYRENE
Namchul Jung, Minhyuk Yun, Sangmin Jeon
Department of Chemical Engineering, Pohang University of Science and Technology, Pohang,
Korea
jeons@postech.ac.kr
Polystyrene (PS) was coated onto one side of a silicon cantilever and the variations with
temperature in the deflection and resonance frequency of the PS-coated silicon cantilever were
measured. The difference between the volume expansion coefficients of PS and silicon induced
the cantilever to bend, and this deflection was used to determine the glass transition temperature
as well as the physical properties of the PS sample. In addition, the variation in the resonance
frequency of the cantilever was used to determine the temperature dependence of the Young’s
modulus of the polystyrene. A substantial hysteresis was observed in the deflection of the PScoated
silicon cantilever, which is attributed to the physical aging of the polystyrene in the glassy
state. Further, the effect of nanoparticles on the glass transition of polystyrene was also
investigated.
[1] N. Jung, H. Seo, D. Lee, C. Ryu and S. Jeon, "Nanomechanical thermal analysis of the glass
transition of polystyrene using silicon cantilevers", Macromolecules, 41, 6873, 2008
[2] N. Jung, S. Jeon, "Nanomechanical Thermal Analysis with Silicon Cantilevers of the
Mechanical Properties of Polyvinylacetate near the Glass Transition Temperature",
Macromolecules, 41, 9819, 2008.
_________________________________________________________________________
The Retardation Effect of Disaccharide on size variation of DMPC Unilamella vesicles
Dong-Myeong Shin(1), Jeong-Ah Seo(1) + , Hyun-Joung Kwon(1), Kyuyong Lee(3), Haeng Sub
Wi(3), Hyuk Kyu Pak(3), Hyung Kook Kim(1), and Yoon-Hwae Hwang(1)*
(1) Department of Nanomaterials Engineering & BK21 Nano Fusion Technology Division, Pusan
National University, Miryang 627-706, Korea
(3) Department of Physics, Pusan National University, Busan 609-735, Korea
+ Current address : Laboratoire de Dynamique et Structure des Matériaux Moléculaires, UMR
CNRS 8024, Université de Lille 1, UFR de Physique, Bât. P5, 59655 Villeneuve d’Ascq Cedex,
France
* Corresponding authors: yhwang@pusan.ac.kr
We studied the size variations of DMPC unilamella vesicles(ULVs), which contain different
disaccharides(trehalose, maltose, and sucrose) and distilled water, with the increase of the waiting
time by using photon correlation spectroscopy. The size of vesicles produced by an elecroformation(EF-ULVs)[1]
method was large (500-1500nm) and by a swelling-extrusion(SE-
ULVs)[2,3] method was small (70-100nm). The increase of vesicle size could be delayed due to
the cell preservation effect of disaccharides in both ULVs. In large-sized EF-ULVs, the
retardation effect of trehalose on size increase of ULVs was better than that of maltose and water.
In small-sized SE-ULVs, all disaccharides showed a good retardation effect on size variation, but
the size fluctuation of SE-ULVs which contain the trehalose was the smallest.

[1] M. I. Angelova, S. Soléau, Ph. Méléard, F. Faucon, P. Bothorel, Prog. Colloid Polym. Sci. 89
(1992) 127.
[2] F. Olson, C. A. Hunt, F. C. Szoka, W.J. Vail, D. Paphadjopoulos, Biochim. Biophys. Acta.
557 (1979) 9.
[3] M. J. Hope, M. B. Bally, G. Webb, P. R. Cullis, Biochim. Biophys. Acta. 812 (1985) 55.
STRUCTURE, DYNAMICS AND HYDRATION OF A COLLAGEN MODEL
POLYPEPTIDE IN AQUEOUS MEDIA
T. Shikata, A. Minakawa and K. Okuyama
Department of Macromolecular Science, Osaka University, Toyonaka, Osaka 560-0043, Japan
shikata@chem.sci.osaka-u.ac.jp
Structure, dynamics and hydration of collagen model polypeptides, (Prolyl-ProlylGlycyl)10
(PPG10), in aqueous media were investigated over a wide temperature range using dielectric
relaxation (DR) techniques from 1 kHz to 20 GHz in frequency. Because DR measurements are
sensitive to the presence of dipoles and their dynamics, conformation and electric state for
carboxy (C-) and amino termini of PPG10 were determined from relaxation times and strength. In
solutions, PPG10 made a mixture of rods with a length and diameter of 8.6 and 1.5 nm,
respectively, which were triple helices of PPG10, (PPG10)3, with the same dimension as observed
in their crystals [1], and random coils of isolated PPG10 with a radus of 1.5 nm. The degree of
dissociation for C-termini was suppressed by the addition of acetic acid in both triple helices and
single coils. The fraction of coils (fcoil) remarkably depended on temperature and also the
concentration of PPG10 (c). Small fcoil values in a low temperature range increased with
temperature and led to fcoil = 1 around 60 ºC irrespective of c. This single coil-to-triple helix
transition was discussed based on the kinetics of chemical reaction, 3PPG10 ↔ (PPG10)3.
[1] K. Okuyama, Connective Tissue Res., 49, 299, 2008
HARD SPHERES: CRYSTALLIZATION AND GLASS FORMATION
P.N. Pusey (1), E Zaccarelli (2), C. Valeriani (1), E. Sanz (1), W.C.K. Poon (1) and M.E. Cates (1)
(1) SUPA, School of Physics & Astronomy, The University of Edinburgh, Mayfield Road,
Edinburgh, EH9 3JZ, UK
(2) Dipartimento di Fisica and CNR-INFM-SOFT, Università di Roma La Sapienza, Piazzale A.
Moro 2, 00185 Roma, Italy
p.n.pusey@ed.ac.uk
Motivated by old experiments on colloidal suspensions, we report molecular dynamics
simulations of assemblies of hard spheres, addressing crystallization and glass formation. The
simulations cover wide ranges of polydispersity s (standard deviation of the particle size
distribution divided by its mean) and particle concentration. No crystallization is observed for s >
0.07. For s < 0.07, we find that increasing the polydispersity at a given concentration slows down
crystal nucleation. The main effect here is that polydispersity reduces the supersaturation since it
tends to stabilise the fluid but to destabilise the crystal. At a given polydispersity (< 0.07) we
find three regimes of nucleation: standard nucleation and growth at concentrations in and slightly
above the coexistence region; “spinodal nucleation”, where the free energy barrier to nucleation
appears to be negligible, at intermediate concentrations; and, at the highest concentrations, a new
mechanism, still to be fully understood, which only requires small re-arrangement of the particle
positions. The cross-over between the second and third regimes occurs at a concentration, ~ 58%
by volume, where the colloid experiments show a marked change in the nature of the crystals
formed and the particle dynamics indicate an “ideal” glass transition.

Ion dynamics in superionic glasses embedded with nanoparticles
Aswini Ghosh
Department of Solid State Physics, Indian Association for the Cultivation of Science, Jadavpur,
Kolkata 700032, India
Email: sspag@iacs.res.in
Ion dynamics in some interesting superionic glass-nanocomposites, embedded with LiI, CdI2, AgI
and Ag2S nanoparticles, has been studied using impedance spectroscopy in a wide frequency and
temperature ranges. Structure of these nanocomposites has been also investigated using electron
microscopy and Fourier transform infrared spectroscopy, and has been correlated with ion
dynamics. The composition dependences of the conductivity and the activation energy of
thesenanocomposites have been compared with those of AgI-doped silver phosphate and borate
glasses. We have studied the ion dynamics the framework of the power law and the electric
modulus formalisms. We have established a correlation between the crossover rate of the mobile
silver ions and the rearrangement of the structural units of glassy networks. Analysis of the
dielectric relaxation in the framework of modulus formalism indicates an increase in the ion-ion
cooperation in the glass compositions with increasing LiI, CdI2, AgI and Ag2S content. The
scaling of the conductivity spectra has been used to interpret the temperature and composition
dependence of the relaxation dynamics.
THERMAL POLING AND STRUCTURAL REARRANGEMENTS IN IONIC OXIDE
GLASSES *
E.I. Kamitsos
Theoretical and Physical Chemistry Institute, National Hellenic Research Foundation, Athens, Greece
eikam@eie.gr
While ferroelectric crystalline materials are used widely in photonics, there is currently intensive
research towards exploring new materials with sufficient and stable non-linear optical (NLO)
properties. Homogeneous glasses do not exhibit even-order optical response such as second
harmonic generation (SHG) due to their centrosymmetric nature. However, post-synthesis
treatments like intensive laser irradiation, thermal poling and crystallization of phases with
optical nonlinearity may induce SHG in glasses. The effects of thermal poling and glass
chemistry as well as the microscopic mechanisms associated with poling are not well understood
at present, and this makes the full exploitation of glasses in photonics difficult. To progress in this
direction, we develop and process by thermal poling different Na ion-containing oxide glasses to
establish correlations between structure/chemistry and NLO response. Infrared and micro-Raman
spectra indicate that poling-induced Na ion migration triggers structural rearrangements in a thin
NLO layer and this leads to the appearance of SHG. Results obtained on different ionic
conducting glasses will be reviewed in this work.
* Support by EC Grant No. MTKD-CT-2006-042301.
CONTROLLING PHASE TRANSITIONS BY AN EXTERNAL FIELD IN THE
PRESENCE OF AN INTERMEDIATE METASTABLE STATE

F. Paladi
Department of Theoretical Physics, State University of Moldova, A.Mateevici str. 60, Chisinau
MD-2009, Moldova
fpaladi@usm.md
The role of intermediate metastable state in the fluctuation-induced transitions between two stable
states is reported. This phase tends to enhance the nucleation rate by lowering the free energy
barrier, and the occurrence of such structural fluctuations indicates that supercooled liquids and
glasses would have a heterogeneous structure [1]. Within the framework of a local equilibrium
assumption, it is stipulated that the force field has, up to proportionality factors related to
diffusion, viscosity and other transport coefficients, the structure of the derivative of a Landautype
free energy function [2]. Kinetic models involving single- and two-order parameters have
been developed by a potential of sixth degree involving four control parameters, taking
additionally into account effects due to asymmetry and the coupling to an external field, which
play an important role in connection with the possibility to control and optimize the transition rate.
It is shown that particular combinations of the control parameters lead to an enhancement of the
nucleation rate by the presence of an intermediate state.
[1] F. Paladi and M. Oguni, Phys.Rev. B, 65, 144202, 2002
[2] G.Nicolis and C.Nicolis, Physica A, 351, 22, 2005
A DERIVATION OF THE VOGEL – FULCHER – TAMMAN RELATION FOR
SUPERCOOLED LIQUIDS
Andrew V. Granato (1)
(1) University of Illinois at Urbana-Champaign, Department of Physics, Urbana, Illinois, USA
Correspondence author: granato@illinois.edu
The non-Arrhenius Vogel-Fulcher-Tamman relation for the viscosity, η , known for about 8
decades, describes simply one of the most characteristic features of supercooled liquids. It may be
written η = η exp ⎡U / k 0 ( T −T0)
⎤
⎣ ⎦ . Using the Interstitialcy Theory of Condensed Matter (ITCM) [1]
and the Dyre, et. al. [2] result demonstrating U is proportional to the shear modulus, G , we
derive this relation and obtain T /T 0 g = γ / ( γ + 1)
and U = U / 0 ( 1+ γ ) . Here, γ is a softening
parameter given by γ =− dlnG/d( T/T0
) and U = U 0 ( Tg)
, the interstitialcy diffusion energy at the
glass temperature. γ is also a fragility parameter ranging from 0 for strong materials to 3 or
above for fragile ones.
[1.] A.V. Granato, Phys. Rev. Lett., 68, 974 (992
[2.] J.E. Dyre, N.B. Olsen and T. Christenson, Phys. Rev., B53, 2171 1996
USE OF MASTER CURVES TO INVESTIGATE THE EFFECT ON DYNAMICS OF A
MODEL CHAIN SYSTEM THAT CONTAINS TORSIONAL BARRIERS
J. Budzien (1)
(1) Department of Materials Engineering, New Mexico Institute of Mining and Technology,
Socorro, NM, USA
jbudz@nmt.edu
This talk reports on constructing master curves using molecular dynamics simulations of beadspring
models. Previous research [1,2] on these systems showed that translational and rotational

dynamics properties collapsed when plotted against some thermostatic properties. Torsional
barriers were added to the systems to investigate their effects on the dynamics. In addition to the
expected slowdown, the dynamics of the systems changed qualitatively so that some of the master
curve parameters no longer hold. Unexpectedly, packing fraction does not construct a master
curve for systems with the torsional barriers, evidently failing to capture the combined density
and temperature effects. However, tracer diffusion coefficients can be used to create master
curves, suggesting that other parameters combining density and temperature effects will generate
master curves. Examples of those other parameters will be presented including one from
experimental work [3].
[1] J. Budzien, J. D. McCoy, and D. B. Adolf, J. Chem. Phys., 121, 10291, 2004
[2] J. V. Heffernan, J. Budzien, F. Avila, T. C. Dotson, V. J. Aston, J. D. McCoy, and D. B.
Adolf, J. Chem. Phys., 127, 214902, 2007
[3] R. Casalini and C. M. Roland, Phys. Rev. B, 71, 014210, 2005
MODELING PROTEIN-MEMBRANE INTERACTIONS USING IMPLICIT
SOLVATION
T. Lazaridis
City College of New York, Chemistry Department, 160 Convent Ave., New York, NY10031
tlazaridis@ccny.cuny.edu
Implicit solvation models have generated a lot of interest thanks to their convenience and speed.
With minimal effort these models can be extended to lipid membranes with even greater payoffs.
We recently extended the EEF1 function for soluble proteins to an implicit membrane model
(IMM1) by making the solvation parameters and the dielectric screening dependent on the
vertical coordinate. The membrane surface charge is modeled by use of the Gouy-Chapman
theory. The transmembrane voltage is also straightforward to incorporate. We have developed
approaches for calculating absolute, pH-dependent membrane binding free energies and
transmembrane helix association free energies and applied these methods to a number of
membrane-active peptides: transmembrane helix dimers, the influenza hemagglutinin fusion
peptide, alamethicin, the membrane targeting domain of phosphocholine cytidylyltransferase,
alpha-synuclein, and proteinase 3.
ION TRANSPORT AND STRUCTURAL RELAXATION: REVISITING THE
CONCEPTS OF COUPLING AND DECOUPLING
M.D. Ingram and C.T. Imrie
School of Natural and Computing Sciences, University of Aberdeen, Aberdeen AB24 3UE,
Scotland, UK
m.d.ingram@abdn.ac.uk
In liquid and glassy state ionics, two behaviours are commonly distinguished: coupled ion
transport (exemplified in fragile melts by CKN) where the decoupling ratio Rτ = τs/τσ =1 from
decoupled ion transport (exemplified in glasses by the AgI:Ag2MoO4 system) where the
corresponding ratio can be as large as 10 12 . We show that these systems actually behave in a
strikingly similar fashion when we compare two experimental parameters, Mσ and Ms, defined by
the equation EA = M.VA. Values of Mσ are obtained from plots of EA,σ versus VA,σ; Ms is obtained
from the pressure dependence of Tg, where Ms = Tg.dP/dTg. Remarkably, we find that Mσ ≈ Ms

(5.2 GPa for CKN and 7.8 GPa for the AgI:Ag2MO4 glass), even though the ion hopping
processes in melt and glass are occurring much faster than are the structural relaxations at Tg.. We
regard “M” as the local “modulus of interaction” quantifying the strength of the ion-matrix
interactions. These interactions in turn influence the elementary processes occurring at very short
times, which initiate ion transport and structural relaxation in both coupled and decoupled
systems, thus blurring the distinction between these two patterns of behaviour.
[1] M.D. Ingram, C.T. Imrie, J. Ledru, J.M. Hutchinson, J. Phys. Chem. B, 112 (2008) 859.
[2] M.D. Ingram, C.T. Imrie, Z. Stoeva, S.J. Pas, K. Funke, H.W. Chandler, J. Phys. Chem.B, 109
(2005) 16567.
PACKAGING BIOLOGICAL MACROMOLECULES AND TRANSLOCATION
M. Muthukumar
Polymer Science and Engineering Department
University of Massachusetts, Amherst, MA 01003
We will discuss how biological macromolecules are packaged in viruses and how they undergo
translocation through pores and protein channels. In the packaging problem, we will consider
many RNA viruses and address the question of whether the diverse chemical sequences or simple
electrostatics control the assembly. A universal model, based simply on non-specific electrostatic
interactions, is able to predict the essential aspects of genome packing in diversely different
viruses, such as the genome size and its density distribution. In the second problem, we will
address how single DNA/RNA molecules navigate through protein channels and synthetic
nanopores, by implementing concepts from polymer physics. Experimentally observed puzzles of
how the translocation speed is sometimes directly and some other times inversely related to
polymer length will be addressed.
Logarithmic decay of the relaxation of protein single-particle correlators
Marco Lagi 1,2 , Piero Baglioni 2 and Sow-Hsin Chen 1,*
1 Department of Nuclear Science and Engineering, Massachusetts Institute of Technology,
Cambridge, MA 02139
2 Department of Chemistry and CSGI, University of Florence, Florence, I 50019, Italy
We present the self-dynamics of protein amino acids of hydrated lysozyme powder [1] around the
physiological temperature by means of molecular dynamics (MD) simulations [2]. The selfintermediate
scattering functions (SISF) of the amino acidic center-of-mass and of the protein
hydrogen atoms display a logarithmic decay over 3 decades of time, from 2 picoseconds to 2
nanoseconds, followed by an exponential α-relaxation. This kind of slow dynamics resembles the
relaxation scenario within the β-relaxation time range [3] predicted by the mode coupling theory
(MCT) in the vicinity of higher-order singularities [4]. These results suggest a strong analogy
between the single-particle dynamics of the protein and the dynamics of colloidal [5], polymeric
[6] and molecular [7] glass-forming liquids. From a biological point of view, this anomalously
slow relaxation could endow proteins with the appropriate resilience in response to the

fluctuations of the external environment. If possible, we shall also report an incoherent quasielastic
neutron scattering experimental result to confirm these predictions.
Reference:
[1] M. Tarek and D. J. Tobias Biophys. J. 79, 3244 (2000)
[2] M. Lagi, P. Baglioni and S.-H. Chen “Logarithmic decay of protein single-particle
relaxations” Phys Rev Lett submitted
[3] H. Frauenfelder, G. Chen et al. Proc. Natl. Acad. Sci. USA, 106, 5129 (2009)
[4] W. Gotze and M. Sperl. Phys Rev E, 66 011405 (2002)
[5] F. Sciortino, P. Tartaglia, et al. Phys Rev Lett, 91 268301 (2003)
[6] A. J. Moreno and J. Colmenero. J Chem Phys, 125 016101 (2006)
[7] H. Cang, V. Novikov, et al. Phys Rev Lett, 90, 197401 (2003)
ELECTROSTATIC ENERGY MODELS FOR STRUCTURE AND DYNAMICS OF
PROTEINS AND RNA
Karl F. Freed 1 , Haipeng Gong 2
(1) James Franck Institute, University of Chicago, Chicago, IL 60637
(2) Department of Biological Sciences and Biotechnology, Tsinghua University Beijing 100084,
China
freed@uchicago.edu
All-atom simulations are enormously simplified when the solvent is replaced by an implicit
solvent model that describes the screening of Coulombic interactions between the solute’s (partial)
charges. Most approaches follow Born’s theory (1920) where the solvent is replaced by a
continuum with a uniform dielectric constant. The Born type models fail drastically for the
hydration energies of multi-valent ions and the energy and absolute pKa shifts when charged
residues are transferred from hydrophilic to hydrophobic media. While the Born model is
equivalent to assuming a uniform distribution of point polarizable molecules, the “newer” Debye
model (1925) describes the solvent by a uniform distribution of point polarizable dipoles using
the static and optical bulk dielectric constants of the solvent and the dipole moments of the
solvent molecules in the gas and liquid phases. The nonlinear interactions between dipoles in the
Debye model produce a spatially varying electrical permittivity due to dielectric saturation of the
highly oriented proximal solvent dipoles. Previous work shows that the Debye model explains
data for the hydration of multi-valent ions, and we use the Debye model to largely eliminate the
discrepancies of the Born model with experiment for transfer energies and pKa shifts [1] and to
test the assumption of a single universal screening function [2] in the generalized Born model.
Combining a generalization to RNA of the Shen-Freed implicit solvent model (for proteins) with
an extension of the Debye model provides the first reasonable implicit solvent model for RNA.
[1] H. Gong, G. M. Hocky, and K. F. Freed, Proc. Natl. Acad. Sci. (US) 105,11146, 2008.
[2] H. Gong and K. F. Freed, Phys. Rev. Lett. 102, 057603, 2009.

PHASE AND GLASS TRANSITIONS OF WATER IN POROUS COPPER
RUBEANATES
T. Yamada (1, 4), R. Yonamine (1), T. Yamada (2, 4) H. Kitagawa (2, 3, 4) and O. Yamamuro (1,
4)
(1) Institute for Solid State Physics, University of Tokyo, 5-1-5 Kashiwanoha Kashiwa, 277-8581,
Japan
(2) Graduate School of Science, Kyusyu University, Fukuoka, 812-8581, Japan
(3) Graduate School of Science, Kyoto University, Kyoto, 606-8502, Japan
(4) JST-CREST, Japan
yamada@issp.u-tokyo.ac.jp
Phase transitions and dynamics of water in confined spaces are interesting both from scientific
and industrial points of view. Copper rubeanate forms a crystalline lattice with pores of ca. 0.6
nm and exhibits high proton conductivity (ca. 0.01 S cm -1 ) as absorbing water vapor [1]. In this
study, the structure and dynamics of water in the nano-pores of copper rubeanate hydrates with
different water contents have been investigated by adiabatic calorimetry, neutron diffraction and
quasielastic neutron scattering (QENS) techniques. In the calorimetric experiments, a glass
transition and a phase transition with a long low-temperature tail were observed around 155 K
and 250 K, respectively. The entropy of the phase transition at the reference temperature 273.15
K was 20.8 J K -1 mol -1 which is similar to that of bulk water, 22.0 J K -1 mol -1 . The neutron
diffraction patterns of water in the pores were of amorphous structure in the whole temperature
range but the peak position and width of the FSDP slightly changed around the phase transition.
A slight change around the phase transition was observed also in the diffusion coefficients from
the QENS data. These results indicate that the transition is a liquid-to-liquid transition as
observed in several porous materials.
[1] H. Kitagawa, Y. Nagao, M. Fujishima, R. Ikeda and S. Kanda, Inorg. Chem. Comm., 6, 346,
2003
NANOMECHANICAL THERMAL ANALYSIS OF THE CYSTALLIZATION OF
POLYETHYLENE
Dongkyu Lee and Sangmin Jeon
Departmetn of Chemical Engineering, Pohang University of Science and Technology, Pohang,
Korea
Jeons@postech.ac.kr
The thermomechanical properties of Polyethylene (PE) have been investigated in the vicinity of
the melting and crystallization temperatures using a PE-coated silicon cantilever. The variations
with temperature in the deflection and resonance frequency of the PE-coated cantilever were
measured to obtain the temperature dependence of the volume and effective modulus of PE with
different crystallinity. In addition, the melting and crystallization temperatures of PE were
determined from the variations in the volume and effective modulus. The thermal hysteresis in
the resonance frequency was found during the melting and crystallization of PE whereas no
hysteresis was observed during glass transition. The difference was attributed to the supercooling
effect of PE.
[1] N. Jung, H. Seo, D. Lee, C. Ryu and S. Jeon, “ Nanomechanical thermal analysis of the glass
transition of polystyrene using silicon cantilever”, Macromolecules, 41, 6873, 2008
[2] N. Jung, S Jeon, “Nanomechanical Thermal analysis with silicon cantilevers of the
mechanical properties of Polyvinylacetated near the glass transition temperature”,
Macromolecules, 41, 9819, 2008

FIRST AND SECOND UNIVERSALITY IN DISORDERED IONIC MATERIALS
D.L. Laughman, R.D. Banhatti and K. Funke
SFB 458 and Institute of Physical Chemistry, University of Münster, Corrensstrasse 30, D-48149
Münster, Germany
k.funke@uni-muenster.de
In ion-conducting materials with disordered structures, there are three different kinds of ionic
motion, all of them collective and cooperative, viz., hops along diffusion pathways, strictly
localised displacements, and vibrations. This report focuses on the hopping motion and the
localised displacements, which cause the “first” and “second” universality, respectively. With the
term “first universality” we convey the notion that virtually the same master curve of the
frequency-dependent conductivity is obtained for a large number of ion-conducting materials, if
time-temperature superposition is used for scaling. These materials include structurally
disordered ionic crystals, glasses, ion-in-polymer systems and ionic liquids. The term “second
universality”, introduced by A.S. Nowick in 1991, refers to the observation that, at sufficiently
low temperatures, the dielectric loss function of any solid electrolyte shows hardly any
dependence on frequency and temperature. This is the Nearly Constant Loss (NCL) effect. The
scaling behaviour of the “first universality” component is shown to provide an effective way to
identify and distinguish the two universalities when plotted versus temperature at constant
frequency. Both conductivity components, including their characteristic variations with frequency
and temperature, can be reproduced via time-correlation functions derived from simple rules for
the ion dynamics. A physical basis is thus provided to understand the NCL phenomenon and to
explain the puzzling finding that it still exists at cryogenic temperatures [1].
[1] D.L. Laughman, R.D. Banhatti and K. Funke, Phys. Chem. Chem. Phys. 11, 3158, 2009
DYNAMICS OF THE WATER INTERCALATED INTO GRAPHITE OXIDE
F. Barroso-Bujans (1), S. Cerveny (1), Á. Alegría (1,2), J. Colmenero (1,2,3)
(1) Centro de Física de Materiales (CSIC-UPV/EHU), Facultad de Química, Apartado 1072,
20080 San Sebastián, Spain
(2) Dpto. de Física de Materiales, Universidad del País Vasco (UPV/EHU) Apartado 1072, 20080
San Sebastián, Spain
(3) Donostia <strong>International</strong> Physics Center, Paseo Manuel de Lardizábal 4, 20018 San Sebastián,
Spain
fbarroso@ehu.es
Graphite oxide (GO) is an oxygen rich derivative of graphite where epoxy and hydroxyl groups
decorate the surface of the graphene sheets whereas the carboxyl groups could be localized at the
edges. These functional groups are responsible of the high hidrophilicity of GO, which can
readily absorb water from the environmental air. The water molecules are almost inherent to this
material and therefore, they deserve a detailed study of their behavior. We have studied the
dynamics of the intercalated water in the interlayer spacing of GO by means of broadband
dielectric spectroscopy (10 -2 Hz – 10 10 Hz and temperatures from 140 to 300K), differential
scanning calorimetry and X-ray diffraction. The interlayer distance during hydration increases
from 5.67Ǻ to 8Ǻ which correspond to the uptake of a water monolayer in the interlayer space of
GO. A clear relaxation due to water molecule reorientation was observed at temperatures lower

than 200K. The temperature dependence of the relaxation times presented a crossover similar to
that observed in water-solution.
Acoustic Dissipation and Density of States in Liquid, Supercooled and Glassy Glycerol
L. Comez
CRS SOFT-INFM-CNR, c/o Universita` di Roma La Sapienza, 00185 Roma, Italy
Dipartimento di Fisica, Universita` di Perugia, Via Pascoli, I-06100 Perugia, Italy
The combined use of Brillouin spectra measured in the visible, ultraviolet and x-ray frequency
regions permits to estimate the acoustic compliance over a wide frequency range between 0.5
GHz and 5 THz. We find that for liquid, supercooled and glassy glycerol, the acoustic compliance
overlaps the incoherent neutron susceptibility in the THz region giving evidence that a
proportionality exists between the acoustic power dissipation and the density of states g(ω) in the
different aggregation phases of matter.
ANOMALOUS DISPERSION OF DINAMIC CONDUCTIVITY IN CHAOTIC MEDIA
V.V. Novikov , O.M. Ianovych
Odessa National Polytechnic University, Odessa, 1 Shevchenko, 65044, Ukraine
frac.novikov@gmail.com.
The work concerns with charge (currents) transport in chaotic dynamic media. It is shown, that
the conductive media may demonstrate hierarchy structures properties over an electric field. The
hierarchy dynamic systems exhibit slowed down relaxation character. The balance in media is
reached by establishment quasi-equilibrium on every hierarchy level of the system. It influences
the frequency dependences of conductivity and dielectric constant. Instead of classical dispersion
2
dependency σ ω −
2α
≈ , the anomalous dependence σ ω −
≈ is observed [1]. The parameter α is a
fractional constant. The model of stage-by-stage averaging of electric field in the dynamic media
(electronic plasma) is proposed. First, during time τ 1 micro currents j
1 will be established in
media. Local conductivity at regions which is bounded by free length size l
1
≈ 1/ τ1
is σ 1 . It is
possible to present an establishment of effective currents j
2 during timeτ 2 , as confluence of the
micro currents j
1 into subclusters, which is characterized by conductivity σ 2 and so on.
Consecutive confluence of the subclusters currents into the ordered currents clusters means a
stage-by-stage removing of currents fluctuations related with chaotic charge transport. The
similar stage-by-stage removing of fluctuations is carried out in renormalization group’s
transformations [2].
It was developed the fractal model of the relaxation times τ and the time fractional
i
differentiation method was used also at the electron transport description in media of chaotic
structure. The research describes dynamics of charge (currents) transport in media of the
anomalous conductivity dispersion.

[1] V.V. Novikov, V.P. Privalko. Temporal fractal model for the anomalous dielectric relaxation
of inhomogeneous media with chaotic structure, Phys. Rev. E, 64,031504, 2001.
[2] Novikov V.V., Physical properties of fractal structures, p.203, 2006, in the book “Fractals,
diffusion and relaxation in disordered complex systems” Edited by Stuart A. Rice, Guest editors:
William T. Coffey and Yuri P. Kalmikov.

FLUORESCENCE CORRELATION SPECTROSCOPY STUDY OF MOLECULAR
PROBE DIFFUSION IN POLYMER MELTS
K. Koynov (1), G. Fytas (2), G. Floudas (3), H.J. Butt (1)
(1) Max-Planck-Institute for Polymer Research, 55128 Mainz, Germany
(2) Departments of Chemistry and Materials Science and Technology, University of Crete, 71110
Heraklion, Greece
(3) Department of Physics, University of Ioannina, 45110 Ioannina, Greece
koynov@mpip-mainz.mpg.de
Fluorescence correlation spectroscopy (FCS) is a powerful tool for investigation of the diffusion
and transport properties of fluorescent molecules, macromolecules or nanoparticles in various
environments. In spite of its great potential and high versatility, so far the method was applied
mainly in aqueous environments. We used FCS to measure the diffusion coefficient of small
molecule chromophores in bulk polydimethysiloxane (PDMS) and 1,4-polyisoprene (PI) linear
homopolymers with different molecular weights at temperatures well above the polymer glass
transition. The unique, single molecule sensitivity of the FCS technique allows studies at
nanomolar tracer concentrations, ensuring that the tracers do not modify the matrix polymer
properties. For all systems we observed that the diffusion rate does not follow the surrounding
viscosity, which is extremely increased for high molecular weight polymers. Instead the diffusion
coefficient of small tracer is strongly correlated to the polymer segmental dynamics while it keeps
particle characteristics. To address the effect of chain topology we have compared the tracer
diffusion in linear and star shaped 1,4-polyisoprene at temperatures well above the glass
transition. In 3-arm star PI, the small molecular tracers revealed two diffusion modes. The fast
mode had the same magnitude and temperature dependence as the tracer diffusion coefficient in
linear PI. The slow mode diffusion, which was found only in the star polymer, is apparently
related to topological restrictions that may cause retention of the tracer.
AMORPHOUS PHASE DYNAMICS AT THE GLASS TRANSITION IN GLASS
FORMERS: CONFINEMENT EFFECTS ON THE CHARACTERISTIC
COOPERATIVITY LENGTH
A. Saiter, L. Delbreilh, E. Dargent, J. Grenet, and J.M. Saiter
Laboratoire PBS, FRE 3101, LECAP, Institute for Materials Research. – Université de Rouen,
Faculté des Sciences,
Avenue de l’Université BP 12, 76801 Saint Etienne du Rouvray, France
Correspondence author: allison.saiter@univ-rouen.fr
In glassy or semi-crystalline polymers, relaxation processes in the amorphous phase are known to
be cooperative phenomena and the molecule motions depend on neighbour’s motions [1]. Adam
and Gibbs [2] have introduced the notion of Cooperative Rearranging Region (CRR) defined as a
subsystem which can rearrange its configuration into another independently of its environment
upon sufficient thermal fluctuations.
In this work, we perform a review of our last results concerning the evolution of the CRR size in
different glass formers (like PET [3], PLA [4], PC, PMMA), and also in inorganic glassy systems
[5], for which the structural relaxation processes are constrained by different ways: (1) presence
of nanoparticules (like Montmorillonite), (2) presence of crystalline phase (induced by thermal
treatment or drawing effects), (3) geometric confinement in multilayer systems, (4)
dimensionality increase in inorganic glasses. In all cases, we put in evidence that the
characteristic cooperativity length decreases when the structural relaxation processes are
constrained.

[1] S. H. Glarum, J. Chem. Phys., 33, 639, 1960
[2] G. Adam, J. H. Gibbs, J. Chem. Phys., 43, 139, 1965
[3] N. Delpouve, A. Saiter, J. Mano, E. Dargent, Polymer, 49, 3130, 2008
[4] C. Lixon, N. Delpouve, A. Saiter, E. Dargent, Y. Grohens, Europ. Poly. Journal, 44, 3377,
2008
[5] A. Saiter, J.M. Saiter, R. Golovchak, M. Shpotyuk and O Shpotyuk, J. Phys.: Condens. Matter,
21, 07510, 2009
DOES ATOMISTIC SIMULATION GIVE A REALISTIC PICTURE OF THE GLASS
TRANSITION
Armand Soldera (1), Noureddine Metatla (1) Alexandre Beaudoin (1), Sylvère Said (2), and Yves
Grohens (2)
(1) Department of Chemistry, Université de Sherbrooke, Sherbrooke (Québec), J1K 2R1, Canada
(2) Université de Bretagne Sud, L2PIC, Centre de Recherche, rue St Maudé, 56100 Lorient,
France
Armand.Soldera@USherbrooke.ca
To describe the vast domain of relaxation times occurring at the glass transition, molecular
modelling was revealed as a strongly beneficial tool to complement existing theories. In fact,
among the different kinds of simulations, the coarse-grained approach remains the most
appropriate technique to deal with the time spreading phenomenon. Alternatively, atomistic
simulation (AS) is more appropriate to treat the effect of small variations in the atomistic
architecture of the repeat unit on the value of Tg. However, the range of times accessible by AS is
undeniably lower than the Rouse time. Despite this fact, transition temperatures that are usually
related to Tgs have been determined using this approach. The restricted description of the phase
space (domain of times covered by AS, typical length, number of limited points in the
configurational space) questions the adequacy of correlating Tg determined by AS (Tg AS ) to the
experimental Tg (Tg exp ). A procedure is then proposed which yields reproducible Tg AS of a series of
vinylic polymers at different cooling rates [1]. Link with Tg exp was carried out through the wellestablished
WLF equation [2]. By comparing the different contributions of the variation of the
heat capacity at Tg, it is shown that the deficiency in reproducing perfectly the experimental leap
is due to a poor representation of conformational changes.
[1] N. Metatla and A. Soldera, Mol. Simul., 32, 1187, 2006.
[2] A. Soldera and N. Metatla, Physical Review E, 74, 061803, 2006.
EFFECTS OF POLYMERIZATION, CRYSTALLINITY AND MOISTURE ON THE
GLASS TRANSITION TEMPERATURE OF CARBOHYDRATE MATERIALS
K. Kawai (1), K. Fukami (2), P. Thanatuksorn (3), C. Viriyarattanasak (3) and K. Kajiwara (3)
(1) Graduate School of Biosphere Science, Hiroshima University, 1-4-4 Kagamiyama, Higashi-
Hiroshima, Hiroshima 739-8528, Japan.
(2) San-ei Sucrochemical Company Limited, 24-5 Kitahama-cho, Chita, Aichi 478-8503, Japan.

(3) School of Bioscience and Biotechnology, Tokyo University of Technology, 1404-1 Katakura,
Hachioji, Tokyo 192-0982, Japan.
kawai@hiroshima-u.ac.jp
Carbohydrate is one of major ingredients of food and usually exists as amorphous state. Since
amorphous carbohydrate often causes crystallization and/or glass transition during processing or
storage, glass transition temperature (Tg) is an important parameter for the control of the physical
property change. Recently fructo-oligosaccharide has attracted much attention for multi benefits
such as dietary fiber, prebiotic nature, fat mimetic material and promoter of the absorption of
calcium. There are some studies on the Tg of fructo-oligosaccharide [1,2]. The published data,
however, were not large enough to permit prediction of Tg of fructo-oligosaccharide. In this study
Tg of various types of fructo-oligosaccharide were investigated by using DSC, and effects of
polymerization (DP), crystallinity and moisture on the Tg of fructo-oligosaccharide were revealed.
Furthermore, these results were compared with those of malto-oligosaccharide reported in
previous studies. Effects of crystallinity and moisture content on Tg roughly agreed between
fructo-oligosaccharide and malto-oligosaccharide. Effect of DP on Tg, on the other hand,
disagreed, and it was found that fructo-oligosaccharide was lower Tg than that of maltooligosaccharide
at each DP.
[1] J. E. Zimeri and J. L. Kokini, Carbohydr. Polym., 48, 299, 2002
[2] S. N. Ronkart, M. Paquot, C. Fougnies, C. Deroanne and C. S. Blecker, Food Hydrocol., 23,
922, 2009

INFLUENCES OF DOMAIN STRUCTURES ON THE BULK AND SURFACE
DYNAMICS OF ROOM TEMPERATURE IONIC LIQUIDS
Makoto YAO
Department of Physics, Kyoto University, 606-8502 Kyoto, Japan
yao@scphys.kyoto-u.ac.jp
Based upon our recent experiments on room temperature ionic liquids (RTILs) using ultrasonic
spectroscopy [1], surface dynamic light scattering [2,3,4] and microwave spectroscopy [5], we
will discuss (A) how does the interconnecting polar- and nonpolar-domain structures that were
predicted by computer simulations [6] and verified by X-ray small angle scattering [7] influence
on the dynamics in the bulk RTILs?, (B) what are the relevant parameters that should be added
to the molar conductivity ratio [8] to describe the physical and chemical properties of RTILs,
incorporating the domain structures?, (C) how are the domain structures compatible with the
surface structures?
[1] W. Makino, R. Kishikawa, M. Mizoshiri, S. Takeda and M. Yao, J. Chem. Phys., 129,
104510, 2008.
[2] Y. Ohmasa, T. Hoshino, R. Osada and M.Yao, Chem. Phys. Letters, 455, 184, 2008.
[3] T. Hoshino, Y. Ohmasa, R. Osada and M.Yao, Phys. Rev. E, 78, 061604, 2008.
[4] R. Osada, T. Hoshino, K. Okada, Y. Ohmasa and M. Yao, J. Chem. Phys. 130 184705, 2009.
[5] M. Mizoshiri, T. Nagao, Y. Mizoguchi, and M. Yao, in preparation.
[6] J.N. Canongia Lopes and A. A. Padua, J. Phys. Chem. B, 110, 3330, 2006.
[7] A. Triolo, O. Russina, H.-J. Bleif, and E. Di Cola, J. Phys. Chem. B, 111, 4641, 2007.
[8] H. Tokuda, S. Tsuzuki, M. A. B. H. Susan, K. Hayamizu, M. Watanabe, J. Phys. Chem. B,
110, 19593, 2006.
COUPLING AND DECOUPLING DYNAMICS IN ION GELS PMMA/EMITFSI
M. Kofu (1), S. Tatsumi (1), T. Someya (1), V. Garcia-Sakai (2), K. Ueno (3), T. Ueki (3), M.
Watanabe (3) and O. Yamamuro (1)
(1) Institute for Solid State Physics, University of Tokyo, 5-1-5 Kashiwanoha, Chiba 277-8581,
Japan
(2) Rutherford Appleton Laboratory, Chilton, Didcot, OX11 0QX, UK
(3) Yokohama National University, 79-5 Tokiwadai, Hodogaya-ku, Kanagawa 240-8501, Japan
kofu@issp.u-tokyo.ac.jp

Ion gels (IGs) consist of network polymer, PMMA (poly(methylmethacrylate)), and ionic liquid,
EMITFSI (1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide). The IGs form
transparent, soft, and strong membranes with high ionic conductivity, attracting much attention
in applications for various electrochemical devices, actuators and so on. However, the basic
physical properties of IGs have not been clarified yet. In order to investigate the dynamics of
IGs, especially on the coupling and decoupling between the polymer and ion liquid, we have
performed quasielastic neutron scattering (QENS) measurements for the IGs PMMA1x/EMITFSIx
(x=0.10 and 0.27). PMMA or EMITFSI were selectively deuterated to observe the
motion of another component with many H atoms. All of QENS spectra were reproduced well
by two motions with different relaxation times. The faster motion, which did not change much
with temperature, may be related to the side-chain motions of PMMA and intraionic motions of
EMI ions. The slower motions should be diffusions of PMMA and EMITFSI with larger
activation energies. The diffusion coefficient of PMMA and its temperature dependence were
different from those of EMITFSI in the IG with x=0.10. It is remarkable that the diffusion
coefficients of PMMA and EMITFSI lie on the same line at lower temperature but different
from each other at higher temperature in the IG with x=0.27, indicating the coupling-decoupling
crossover.
CALORIMETRIC AND NEUTRON SCATTERING INVESTIGATIONS ON A TWO-
DIMENSIONALLY ORDERED STRUCTURE OF ICE CRYSTALLIZED FROM
UNDERCOOLED AQUEOUS SOLUTIONS
A. Inaba
Research Center for Structural Thermodynamics, Graduate School of Science, Osaka University,
Toyonaka, Osaka 560-0043, Japan
inaba@chem.sci.osaka-u.ac.jp
We report calorimetric [1,2] and neutron scattering [3,4] investigations on a two-dimensionally
ordered structure of ice crystallized from undercooled aqueous solutions. The material added to
water is a good glass-former such as glycerol, diethylene glycol, and so on. We investigated the
phase behavior first [1] to find the best condition to prepare the 2-D ice. The composition of the
solutions was found to be about 55% (w/w), irrespective of material. The composition and the
heat capacity of the maximally freeze-concentrated solution, i.e. the non-crystallizing phase that
remains after water’s partial crystallization, were investigated [2]. The heat capacity of the 2-D
ice between T = 5 K and T = 15 K obtained for the glycerol/water system is found to be
consistently larger than that of hexagonal ice (ice Ih) by an average of 1.3% [2].

[1] A. Inaba and O. Andersson, Thermochim. Acta 461 (2007) 44.
[2] O.D. Camacho P., A. Inaba and O. Andersson, Chem. Phys. Lett., (2009) in press.
[3] A. Inaba, N. Sakisato, A.K. Bickerstaffe and S.M. Clarke, J. Neutron Research 13(1-3)
(2005) 87.
[4] A. Inaba, Pure Appl. Chem. 78(5) (2006) 1025.
THERMAL HYSTERESIS OF DIELECTRIC PERMITTIVITY AND CHARGE
TRANSPORT IN CHARGE TRANSFER COMPLEXES
T. Mahfoud (1), G. Molnár (1 ) , S. Bonhommeau (1), S. Cobo (1), L. Salmon (1), P. Demont (2),
A. Bousseksou (1)
(1) CNRS, Laboratoire de Chimie de Coordination, Université de Toulouse, UPS, INPT, LCC,
31077 Toulouse, France
(2) Laboratoire de Physique des Polymères, CIRIMAT- Institut Carnot, Université de Toulouse
III, 31062 Toulouse, France
demont@cict.fr
Dielectric measurements and charge transport were performed on charge transfer (CT)
complexes. Complex permittivity and conductivity data were obtained as a function of
temperature (120-350K) and frequency(10 -2 to 10 6 Hz) on Rb0.8Mn[Fe(CN)6]0.931.62H2O and
Co3[W(CN)8]2(pyrimidine)4 6 H2O compounds using broadband dielectric spectroscopy. CT
phase transition is characterized by hysteresis loop of dielectric permittivity. For both
compounds, a frequency independent dielectric peak in the ε’(T) curves is observed close to the
phase transition temperature. Dielectric behavior is interpreted in terms of ferro-paraelectric
transition. The CT phase transition is also accompanied by a large thermal hysteresis loop of the

electrical conductivity where the low temperature phase is more conductive than the high
temperature phase. The charge transport in CT complexes is associated with a conduction
relaxation and reveals universal conductivity behavior of disordered systems [1]. Small polaron
hopping is assigned to the intervalence electron transfer between transition metal sites of CT
complex.
[1] G. Molnár, S. Cobo, T. Mahfoud, E. J.M. Vertelman, P. J. van Koningsbruggen, P.Demont,
A. Bousseksou, J. Phys. Chem. C, 113, 2586, 2009
Dielectric and conductometric properties of differently flexible polyions: a scaling
approach
Simona Sennato, Domenico Truzzolillo, and Cesare Cametti
Dipartimento di Fisica, Università di Roma La Sapienza and CRS CNR-INFM SOFT Piazzale
A. Moro 5, I-00185 - Rome (Italy)
simona.sennato@roma1.infn.it
We investigated the d.c. electrical conductivity of aqueous solutions of polyelectrolytes of
different chemical structures, different flexibility and different molecular weight, over an
extended concentration range, from dilute to the concentrated regime [1,2]. The electrical
conductivity was analyzed in the framework of the scaling theory of polyelectrolyte solutions [3]
and the fraction of free counterions released into the aqueous phase, thanks to the ionization of
the ionic groups of the polyion chains, was determined. Our results show that the counterion
condensation strongly varies as a function of the polyion concentration, giving support to the
fact that the effective charge of a polyion chain depends on the polyion concentration regime.
Moreover, the distribution of free counterions in the bulk solution is influenced by the presence
and, even more, by the conformation of neighbouring chains in the solution. The intermediate
dielectric relaxations associated with the counterion polarization were characterized by the

dielectric strength ∆ε and the relaxation frequency ν, whose dependence on the polyion
concentration is governed by exponents that, according to the concentration regime experienced,
are in very good agreement with the ones determined by means of the zero-shear viscosity
measurements.
[1] D. Truzzolillo, C. Cametti, S.Sennato, PCCP 11:1780, 2009
[2] D Truzzolillo, F Bordi, C Cametti, S Sennato, Phys. Rev. E, 79, 011804, 2009
Molecular dynamics of the mono, di and polysaccharides studied by dielectric
spectroscopy
K. Kaminski 1 , P. Wlodarczyk 1 . M. Paluch 1 ,J. Ziolo 1 , K.L. Ngai 2
1
Institute of Physics, Silesian Univ., ul. Uniwersytecka 4, 40-007 Katowice, Poland
2
Naval Research Laboratory, Washington DC 20375-5320, USA
Broadband dielectric relaxation studies were performed on the carbohydrates at ambient and
elevated pressures. Dielectric loss spectra obtained at p=0.1MPa revealed presence of the two
relaxation modes in the liquid phase of the D-fructose and D- glucose. The faster one is
structural relaxation which governs liquid-glass transition and the slower one, not observed until
now, can be assigned to the long range density ordering leading to formation of the clusters. In
the glassy state of the mono-, di- and polysaccharides two secondary relaxation processes can be
detected. The faster one (γ) has the same dielectric characteristic in all carbohydrates. Thus it
was assumed that the same molecular motions govern this process. Pressure experiments
showed that γ- relaxation is insensitive to pressure. Hence it is relaxation of intramolecular
origin. Contrast situation was noted in the case of slower secondary relaxation (β). Pressure
measurements indicated that this process can be of intermolecular origin. However we also

showed that β relaxation in disaccharides and polysaccharides is related to the motions of the
monosaccharide units around glycosidic linkage. Thus activation energy of the β- relaxation can
be direct measure of the rigidity of the di or polysaccharides. Finally we present dielectric loss
spectra recorded in acethyl derivative of the disaccharide maltose and compared to that
measured for maltose.
MECHANISMS FOR THE TEMPERATURE-DEPENDENT DYNAMICS OF PROTEIN
HYDRATION WATERS: NMR SPECTROSCOPY AND MD SIMULATION STUDIES
Sorin Lusceac and Michael Vogel
Institut für Festkörperphysik, Technische Universität Darmstadt, Hochschulstraße 6, 64289
Darmstadt, Germany
michael.vogel@physik.tu-darmstadt.de
We use NMR spectroscopy and MD simulations to study the temperature-dependent dynamics
of water in the hydration shells of myoglobin, elastin, and collagen. All results show that the
hydration waters exhibit similar dynamical behaviors when using comparable hydration levels
of h=0.2-0.5 [1-3]. Water dynamics is characterized by strongly nonexponential correlation
functions and, in the deeply supercooled regime, the correlation times follow an Arrhenius law
with activation energy Ea≈0.5 eV. Although the temperature dependence may be stronger in the
weakly supercooled regime, including the possibility of non-Arrhenius behavior, we do not
observe a sharp fragile-to-strong transition at T≈220 K. However, our experimental and
computational data consistently show that the mechanisms for the water motion continuously
change upon cooling. Specifically, the hydration waters exhibit small-step translational
diffusion and large-step translational jumps above and below T≈220 K, respectively. Likewise,
the rotational motion is isotropic at high temperatures and restricted at low temperatures. The
latter water dynamics involves anisotropic large-angle jumps, probably strongly distorted π flips.
MD data reveal that changes of the motional mechanisms are accompanied by an increase of
order in the hydrogen-bond network at the protein-water interfaces.
[1] M.Vogel, Phys. Rev. Lett., 101, 225701, 2008
[2] S.A. Lusceac, M.R. Vogel, and C.R. Herbers, arXiv:0904.4424
[3] M. Vogel, arXiv:0902.3520

FREQUENCY DEPENDENCE OF THE NEARLY CONSTANT LOSS EFFECT AS
REVEALED BY SODIUM BORATE GLASSES AT CRYOGENIC TEMPERATURES
D. Laughman (1), K. Funke (1)
(1) Institut für Physikalische Chemie and SFB 458, Westfaelische Wilhelms-Universitaet,
Corrensstrasse 30, D-48149, Muenster, Germany
k.funke@uni-muenster.de
The ubiquity of the nearly constant loss (NCL) effect was popularized by Nowick in 1991 when
he declared it to be a ‘new universality’ after experimentally verifying its presence in a number
of dissimilar disordered materials [1]. Initially, the term NCL was limited in its use to describe a
nearly frequency-independent dielectric loss, typically observed at low temperatures or
sufficiently high frequencies. Subsequently, studies showed that NCL results from the localized
dynamics of charged species influenced by Coulombic interactions with one another. Model
studies by Dieterich that revealed the NCL is more completely described by a frequencydependent
conductivity in a log-log plot which assumes a slope of two at low frequencies,
transitioning to a slope of one, and finally a slope of zero with increasing frequency [2]. This
three-staged frequency dependence has recently been verified experimentally, in a study of
nominally pure amorphous boron oxide containing traces of water [3]. Experimental evidence
for several sodium borate glasses is now presented which shows how the dynamics of sodium
ions at cryogenic temperatures provide further insight into the frequency-dependence of NCL.
Methods for isolating the low temperature NCL from network and hopping related dynamics
will be discussed thus illustrating the rich complexities defining the frequency- and
temperature-dependence of the conductivity of disordered ion-conducting materials.
[1] W. K. Lee, J. F. Liu and A. S. Nowick, Physical Review Letters, 67, 1559, 1991
[2] T. Hoehr, P. Pendzig, W. Dieterich and P. Maass, Phys. Chem. Chem. Phys., 4, 3168, 2002
[3] D. Laughman, R. Banhatti and K. Funke, Phys. Chem. Chem. Phys., 11, 3158, 2009
THE TEMPERATURE DEPENDENCE OF FREE VOLUME IN PHENYL
SALICYLATE AND ITS RELATION TO STRUCTURAL DYNAMICS: A POSITRON
ANNIHILATION LIFETIME AND PRESSURE-VOLUME-TEMPERATURE STUDY.
G. Dlubek(1), M. Q. Shaikh(2), K. Raetzke(2), F. Faupel(2), J. Pionteck(3) and M. Paluch(4).

1) ITA Institute for Innovative Technologies, Köthen/Halle, Wiesenring 4, D-06120 Lieskau
(Halle/S.), Germany.
2) Institute for Materials Science, Chair for Multi-component Materials, Faculty of
Engineering, Christian-Albrecht-University of Kiel, D-24118 Kiel, Germany.
3) Leibniz Institute for Polymer Research Dresden, Hohe Strasse 6, D-01069 Dresden,
Germany.
4) Institute of Physics, Silesian University, Uniwersytecka 4, 40-007 Katowice, Poland.
e-mail: msh@tf.uni-kiel.de
Positron Annihilation Lifetime Spectroscopy (PALS) and Pressure-Volume-Temperature (PVT)
experiments were performed to characterize the temperature dependent microstructure of the
hole free volume in the low molecular weight glass-former phenyl salicylate (Salol). The
volume distribution of sub-nanometer size holes, characterized by its mean and standard
deviation σh, was calculated with the help of PALS data. Crystallization of the amorphous
sample was observed in the temperature range above 250 K, which leads to a vanishing of the
positronium formation. The positronium signal recovered after melting at 303 K. A combination
of PALS with PVT data enabled us to calculate the specific density, Nh’, the specific volume, Vf,
and the fraction of holes, fh, in the amorphous state. From comparison with dielectric
measurements in the temperature range above TB = 265 K, it was found that the primary
structural relaxation slows down with temperature, faster than the shrinkage of the hole free
volume Vf would predict, on the basis of the Cohen-Turnbull (CT) free volume theory. CT plots
can be linearized by replacing Vf of the CT theory by (Vf - ∆V), where ∆V is a volume correction
term. This was interpreted as indication that the lower wing of the hole size distribution contains
holes too small to show a liquid-like behavior in their surroundings.
UNIVERSAL SCALING BETWEEN RELAXATION AND CAGED DYNAMICS IN
GLASS-FORMING LIQUIDS, POLYMERS AND MIXTURES
A. Ottochian (1), C. De Michele (2,3), and D. Leporini (1,3)
(1) Dipartimento di Fisica 'Enrico Fermi', Universita` di Pisa, Largo B. Pontecorvo 3, I-56127
Pisa, Italy

(2) Dipartimento di Fisica, Universita` di Roma, 'La Sapienza' Piazzale Aldo Moro, 2, 00185
Rome, Italy
(3) INFM-CRS Soft, Piazzale Aldo Moro 2, 00185 Roma, Italy
dino.leporini@df.unipi.it
On approaching the glass transition, particles become trapped in transient cages -in which they
rattle on picosecond timescales- formed by their nearest neighbours; the particles spend
increasing amounts of time in their cages as the average escape time, or structural relaxation
time, increases from a few picoseconds to thousands of seconds through the transition. We show
computer simulations that, when compared with experiments, reveal the universal correlation of
the structural relaxation time (as well as the viscosity) and the rattling amplitude from glassy to
low-viscosity states for molecular liquids and polymers over about eighteen decades of
relaxation times [1]. According to the emerging picture, the glass softens when the rattling
amplitude exceeds a critical value, in agreement with the Lindemann criterion for the melting of
crystalline solids and the free-volume model for polymers.
[1] L.Larini, A.Ottochian, C. De Michele, and D.Leporini, Nature Physics, 4, 42, 2008
Hidden Macroscopic Shear Elasticity in Viscous Liquids
L. Noirez, H. Mendil-Jakani, P. Baroni
Laboratoire Léon Brillouin (CEA-CNRS), Ce-Saclay, 91191 Gif-sur-Yvette Cedex, France
Liquids are condensed states of the matter. How a condensed state is flowing? How
the energy stored in the condensed state accommodates to flow? Here, we show that it is
possible to probe this cohesive energy. We measure for the first time, the macroscopic
shear elasticity so far hidden in the liquid state[1]. To extract this solid-like contribution,
we examine the dynamic response of viscous liquids, molten polymers submitted to a small
(linear) mechanical oscillatory shear solicitation. The scan versus oscillation frequency
allows the construction of the dynamic profile of the sample displaying the elastic shear
modulus (G’) and the viscous modulus (G”). The identification of a non-vanishing
macroscopic shear elasticity (G’ -> G0 when the frequency vanishes) implies that so far
neglected long range correlations contribute to the flow properties. This identification of
macroscopic elastic properties should allow to understand and to anticipate multiple

phenomena (over large time scale relaxations, spectacular instabilities, spurt effect, "sharkskin"
instability[2]) incomprehensible with respect to the conventional scheme, particularly
visible in highly viscous liquids like glass-former liquids or polymeric melts. A special
attention is paid to polymers in the light of the elegant formalisms of Rouse and
reptation[3], and of the experimental description[4] interpreting the shortest to the largest
molecular length dynamics. In the viscoelastic description, the macroscopic dynamic
behaviour is representative of the elementary molecular dynamics. This elementary
dynamic is defined by the “terminal time”, the ultimate limit before each elementary
molecule flows. This single chain picture which is usually adopted, neglects intermolecular
interactions and thus ignores the cohesive nature of the fluidic state.
References
[1] H. Mendil, P. Baroni, L. Noirez, Eur. Phys. J. E 19 (2006) 77, L. Noirez, H. Mendil, P.
Baroni, in press Polymer Int. (2009).
[2] M.D. Graham, Chaos, 9 (1999) 154.
[3] PG de Gennes, Scaling Concepts in Polymer Physics, Cornell university Press (1979).
[4] M. Doi, S.F. Edwards, The Theory of polymer Dynamics, Clarendon Press, Oxford
(1986).
FTIR STUDY ON RECIPROCAL PROTEIN↔MATRIX EFFECTS IN DRY
AMORPHOUS SACCHARIDE SYSTEMS
S. Giuffrida (1), G. Cottone (1) and L. Cordone (1)
(1) Dipartimento di Scienze Fisiche ed Astronomiche, Università degli Studi di Palermo, Via
Archirafi 36, I-90123 Palermo, Italy
giuffrid@fisica.unipa.it
Saccharides are widely used as protecting agents for biostructures. An inhibited dynamics,
dependent on the amount of residual water, has been reported [1] for carboxy-myoglobin
(MbCO) in low-water trehalose matrices. In the same systems, a mutual protein↔matrix
structural and dynamic influence (coupling) has been observed [2], suggesting that the protein-

solvent master/slave model does not apply here. To better characterize the reciprocal effects, we
performed an Infrared Spectroscopy (FTIR) study on the stretching band of the bound CO
molecule (COB) and on the Water Association Band (WAB) in dry amorphous saccharide
matrices, with different sugars and protein/sugar ratios. Such bands have already been exploited
for the simultaneous study of the thermal evolution (20-300K) of the embedded biostructure and
of the matrix; indeed, the COB is a widely used protein spectroscopic marker, and the WAB a
very sensitive probe for the low-water matrix. In all the systems, the reduction of sugar content
is reflected in the progressive increase of the A0 component of the COB, as expected, and the
extent of such increase is peculiar of the each sugar. At variance, the WAB shows an unusual
dependence on the protein/sugar ratio, ascribed to changes in the strength of the hydrogen-bond
network. This behavior allows to make a classification on the basis of protein-solvent coupling.
We suggest a strong coupling is needed for an effective protection of the protein.
[1] L. Cordone, G. Cottone, S. Giuffrida, G. Palazzo, G.Venturoli, C. Viappiani, Biochim.
Biophys. Acta-Prot. Proteom. 1749, 252, 2005 and references therein.
[2] S. Giuffrida, G. Cottone, L. Cordone, Biophys. J. 91, 968, 2006
DIELECTRIC STUDIES OF SEGMENTAL AND GLOBAL CHAIN DYNAMICS IN
POLYETHERS HAVING DIFFERENT INTERMOLECULAR INTERACTIONS AND
ARCHITECTURE
S. Kripotou, A. Kyritsis
Department of Physics, National Technical University of Athens, Zografou Campus, 15780
Zografou, Greece
roulak@central.ntua.gr
Segmental and global chain motions of polyethers are investigated by means of Broadband
Dielectric Spectroscopy. The relationship between the local segmental and the global chain
dynamics, and the factors which affect this relationship is an unresolved problem in the study of
condensed matter [1-3]. In the present study the influence of chemical structure, architecture
and intermolecular interactions on the dynamics of the α (segmental motion) and the normal
mode (global chain motion) relaxations are investigated. Poly(propylene oxide) and
poly(butylene oxide) with different chain ends (-OH, -Me, -NH2) and different architectures
(linear, three armed and cyclic) are investigated. Information on the relaxation time, the
relaxation strength and the shape of the relaxation function are extracted by fitting the dielectric
data for both relaxations with model functions. The results are discussed in terms of the timetemperature
superposition breakdown and the universality of chain dynamics in polymers [1-3].

[1] K.L. Ngai, D.J. Plazek, Rubber Chem. Tech. Rubber Rev., 68, 376, 1995
[2] Y. Ding, A.P. Sokolov, Macromolecules, 39, 3322, 2006
[3] K.L. Ngai, D.J. Plazek, C.M. Roland, Macromolecules, 41, 3925, 2008
RELATIONSHIP BETWEEN THE GLASS TRANSITION OF MYOGLOBIN-WATER-
DISACCHARIDE SYSTEMS AND PROTEIN THERMAL DENATURATION
G. Bellavia(1), G. Cottone(1), S. Giuffrida(1), L. Cordone(1), A. Cupane(1)
(1) Dipartimento di Scienze Fisiche e Astronomiche. – University of Palermo, Via Archirafi, 36,
I-90123, Palermo, Italy
bellavia@fisica.unipa.it
We report a Differential Scanning Calorimetry study on the relationship between the thermal
denaturation (Tden) of ferric myoglobin in water/sugar mixtures containing non–reducing
(trehalose [1], sucrose) or reducing (maltose, lactose) disaccharides, and the glass transition
temperature of the systems (Tg). At high water content, homogeneous glass formation does not
occur; regions of glass form, whose Tg does not vary with the sugar content, and the sugar
barely affects the myoglobin Tden. At suitably low water content, by lowering the temperature,
the whole systems undergo glass transition whose Tg is determined by the water content,
following the Gordon Taylor behaviour; Tden increases by decreasing the hydration regardless of
the sugar, such effect being entropy driven. The presence of the protein is found to lower the Tg
with respect to binary water-disaccharide systems [2]. Furthermore, for non–reducing sugars,
plots of Tden vs. Tg give linear correlations, while for reducing sugars data exhibit an erratic
behaviour below a critical water/sugar ratio, which depends on the particular disaccharide. We
ascribe this behaviour to the likelihood that in the latter samples proteins have undergone
Maillard reaction [3] before thermal denaturation.
[1] G. Bellavia, L. Cordone, A. Cupane, J. Therm. Anal. Calor., 95, (2009) 699–702.
[2] Y. Roos, J. Therm. Anal. Calor., 48 (1997) 535–544.
[3] F. Ledl, E. Schleicher, Angewandte Chemie – Int. Ed., 29 (1990) 565–706.
ANHARMONICITY AND ACOUSTICAL PHONONS IN GLASSES

C. Levelut and J. Pelous
Laboratoire des Colloïdes, Verres et Nanomatériaux, Université Montpellier II, place E. Batillon,
cc 69, 34095 Montpellier CEDEX, France
Claire@lcvn.univ-montp2.fr
Mechanical properties of glasses are strongly affected by the structural relaxation around the
glass transition temperature. The identification of chemical composition dependent feature on
the one hand and universal behavior in elastic properties one the other hand are useful for the
understanding of the glass transition phenomenon. Correlations of the elastic properties with the
glass transition temperature Tg, fragility [1,2,3] or Gruneisen constant characteristic of
anharmonicity [4] have been previously proposed and discussed in this framework.
We have collected data obtained by Brillouin scattering experiments in various glasses from low
temperature to Tg in order to identify the different processes responsible of the acoustical
attenuation in glasses. A large plateau observed in a large temperature interval below Tg and
common to the glasses investigated can be attributed to anharmonic process dominant at
hypersonic frequencies. Moreover, using the Poisson ratio calculated from the longitudinal and
transversal sound velocity, correlation of the elastic behavior with fragility is probed. A
Gruneisen parameter has been also deduced and compared to other determinations.
[1] V.N. Novikov and A.P. Sokolov, Nature (London) 431, 961, 2004
[2] V.N. Novikov, Y. Ding and A. P. Sokolov, Phys. Rev. E, 71, 061501, 2005
[3] S. V. Nemilov, Journal of Non-Cryst. Solids, 353, 4613, 2007
[4] B. D. Sanditov, Sh. B. Tsydypov and D.S. Sanditov, Acoustical Physics, 53, 594, 2007
RHEOLOGY OF COLLOIDAL SUSPENSIONS AND MODE-COUPLING THEORY
M. Siebenbuerger (1), J. J. Crassous (1), and M. Ballauff (1), D. Hajnal (2), O. Henrich (2), and
M. Fuchs (2)
(1) Physikalische Chemie I, University of Bayreuth, 95440 Bayreuth, Germany
(2) Fachbereich Physik, Universität Konstanz, 78457 Konstanz, Germany

matthias.ballauff@uni-bayreuth.de
We present a comprehensive rheological study of a suspension of thermosensitive particles
dispersed in water. The volume fraction of these particles can be adjusted by the temperature of
the system in a continuous fashion. Due to the finite polydispersity of the particles (standard
deviation: 17%), crystallization is suppressed and no fluid-crystal transition intervenes. Hence,
the moduli G' and G'' in the linear viscoelastic regime as well as the flow curves (shear stress as
the function of the shear rate) could be measured in the fluid region up to the vicinity of the
glass transition. Moreover, flow curves could be obtained over a range of shear rates of 8 orders
of magnitude while G' and G'' could be measured spanning over 9 orders of magnitude. Special
emphasis has been laid on precise measurements down to the smallest shear rates/frequencies. It
is demonstrated that mode-coupling theory generalized in the integration through transients
framework provides a full description of the flow curves as well as the viscoelastic behavior of
concentrated suspensions with a single set of well-defined parameters.
SAXS AND FTIR STUDY ON MBCO-SACCHARIDE AMORPHOUS SYSTEMS
A. Longo (1), S. Giuffrida (2), M. Panzica (2), G. Cottone (2) and L. Cordone (2)
(1) Istituto per lo Studio dei Materiali Nanostrutturati (ISMN), CNR, Via Ugo La Malfa 153,
Palermo, I-90146, Italy
(2) Dipartimento di Scienze Fisiche e Astronomiche, Università degli Studi di Palermo, Via
Archirafi 36, Palermo, I-90123, Italy
panzica@fisica.unipa.it
Trehalose is a well-known bioprotecting disaccharide, whose efficiency has been long assessed.
The mechanism of trehalose-based bioprotection is still matter of debate and many theories
have been proposed, which rely mainly on the role of water and on the physical properties of the
external matrix [1,2]. Here we report Small Angle X-Ray scattering (SAXS) and Infrared
Spectroscopy (FTIR) results on carbonmonoxy-myoglobin (MbCO) embedded in amorphous
matrices of trehalose or sucrose, at very low hydration level. SAXS data show the occurrence of
~15 nm local domains in protein-trehalose systems, which are absent in protein-sucrose systems

and in the absence of protein. These domains become larger by increasing the sample hydration.
The comparison between SAXS and FTIR data led us to assign this feature to protein-deprived
regions, which better incorporate water than the protein rich background. We suggest that these
domains might play a buffering role against the daily variations of atmospheric moisture in
anhydrobiotic organisms, giving a hint for rationalizing the superior trehalose protective effects,
in terms of structural properties of the whole protein-sugar system.
[1] J.H. Crowe, Adv. Exp. Med. Biol. 594, 143, 2007 and reference therein
[2] L. Cordone, G. Cottone, S. Giuffrida, J. Phys.: Condens. Matter 19, 205110, 2007
APPLICABILITY OF SUMMERFIELD SCALING AND THE CONCEPT OF TIME-
DEPENDENT ROTATIONAL DIFFUSION TO MODEL RELAXATIONAL
FEATURES IN DIELECTRIC LOSS SPECTRA OF GLYCEROL AND
THIOGLYCEROLS
Radha D. Banhatti, Elisabeth Fellberg, Klaus Funke
Department of Physical Chemistry and SFB 458, University of Muenster, Corrensstr. 28/30, D-
48149, Muenster, Germany.
banhatt@uni-muenster.de
Dielectric loss and conductivity spectra of glycerol, thioglycerol and dithioglycerol have been
measured from above their glass transition temperatures to room temperature and from a few
mHz to a few MHz with a view to see the qualitative difference in their features, due to a
progressive replacement of the OH bonds by SH bonds. Our idea was to test a model developed
by us based on time-dependent rotational diffusion to explain the so-called excess wing feature
which is much under debate in molecular glass-formers and in polymers. During the course of
the investigation, we found the startling result that Summerfield scaling works in all three
systems implying that the DC conductivity and the relaxational features are activated in the
same way. We show that there are exciting implications: a) the model concept works very well
in modelling such scaled dielectric loss spectra; b) the frequency-dependent rotational diffusion
bears the well-known features of the “first universality”; c) both scaling and modelling provide
the first ever insight into the vehicle mechanism proposed for proton conduction. Additionally,
we show that our model of time-dependent rotational diffusion allows us to focus on material
specific features, which helps cast a light on the size scale involved in the rotational process.

LOCAL DYNAMICS OF METALLIC LIQUIDS AND GLASSES
T. Egami (1,2,3), V. A. Levashov (2) and J. R. Morris (1,3)
(1) Department of Materials Science and Engineering, University of Tennessee, TN 37996,
USA
(2) Department of Physics and Astronomy, University of Tennessee, TN 37996, USA
(3) Oak Ridge National Laboratory, Oak Ridge, TN 37831, USA
egami@utk.edu
Why viscosity of a supercooled liquid increases so rapidly with decreasing temperature is one of
the major mysteries in physics of liquids. We examine this question through the spatial and
temporal correlations among the local stress fields. Since viscosity can be given in terms of the
autocorrelation function of shear stress field through the Kubo formula, we express the
macroscopic correlation function by spatial and temporal correlation functions of atomic level
stresses. We show that atoms communicate through dynamic stress fields, and spatial extension
in correlation and lifetime of such fields determine viscosity. Dynamic stress fields are spatially
inhomogeneous, representing dynamic heterogeneity. This work is a part of our effort to
describe the structure dynamics of liquids and glasses through the atomic level stresses, rather
than through the hard-sphere model. At high temperatures the self-energy of the local stress
fields obeys the equipartition theorem [1], suggesting that the dynamics of a liquid is described
by a collection of harmonic oscillators, represented by the atomic level stresses. Together with
the concept of the critical strain for local topological instability, various properties, including
the glass transition [2], can be elucidated. This work was supported by the Department of
Energy, Office of Basic Energy Sciences.
[1] V. A. Levashov, et al., Phys. Rev. B, 78, 064205 (2008).
[2] T. Egami, et al., Phys. Rev. B, 76, 024203 (2007).
MOLECULAR MODELING OF THE GLASS TRANSITION IN
POLY(METHYL)METHACRYLATE BULK AND THIN FILMS
Alexandre BEAUDOIN (1), Noureddine METATLA (1) and Armand SOLDERA (1)
(1)Département de chimie, Université de Sherbrooke, Sherbrooke (Québec) J1K2R1, Canada
Armand.Soldera@USherbrooke.ca
The glass transition (Tg) remains one of great nature mysteries and controversies still exist in the
polymer science field. To this day, no single theoy is suitable to entirely explain this

phenomenom. Many factors affect the value of Tg such as polymer rigidity, interactions,
tacticity and the thickness of the polymer film. Atomistic simulation is of particular interest
since small changes in molecular architecture can be envisioned. However, it covers a very
small domain of time. Nevertheless a spectific procedure has been proposed [1] revealing
reproducibility in simulated Tgs. Moreover these values can be correlated to experimental data
through the established WLF relation [2]. Can this prodecure be applied to the study of variation
of Tg between the bulk and the polymer film [3]? It is the purpose of this poster.
Poly(methyl)methacrylate (PMMA) is then chosen since it offers a special regard to the study of
the glass transition: according to the tacticity of its chain, a different value of Tg is exhibited. By
revealing this difference at the atomistic level, molecular modeling proposes an additional asset
in gaining insight into the perplexing problem of the glass transition phenomenon. This poster
intends to show the agreement between simulated and experimental Tgs. Preliminary results on
simulated PMMA thin films are exposed: they actually show an expected decrease in Tg. Some
hints on the atomistic nature of this phenomena can thus be provided.
[1] N. Metatla and A. Soldera, Mol. Simul., 32, 1187, 2006.
[2] A. Soldera and N. Metatla, Physical Review E, 74, 061803, 2006.
[3] Y. Grohens, L. Hamon, G. Reiter, A. Soldera, and Y. Holl, European Physical Journal E, 8,
217, 2002.
IS THE JOHARI-GOLDSTEIN SECONDARY RELAXATION INTERRELATED TO
THE STRUCTURAL RELAXATION?
Khadra Kessairi (1,2), Simone Capaccioli (1,3), Daniele Prevosto (3), Soheil Sharifi (1), Mauro
Lucchesi (1,3) and Pierangelo Rolla(1,3)
(1) Dipartimento di Fisica, Università di Pisa, Largo Pontecorvo 3, I-56127, Pisa, Italy
(2) PolyLab, Largo Pontecorvo 3, I-56127, Pisa, Italy
(3) CNR-INFM, polyLab, Largo Pontecorvo 3, I-56127, Pisa, Italy
Karima_mn@yahoo.fr
The intermolecular secondary relaxation is considered as an universal feature of the glassy
dynamics and for this reason a possible connection to the structural relaxation and the glass
transition phenomenon is expected [1]. A recent NMR study [2] found direct evidence that α-
and JG β- relaxations are mutually correlated. Following this idea, we studied by broadband
dielectric spectroscopy the JG β-relaxation of rigid polar molecules in an apolar system, over a
wide range of temperature and pressure. Our results showed the overall superposition of the loss

spectra measured at different T-P combinations with an invariant α- relaxation time (τα ): that is,
the shape of the structural relaxation function depends only on τα and τβ. These novel and
model-independent evidences indicate the relevance of the JG relaxation phenomenon in glass
transition.
[1] K. L. Ngai and M. Paluch, J. Chem. Phy., 120, 857, 2004
[2] R. BÖhmer, G. Diezemann, B. Geil, G. Hinze, A. Nowaczyk, M. Winterlich, Phys. Rev. Lett,
97, 35701, 2006
Dynamics of protein and RNA under different hydration environments
1,3,4 J. H. Roh, 1 R. M. Briber, 3 A. Damjanovic, 2 D. Thirumalai, 3 S. A. Woodson, 5 S. Khodadadi
and 5 A. P. Sokolov
1 Department of Materials Science and Engineering, 2 Biophysics Program, Institute For Physical
Science and Technology, University of Maryland, College Park, MD
3 T. C. Jenkins Department of Biophysics, Johns Hopkins University, Baltimore, MD
4 Center for Neutron Research, National Institute of Standards and Technology, Gaithersburg,
MD
5
Department of Polymer Science, University of Akron, Akron, OH
ABSTRACT
Understanding dynamics of biopolymers (protein, RNA, and DNA) under physiological
conditions is critical for unraveling the detailed microscopic mechanism of their biological
functions. Hydration water is an integral part of the biomolecular structure that affects both
dynamics and biological functions. Extensive neutron scattering and computational studies have
suggested that the dynamics of proteins are controlled by the dynamical properties of the
hydration water such as viscosity and fluctuation of the H-bond network. One of the general
views in the field is that solvent “slaves” the dynamics of biomolecules. In this work we
compared dynamics of two different biopolymers (tRNA and protein lysozyme) at different
levels of hydration using quasi-elastic neutron scattering and dielectric spectroscopy. Our
results suggest that the dynamics of tRNA are more strongly affected by hydration water than

that of lysozyme. An increase in hydration water facilitates conformational motions in tRNA
with a significant decrease of relaxation time, while much weaker changes with hydration are
found in lysozyme. Our analysis reveals that amplitude of the motions in fully hydrated tRNA is
about twice larger than those of fully hydrated lysozyme (7 Å for tRNA and 3 Å for lysozyme).
This remarkable difference in dynamical characteristics of the conformational motions
originates from different hydration micro-environments including more free hydrophilic sites in
the tRNA molecule. Our results imply that dynamics of biopolymers is not determined solely by
the dynamics of bulk solvent, but depends on mutual dynamical environments and interactions
between the biopolymers and the hydration water.
NOVEL POLYMER LITHIUM ELECTROLYTES BASED ON IONIC LIQUIDS
B. Huber, B. Roling
Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein Straße, 35032 Marburg,
Germany
huberb@staff.uni-marburg.de
Lithium electrolytes, based on mixtures of alkyl carbonates or non conducting polymers with
lithium salts, have been studied for several years. They are widely used as liquid or gel-like
electrolytes [1].
We report new polyelectrolytes which overcome some of the drawbacks of the systems
mentioned above, as there are leakage problems and physical instabilities of the gels. These
imidazolium bis(trifluoromethanesulfonyl)imide (TFSI) based electrolytes are polymerized
ionic liquids (IL), showing most of the advantages of IL such as thermal and electrochemical
stability as well as high ionic conductivity.
In addition to previous works [2], our major attention is an enhancement of the lithium
transference number which can be achieved by two different strategies: immobilisation of
( n−1)
−
imidazolium cations and advancement of Li −[
TFSI]
complex mobility by using suitable
n
zwitterions [3].
Also the correlation between the microstructure of the polymers and their conductivity
properties were of special interest. In addition to a comprehensive structural polymer analysis,
we investigated the electrochemical and conducting properties by CV, ac impedance
spectroscopy and pulse field gradient NMR.
[1] Passerini et al., J. Electrochem. Soc., 152, A978, 2005

[2] Mecerreyes et al., Electrochem. Comm., 8, 482, 2006
[3] Ohno et al., J. Mater. Chem., 11, 1057, 2001
ION DYNAMICS IN IONIC LIQUIDS: CORRELATION BETWEEN CHARGE
TRANSPORT AND SHEAR FLOW
A. Šantić (1,2), M. Mutke (1,3), R. D. Banhatti (1), W. Wrobel (4), K. Funke (1)
(1) Institute of Physical Chemistry and SFB 458, University of Münster, Corrensstraße 30, D-
48149, Germany
(2) NMR Center, Ruđer Bošković Institute, Bijenička c. 54., 10000 Zagreb, Croatia
(3) NRW <strong>International</strong> Graduate School of Chemistry, University of Münster, Germany
(4) Faculty of Physics, Warsaw University of Technology, Koszykowa 75, 00-662 Warszawa,
Poland
santic@uni-muenster.de
The ion dynamics in three imidazolium-based ionic liquids (ILs), BMIm-BF4, HMIm-BF4 and
BMIm-PF6 have been investigated by measuring the frequency-dependent conductivity and
shear fluidity (inverse viscosity).
For all ILs, DC conductivity and DC fluidity show non-Arrhenius temperature dependence and
superimpose exactly, if their respective inverse temperature axes are slightly shifted. Strikingly,
fluidity taken at a particular temperature corresponds to conductivity taken at a slightly lower
temperature, not only for the DC values, but in the entire frequency range studied. For BMIm-
BF4, these aspects have been analyzed within the framework of the MIGRATION concept [1].
We find that the same activation energy for the elementary displacement of an individual ion is
involved in both flow of charge and shear flow. However, in order to contribute to charge
transport or shear flow, this elementary step of an ion has to be followed by suitable movements
of neighbouring ions. For shear flow, these latter movements need to fulfil more specific
requirements than for flow of charge, which results in slower ion dynamics. In particular, we are
able to show that replacement of the anion (BMIm-PF6) rather than the cation (HMIm-BF4) has
a larger effect in further slowing down the ion dynamics of shear flow. These findings and their
implications will be presented in detail.
[1] A. Šantić, W. Wrobel, M. Mutke, R. D. Banhatti, K. Funke, Phys. Chem. Chem. Phys., 2009,
DOI: 10.1039/B904186A

DYNAMICS OF POLY(VINYL METHYL ETHER) AT THE LIGHT OF THE MODE-
COUPLING THEORY.
S. Capponi(1), A. Arbe(2), F. Alvarez(2,3), J. Colmenero(1,2,3), B. Frick(4), JP Embs(5)
(1)Donostia <strong>International</strong> Physics Center (DIPC), San Sebastián, Spain
(2)Centro de Física de Materiales (CSIC-UPV/EHU) - Materials Physics Center (MPC), San
Sebastián, Spain
(3)Departamento de Física de Materiales (UPV/EHU), San Sebastián, Spain
(4)Institute Laue-Langevin (ILL), Grenoble, France
(5)LNS/ETHZ & PSI, Zurich, Switzerland
sara_capponi@ehu.es
Despite the success of mode-coupling theory (MCT) in describing the behavior of many glassformers,
its applicability to real polymers remains unclear. Here we consider the case of
poly(vinyl methyl ether) (PVME). Fully atomistic molecular dynamics simulations have been
first validated with neutron scattering results. Then, MCT phenomenological predictions have
been consistently checked on the self-correlation functions of different kinds of atoms. The
unusually high value found for the λ-exponent parameter is close to that reported for
polybutadiene [1] and simple polymer models with intramolecular barriers [2]. We speculate a
higher-order transition for real polymers arising from two simultaneous mechanisms for
dynamic arrest: intermolecular packing and intramolecular barriers for conformational changes,
specific of macromolecules [1,2].
[1] Colmenero, J. et al, J. Phys.: Condens. Matter 19, 205127 (2007)
[2] Bernabei, M. et al, Phys. Rev. Lett. 101, 255701 (2008)
ULTRA FINE STRUCTURE OF THE SHORT RANGE ORDER OF THE CU65ZR35
AND CU35ZR65 METALLIC GLASSES
G. Almyras(1), Ch. E. Lekka (2) and G.A.Evangelakis (1)
(1) Department of Physics, University of Ioannina, Ioannina 45110, Greece
(2) Department of Materials Science and Engineering, University of Ioannina, Ioannina 45110,
Greece
gevagel@cc.uoi.gr

We present Molecular Dynamics simulations (MD) results referring to the microstructure of two
representatives CuZr Metallic Glasses (MG) (Cu65Zr35 and Cu35Zr65). From the microscopic
analysis of the glassy structures of both systems we found that they are mainly composed by
small Icosahedral-like clusters (ICO) that are interconnected and/or interpenetrating, in
agreement with previous studies. The detailed exploration of their possible interconnections
revealed that the structural characteristics of the systems may be satisfactorily reproduced by
considering only 13 and 15-atom ICO clusters that are interpenetrating with predefined ways,
thus explaining the existence of the short range order which is a typical characteristic of these
MGs. The approach is based on geometrical considerations for the possible combinations of the
ICO-like clusters in conjunction with the restriction of the systems’ composition. Several
polyicosahedral superclusters (PSC) are thus predicted and subsequently verified by the analysis
of the MD equilibrium configurations. It turns out that there are “magic” numbers for the PSCs
that are dictated from the combination of both the geometry of the interpenetrating ICOs and the
stoichiometry of the system and that these numbers are identical for both compositions, the only
difference being their relative amplitudes. Interestingly, the radial distribution function
calculated by considering only the central atoms of the participating ICOs in the PSCs
reproduces very well the experimental data. The energetic and electronic stability of some
representative small free standing PSCs were further investigated and verified by means of
calculations based on the Density Function Theory. We believe that the present results elucidate
the microstructure of these MGs and that they could be of use for the description of more
complex systems and possibly for the design of new MGs with improved properties.
[1] 1.D.B. Miracle, Nat. Mater. 3, 697, 2004
[2] Ch.E. Lekka, A. Ibenskas, A.R. Yavari and G.A. Evangelakis, Appl. Phys. Lett. 91, 214103,
2007
[3] M. Wakeda, Y. Shibutani, S. Ogata and J. Park, Intermetallics 15, 139, 2007
[4] A.E. Lagogianni, G.A. Almyras, Ch.E. Lekka, D.G. Papageorgiou, G.A. Evangelakis, J.
Alloys and Comp. in press
[5] H.W. Sheng, W.K. Luo, F.M. Alamgir, J.M. Bai and E. Ma, Nature 439 (2006), p. 419
CU-ZR AND CU-ZR-AL CLUSTERS: BONDING CHARACTERISTICS AND
MECHANICAL PROPERTIES
Ch. E. Lekka (1) and G.A.Evangelakis (2)

(1) Department of Materials Science and Engineering, University of Ioannina, Ioannina 45110,
Greece
(2) Department of Physics, University of Ioannina, Ioannina 45110, Greece
chlekka@cc.uoi.gr
We present Density Functional Theory (DFT) calculations results on some representative
clusters (Cu7Zr6 and Cu10Zr5) and their interconnections (touching and interpenetrating). The
choice of these clusters and their combinations is dictated from previous Molecular Dynamics
(MD) simulations results on the Cu60Zr40 model Metallic Glass (MG) where they were found
to be the most abundant microstructural units. In addition, aiming in gaining inside on the
experimental finding referring to properties improvement upon small Al additions in the CuZr
MGs, we performed calculations for the same systems in which Al substitutional atoms were
incorporated into the clusters. In all cases we analyzed the electronic structures and we deduced
the corresponding bonding characteristics. Moreover, in order to reveal the electronic
modifications these systems subsist under mechanical deformation we performed non
equilibrium calculations by applying tensile solicitations and we deduced the basic alterations
that are responsible for the systems’ responses. It turns out that Al has elemental bonding
preference; its presence in the clusters and in their interconnections alters significantly their
electronic structure by introducing new low-energy states, while significant charge transfer
occurs upon mechanical deformation. The present results are in line with the available
experimental findings and provide inside on the fundamental issues that are related with the
improvement of the glass forming ability and of the mechanical properties in the systems that
contain small Al additions.
[1] 1.D.B. Miracle, Nat. Mater. 3, 697, 2004
[2] Ch.E. Lekka, A. Ibenskas, A.R. Yavari and G.A. Evangelakis, Appl. Phys. Lett. 91, 214103,
2007
[3] M. Wakeda, Y. Shibutani, S. Ogata and J. Park, Intermetallics 15, 139, 2007
[4] A.E. Lagogianni, G.A. Almyras, Ch.E. Lekka, D.G. Papageorgiou, G.A. Evangelakis, J.
Alloys and Comp. in press
[5] H.W. Sheng, W.K. Luo, F.M. Alamgir, J.M. Bai and E. Ma, Nature 439 (2006), p. 419
CHAIN DYNAMICS OF CROSS-LINKED EPOXY IN THE VICINITY OF GLASS
TRANSITION
P. H. Lin and R. Khare

Department of Chemical Engineering, Texas Tech University, Lubbock, Texas 79409, USA.
rajesh.khare@ttu.edu
The glass transition temperature of crosslinked epoxy can be altered by more than 100 K by a
change in the crosslinking agent. We have used molecular simulations to study the chain
dynamics in crosslinked epoxy near the glass transition temperature to gain insights into the
molecular mechanisms underlying this phenomenon. Well-relaxed atomistic models of
crosslinked epoxy were created by employing the simulated annealing polymerization approach
that was recently developed by us for efficient construction of these structures [1]. The specific
systems studied consist of diglycidyl ether of bisphenol-A (DGEBA) as the epoxy while the
crosslinker molecules studied were trimethylene glycol di-p-aminobenzoate (TMAB) and
poly(oxypropylene) diamines of different chain lengths. The glass transition temperature of
these crosslinked epoxy structures was determined by monitoring the volume-temperature
behaviour in a stepwise MD cooling run. The chain dynamics of cross-linked epoxy systems
near the glass transition was characterized with respect to the local translational and
orientational mobility. Furthermore, dynamic heterogeneity was also studied by identifying the
mobile and immobile domains in the system by using the approach described in the previous
work [2].
[1] P.H. Lin and R. Khare, Macromolecules, in press.
[2] A.R.C. Baljon, J. Billen, and R. Khare, Phys. Rev. Lett., 93, 255701, 2004.
A STATISTICAL-MECHANICAL THEORY OF SLOW DYNAMICS NEAR THE
GLASS TRANSITION
Michio Tokuyama
World Premier <strong>International</strong> Research Center, Advanced Institute for Materials Research,
Tohoku University, Sendai 980-8577, Japan
tokuyama@fmail.ifs.tohoku.ac.jp
A statistical-mechanical theory of slow dynamics in multi-component glass-forming systems
including colloidal suspensions is presented from a unified point of view. A rigorous
formulation is established for the dynamics of particles by using the Tokuyama-Mori projection
operator method [1]. The diffusion equations for the coherent- and the incoherent-intermediate
scattering functions are derived from a first principle, where the memory functions are
convolutionless in time [2]. By using the mode-coupling theory (MCT) approximation [3], the
memory functions are then calculated analytically. The alternative mode-coupling equations are
thus derived and are compared with the conventional mode-coupling equations based on the

Mori projection operator method [4]. The reason why new equations are required is explained
logically by comparing the simulation results with the solutions of MCT equation. Within the
same formulation, a simple analytic form of the long-time self-diffusion coefficient is also
proposed. The predictions for the control parameter dependence of the long-time self-diffusion
coefficient are shown to be in excellent agreement with available experimental data and
simulation results [5].
[1] M. Tokuyama and H. Mori, Prog. Theoret. Phys. 55 (1976) 411.
[2] M. Tokuyama, to be submitted.
[3] W. Gotze, in Liquids, Freezing and Glass Transition, edited by J. P. Hansen, D. Levesque,
andJ J. Zinn-Justin (North-Holland, Amsterdam, 1991).
[4] H. Mori, Prog. Theoret. Phys. 33 (1965) 423.
[5] M. Tokuyama, Physica A 388 (2009) 3083.
THEORETICAL INVESTIGATION OF IONIC LIQUIDS: THE DYNAMICAL
BEHAVIOR OF IONS THROUGH INTERIONIC INTERATIONS
Tateki Ishida (1)
(1) Department of Theoretical and Computational Molecular Science, Institute for Molecular
Science, 38 Nishigo-Naka, Myodaiji, Okazaki 444-8585, Japan
ishida@ims.ac.jp
Ionic liquids (ILs) are physically and chemically interesting liquids from the viewpoint of the
fact that those are different from molten salts. ILs are consisted of cations and anions and it is
considered that their characteristics are determined by the interionic interaction between both
ionic species. In particular, Coulomb interactions are one of major driving forces to govern
many properties of ILs. Also, polarization effects due to many-body interactions are considered
to be important. Therefore, we focus on the interionic dynamics of an IL, 1-Butyl-3-
Methylimidazolium cation with [PF6] -
, [BMIm][PF6]. With the theoretical and computational
study, we investigate the interionic interaction in the IL and the polarization effects on the
system. We employ computer simulation methods to pursue the understanding of interionic
properties in ILs at molecular level. The interionic dynamics in the IL and the effect of
polarization on the dynamics of the IL system will be shown and discussed with our results by
molecular dynamics simulation methods. (This work is supported in part by the Ministry of
Education, Culture, Sports, Science and Technology (MEXT) of Japan (20031027 (TI)).)

HETEROGENEOUS DYNAMICS OF IONIC LIQUIDS FROM MOLECULAR
DYNAMICS SIMULATIONS
J. Habasaki
Tokyo Institute of Technology, Nagatsuta 4259, Yokohama, Japan
habasaki.j.aa@m.titech.ac.jp
Molecular dynamics simulations have been performed to study the complex and heterogeneous
dynamics of ions in ionic liquids [1,2]. The dynamics of cations and anions in 1-methyl-3-ethyl
imidazolium nitrate (EMIM-NO3) are characterized by van-Hove functions and the
corresponding intermediate scattering functions, Fs(k,t), and elucidated by the trajectories
augmented using singular spectrum analysis (SSA). Change in the slope in a plot of the
diffusion coefficient against temperature is found at around 410 K in the simulation.
Heterogeneous dynamics with the presence of both localized ions and fast ions capable of
successive jumps were observed at long time scales in the self-part of the van-Hove functions
and in the trajectories. Non-Gaussian dynamics are evidenced by the self part of the van Hove
functions and wave number dependence of Fs(k,t), and characterized as Lévy flights [3], where
jumps are not typical ones. Multifractality also contributes to the heterogeneous dynamics as
found in ionically conducting glasses [4].
[1] J. Habasaki and K. L. Ngai, J. Chem. Phys. 129 (2008) 194501.
[2] J. Habasaki and K. L. Ngai, Analytical Sciences 24 (2008) 1321.
[3] M. F. Shlesinger, G. M. Zalavsky and J. Klafter, Nature 363 (1993) 31.
[4] J. Habasaki and K. L. Ngai, J. Chem. Phys. 122 (2005) 214725.
Origin of slow relaxations in super cooled liquids
T. Ekimoto(1), T. Odagaki (2) and A. Yoshimori (1)
(1) Department of Physics, Kyushu University, Fukuoka 812-8581, Japan
(2) Department of Science, Tokyo Denki University, Saitama 350-0394, Japan
T.Ekimoto@cmt.phys.kyushu-u.ac.jp
The free energy landscape (FEL) picture is a useful method for understanding complex systems
in physics, chemistry, and biology. One of the main interests is how the representative point
moves on the rugged free energy surface which is composed of basins and barriers between
them. In the glass transition, the FEL picture [1] explains thermodynamic properties [2]. Hence
it is a challenging problem that how one can understand dynamical properties in the FEL picture.

We analyze the dynamics of the representative point in the FEL on the basis of the Langevin
equation, where the FEL acts as the driving potential. In order to understand the basic relations
between dynamics in the FEL and relaxation processes in super cooled liquids, we employ a
simple two dimensional FEL surface defined by sum of the Gaussian functions; basins are
placed on a regular lattice and we consider stable and meta-stable state. By solving the
Langevin equation numerically, we obtain the mean square displacement, the generalized
susceptibility, and the escape time from basins. We find alpha, Johari-Goldstein (JG), and fastbeta
processes separate as the temperature is reduced; the relaxation time of fast-beta process is
roughly temperature independent and the relaxation process of alpha and JG process strongly
depends on temperature.
[1] T. Odagaki, T. Yoshidome, A. Koyama, and A. Yoshimori, J. Non-Cryst. Solids, 352, 4843,
2006
[2] T. Odagaki and A. Yoshimori , J. Non-Cryst. Solids, 355, 681, 2009
FROM THE COUPLING OF ELEMENTARY SUBSYSTEMS TO AN
UNDERSTANDING OF DYNAMIC HETEROGENEITIES IN A GLASS-FORMING
MODEL SYSTEM
A. Heuer, O. Rubner and C. Rehwald
Institut für Physikalische Chemie, WWU Münster, D-48149 Münster
We analyze the dynamics of the binary Lennard-Jones system via computer simulations for
largely different system sizes (65

and (4), are directly related to observables which can be extracted from the analysis of fourpoint
correlation functions.
[1] O. Rubner, A. Heuer, Phys. Rev. E 78, 011504, 2008.
[2] A. Heuer, J. Phys.: Cond. Mat. 20, 373101, 2008.
Comparative electrical study of CaCu3Ti4O12 glass and ceramics
C. H. Song, Y. S. Yang *
Department of Nanomaterials Engineering, RCDAMP, Pusan National University, Korea,

CaCu3Ti4O12 (CCTO) has attracted much attention due to its high dielectric constant over the wide
temperature range (100-700 K), without showing any ferroelectric phase transition. A number of
theoretical and experimental studies have been performed to elucidate the origin of this large dielectric
constant. One of the very plausible explanations for the large dielectric constant is inter-barrier layer
capacitance. The large dielectric response of CCTO ceramics above room temperature, ranging in the
order of 10 3 ~10 5 has been also found to be very sensitive to the sample preparing conditions. Most
work have been concerned with ceramics, thin films and single crystals but there have been no reports
of CCTO glass. The question then arises as to what the dielectric response in glass where the only
isotropic disordered structural state exists without crystalline grain boundaries. The crystalline phase
in this study is obtained by crystallization of glass, which is the different sample preparation process
from previously known method. In this work we present electrical properties of CCTO glass and
ceramics in the broad temperature range.
[1] C. C. Homes et al, Science 293, 673 (2001)
[2] D. C. Sinclair et al, Appl. Phys. Lett. 80, 2153 (2002)
Email: ysyang@pusan.ac.kr
TEL: +82-51-510-2958, +82-55-350-5837, FAX: +82-55-350-5837
HEAT CAPACITIES OF SIMPLE MOLECULAR GLASSES
S. Tatsumi, S. Aso, Y. Moriya, D. Hosaka, and O. Yamamuro
Institute for Solid State Physics, The University of Tokyo, 5-1-5 Kashiwanoha, Kashiwa, Chiba, 277-
8581, Japan
sk_tatsumi@issp.u-tokyo.ac.jp
How do simple molecules without any intramolecular degrees of freedom show glass transitions? This
is a very important question for elucidating the origin of the glass transition. The largest difficulty in
observing glass transitions of simple molecular systems is competing crystallization on cooling.
Various rapid-cooling methods have been developed to avoid the crystallization on cooling. The most
rapid one is the vapor-deposition (VD) in which sample vapor is deposed on a cold substrate slowly.
The cooling rate of VD method is estimated to be larger than 10 7 K/s in the ideal VD condition. Some
of the earlier calorimetric works [1-3] reported that the glassy states of methanol, butyronitrile, and 1pentene
were realized by the VD method and they gave rise to glass transitions before crystallization.
Recently, we have constructed a novel adiabatic calorimeter which enable us to make vapor-deposition
at 5 K. This temperature is much lower than the previous VD temperature (ca. 40 K). In our
presentation, we will show the structure of the calorimeter and the heat capacity data of some
molecular glasses, which is simpler than those studied before.
[1] M. Sugisaki, H. Suga and S. Seki, Bul. Chem. Soc. Jpn., 41, 2586, 1968
[2] H. Hikawa, M. Oguni and H. Suga, J. Non-cryst. Solids, 101, 90, 1988
[3] K. Takeda, O. Yamamuro and H. Suga, J. Phys. Chem., 99, 1602, 1995

MACROPOROUS POLYMER HYDROGELS FORMED FROM ACRYLATE MODIFIED
POLYVINYL ALCOHOL MACROMERS
A.A. Artyukhov (1), M.I. Shtilman (1), A.P. Fomina (1), D.E. Lesovoy (1), A.N. Kuskov (1), A.M.
Tsatsakis (2) and Α.K. Rizos (3)
(1) D. I. Mendeleyev University of Chemical Technology, 9 Miusskaya Square, Moscow 125047,
Russia
(2) University of Crete, School of Health Sciences, Heraklion 71003, Crete, Greece
(3) University of Crete, Department of Chemistry, and FORTH - IESL, P.O. Box 2208, Heraklion
71003, Crete, Greece
rizos@chemistry.uoc.gr, rizos@iesl..forth.gr
Macroporous polymeric hydrogels for the last several years have found broad application in areas
connected with medicine, especially in such new disciplines as cell and tissue engineering. In the
present work a novel combined approach is proposed for the preparation of polyvinyl alcohol
macroporous hydrogels by cross-linking of polyvinyl alcohol acrylic derivatives in the presence of
heterophase of frozen solvent. The influence of different factors and reaction conditions on the crosslinked
hydrogel formation process was studied. The high yield of products (80-95 %) was observed
when the reaction was realized at temperature range -12 to -18 о С, concentration of macromer 4-12
weight %, and amount of initiator 0.8 - 1.6 mg/ml. Moreover, the equilibrium swelling of synthesized
macroporous hydrogels was investigated and it was shown that the synthesized cross-linked hydrogels
are characterized by high water absorption which is weakly depended on solution pH and ionic force
values.
POSITRON ANNIHILATION AND BROADBAND DIELECTRIC SPECTROSCOPY: A
SERIES OF PROPYLENE GLYCOLS
J. Bartoš (1), O. Šauša (2), M. Köhler (3), H. Švajdlenková (1), P. Lunkenheimer (3), J. Krištiak (2)
and A. Loidl (3)
(1) Polymer Institute of SAS, Dúbravská cesta 9, SK - 842 36 Bratislava, Slovak Republic
(2) Institute of Physics of SAS, Dúbravská cesta 9, SK - 842 28 Bratislava, Slovak Republic
(3) Experimental Physics V, Center for Electronic Correlations and Magnetism, University of
Augsburg, D - 86135 Augsburg, Germany
upolbrts@savba.sk

We report phenomenological analyses of the annihilation behaviour of ortho - positronium (o-Ps)
measured by positron annihilation lifetime spectroscopy (PALS) and the relaxation behaviour
investigated by broad-band dielectric relaxation spectroscopy (BDS) in a series of propylene glycol
glass-formers. These include propylene glycol (PG), dipropylene glycol (DPG), tripropylene glycol
(TPG) and poly (propylene glycol) (PPG 4000). A number of empirical correlations between both the
annihilation and the relaxation quantities have been found. The phenomenological evaluation of the
found quasi–sigmoidal τ 3 −T
dependences reveals the three characteristic PALS temperatures PALS
T g ,
T
PALS
b1
= 1.
18 −1.
28Tg
andT
PALS
b2
= 1.
42 −1.
53Tg
, with the two latter relative temperatures decreasing
with the fragility of the material. The onset of the high-temperature plateau in theτ 3 −T
plot at T b2
occurs when τ 3 matches the mean relaxation time of the primary α - process. In addition, it is
approximately related to a crossover of the α - relaxation time τα (T ) from non - Arrhenius to
Arrhenius character and coincides with the crossovers in the further dielectric parameters, i.e.
relaxation strength and spectral width of the main process in the PG’s samples. Finally, the slighter
bend effect at T b1
in a series of PG’s appears to be related either to the high - frequency tail of the
primary α proces or to the secondary γ relaxation. In summary, all the empirical coincidences further
support a very close connection between the PALS response and the dielectric relaxation behavior in a
series of propylene glycol glass - forming systems.
ANOMALY OF THE ROTATIONAL NONERGODICITY PARAMETER OF GLASS
FORMERS PROBED BY HIGH FIELD ELECTRON PARAMAGNETIC RESONANCE
V. Bercu (1,2,3), M. Martinelli (2), C. A. Massa (2), L. A. Pardi (2), E. A. Rössler (4), and D. Leporini
(1,5)
(1) Dipartimento di Fisica “Enrico Fermi,” Università di Pisa, Largo B. Pontecorvo 3, I-56127 Pisa,
Italy
(2) IPCF-CNR, via G. Moruzzi 1, I-56124 Pisa, Italy
(3) Department of Physics, University of Bucharest, Magurele, RO-76900 Bucharest, Romania
(4) Experimentalphysik II, Universität Bayreuth, Universitätsstraße 30, D-95440 Bayreuth, Germany
(5) INFM-CNR, Largo B. Pontecorvo 3, I-56127 Pisa, Italy
dino.leporini@df.unipi.it
Exploiting the high angular resolution of high field electron paramagnetic resonance measured at 95,
190, and 285 GHz we determine the rotational nonergodicity parameter of different probe molecules
in the glass former o-terphenyl and polybutadiene in a model-independent way [1]. Our results clearly
show a characteristic change in the temperature of the nonergodicity parameter proving a rather sharp
dynamic crossover in both systems, in contrast to previous results from other techniques.

[1] V.Bercu, M.Martinelli, C.A.Massa, L. A. Pardi, E.A Rössler and D.Leporini, J.Chem.Phys.,
129, 081102 (R), 2008
ESR EVIDENCE FOR TWO COEXISTING LIQUID PHASES IN DEEPLY SUPERCOOLED
BULK WATER
D. Banerjee (1), S.N. Bhat (1), S.V. Bhat (1) and D. Leporini (2)
(1) Department of Physics, Indian Institute of Science, Bangalore 560 012, India
(2) Dipartimento di Fisica "Enrico Fermi", Universita’ di Pisa, Largo B. Pontecorvo 3, I-56127 Pisa,
Italy and SOFT-INFM-CNR, Largo B. Pontecorvo 3, I-56127 Pisa, Italy
dino.leporini@df.unipi.it
Using Electron Spin Resonance spectroscopy (ESR), we measure the rotational mobility of probe
molecules highly diluted in deeply supercooled bulk water and negligibly constrained by the possible
ice fraction [1]. The mobility increases above the putative glass transition temperature of water, Tg
=136 K, and smoothly connects to the thermodynamically stable region by traversing the so called 'no
man's land' (the range 150-235 K) where it is believed that the homogeneous nucleation of ice
suppresses the liquid water. Two coexisting fractions of the probe molecules are evidenced. The two
fractions exhibit different mobility and fragility, the slower one is thermally activated (low fragility)
and is larger at low temperatures below a fragile-to-strong dynamic crossover at about 225 K. The
reorientation of the probe molecules decouples from the viscosity below 225 K.
[1] D. Banerjee, S. N. Bhat, S. V. Bhat, D. Leporini, Proceedings of the National Academy of
Sciences of the United States of America, in press.
DIELECTRIC PROPERTIES OF BLOCK COPOLYMERS BASED ON PVDF AND
POLY(CYANO COMONOMERS) BLOCKS
A. Meskini 1,2 *, M. Raihane 1 , I. Stevenson-Royaud 2 , G. Boiteux 2 , G. Seytre 2 , B. Ameduri 3 ,
1) Laboratoire de Chimie Bioorganique et Macromoléculaire- F.S.T - Avenue Abdelkrim Khattabi, BP
549, 40000 Marrakech, Morocco
2) Laboratoire des Matériaux Polymères et des Biomatériaux, Bât. ISTIL, 15 Bd. Latarjet, 69622,
Villeurbanne, France

3) Ingénierie et Architectures Macromoléculaires, ICG, Ecole Nat. Sup. de Chimie de Montpellier, 8
Rue Ecole Normale, 34296 Montpellier, France
meskini@gmail.com
The syntheses of poly(vinylidene fluoride)-b-poly(AN, MAN, VCN) block copolymers, using the
iodine transfer polymerization (ITP) of acrylonitrile (AN), méthacrylonitrile (MAN) and vinylidene
cyanide (VCN), in the presence of PVDF-I, are presented. In a first step, the ITP of vinylidene fluoride
(VDF) with C6F13I initiated by tert-butyl peroxypivalate is achieved. This ITP led to two different
isomeric oligomers (PVDF-I) bearing either -CH2I or –CF2I end-groups. Second step, those
fluorinated blocks were used latter as macromolecular chain transfer agents to achieve the ITP with
cyanide monomers. The synthesized samples were characterized by 19 F and 1 H NMR, SEC, wide angle
X-ray diffraction, TGA end DSC. The influence of the copolymer compositions on dielectric
properties has been investigated. Dielectric analyses show several relaxations processes associated
with long-range molecular motions near the glass transition temperatures of both blocks. These
behaviors are discussed in terms of molecular interaction and mobility as a function of composition.
Dynamics of an ergodic to non-ergodic phase transition within a long-range ordered phase
J. Ll. Tamarit (1), L.C.Pardo (1), M. Zuriaga (2), P. Lunkenheimer (3), N. Veglio(1), F.J. Bermejo (4),
M. Barrio(1), and A. Loidl (3)
(1) Grup de Caracterització de Materials, Department of Physics and Nuclear Engineering, Group of
Characterization of Materials, ETSEIB, Diagonal 647, Universitat Politècnica de Catalunya,
Barcelona, Spain
(2) IFFAMAF, Facultad de Matemática, Astronomía y Física, Universidad Nacional de Córdoba,
Ciudad Universitaria, 5000 Córdoba, Argentina
(3) Experimental Physics V, Center for Electronic Correlations and Magnetism, University of
Augsburg, 86135 Augsburg, Germany
(4) CSIC - Department of Electricity and Electronics, University of the Basque Country, P.O. Box 664,
48080 Bilbao, Spain
jose.luis.tamarit@upc.edu
According to the original work of Johari and Goldstein [1], secondary relaxation processes not coming
from intramolecular relaxations are know as a universal feature of disordered phases. In general, such
β-processes are assigned to regions with lower density where part of the molecules are located [2] or

to small-angle reorientations performed by all the molecules [3]. In this work a new microscopic
picture is presented giving rise to the same macroscopic properties. Halogenomethanes CBr2Cl2 and
CBrCl3 are known to display a glass-like transition within their low-temperature monoclinic “ordered”
phases where strongly restricted reorientational motions appear. This transition from the ergodic to the
non-ergodic state is associated with the freezing of the exchange positions between Cl and Br atoms.
The dynamics of these simple globular-shaped and rigid molecules has been explored by dielectric
spectroscopy and nuclear quadrupole resonance (NQR). Information on the origin of α- and βrelaxations
in the dielectric spectra is obtained via the investigation of the isomorphous phase of CCl4
by NQR. A new microscopic mechanism underlying the glassy dynamics is proposed: The four
molecules in the asymmetric unit cell are dynamically non-equivalent with respect to their molecular
environment and thus perform jumps with different time scales, which are identified with the two
relaxation processes.
[1] G. P. Johari and M. Goldstein, J. Chem. Phys. 53 (1970) 2372.
[2] G. P. Johari, Ann. N.Y. Acad. Sci. 279 (1976) 117.
[3] F. H. Stillinger, Science 267 (1995) 1935.
DISTANCE MATRIX ANALYSIS OF THE MONOMER DYNAMICS IN POLYMER MELTS
F. Puosi (1), A. Ottochian (1) and D. Leporini (1,2)
(1) Dipartimento di Fisica 'Enrico Fermi', Universita` di Pisa, Largo B. Pontecorvo 3, I-56127 Pisa,
Italy
(2) INFM-CRS Soft, Piazzale Aldo Moro 2, 00185 Roma, Italy
francesco.puosi@df.unipi.it
The trajectories of a system of particles can be indirectly visualized by means of the so-called distance
matrix, i.e. the squared displacement of a particle between two different times. We applied this
technique to the analysis of the monomer dynamics in Molecular Dynamics computer simulations of a
polymer melt. The graphical plot of the distance matrix shows the presence of well defined squared
regions where the value of the matrix is almost constant, corresponding to the permanence of the
particles close to one region in space for a relatively large amount of time. The origin of this structure
can be identified with the trapping of particles, on approaching the glass transition, in transient cages
formed by the nearest neighbors where they exhibits rattling motions on picosecond timescales. The
escape of a particle from its cages takes places with large displacement on a small time interval,
involving particles up to its second correlation shell. In order to make more clear this kind of motion
we have considered the self part of the Van Hove function, the distribution of the displacement of a
particle, for two different timescales corresponding to the vibrational motion and the structural
relaxation.

QUASIELASTIC NEUTRON SCATTERING STUDY ON THERMAL GELATION IN
POLYSACCHARIDE AQUEOUS SOLUTIONS
N. Onoda-Yamamuro (1), H. Nomura (1) and O. Yamamuro (2)
(1) College of Science and Engineering, Tokyo Denki University, Hatoyama, Hiki-gun, Saitama 350-
0394, Japan
(2) Institute for Solid State Physics, University of Tokyo, 5-1-5 Kashiwanoha, Kashiwa, Chiba 277-
8581, Japan
yamamuro@u.dendai.ac.jp
Thermoreversible gelation of polymer hydrogels are driven by various cooperative non-covalent
interactions. The gelation happens on heating or cooling depending on the interctions.
Methylcellulose gels on heating owing to hydrophobic interactions. Agarose gels on cooling owing to
hydrogen bond formation. Kappa-carrageenan gels on cooling owing to hydrogen bond formation and
week electrostatic interaction. It is our ultimate interest whether the dynamics of local and
microscopic motion of polymer and water molecules changes or not when macroscopic dynamics
changes on thermal gelation. We have studied the dynamics of water and polymer molecules in these
polysaccharide aqueous solutions by quasi-elastic neutron scattering (QENS) [1]. The dynamic
structure factor, S(Q,E), was fitted well to the sum of the quasielastic (Lorentzian) and elastic
components. The self-diffusion coefficient D of water molecules was obtained from the Qdependence
of the HWHM of the Lorentzian function, while the mean square displacement of
polymer molecules was obtained from the Q-dependence of the elastic intensity. The parameter
abruptly decreased and D bent around the gelation temperature. The present results revealed that the
microscopic motions of both water and polymer molecules in these polysaccharide aqueous solutions
give rise to dynamical slowing down on thermal gelation.
[1] N. Onoda-Yamamuro, O. Yamamuro, Y. Inamura and H. Nomura, Physica B Condens. Matter,
393, 158, 2007
POWER LAW BEHAVIOR IN DENSITY OF FRACTAL NANO PARTICLE
AGGREGATIONS FORMED ON A FERROFLUID SURFACE
I. Takahashi and K. Ueda
Faculty of Science and Technology, Kwansei Gakuin University, Sanda 6691337, Japan
z96019@kwansei.ac.jp
Fine particles under confined geometry often show unexpected distributions and dynamics. Structural
studies on fine particles confined in narrow gaps (2D), tubes (1D) and those on surface and interface
of thin films have thus attracted considerable attention. In the present study, by utilizing surface-

sensitive X-ray diffraction techniques, a self-organized structure of paramagnetic nano particles
densely formed on a ferrofluid surface is investigated [1]. Diffuse scattering component of X-ray
reflectivity reveals fractal aggregations on the free surface with fractal dimension of 1.3, indicating a
chain-like structure of paramagnetic fine particles with diameter of 11 nm [2]. Under magnetic field
normal to the surface, we found that particle density at the surface shows a power law decay given by
1/f a within the range between 1 Hz to 10000 Hz, where f is frequency of the magnetic field. We
consider that the decay of the surface layer at very low frequencies has some relationship with a glassy
nature of the fractal aggregations.
[1] I. Takahashi et al., Journal of Physics: Condensed Matter Vol.10 (1998) 4489-4497
[2] I. Takahashi et al., Journal of Applied Crystallography Vol.36 (2003) 244-248
NANOMECHANICAL THERMAL ANALYSIS OF POLYSTYRENE CONFINED TO
NANOPOROUS ALUMINA
Moonchan Lee, Sangmin Jeon*
Department of Chemical Engineering, Pohang University of Science and Technology, Pohang, Korea
*jeons@postech.ac.kr
Structure and morphology of polymers in nanoscale confinement have recently attracted considerable
interest due to their unique segmental dynamics different from properties in bulk systems. We
investigated the confinement effect on glass transition temperature of polystyrene(PS) using
nanoporous alumina microcantilever. An anodic aluminum oxide (AAO) layer was fabricated on an
aluminum specimen through two-step anodization method, followed by AAO cantilever fabrication
using photolithography and electrochemical etching. Each resulting AAO cantilever has hexagonally
ordered nanowells with high aspect ratio. The nanowells of AAO cantilever were then filled with PS
by drop-casting method and the variations with temperature in the deflection and resonance frequency
of the PS-filled AAO cantilever were measured.
[1] N. Jung, H. Seo, D. Lee, C. Ryu and S. Jeon, “Nanomechanical thermal analysis of the glass
transition of polystyrene using silicon cantilevers”, Macromolecules, 41, 6873, 2008.
[2] P. Lee, J. Lee, N. Shin, K. Lee, D. Choi, W. Hwang, H. Park, D. Lee and S. Jeon,
“Microcantilevers with nanochannels”, Advanced Materials, 20, 1732, 2008.

Low temperature thermal and acoustic properties of permanently densified vitreous GeO2
Giovanni Carini Jr, Giovanna D’Angelo, Gaspare Tripodo,
Dipartimento di Fisica, Università di Messina, Salita Sperone 31, I-98166 Messina, Italy
Laura Orsingher, Aldo Fontana
Dipartimento di Fisica, Università di Trento, Via Sommarive 14, 38050 Povo, Trento, Italy
INFM CRS-SOFT, c/o Università di Roma “La Sapienza”, 00185, Roma, Italy
Samples of glassy GeO2, a prototype of strong glasses, were permanently densified by pressures up to
6 GPa achieving more than 20% of densification. Vitreous germania was prepared by conventional
melt-quenching and then densified using a HT-HP multi-anvil apparatus. Cylindrical blocks of glassy
GeO2 were compressed at 2, 4 and 6 GPa and then heated at 673 K for 2 minutes under pressure
achieving densities of 3.994 g/cm 3 , 4.21 g/cm 3 and 4.52 g/cm 3 , respectively. The simultaneous use of
hydrostatic pressure and high temperature in the process ensured the homogeneity of the glasses and
the permanent densification of the samples. No modification of the density and of the structure has
been detected after one year. Density dependence of the low temperature properties of these glasses
were investigated by means of calorimetric and ultrasonic measurements over the temperature range
between 0.4 K and 300 K.
When reported in a plot of Cp/T 3 vs T over the range between 2 K and 25 K, the specific heat Cp shows
a bump which shifts towards higher temperatures and decreases markedly in magnitude with
increasing density. At temperatures below 2 K, an additional contribution over that predicted by the
Debye theory is observed: Cp follows an approximately linear temperature dependence disclosing a
well-definite decrease with increasing glass density. By comparison with the observations in normal v-
GeO2, we conclude that glass densification reduces the excess density of low-energy vibrational states
over the Debye prediction, affecting significantly the density of two-level systems which are the
source for the linear term. Moreover the results prove unambiguously that the density variations of the
low-energy vibrational dynamics cannot be accounted for by the modifications of the elastic
continuum.
Acoustic properties of normal and densified vitreous GeO2 were investigated between 1.6 and 300 K
over the frequency range between 10 and 50 MHz. In normal GeO2, the acoustic attenuation rises with
increasing temperature until it reaches a plateau which extends up to about 10 K; this region is
governed by a strong coupling between two-level systems and phonons which is governed by a
mechanism of incoherent tunneling. At higher temperatures, the attenuation increases up towards a
broad peak, whose maximum shifts to higher temperatures as the ultrasonic driving frequency is

increased. These observations imply that, in the temperature range above about 20 K, the acoustic
behaviours are governed by thermally activated relaxations of structural defects. The velocity of 10
MHz longitudinal sound waves decreases with increasing temperature exhibiting a slope continuously
changing for temperatures varying between about 10 K and 220 K. At about 250 K the velocity shows
a minimum and then begins to increase for even higher temperatures. In densified (at 6 GPa) glassy
GeO2, an acoustic attenuation plateau having a magnitude smaller than that observed in normal v-
GeO2 is revealed over the temperature range between 2 K and 10 K. Quite differently, for
temperatures above 10 K, the relaxation loss and the temperature coefficient of the sound velocity
result to be considerably suppressed: these findings evidence that the number of relaxing particles is
strongly reduced by compacting the glass.
LOCAL AND COOPERATIVE SEGMENTAL DYNAMICS IN MODEL HETEROCYCLIC
POLYMER NETWORKS
Giuseppe Carini
Dipartimento di Fisica, Università di Messina, Salita Sperone 31, I-98166 Messina, Italy
Correspondence author: carini@unime.it
Accurate examinations of fragility data over a wide range of amorphous polymers [1] revealed that a
decrease of the dynamic fragility m is paralleled by an increase of the thermodynamic fragility,
evaluated by the change in heat capacity at Tg. The puzzling aspect concerning polymer fragility also
regards heterocyclic polymer networks (HPN), a class of materials where the density of cross-links
between the molecular units can be changed without altering the chemical structure. In these systems,
based on isocyanurate rings, it is possible to change the ratio of bi-functional to monofunctional
monomers in the reaction mixture giving rise to systematic changes of the effective network densities
and keeping their overall chemical structure essentially unchanged.
The observations of distinct calorimetric and mechanical transitions have been associated to an
inherent homogeneity characterizing the amorphous structure of HPNs. The temperature dependences
of the storage (E’) and loss (E”) moduli of HPNs, investigated between 100 K and 450 K by
mechanical waves of frequencies ranging between 0.3 and 30 Hz, reveal anelastic behaviours which
are mainly governed by the secondary β- and primary α-relaxations. The increase of the effective
cross-links or network density was accompanied by a systematic shift of the glass transition interval to
higher temperatures and by an enhancement of the dynamic fragility m. In clear contrast with this
observation, the thermodynamic fragility decreases with increasing network density.
[1] D. Huang, G. B. McKenna, J. Chem. Phys. 114, 5621-5630 (2001).

EFFECT OF BLENDING ON THE CHAIN DYNAMICS OF THE "LOW Tg" COMPONENT
IN NON-ENTANGLED POLYMER BLENDS.
Silvia Arrese-Igor (1), Ángel Alegría (1,2), Juan Colmenero (1,2,3)
(1) Centro de Física de Materiales CSIC-UPV/EHU, Paseo Manuel de Lardizabal 3, 20018, Donostia-
San Sebastián, Spain.
(2) Dpto. de Física de Materiales UPV/EHU, Paseo Manuel de Lardizabal 3, 20018, Donostia-San
Sebastián, Spain.
(3) Donostia <strong>International</strong> Physics Center DIPC. Apartado 1072, 20080, Donostia-San Sebastián,
Spain.
Correspondence author: waaarirs@ehu.es
The effect of blending on the dynamics of polymers is a relevant topic from both a technological and a
theoretical point of view. The separated segmental dynamics of each component in the blend and its
phenomenology have been extensively studied in the last decade: i) the slowing down or speeding up
of the individual relaxation times of each component, ii) the broadening of the relaxation function with
respect to the pure polymer behaviour, and iii) the "confinement" of the fast component by the slowly
relaxing matrix in blends with large dynamic asymmetry and small concentration of the fast
component. In comparison, there are fewer works dealing with the effect of blending on the individual
chain dynamics of different components in a blend. The relation between the segmental relaxation and
the intrinsic segmental friction driving chain dynamics makes natural the expectation of some parallel
phenomenology for terminal relaxation. Here, we have characterised the effect of blending on the
segmental and chain dynamics of the "fast" component (PI) in blends with very large dynamic
asymmetry, and molecular weights below the entanglement limit. On the one hand, the large
difference in the glass transitions of the two homopolymers (~ 170K) enhances any possible effects.
On the other hand, the low molecular weights of both components exclude entanglement effects from
data interpretation.
BROADBAND DIELECTRIC SPECTROSCOPY OF POLY (2-ETHOXYETHYL
METHACRYLATE-CO-2,3 DIHYDROXYPROPYL METHACRYLATE) MEMBRANES
M. Carsí (1), R. Díaz-Calleja (1), M.J. Sanchis (1), J. Guzmán (2), E. Riande (2)
(1)Instituto de Tecnología Eléctrica, ETSII, UPV, Spain
(2)Instituto de Ciencia y Tecnología de Polímeros (CSIC), Madrid, Spain.

The dielectric relaxation behavior of a copolymer membrane series of 2-ethoxyethyl methacrylate and
2,3 dihidroxypropylmethacrylate has been studied using BDS in the frequency domain of 10 -2 to 10 8
Hz at temperatures between 123 and 473 K. The spectra show almost three relaxation processes and at
high temperature and low frequencies an important conductive contribution. The study of chain
dynamics requires of a good deconvolution of overlapping peaks. As a consequence of the fact that a
Debye-type relaxation covers 2.28 decades in the frequency domain, but it becomes a Dirac delta
function in the relaxation time spectra, compliance relaxation processes are better defined in the
retardation time spectra than in the loss spectra in the frequency domain. Retardation spectra were
obtained by the linear phenomenological theory, using a Tikhonov regularization technique[1]. The αprocess
corresponds to the cooperative relaxation correlated to the glass transition and arises from
main-chain cooperative micro-brownian motions and follows VFT behavior. The β-process originates
from side-chain rotation of the asymmetric side group about the C-C bond connecting it to the polymer
backbone. At lower temperature appears a γ-process that can be attributed to the response of the
ethoxy group in the side chain.
[1] G. Domínguez-Espinosa D. Ginestar, M.J. Sanchis, R. Díaz-Calleja, E. Riande, Journal Chemical
Physics 129, 104513, 2008
EFFECT OF SPATIAL CONFINEMENT ON THE BOSON PEAK
R. Zorn
IFF, Forschungszentrum Jülich, 52425 Jülich, Germany
r.zorn@fz-juelich.de
During the last decade the influence of spatial confinement on the low frequency vibrational density of
states (VDOS), the so-called boson peak (BP), of glass-forming materials was intensively studied [1].
The experiments were mostly done using hard matrices (e.g. nanoporous silica) to confine the material.
The general effect observed was a suppression of the VDOS at frequencies below the BP maximum.
Recently, experiments were done using a ‘soft’ confinement in microemulsion droplets [2] showing a
qualitatively opposite effect. In this paper results from a simple numerical model with force-constant
disorder are presented in addition. The boundary conditions of the model were varied to mimic hard
and soft confinement. The striking similarity between the numerical results and the experiments
suggests that the experimentally observed effect is neither a genuine confinement effect (as proposed
for the glass transition), nor an interface effect, but rather due to the imposed boundary condition. The
result also supports the claim that the maximum observed in such models (being a remnant of the van-
Hove singularity of the crystal) corresponds indeed to the BP of the experiment.
[1] e.g. R. Zorn, B. Frick, L. Hartmann, F. Kremer, A. Schönhals and D. Richter, Physica B, 350,
e1115, 2004
[2] R. Zorn, M. Mayorova, D. Richter and B. Frick, Soft Matter, 4, 522, 2008

DIELECTRIC SPECTROSCOPY AS A PROBE TO STUDY PHYSICAL AGING IN
PMMA/SILICA NANOCOMPOSITES
V. Boucher (1), D. Cangialosi (2), A. Alegrìa (1),(3), J. Colmenero (1),(2),(3), I. Pastoriza-Santos (4),
L. M. Liz-Marzan (4),
(1) Donostia <strong>International</strong> Physics Center, Paseo Manuel de Lardizabal 4, 20018 San Sebastián, Spain
(2) Facultad de Química, Centro de Física de Materiales Centro Mixto (CSIC-UPV/EHU), Apartado
1072, 20080 San Sebastián, Spain
(3) Departamento de Física de Materiales, Universidad del País Vasco (UPV/EHU),
Apartado 1072, 20080 San Sebastián, Spain
(4) Universidad de Vigo, Deptartamento de Química Física Unidad Asociada CSIC, 36310 Vigo,
Spain
sckboucv@.ehu.es
Polymer nanocomposites can exhibit markedly improved thermal, mechanical, optical and physicochemical
properties when compared to bulk polymers. Despite the large amount of work performed,
the time evolution of nanocomposites properties towards those of the equilibrium below the glass
transition temperature (Tg), the so-called physical aging, still has to be clarified [1]. Indeed, physical
aging results in many deleterious effects ranging from embrittlement to reduction in permeability.
The aim of this work is the application of dielectric spectroscopy for the investigation of the physical
aging below Tg in poly(methyl methacrylate) (PMMA)/silica nanocomposites. This method consists in
measuring isothermally the change in the dielectric strength (∆ε) of PMMA secondary relaxation
process, that dominates the dielectric response overall below Tg, with time. Indeed, due to the
densification of the system, such a parameter is found to decrease during physical aging. This is
rationalized by the fact that the temperature dependence of ∆ε mimics that of standard
thermodynamic properties (volume, enthalpy) [2] observed in glass formers.
We demonstrate how the physical aging is accelerated in presence of well-dispersed silica particles in
PMMA. Considering that the presence of silica particles only affects the surface to volume of PMMA
ratio, this result supports the hypothesis of the disappearance of defects at the interface between
polymer and silica during physical aging [3].
[1] R.D. Priestley, Soft Matter, 5, 919, 2009
[2] G. Power, G.P. Johari, J.K. Vij, J. Chem. Phys., 119, 435, 2003
[3] D. Cangialosi, M. Wübbenhorst, J. Groenewold, E. Mendes, H. Schut, A. van Veen, S.J. Picken,
Phys. Rev. B, 70, 224213, 2004

THE USE OF THE FINAL THERMALLY STIMULATED DISCHARGE CURRENT
TECHNIQUE TO STUDY THE MOLECULAR MOVEMENTS AROUND GLASS
TRANSITION
E. R. Neagu 1,2 , C. J. Dias 1 , R. M. Neagu 2 , M. C. Lança 1
and J.N. Marat-Mendes 1
1
Departamento de Ciência dos Materiais, I3N/CENIMAT, Faculdade de Ciências e Tecnologia,
Universidade Nova de Lisboa, 2829-516, Caparica, Portugal
2
Department of Physics, Technical University of Iasi, Iasi 700050, Romania
neagu@dcm.fct.unl.pt
The electrical methods used to study the molecular movements are based on the movement of the
dipoles under DC or AC electric field. We have proposed recently a combined measuring protocol to
analyze charge injection/extraction, transport, trapping and de-trapping. During an electric polarization
process besides the polarization charge, electric charge is injected into the material. This charge is
partially transported and partially trapped into the material, depending on the material properties and
on the experimental conditions. As a consequence, the structure is decorated with space charge and
during the subsequent heating we are observing an apparent peak and the genuine peaks that are
related to dipole randomization and charge de-trapping. The aim of this paper is to present the results
obtained for Kapton. The relaxation parameters for local and collective molecular movements are
determined by analyzing the experimental thermograms.
[1] E.R. Neagu and J.N. Marat-Mendes, I E E E Trans. Diel. Electrical Insul. 11, 249, 2004
[2] E. R. Neagu and A. Vasiliku-Dova, Appl. Phys. Lett. 88, 1, 2006.
ON THE WIDTH OF THE FINAL THERMALLY STIMULATED DISCHARGE CURRENT
PEAK
E. R. Neagu 1,2 , C. J. Dias 1 , R. M. Neagu 2 , M. C. Lança 1 , R. Igreja 1 , P. Inácio 1 and J.N. Marat-Mendes 1
1
Departamento de Ciência dos Materiais, Secção de Materiais Electroactivos (I3N/CENIMAT),
Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa, 2829-516, Caparica, Portugal
2
Department of Physics, Technical University of Iasi, B-dul D. Mangeron 67, Iasi 700050, Romania
neagu@dcm.fct.unl.pt
The thermally stimulated discharge current (TSDC) method is a very sensitive technique to analyze
the movement of dipoles and of space charge (SC). In the variant known as windowing polarization
the experimental conditions are chosen so that the current is assumed to be determined by dipoles
randomization. To increase the selectivity of the method we have proposed a variant of the TSDC
method, namely the final thermally stimulated discharge current (FTSDC) technique [1,2]. The
experimental conditions can be selected so that the FTSDC is mainly determined by dipole
randomization or SC detrapping. The aim of this paper is to analyze if the elementary peaks obtained

y the two methods can be assumed as elementary Debye peaks and to determine the best
experimental conditions to obtain a narrow experimental peak. The best theoretical approach to
describe an elementary thermogram will be underlined.
[1] E.R. Neagu and J.N. Marat-Mendes, I E E E Transactions Diel. Electrical Insul. 11, 249, 2004
[2] E.R. Neagu and R.M. Neagu, J. Appl. Phys. 100, 074107, 2006.
Effective interaction between polyelectrolyte-colloid complexes: double layer theory and detailed
MC simulations
D. Truzzolillo, S. Sennato, F. Bordi, F. Sciortino
Dipartimento di Fisica, Università di Roma La Sapienza and CRS CNR-INFM SOFT Piazzale A.
Moro 5, I-00185 - Rome (Italy)
domenico.truzzolillo@roma1.infn.it
In the last year we studied by means of Dynamic Light Scattering and Electrophoretic measurements
the influence of the temperature on a suspension of polyelectrolyte-colloid complexes showing how
this parameter influences the phenomena of reentrant condensation and charge inversion that
characterize the observed stable cluster phase [1]. Through MC simulations, we showed that this
behaviour in free salt solutions is well described by an extension of the double layer theory [2] to
heterogeneously charged particles. Within this framework, the cluster growth may be viewed as a
thermally activated process. Via detailed MC simulations we want to investigate the role that some
environmental parameters have on the effective electrostatic interactions between the complexes,
comparing these results with the prediction of the double layer theory. Right now we are studying the
effect of ionic strength on the charge ordering of the adsorbed polymer layer and effective interaction
in order to have further insight onto the the phenomenology that the increasing of this parameter
produces. This aspect of our simulation work is aimed to give an interpretation to experimental results
we have already obtained studying liposome-polyelectrolyte complexes [3] at different simple salt
concentrations.
[1] S. Sennato et al. Langmuir, 24 (21), 12181, 2008.
[2] D. Velegol et al.. Langmuir 17, 7687, 2001.
[3] F. Bordi et al. Phys. Rev. E, 71, 050401 2005.

Basic investigation of the Li4Ti5O12 electrode using impedance spectroscopy
S. Krüger(1), S. Indris(2) and B. Roling(1)
(1) Fachbereich Chemie, Philipps-Universität Marburg, 35032 Marburg, Germany
(2) Karlsruhe Institute of Technology, 76344 Eggenstein-Leopoldshafen, Germany
steffen.krueger@chemie.uni-marburg.de
Currently, a lot of research effort is devoted to the development of lithium ion batteries with improved
performance, e.g. for electrical vehicles. In such batteries, the electrode materials play an important
role for achievable energy and power densities. Since graphite anodes form a passivating layer on their
surface when coming in contact with typical battery electrolytes, there is an intensive search for better
anode materials. One interesting material is Li4Ti5O12 (LTO) which shows evidence of high
reproducibility over several charge/discharge cycles, high stability of capacity and high power
densities. In previous
studies[1-3] a wide range of models was used in order to explain the resistive and capacitive behaviour
of LTO in batteries.
In this study, ac impedance spectroscopy is used to identify and analyse different processes in the LTO
materials and at the LTO/electrolyte interface. In particular, the influence of the LTO microstructure
on the impedance is analysed.
[1] X. L. Yao, S. Xie, H. Q. Nian and C. H. Chen, J. Alloys Comp., 465, 375, 2008
[2] W. Lu, I. Belharouak, J. Liu and K. Amine, J. Electro. Soc., 154(2), A114, 2007
[3] H. Kitaura, A. Hayashi, K. Tadanaga and M. Tatsumisago, J. Electro. Soc., 156(2), A114, 2009
DYNAMICS OF ASYMMETRIC POLYMER BLENDS.
Juan Colmenero (1,2)
(1) Centro de Física de Materiales (CSIC-UPV/EHU) – Materials Physics Center (MPC), Apto. 1072,
20080, San Sebastián, Spain.
(2) Donostia <strong>International</strong> Physics Center (DIPC), Apto. 1072, 20080, San Sebastián, Spain.
Correspondence author: juan.colmenero@ehu.es
Miscible polymer blends are systems of wide technological interest whose dynamical and rheological
properties can be tuned by varying the mixture composition. They are also very interesting systems
from a basic scientific point of view. Even being miscible, these systems are dynamically
heterogeneous: starting from two homopolymers with different mobility (different glass transition
temperatures Tg) two separated segmental relaxations are still observed in the miscible blend state.
When the difference in segmental mobility (Tg) of the two-homopolymer components is not too high,
they exhibit qualitative similar dynamic features in the blend. However, a rather different scenario
emerges for low concentration of the fast component, if the two homopolymers display very different
Tg’s. In this case, the two components in the blend exhibit strong dynamic immiscibility, with a large
separation (dynamic asymmetry) in their respective relaxation times. In such conditions the motion of

the fast component seems to be strongly restricted (“confined”) by the slowly relaxing matrix formed
by the slow component. We have carried out a thorough investigation of dynamic properties of
asymmetric polymer blends by combining different experimental techniques and molecular dynamics
simulations. Here we summarize the results obtained mainly focusing on the effect of temperature and
pressure on the dynamics of the “confined” fast component.
BACK TO BASICS: MECHANISMS OF CHAIN AND SEGMENTAL RELAXATION IN
POLYMERS
A. P. Sokolov
Department of Polymer Science, The University of Akron, Akron, OH, USA
alexei@uakron.edu
Classical theories of polymer dynamics assume the same friction mechanism for segmental and chain
relaxation. However, it is well-known that chain and segmental dynamics in many polymers exhibit
different temperature variations. This observation indicates a difference in friction mechanisms that
control macromolecular dynamics on local (segmental) and global (chain) scales.
This talk discusses differences in the dynamics on various length and time scales. We emphasize
significant influence of chemical structure and molecular weight on segmental dynamics (fragility) in
polymers. We demonstrate that the backbone flexibility alone is not the main parameter controlling
fragility. Side group flexibility relative to the backbone flexibility plays a crucial role. Analysis of
many polymers demonstrates rather weak influence of the chemical structure and molecular weight on
the temperature dependence of the chain relaxation when presented vs Tg/T. We propose that the main
difference between segmental and chain friction mechanisms is related to chain flexibility, frustration
in molecular packing and dynamic heterogeneities that affect only local (segmental) dynamics, but are
essentially averaged out on the time and length scale of the global chain relaxation.
GLASSFORMING PHASES WITH LONG-RANGE ORDERING
M. Massalska-Arodź (1), J.Krawczyk (1), A.Inaba (2), M. Jasiurkowska (1), E. Juszyńska (1)
(1) The Henryk Niewodniczanski Institute of Nuclear Physics, Polish Academy of Sciences,
Radzikowskiego 152, 31-342 Kraków, Poland
(2) Research Center for Structural Thermodynamics, Osaka University, Osaka 560-0043, Japan
Maria.Massalska-Arodz@ifj.edu.pl
Glass is regarded as a metastable phase with macroscopic scale of life time where some degrees of
freedom are frozen. The examples of organic substances were chosen where a phase(s) with some long
range ordering of molecules vitrifies. Among them there are plastic crystalline phases, liquid

crystalline phases (liquid- and crystal-like) and disordered crystalline phases. Features of the
temperature changes in diffraction pattern, heat capacity and dynamics (relaxational and vibrational)
observed near glass transition will be presented. Relation between character of structural relaxation
above Tg and density of states in glass will be discussed.
[1] M. Massalska-Arodź, Graham Williams, D.K. Thomas, J.W. Jones and R. Dąbrowski,
J.Phys.Chem. B, 103, 4197, 1999
[2] M.Massalska-Arodź, J. Krawczyk, J. Procyk and F. Kremer, Phase Trans., 80, 687, 2007
[3] E. Juszyńska, M. Massalska-Arodź, I. Natkaniec and J. Krawczyk, Physica B, 403, 109, 2008.
[4] A. Inaba, H. Suzuki, J. Krawczyk and M. Massalska-Arodź, Chem. Phys. Lett., 463, 90, 2008
[5] M. Jasiurkowska, J. Ściesiński, J.Czub, M. Massalska-Arodź, R. Pełka, E. Juszyńska, Yasuhisa
Yamamura and Kazuya Saito, J.Phys.Chem. B 113, 7335, 2009
[6] M.Massalska-Arodź, A.Inaba and J.Krawczyk „Dielectric relaxation in 4-n-butylbenzoesan-4’cyano-3’
fluorophenyl”, in preparation.
A NOVEL MICRO-CELL FOR MEASUREMENTS OF DIFFERENTIAL CAPACITANCE
AT METAL/RTILs INTERFACES
M. Drüschler, B. Huber, B. Roling
Fachbereich Chemie, Philipps-Universität Marburg, 35032 Marburg, Germany
drueschm@staff.uni-marburg.de
Room temperature ionic liquids (RTIL) show interesting properties leading to a wide range of
applications [1]. The number of scientific publications has increased tremendously over the last few
years. However, electrochemical properties have not been investigated in detail yet. Mainly the
electrochemical double layer at the interface between an RTIL and another homogeneous phase, e. g. a
metal wire, have not been studied in a satisfying manner although the knowledge of its structure and
properties is essential for a multiplicity of implementations. Within this work, RTILs were analyzed
by means of Karl Fischer titration, cyclic voltammetry and impedance spectroscopy. The
measurements were carried out by means of a novel micro cell with special features. The cell can be
operated with an amount of 40 µL and at different conditions such as in vacuo or under inert gas
atmosphere. In addition the electrodes can be exchanged easily by means of an applicable connector
system. The measurement results are discussed against the background of a recently published theory
of the electrochemical double layer at metal/RTILs interfaces [2].
[1] P. Hapiot, C. Lagrost, Chem. Rev., 108, 2238, 2008
[2] A. A. Kornyshev, J. Phys. Chem. B, 111, 5545, 2007

RELAXATION MECHANISMS IN IBUPROFEN AMORPHOUS DRUG
A.R. Brás (1), J.P. Noronha (1), A. Schönhals (2), F. Affouard (3), M. Dionísio (1) and N. T. Correia
(1)
(1) REQUIMTE, Departamento de Química, Faculdade de Ciências e Tecnologia, Universidade Nova
de Lisboa, 2829-516 Caparica, Portugal
(2) BAM Federal Institute of Materials Research and Testing, Unter den Eichen 87, D-12205 Berlin,
Germany
(3) Laboratoire de Dynamique et Structure des Matériaux Moléculaires, UMR CNRS 8024, BAT P5,
Université Lille 1, 59655 Villeneuve d'Ascq, France
n.correia@dq.fct.unl.pt
Amorphous drugs and excipients are markedly more soluble than their crystalline counterparts and
have recently received considerable attention from pharmaceutical industries. A detailed description of
their molecular motions and their temperature dependencies is thus particularly relevant not only from
a fundamental point of view but also for technical applications such as storage and shelf life
improvements. In this context, the work here presented has been focused in the establishment of the
amorphization/crystallization conditions of the non-steroidal anti-inflammatory worldwide used
Ibuprofen and the evaluation of the molecular dynamics in the amorphous liquid and glassy states
using broadband dielectric relaxation spectroscopy (10 -1 9
- 10 Hz) over a wide temperature range (143
K to 363 K). A rich relaxation map was obtained with identification of different relaxation processes
such as the main α-relaxation, βJ-G Johari-Goldstein and γ secondary relaxations. Moreover, in the
supercooled liquid state, an additional Debye-type process was also found which, unlike to the wellknown
Debye type process observed in monohydroxy alcohols, possesses a magnitude much lower
than the main α-relaxation. The origin of the different relaxation processes was investigated and
associated with dynamics of hydrogen-bonded aggregates found in Ibuprofen such as dimers and
trimers either cyclic or linear which were confirmed from Infra-red spectroscopy, electrospray
ionization mass spectrometry and predicted by Molecular Dynamics simulations.
Acknowledgement: Financial support to Fundação para a Ciência e Tecnologia (FCT, Portugal)
through the project PTDC/CTM/64288/2006 and the Pessoa partnership Hubert Curien is
acknowledged. A. R. Brás acknowledges FCT for a PhD grant SFRH/BD/23829/2005.
QUANTITATIVE DIELECTRIC PERMITTIVITY INVESTIGATION OF POLYMERS AND
POLYMER BLENDS USING ELECTROSTATIC FORCE MICROSCOPY
G. A. Schwartz(1), R. Arinero(2), C. Riedel(1,3), Ph. Tordjeman(4), A. Alegria(1,5) and J.
Colmenero(1,3,5)
(1) Centro de Física de Materiales CSIC-UPV/EHU, Edificio Korta, 20018 San Sebastián, Spain.
(2) Institut d’Electronique du Sud (IES), Université Montpellier II, 34095 Montpellier Cedex, France.

(3) Donostia <strong>International</strong> Physics Center, Paseo Manuel de Lardizabal 4, 20018 San Sebastián, Spain.
(4) Institut de Mécanique des fluides (IMFT), 1 Allée du Professeur Camille Soula, 31400 Toulouse,
France.
(5) Departamento de Física de Materiales UPV/EHU, Facultad de Química, 20080 San Sebastián,
Spain.
Correspondence author: schwartz@ehu.es
Dielectric relaxation (DR) has shown to be a very useful, extended and versatile technique to study
dielectric materials and in particular polymers and other glass formers. DR studies allow obtaining
valuable information about the molecular dynamics of the system under investigation at different
length and time scales. However, the standard DR has a fundamental limitation: it has no spatial
resolution. We have recently developed a novel approach that allows quantitatively measuring the
local dielectric permittivity of thin films in one point by means of electrostatic force microscopy. The
proposed experimental method is based on the detection of the local electric force gradient at different
values of the tip-sample distance. The value of the dielectric permittivity is then calculated by fitting
the experimental points using the Equivalent Charge Method. In this work we show how this approach
can be extended in order to obtain for the first time quantitative dielectric images of polymer and
polymer blend thin films. The proposed method gives not only good dielectric contrast between the
two phases in polymer blends but excellent lateral resolution and quantitative values of the dielectric
permittivity. In particular we have studied neat poly(vinyl acetate) and polystyrene and the
corresponding polymer blends. This new approach opens the door for quantitative studies of the
dielectric response in polymers, nano-structured materials and soft-matter in general.
ION DIFFUSION IN ELECTROLYTES STUDIED BY MEANS OF INELASTIC X-RAY
SCATTERING
S. Elisei (1), G. Monaco (2) and D. Fioretto (3)
(1) Centro di Ricerca sulle Biomasse, Università degli Studi di Perugia, I-06125, Perugia, Italy
(2) European Synchrotron Radiation Facility, BP 220, F-38043, Grénoble Cedex 9, France
(3) Dipartimento di Fisica, Università degli Studi di Perugia, I-06125, Perugia, Italy and CNR-INFM
CRS Soft, Università di Roma “La Sapienza”, I-00185, Roma, Italy
elisei@crbnet.it
Inelastic X-ray Scattering (IXS) has been used for the first time to investigate diffusion processes of
simple electrolytes in water solutions at the ns-ps timescale and at 1-35 nm -1 q values. Modern
generalized hydrodynamic theories predict the presence of a relaxation in the diffusion coefficient of
ions in this temporal and spatial range [1]. Here we report on the diffusion coefficients of I - ions in
Lithium Iodide (LiI) water solutions at different temperatures and concentrations of solute measured at

the ID-16 beamline at the European Synchrotron Radiation Facility (ESRF). The spectra have been
fitted using a single Lorentzian peak for the ions’ contribution and an empirical function for the
solute’s contribution. Molecular dynamics simulations have been used to determine the weight of the
two mentioned contributions. Our results show that it is possible to investigate diffusion by means of
IXS and that there is an increase in the value of diffusion coefficient of the I - ions in the ns-ps scale
with respect to the macroscopic one, as predicted by theory.
[1] J.-F. Dufrêche, O. Bernard, P. Turq, A. Mukherjee and B. Bagchi, Phys. Rev. Lett., 88-9, 5902,
2002
VISCOELASTIC PROPERTIES OF COMPOSITES WITH CHAOTIC FRACTAL
STRUCTURE
V.V.Novikov, O.V.Kysil
Odessa National Polytechnic University, 65044 Odessa, avenue Shevchenko 1, Ukraine
frac.novikov@gmail.com
In this work we consider composites with fractal structure, which content a component with negative
shear modulus (the negative rigidity). The composites with such inclusions have higher rigidity and
mechanical damping in comparison with pure components which constitute the composite.
Interpretation of the negative shear modulus is based on behavior of a construction which looks like a
curved ruler in the form of the letter “S” in previously strained state [1]. If apply the tangential forces
the curved ruler will not resist to external stress, and will assist the displacement along the applied
forces. Thus, the constant of proportionality (shear modulus) between the tangent stresses and the
shear will be negative. Such a constructions are not stable. To stabilize a construction it is possible, if
include it into a matrix with stable properties, for example, in a polymeric compound. Thus, it is
possible to create the composite material consisting of inclusions with the negative shear modulus and
a matrix-polymer with the positive shear modulus.
In paper [1] the analysis of influence of inclusions with the negative shear modulus on an effective
shear modulus of the composite was carried out on the basis of formulas Hashin-Strikman [1-2] which
were obtained if suppose, that properties do not depend on a scale.
We consider the dependency of viscoelastic properties of
inhomogeneous medium with chaotic, fractal structure on a scale. The
calculations of the viscoelastic properties depending on interface layer
properties were carried out on the basis of the fractal structure model
and an iterative averaging method [2]. The interface layer properties
differ from properties of filling particles and polymeric matrix (fig. 1).
1 - the thickness δ of the interface layer; 2 – the interface layer; 3 – the particle; 4 – the polymeric
matrix with pure polymer properties

Fig. 1. Structure model of the complex particle in an aggregate.
The proposed method allows to predict the properties not only model, but also real composites.
The comparison of calculation and experimental data shows their close agreement.
[1] R. S. Lakes Phys. Rev. Let. 86, 2897, 2001
[2] V. V. Novikov, K. W. Wojciechowski, Physical Status Solidi B, 242, 645-652, 2005
ELECTRODE POLARIZATION IN GLASS ELECTROLYTES
C. R. Mariappan, T. P. Heins and B. Roling
Department of Chemistry, University of Marburg, Hans-Meerwein-Strasse, 35032 Marburg, Germany
mariappa@staff.uni-marburg.de.
Electrical interfacial capacitance of different Na-Ca-phosphosilicate glasses with blocking Pt electrode
is investigated by means of ac impedance spectroscopy. At low applied dc bias voltages, we detect a
linear capacitance regime with capacitance values considerably larger than found for ionic liquids with
similar ion concentrations and also considerably larger than expected theoretically from the Na + ion
radius and the Debye length [1]. On the other hand, the bias voltage dependence of the differential
interfacial capacitance exhibits strong similarities to ionic liquids, namely a differential capacitance
maximum at intermediate voltages and a strong drop of the differential capacitance at high voltages.
We suggest that the large differential interfacial capacitance is due to pseudo-capacitance effects in
parallel to the double layer capacitance [2].
[1] A. A. Kornyshev, J. Phys. Chem. B 111, 5545 (2007).
[2] B. E. Conway, ‘Electrochemical Supercapacitors’, Kluwer Academic / Plenum Publishers, New
York, 1999
DYNAMICS IN ULTRATHIN LIQUID FILMS STUDIED BY SIMULTANEOUS
DIELECTRIC SPECTROSCOPY (DS) AND ORGANIC MOLECULAR BEAM DEPOSITION
(OMBD)
S. Capponi (1), S. Napolitano (1), S. Rozanski (1), G. Couderc (2), Norwid-Rasmus Behrnd (2), Jürg
Hulliger (2), M.Wübbenhorst (1)
(1) Department of Physics and Astronomy, Katholieke Universiteit Leuven, Celestijnenlaan 200D,
Leuven, 3001, Belgium.
(2) Department of Chemistry and Biochemistry, University of Berne, Freiestr. 3, 3012 Berne,
Switzerland.
simona.capponi@fys.kuleuven.be

Glass forming liquids show deviations from their cooperative bulk-dynamics when they are
geometrically confined to nanometer dimensions. In this context, ultrathin films of glass forming
liquids are of particular interest, since both the dimension (thickness) and the surface interactions can
be controlled in an independent way. This paper is devoted to a study of the structural relaxation
dynamics in ultrathin films of H-bonded liquids by means of broadband dielectric spectroscopy.
To prepare and investigate nm-thin organic liquid films of adjustable thickness, we have employed
organic molecular beam deposition (OMBD) in combination with an open capacity sensor
(interdigitated comb electrode) and a crystal microbalance (QCM), which allow the simultaneous
monitoring of the dielectric spectra and the film thickness during deposition and desorption.
First measurements on glycerol, threitol and xylitol have demonstrated the high sensitivity and
flexibility of this technique, yielding accurate dielectric relaxation spectra in liquid films as thin as 0.7
nm for glycerol. Recent results from systematic studies will be discussed in detail together with
potentially new applications of our approach.
THE DIELECTRIC ALPHA-RELAXATION OF POLYMER SYSTEMS AND THE ADAM-
GIBBS APPROACH
A. Alegría
Centro de Física de Materiales Centro Mixto (CSIC-UPV/EHU), Apartado 1072, 20080 San Sebastián,
Spain
Departamento de Física de Materiales, Facultad de Química, , Universidad del País Vasco
(UPV/EHU),
Apartado 1072, 20080 San Sebastián, Spain
angel.alegria@ehu.es
In this talk I will summarize the recent progress obtained by our group in the application of the Adam-
Gibbs (AG) approach, relating the dynamic and thermodynamic behaviors, to the dielectric relaxation
of polymer materials. The applicability of the AG approach for the segmental relaxation of a wide
variety of polymers, including both the equilibrium and the non-equilibrium range around the glass
transition, will be presented first followed by a discussion on the extension of the AG approach to
experiments above atmospheric pressure (up to 300MPa) on standard polymers. Finally, it will be
shown how the AG approach combined with the self concentration concept has given rise to a
predictive model for the component dynamics of multicomponent polymer systems, namely, athermal
polymer-polymer blends and concentrated polymer solutions. The implications of all these results on
the nature of the polymer segmental dynamics will be highlighted.

SEGMENTAL DYNAMICS OF SEMICRYSTALLINE POLY(VINYLIDENE FLUORIDE)
NANORODS
Jaime Martín (1), Carmen Mijangos(1), Alejandro Sanz (2), Tiberio A. Ezquerra (2), Aurora Nogales
(2)
(1) Instituto de Ciencia y Tecnología de Polímeros, CSIC. C/ Juan de la Cierva 3, Madrid 28006,
Spain
(2) Instituto de Estructura de la Materia, CSIC. Serrano 121, Madrid 28006, Spain
Correspondence author: emnogales@iem.cfmac.csic.es
The dynamics of a semicrystalline poly(vinylidene fluoride) (PVDF) confined within alumina
templates of cylindrical nanopores is studied by means of dielectric spectroscopy. In this study we
demonstrate how the counterbalance between spatial confinement and interfacial interactions controls
at the nanometre level, the dynamic and semicrystalline structure of the polymer. A strong deviation of
the relaxation behaviour of PVDF embedded within the nanopores is observed as compared to that of
the bulk. In particular the dielectric measurements reveals, for pore sizes of the order of 20 nm, the
existence of a highly constrained relaxation associated to the polymer-alumina interfacial layer. In
particular, for pore sizes of the order of 20 nm, the existence of a highly constrained relaxation
associated to the polymer-alumina interfacial layer. When the PVDF is confined to this level in
alumina templates, most of the chains are located in the interfacial region, where the mobility is
severely restricted, and because of that, crystallization is inhibited [1]
[1] J. Martín, C. Mijangos, A. Sanz, T.A. Ezquerra, A. Nogales, Macromolecules (In press)
DOUBLE LAYER CAPACITANCE OF IONIC LIQUIDS: WHAT CAN ONE LEARN FROM
CYCLIC VOLTAMMETRY AND IMPEDANCE SPECTROSCOPY?
B. Roling, M. Drüschler, B. Huber
Department of Chemistry, University of Marburg, Hans-Meerwein-Strasse, 35032 Marburg, Germany
roling@staff.uni-marburg.de
The theoretical understanding of the double layer structure in ionic liquids (ILs) is a challenging task.
Due to the high ion concentrations, well-known electrochemical mean-field theories, like the Gouy-
Chapman theory, are not applicable. In recent years, new theoretical approaches based on lattice gas
models [1] and on molecular dynamics simulations [2] have been developed.

From an experimental point of view, the influence of impurities and of water on the electrochemical
properties of ILs is not yet fully understood [3]. In this contribution, we analyse cyclic
voltammograms and impedance spectra of ILs based on imidazolium and pyrrolidinium cations. We
find that a high purity and a careful dehydration of ILs are essential for an unambiguous extraction of
the potential-dependent double layer capacitance from impedance spectra.
[1] A. A. Kornyshev, J. Phys. Chem. B, 111, 5545, 2007.
[2] M. V. Federov, A. A. Kornyshev, J. Phys. Chem. B, 112, 11868, 2008.
[3] S. Randström et al, Electrochim. Acta, 53, 6397, 2008.
INVESTIGATION OF THE EFFECT OF INTERMOLECULAR INTERACTIONS ON THE
MOLECULAR DYNAMICS OF POLY(BUTYLENE OXIDE)
A. Panagopoulou, S. Kripotou, A. Kyritsis, P. Pissis
Department of Physics, National Technical University of Athens, Zografou Campus, 15780 Zografou,
Greece
akyrits@central.ntua.gr
Poly(butylene oxide) of low molar mass was selected as model system for the investigation of
segmental and global chain dynamics using Broadband Dielectric Spectroscopy. Poly(butylene oxide)
possess non-zero components of the dipole moment both parallel and perpendicular to the main chain.
Dielectric spectroscopy probes segmental (α relaxation) and global chain motions (nm relaxation),
which correspond to the rotational fluctuations of dipole component perpendicular to the main chain
and to the fluctuation and orientation of the end-to-end polarization vector of the chain, respectively
[1]. The intermolecular interactions in the systems under study are tuned by changing the chain end
groups (-OH and -Me). Dynamics of poly(butylene oxide) chain are investigated in the case that both
ends are free (homopolymer) and that one chain end is fixed (poly(ethyelene oxide)-poly(propylene
oxide) diblock copolymer). Effects on secondary relaxations are also discussed.
[1] H. Watanabe, Macromol. Rapid Commun. 22, 127, 2001
GLASS TRANSITIONS AND HIERARCHICAL DYNAMICS OF IONIC LIQUIDS
O. Yamamuro (1), T. Yamada (1), S. Tatsumi (1), M. Kofu (1), M. Nakakoshi (2) and M. Nagao (3)
(1) Institute for Solid State Physics, University of Tokyo, 5-1-5 Kashiwanoha, Kashiwa, Chiba 277-
8581, Japan
(2) Inst. Anal. Center, Yokohama Nat. Univ., Yokohama 240-8501, Japan

(3) NCNR, NIST, 100 Bureau Drive, Gaithersburg, MD20899-6100, USA
yamamuro@issp.u-tokyo.ac.jp
Ionic liquids (ILs) are very interesting materials not only for various applications but also for basic
science of liquids. Most of ILs have glass transitions at low temperatures and related temperature
dependence of viscosity is not understood from Stokes-Einstein scenario. This can be related to
hierarchical structure and dynamics of ILs. Most of cations of ILs have core parts with positive charge
and also have mostly neutral methyl-groups and longer alkyl-groups. Furthermore, it was recently
found that ILs have separating ionic and neutral (alkyl-chain) domains of a nanometer scale. They may
have different time scales of diffusive motions. The purpose of our study is to clarify the hierarchical
structure and dynamics of ILs by using various neutron scattering techniques. The neutron diffraction
pattern of fully-deuterated 1-octyl-3-methyimidazolium chloride (d-C8mimCl) exhibited peaks at 2.8 ,
11, and 14 nm -1 , which are considered to be due to the correlations of domains, ions, and alkylchains,
respectively. The intermediate scattering function of d-C8mimCl obtained from neutron spin-echo
(NSE) showed fast and slow relaxations depending on temperature. The fast and slow motions may be
related to the local motion of alkyl-chain and the diffusion of ions, respectively. The time-scale of
domain motion was found to be slower than 10 ns from the NSE measurement at Q = 2.8 nm -1 . Thus,
we have mostly clarified the hierarchical dynamics of C8mimCl by neutron scattering.
MOLECULAR DYNAMICS OF HYPERBRANCHED POLYMERS WITH URETHANE AND
UREA LINKAGES
K.Raftopoulos(1), A.Kyritsis(1), M.Abdel Rehim(2), Sh.Said Shabaan (3), A.Ghoneim (3), G.Turky
(3)
(1) Department of Physics, National Technical University of Athens, Athens, Greece
(2) Packing and Packaging Materials Department, National Research Centre, Cairo, Egypt
(3) Microwave Physics and Dielectrics Department, National Research Centre, Cairo, Egypt
kraftop@central.ntua.gr
Differential Scanning Calorimetry (DSC), Thermally Stimulated Depolarization Currents (TSDC) and
Dielectric Relaxation Spectroscopy (DRS) have been employed complementary to study molecular
dynamics of aliphatic and aromatic Hyperbranched (HB) Polymers with either urea or urethane
linkages. Glass Transition has been studied by DSC. Intense conductivity effects do not allow for the
study of the α relaxation (dynamic glass transition). Two secondary relaxations, β and γ with
decreasing temperature/increasing frequency, were studied by DRS. β relaxation, attributed to motions
of branched units with polar groups, seems to be typical of HB Polyurethane structures as it does not
arise in linear counterparts. γ relaxation is attributed to either –OH (HB Urethane) or –NH2 (HB Urea)
end groups, being faster for the latter. It is also affected from the structure, being faster for aliphatic
HB polymers. Charge carrier motion is observable even in the glassy state. Aliphatic HB Polyurea dc
conductivity exhibits VTF behavior suggesting coupling with molecular motions in the glassy state.

A DIELECTRIC STUDY OF THE OLIGOMER-TO-POLYMER TRANSITION IN
PROPYLENE GLYCOL CHAINS
C. Gainaru (1), R. Böhmer (1)
(1) Fakultät für Physik, TU Dortmund, 44221 Dortmund, Germany
The polymer dynamics sets in at times longer than those characterizing the structural rearrangements
and the delay between the α-process (monomer dynamics) and the slowest relaxation mode (the
reorientation of the overall chain) increases with the chain length. For long, but non-entangled chains,
the thoroughly investigated polymer dynamics is well described by the Rouse theory [1]. However,
there is only little information regarding the dynamics of short chains [2,3]. Using dielectric
spectroscopy we present the evolution of the dielectric response including both the α- and the polymer
dynamics when the molecular size of polypropylene glycol (PPG) is systematically changed from one
to a few hundred monomers. For PPG, as for some other polymers, a large dipole moment is formed
along their chain by the superposition of the individual monomeric contributions. This end-to-end
dipole moment provides a strong coupling to the electric field, making the dielectric technique best
suited for the investigation of the overall chain dynamics. We discuss the influence of the molecular
size upon the local dynamics (α-process) and upon the strength and time scale of the chain’s dielectric
response.
[1] P.E. Rouse, J. Chem. Phys., 21, 1272, 1953
[2] S. Kariyo, C. Gainaru, H. Schick, A. Brodin, V.N Novikov and E.A. Rössler, Phys. Rev. Lett., 97,
207803, 2006
[3] Y. Ding, A. Kisliuk and A.P. Sokolov, Macromolecules, 37, 161, 2004
Diffusion and relaxation in a monohydroxy alcohol
R. Gainaru (1), C. Gainaru (1), S. Schildmann (1), R. Böhmer (1)
(1) Experimentelle Physik III, T.U. Dortmund, 44227 Dortmund, Germany
catalin.gainaru@uni-dortmund.de
Viscous monohydroxy alcohols, also water, exhibit in their dielectric spectra the so called Debye
process [1]. This relaxational feature corresponds to degrees of freedom which are about 100 times
slower than those giving rise to the structural rearrangements (α-process). In spite of numerous
experimental investigations, the nature of these slow “superstructure” relaxation modes is not agreed

upon, although it is clear that they are to be related with the presence of hydrogen bonds. In particular,
the research in this field needs to address whether the aliphatic protons and those participating in an Hbond
network can be distinguished, for instance on the basis of their structural and dynamical
properties.
As a step in this direction we performed field-gradient diffusion NMR experiments on 2-ethyl-1hexanol.
The diffusion coefficients, obtained for a range of temperatures, are discussed together with
those obtained from broad-band dielectric spectroscopy. In addition, spin-lattice relaxation times were
measured to check if this dielectrically strongly active Debye process carries also a specific NMR
signature.
[1] L-M. Wang, R. Richert, J. Chem. Phys., 121, 11170, 2004

ELASTIC AND QUASI-ELASTIC NEUTRON SCATTERING INVESTIGATIONS OF
MOLECULAR MOTIONS IN SYSTEMS OF BIOPHYSICAL INTEREST
S. Magazù
Department of Physics, University of Messina, Sperone 31, Messina, I-98166, Italy
smagazu@unime.it
The present work is addressed to the study of the role of the instrumental resolution in Elastic
Incoherent Neutron Scattering (EINS). The Self Distribution Function (SDF) procedure is presented
and connected to the measured EINS intensity profile. This procedure allows to evaluate both the total
and the partial Mean Square Displacement (MSD), through the total and the partial SDFs [1,2]. The
SDF and Gaussian procedures are compared by applying the two approaches to EINS data collected
by the IN13 backscattering spectrometer (ILL, Grenoble) on systems of biophysical interest, such as
homologous disaccharides, i.e. sucrose and trehalose, and lysozyme. As far as the disaccharide
mixtures are concerned, the partial MSD behaviours of sucrose and trehalose are equivalent in the
high-r domain, whereas they are different in the small-r domain; this result suggests that the higher
structure sensitivity of sucrose with respect to trehalose should be related to the small spatial
observation windows. This analysis, which clarifies the observed differences in the hydrogen bonded
network of the water-disaccharide mixtures, can justify the highest bioprotectant effectiveness of
trehalose in comparison with sucrose.
[1] S. Magazù, G. Maisano, F. Migliardo, G. Galli, A. Benedetto, D. Morineau, F. Affouard, M.
Descamps, J. Chem. Phys., 129, 155103, 2008.
[2] S. Magazù,G. Maisano, F. Migliardo, A. Benedetto, Phys. Rev. E, 79, 041915, 2009
SYNTHESIS AND CHARACTERIZATION OF AMPHIPHILIC POLY-N-
VINYLPYRROLIDONE NANOPARTICLES CONTAINING INDOMETHACIN
A.N. Kuskov (1), A.A. Voskresenskaya (1), A.V. Goryachaya (1), M.I. Shtilman (1), A.M. Tsatsakis
(2) and Α. K. Rizos (3)
(1) D.I. Mendeleyev University of Chemical Technology, 9 Miusskaya Square, Moscow 125047,
Russia
(2) University of Crete, School of Health Sciences, Heraklion 71003, Crete, Greece
(3) University of Crete, Department of Chemistry, and FORTH - IESL, P.O. Box 2208, Heraklion
71003, Crete, Greece
rizos@chemistry.uoc.gr, rizos@iesl..forth.gr
Amphiphilic poly-N-vinylpyrrolidone derivatives (Amph-PVP) with different molecular weight of
hydrophilic PVP fragment and one terminal hydrophobic n-alkyl fragment of different length were
synthesized for the preparation of nano-scaled particles in aqueous media. Indomethacin was
incorporated into the hydrophobic inner core of the nanoparticles as a typical model drug delivery
system. The size of the particles formed was less than 200 nm with narrow monodisperse size
distribution. The nanoparticle size slightly increased with the amount of indomethacin encapsulated
into the inner core of Amph-PVP particles. The critical aggregation concentration as determined by
fluorescence spectroscopy was in the micromole range which is lower than the values that are
common for low molecular weight surfactants. An increase of polymer hydrophilic fragment
molecular weight produced larger nanoaggregates. In vitro release experiments using indomethacinloaded
Amph-PVP nanoparticles exhibited the sustained release behavior without any burst effect for
most polymer samples.
INS STUDY ON THE DYNAMICAL PROPERTIES OF MELT-FORMED AND DAMAGE-
FORMED AMORPHOUS TREHALOSE
F. Affouard (1), M. Descamps (1), S. Magazù (2), F. Migliardo (1,2), J. F. Willart (1)

(1) Laboratoire de Dynamique et Structure des Matériaux Moléculaires, University of Lille 1, UMR
CNRS 8024 - 59655 Villeneuve d’Ascq CEDEX, France
(2) Department of Physics, University of Messina, Sperone 31, Messina, I-98166, Italy
fmigliardo@unime.it
The innovative research field on bioprotectant systems has been originated from a growing demand
from many biotechnological industrial research laboratories and processing industries to improve the
quality and safety of food and other high added-value products, as well as to develop new technologies
of stabilization and conservation.
It is well known that Nature can provide very precious suggestions to be applied in food science and
public health. As an example, extremophiles [1], living in extreme environments, are useful modelsystems,
since the adaptation strategies they have developed can suggest innovative methodologies to
be used for stabilizing biological molecules. The research on trehalose, a glucose disaccharide, moves
from the observation that many extremophiles, such as, for example, brine shrimps (Artemia salina),
cryptobiontes (Phylum Tardigrada), bacteria (Escherichia coli) and plants (Myrothamnus flabellifolia),
show extraordinary surviving capabilities to environmental stress conditions, such as dehydration and
freezing, thanks to the synthesis of the disaccharide, which allows them to undergo in a cryptobiotic
(“hidden life”) state and to re-activate the vital functions when the external conditions come back
favorable to the life.
The objective of the proposed study is to compare the relaxational versus vibrational properties of
trehalose obtained by using different preparative methods: the first system is trehalose obtained
following a classical procedure of cooling, the second one is trehalose obtained by direct low
temperature solid state vitrification [2]. Amorphous media are industrially prepared following mainly
these protocols which affect their bioprotection effectiveness. The data analysis reveals a different
temperature dependence of the low frequency vibrational contribution on preparative methods.
[1] L. J. Rothschild, R. L. Mancinelli, Nature, 409, 1092, 2001
[2] M. Descamps, J.-F. Willart, E. Dudognon, V. Caron, Journal of Pharmaceutical Sciences, 96, 1398,
2007
THE SELF-DIFFUSION OF ZWITTERIONIC AND ANIONIC LIPIDS IN BILAYERS
M. Rudakova (1) and A. Filippov (1)
(1) Department of Molecular Systems Physics, Kazan State University, 420008 Kazan, Russia
maduduka@yandex.ru
Lipids are the structure basis of biological membranes. The state and the composition of lipid
compounds is the main factor which determines biomembrane properties. In particular, membrane
protein functioning is depended on lipids phase state. In recent times, we notice an increasing interest
in the investigation of mixtures of the zwitterionic and the anionic lipids systems [1]. Also the very
excite areas are the interaction of these mixture lipid system with cholesterol, gangliosides, proteins
and the existing of the phase domains (“rafts”) in these lipid systems [2].
Lipid translational self-diffusion has been investigated for dioleoylphosphatidylcholine (DOPC)/
dioleoylphosphatidylglycerol (DOPG) and dioleoylphosphatidylcholine
(DOPC)/dioleoylphosphatidylglycerol (DOPG)/ cholesterol lipid systems in lamelar liquid crystalline
(Lα) phases by NMR pulse field gradient (NMR PFG) method. The phase diagram of these lipid
systems was determined. Also we cleared up a question about conditions of forming Lα phase and coexisting
of liquid crystalline ordered and liquid crystalline disordered phases.
This work was supported by Russian Foundation for Basic Research (09-04-01355-a).
[1] A. Filippov, G. Oradd, G. Lindblom, Chemistry and Physics of Lipids, 159, 81-87, 2009
[2] C. Yuan, L. J. Johnston, Biophysical Journal, 79, 2768–2781, 2000

NMR STUDY OF FATTY ACIDS BINDING SITES ON HUMAN SERUM ALBUMIN
A. Gumerova (1), A. Filippov (1)
(1) Kazan State University, 420008, Kremlevskaya 18, Kazan, Russia
Alisa.gumerova@mail.ru
It is known, that binding of exogenous and endogenous ligands can result modifications of
conformation of albumin molecules. Under the influence of pathological conditions, the integration of
the albumin molecule with metabolic products results in a new distribution of its fractions, wherein the
total concentration of serum albumin often is unchanged. Such kind of variability of serum albumin
structure is observed with cancer diseases and can be registered by examination of binding parameters
of several substrates to the albumin [1].
We used NMR method for determining binding sites of fatty acids on human serum albumin (HSA) by
competitive displacement of 13C-methyl-labeled oleic acid. In two-dimensional [1H,13C]
heteronuclear single quantum coherence NMR spectra resonances are correspond to the oleic acids
binding sites of albumin [2]. Binding of molecules to these sites can be followed by their displacement
of oleic acids. Furthermore, the amount of bound ligand at each site can be determined from changes
in resonance intensities. That let to us investigate an alterations of serum albumin conformation, which
have been induced by metabolite- or tdrug-binding to the molecule, by influence of physic-chemical
characteristics.
[1] C. Kazmierczak, A. Gurachevsky, G. Matthes, V. Muravsky, Clinical Chemistry, 52, 1, 2006
[2] R. W. Sarver, H. Gao, F. Tian, Analytical Biochemistry 347, 297, 2005
THE DEFECT DIFFUSION MODEL AND VOLUME VS. TEMPERATURE EFFECTS IN
GLASS-FORMING LIQUIDS*
J. T. Bendler (1), J. J. Fontanella (2), M. F. Shlesinger (2,3) and M. C. Wintersgill (2)
(1) BSC, Inc., Rapid City, SD 57702, USA
(2) Physics Department, U. S. Naval Academy, Annapolis, MD 21402, USA
(3) Office of Naval Research, Code 30, 875 N. Randolph St., Arlington, VA 22203, USA
fontanel@comcast.net, jjf@usna.edu
The defect diffusion model (DDM) of glass-forming liquids has been used to describe many properties
of glass-forming liquids [1]. Most recently, a quantitative treatment of the glass transition in both bulk
and nanoscale films has been given [2]. In addition, the ratio of the apparent isochoric activation
energy to the isobaric activation enthalpy, EV*/H* or EV/ EP, has been evaluated [1,3]. In ref. 3 it is
shown how the volume change that accompanies clustering of defects is the primary factor that
determines the ratio. In the present work, the analysis of volume vs. temperature effects in glassforming
liquids is extended. For example, it is shown how the correlation of the ratio EV*/H* with
monomer volume that has been reported by Floudas and co-workers [4] follows naturally from the
DDM. In addition, the effect of pressure on the ratio is calculated.
[1] J. T. Bendler, J. J. Fontanella and M. F. Shlesinger, AIP Conference Proceedings, Volume 982, 5th
<strong>International</strong> Workshop on Complex Systems, eds. M. Tokuyama, I. Oppenheim and H. Nishiyama, p.
215-218, (American Institute of Physics, New York, 2008)
[2] J. T. Bendler, J. J. Fontanella, M. F. Shlesinger and M. C. Wintersgill, J. Computational and
Theoretical Nanoscience, 56, 1, 2009
[3] J. T. Bendler, J. J. Fontanella, M. F. Shlesinger and M. C. Wintersgill, J. Non-Cryst. Solids, to be
published
[4] G. Floudas, K. Mpoukouvalas and P. Papadopoulos, J. Chem. Phys., 124, 074905, 2006
*Work supported in part by the Office of Naval Research.

ELECTRICAL RELAXATION IN NOVEL FLUORINATED POLYCARBONATES*
T. S. Filipova (1), D. A. Boyles (1), J. T. Bendler (2), C. A. Edmondson (3), J. J. Fontanella (3), M. F.
Shlesinger (3,4) and M. C. Wintersgill (3)
(1) Dept. of Chemistry and Chemical Engineering, South Dakota School of Mines and Technology,
Rapid City, SD, 57701, USA
(2) BSC, Inc., Rapid City, SD 57702, USA
(3) Physics Department, U. S. Naval Academy, Annapolis, MD 21402, USA
(4) Office of Naval Research, Code 30, 875 N. Randolph St., Arlington, VA 22203, USA
mwinter@comcast.net, mwinter@usna.edu
The homopolycarbonate of bis[4-(4-hydroxyphenyl)phenyl]propane (TABPA-PC) and
homopolycarbonate of 2-(4-(4-hydroxyphenyl)phenyl)-2-phenylpropane (TriBPA-PC) have been
previously reported [1,2,3]. These two polymers have been modified by fluorine substitution for one
or more aryl hydrogen atoms. The resulting polycarbonates are (1) the homopolymer of a difluorinated
tetraaryl monomer (DiF-TABPA-PC) and (2) the homopolymer of a monofluorinated triaryl monomer
(F-TriBPA-PC). Dielectric relaxation studies have been carried out from 10 to 10 5 Hz over the
temperature range 5K to 570K in vacuum and over the temperature range 250K to 326K at pressures
up to 0.3 GPa. The vacuum results allow the study of both the α and γ relaxations while the high
pressure results are for γ only. The vacuum results for the γ relaxation for DiF-TABPA-PC are
interesting in that the height of the peak for isochronal plots increases strongly as temperature
increases. This is similar to the behaviour of the γ relaxation in bisphenol A polycarbonate (BPA-PC).
However, the γ relaxation strength is much greater for DiF-TABPA-PC than for BPA-PC and the
activation enthalpy is larger. The high pressure results for the γ relaxation are interesting because the
pressure shift of a peak for DiF-TABPA-PC is on the order of 200 K/GPa and this is as large as is
observed for the α relaxation for many polymers. For example, the shift of the α relaxation with
pressure for poly(propylene oxide) is about 200 K/GPa [4] and that for poly(ethylene oxide) is about
half that [5]. However, the very large shift with pressure for the γ relaxation is not surprising since it
has recently been shown that the shift for the α relaxation for BPA-PC is one of the largest observed
for polymeric materials, 520 K/GPa, [6]. A model is presented that accounts for the results.
[1] J. T. Bendler, J. C. Schmidhauser and K. L. Longley, US Patent 5,281,689 (1994); J. T. Bendler, J.
C. Schmidhauser and K. L. Longley, US Patent 5,319,149 (1994)
[2] T. Filipova, J. Reams, D.A. Boyles, Polymer Preprints, 46, 971, 2005
[3] D. A. Boyles, T. S. Filipova, J. T. Bendler, G. Longbrake and J. Reams, Macromolecules, 38, 3622,
2005
[4] J. J. Fontanella, M. C. Wintersgill, J. P. Calame, M. K. Smith and C. G. Andeen, Solid St. Ionics,
18-19, 253 1986
[5] M. C. Wintersgill, J. J. Fontanella, P. J. Welcher and C. G. Andeen, J. Appl. Phys., 58, 2875, 1985
[6] K. Mpoukouvalas, N. Gomopoulos, G. Floudas, C. Herrmann, A. Hanewald and A. Best, Polymer,
47, 7170, 2006
*Work supported in part by the Office of Naval Research.
RELAXATION PROCESSES IN THE AMORPHOUS PHASE OF POLY(METHYL-
PENTENE) :
THE PRELIMINARY EVENT PARADIGM
L. David (1), L. Cavetier (1), I. Stevenson-Royaud (1), S. Etienne (2,3)
(1) Université de Lyon, Université Lyon 1, UMR CNRS 5223 IMP, Laboratoire des Matériaux
Polymères et Biomatériaux, Bât. ISTIL, 15 Bd A. Latarjet F69622 Villeurbanne Cedex France.
(2) Nancy Université, Institut Jean Lamour, UMR 7198 CNRS, Dpt SI2M - Parc de Saurupt – CS
14234, F54042 Nancy Cedex France

(3) Nancy Université, Ecole Européenne d’Ingénieurs en Génie des Matériaux, 6 rue Bastien Lepage,
BP 630 – F54010 Nancy Cedex France
Serge.Etienne@eeigm.inpl-nancy.fr
Poly(methyl-pentene) (PMP) is a semi-crystalline polymer exhibiting excellent optical properties. This
optical clarity, which is unusual for semicrystalline materials, is due to similar densities of both the
crystalline and the amorphous phases. Despite this remarkable behavior, few research works have
been published on its dynamic properties (see e.g. Ref. 1). The present paper reports a study of
relaxation processes in the amorphous phase in PMP. Experiments have been carried out by means of
high resolution mechanical spectroscopy [2]. Scanning was performed in a wide frequency and
temperature range, thus allowing to capture low temperature and α relaxation processes occurring in
the amorphous phase (and αc relaxation in the crystalline phase as well) as shown in Figs 1 and 2.
It appears that the non crystalline phase of PMP is a fragile glass former liquid. The analysis of the
experimental data does not indicate that the low temperature relaxation phenomenon, which is the only
secondary process experimentally observed, can be regarded as the preliminary event of the α
relaxation. The question about the identification of (i) the so called Johari-Goldstein (JG) relaxation,
(ii) the secondary relaxation actually observed and (iii) the preliminary event of the main relaxation in
fragile glass formers is stressed again [3].
[1] A. Danch, Journal of Thermal Analysis and Calorimetry, 91 (2008) 733-736
[2] S. Etienne, L. David, M. Mitov, P. Sixou and K.L. Ngai, Macromolecules, 28, 5758-5764 (1995)
[3] S. Etienne, N. Hazeg, E. Duval, A. Mermet, A. Wypich, L. David, Journal of Non-Crystalline
Solids, 353, 3871-3878 (2007)
S. Etienne, C. Lamorlette and L. David, Journal of Non-Crystalline Solids, 235-237, 628-634 (1998)
S. Etienne, Journal de Physique IV, 2, C2 41-C2 50 (1992)
ϕ (rad)
0.25
0.20
0.15
0.10
0.05
β
F=0.036Hz
F=0.12Hz
F=0.4Hz
0.00
-200 -150 -100 -50 0 50 100
Temperature (°C)
Fig.1:isochronal loss factor spectra
α
α c
τ (s)
10 13 Iso-structural regime
10 12
10 11
10 10
10 9
10 8
10 7
10 6
10 5
10 4
10 3
10 2
10 1
10 0
10 -1
Liquid regime
α c
α
T g ~277K
E a =170kJ/mol
τ 0 =6,0 10 -23 s
: from master curve
: from isochronal measurements
Vogel's law τ=τ 0 exp(-B/(T-T v ))
τ 0 =10 -13 s; B=2370K+/-80K;T v =230K+/-2K
3.0 3.5 4.0 9.0 9.5 10
1000/T(K)
Fig.2: relaxation map

MECHANICAL SPECTROSCOPY OF ROLLING OIL FILMS ON COLD-ROLLED STEEL
SHEETS
L.B. Magalas (1) and S. Etienne (2,3)
(1) AGH, University of Science and Technology, Faculty of Metals Engineering and Industrial
Computer Science, al. MIckiewicza 30, 30-059, Krakow, Poland
(2) Nancy Université, Institut Jean Lamour, UMR CNRS 7198, Département Science et Ingéniérie des
Matériaux, Ecole des Mines - Parc de Saurupt, CS14234, 54042 NANCY Cedex, France
(3) Nancy Université, Ecole Européenne d’Ingénieurs en Génie des Matériaux, 6 rue Bastien Lepage,
54000 Nancy
Serge.Etienne@eeigm.inpl-nancy.fr
High resolution mechanical spectroscopy is a sensitive technique for detecting extremely fine traces of
natural oils. Fine traces of groundnut oil can even be discovered in the form of fine debris left on the
surface of cold-rolled steel sheets. It is shown that a characteristic mechanical loss spectrum occurs in
the low temperature range (from 180K up to 280K) only in the two following cases, namely (i) if
traces of the rolling oil are left on the surface of sheets and (ii) if the clean sheets are covered with a
thin film of the rolling oil (or any other natural or mineral oil).
It is clearly demonstrated that similar mechanical spectra induced by the presence of oil can be
observed in the sub-resonant mechanical spectroscopy if the oil film is deposited on a very soft
cellulose neutral substrate. Therefore the behaviour of the oil alone can be obtained with a high
resolution.
It will be demonstrated that it is possible to assign the mechanical loss phenomena to the steel sheet
(like the Snoek-Koster effect above 500K) and oil separately. In particular, it is shown that the low
temperature relaxation phenomena do not originate from a specific interaction of the steel surface with
oil, as frequently reported in the literature.
VIBRATIONAL DYNAMICS OF PERMANENTLY DENSIFIED GeO2 GLASSES:
DENSIFICATION-INDUCED CHANGES OF THE BOSON PEAK.
L. Orsingher (1,2), A. Fontana (1,2), G. Carini Jr (3), G. Carini (3), G. Tripodo(3), T. Unruh(4), and
U. Buchenau (5)
(1) Dipartimento di Fisica, Università di Trento, I-38050 Povo Trento, Italy
(2) Research center SOFT-INFM-CNR, Università di Roma "La Sapienza", I-00185, Roma, Italy
(3) Dipartimento di Fisica, Università di Messina, Salita Sperone 31, 98166 S. Agata (ME), Italy
(4) Technische Universität München, Forschungsneutronenquelle Heinz-Maier-Leibnitz (FRM II),
85747 Garching, Germany
(5) Institut für Festkörperforschung, Forschungszentrum Jülich, 52425 Jülich, Germany
Topologically disordered systems exhibit universal properties when compared with their crystalline
counterpart. Excess modes over the Debye level are detected in specific heat and neutron inelastic
scattering measurements and appear as a bump in the CP/T 3 and g(E)/E 2 plots (known as boson peak).
Recent numerical simulations and experiments show common features in the BP modification as a
function of macroscopic parameters such as the temperature [1], the pressure [2] or the densification
process [3]. However, controversial results have been reported on the density dependence of EBP .
Vitreous GeO2, one of the main prototypes of strong glasses, was densified at several pressures up to 6
GPa, achieving more than 20% of densification. The density dependence of the vibrational density of
states and of the low temperature properties of these samples were investigated by means of inelastic
neutron scattering and calorimetric measurements. A complete spectroscopic and elastic
characterization was performed by means of inelastic light scattering and ultrasonic techniques [4].
With increasing density, both the boson peak and the bump in CP /T 3 vs. T plot exhibit variations
which are stronger than the elastic medium modification. Nevertheless, the existence of a master curve
both for the reduced DOS and the specific heat data of densified samples proves that the number of
excess modes is constant upon densification. A detailed analysis of the experimental data and a
comparison with different theoretical models will be presented.
[1] G. Baldi, et al., Phys. Rev. Lett. 102, 195502 (2009)
[2] K. Niss et al., Phys. Rev. Lett. 99, 055502 (2007)

[3] A. Monaco et al., Phys. Rev. Lett. 97, 135501 (2006)
[4] L. Orsingher et al., Phil. Mag. 88, 3907 (2008)
DIELECTRIC ANALYSIS OF TIO2 NANO-POWDERS PREPARED BY THE PECHINI
METHOD
M.P.F. Graça, M.A. Valente
Physics Department (I3N) – Aveiro University, Campus Universitário de Santiago, 3810 – 193,
Aveiro – Portugal
correspond author: mpfg@ua.pt
Titania (TiO2) has been widely studied because of its unique optical and chemical properties in
catalysis, photocatalysis and nonlinear optics. It has attracted much attention due to their potential
applications in humidity and oxygen sensitivity, solar energy conversion, hydrogen gas generation,
purification systems and in dielectric devices requiring high dielectric constant and high electric
resistivity.
Many synthetic methods have been reported for the preparation of TiO2 nanocrystals,
including sol–gel reactions, hydrothermal reactions, nonhydrolytic sol–gel reactions, template methods
and reactions in reverse micelles. TiO2 nanocrystals with various morphologies and shapes, such as
nanorods, nanotubes, nanowires and nanospheres can be produced depending on the synthetic method
used. It is also known that their morphology and crystalline structure depends on the type of the used
precursors.
Herein, we report the influence of the thermal treatment temperature on the dielectric
properties of highly crystalline TiO2 nanocrystals prepared by the Pechini method. The XRD result
shows that this material crystallizes mainly in anatase or rutile phase. The transition temperatures from
amorphous to anatase and from anatase to rutile phase are 380ºC and 480ºC, respectively. The
dielectric measurements show that the dielectric constant increases significantly, in the samples with
rutile phase, with the increase of the grain size and decrease of the grain-boundaries. Dielectric
relaxation mechanisms were observed using the Modulus formalism.
ELECTRICAL PROPERTIES OF POLYMER/CARBON BLACK COMPOSITE STUDIED
BY BROADBAND DIELECTRIC SPECTROSCOPY
M. El Hasnaoui (1), M. P. F. Graça (2), M. E. Achour (1) and L. C. Costa (2)
(1) LASTID, Physics Department, University Ibn Tofail, B.P:133, 14000 Kénitra, Morocco
(2) I3N and Physics Department, University of Aveiro, 3810-193 Aveiro, Portugal

mpfg@ua.pt
The physical properties of polymer/conducting particles composites are affected in different ways by
several parameters, such as frequency, concentration, size and shape of the conducting particles.
The purpose of this paper is to study the electrical properties of a dispersion of carbon black (CB)
particles in the ethylene butylacrylate (EBA) copolymer matrix, over the frequency range from 500 Hz
to 15 MHz, for temperatures between 20 and 80 °C, and for volume concentrations near and above the
percolation critical concentration. A non-Debye behavior is observed, corresponding to a distribution
of relaxation times, well fitted by the Cole-Cole model. The interfacial polarization energy, caused by
the presence of carbon black particles, is estimated by the determination of the activation energy of the
different composites from an Arrhenius plot.
DIELECTRIC ANALYSIS OF NEW PHOSPHATE GLASSES CONTAINING A MIXTURE
OF TRANSITION METAL OXIDES
M.A. Valente a*) , L. Bih b) and M.P.F. Graça a)
a) Physics Department (I3N) – Aveiro University, Campus Universitário de Santiago, 3810 – 193,
Aveiro – Portugal
b) Equipe Sciences de Matériaux, FST-Errachidia, Maroc
correspond author: mav@ua.pt
New phosphate glasses in the quaternary system X2O-Nb2O5-MoO3-P2O5, where X=Li and Na
were prepared by the melt quenching method. The introduction of MoO3 in the glass composition was
based on the proposal of analysing the reduction of the molar amount of the alkaline oxide and thus
decreasing the molar ratio between network modifiers and network formers (M/F). This work was
compared with the results obtained in the glasses samples of the ternary system Li2O-Nb2O5-P2O5
presented by Graça et al. [1].
The as-prepared glasses were heat-treated in air, at 550ºC and 650ºC for 4 hours. The structure
of the obtained samples was studied by X-ray powder diffraction (XRD) and Raman spectroscopy and
the morphology by scanning electron microscopy (SEM). The dc (σdc), ac (σac) conductivity and
dielectric measurements were made in function of the temperature and were related with the structural
changes of the glasses
[1] M.P.F. Graça, M.A. Valente, M.G. Ferreira da Silva, Journal of Materials Science, 41 (2006) 1137-
1141

GLASS TRANSITION IN 4-PROPYL-ISOTHIOCYANATOBIPHENYL (3TCB) COMPOUND
M. Jasiurkowska.(1), J. Ściesiński (1), J. Czub (2), R. Pełka (1), A. Serghei (3) , E. Juszyńska (1),
Yasuhisa Yamamura (4), M. Massalska-Arodź (1), F. Kremer (3) and Kazuya Saito (4)
(1) The Henryk Niewodniczanski Institute of Nuclear Physics, Polish Academy of Sciences,
Radzikowskiego 152, 31-342 Kraków, Poland
(2) Institute of Physics, Jagiellonian University, Reymonta 4, 30-059 Kraków, Poland
(3) Institute of Experimental Physics I, University of Leipzig, 04103 Leipzig, Germany
(4) Department of Chemistry, Graduate School of Pure and Applied Science, University of Tsukuba,
Tsukuba, Ibaraki 305-8571, Japan
malgorzata.jasiurkowska@ifj.edu.pl
The studied substance (3TCB) shows only one liquid crystalline phase, the crystal-like smectic E
(SmE) phase with an orthorhombic arrangement of the molecular centres of mass in the layers. X-ray
and dielectric studies point to the conclusion that there is a strong rotation-translation coupling for the
flip-flop rotational motion of molecules in this phase [1,2].
Despite the fact that the glasses of highly ordered smectic phases are known (the glass of
smectic B, H, G) the number of papers considering the nature of this kind of glasses is rather limited.
Adiabatic calorimetry studies indicated that the glass of smectic E may have been formed [3]. IR
spectroscopic and X-ray data of 3TBC provide the evidence supporting the identification of the glass
of smectic E [4]. The IR vibrational bands are assigned in the smectic E phase with the help of the
hybrid B3LYP/6-311++G(d,f) functional calculation. The glass structure of the smectic E phase is
suggested. Diffraction data point out that the layer system in the SmE phase is sustained but the
orthorhombic arrangement of molecules within the layers is slightly disturbed. The X-ray results for
the glass of smectic E are compared with those obtained for the vitreous state of another crystal-like
smectic phase (smectic B). Additionally, the dynamics of the molecules in the vicinity of the glass
transition is studied by dielectric spectroscopy.
[1] M. Jasiurkowska, A. Budziak, J. Czub and S. Urban, Acta Physica Polonica A, 110, 759, 2006
[2] M. Jasiurkowska, A. Budziak, J. Czub, M. Massalska-Arodź and S. Urban, Liq. Cryst., 35, 513,
2008
[3] R. Pełka, Y. Yamamura, M. Jasiurkowska, M. Massalska-Arodź and K. Saito, Liq. Cryst., 35, 179,
2008
[4] M. Jasiurkowska, J. Ściesiński, J. Czub, M. Massalska-Arodź, R. Pełka, E. Juszyńska, Y.
Yamamura and K. Saito,
J. Phys. Chem. B , 113, 7435, 2009
HOW THE CYCLIC DSC EXPERIMENTS CAN PROVIDE VARIOUS RESULTS
P. Honcova, R. Svoboda, P. Kostal, J. Malek
University of Pardubice, Faculty of Chemical Technology, Sq. Cs. Legii 565, 53210 Pardubice, Czech
Republic
roman.svoboda@upce.cz
Enthalpy relaxation studies realized by DSC can be done relatively fast if the cyclic cooling/heating
experiment is performed. When different cooling rates are applied while the subsequent heating
through the glass transition range is carried out at constant heating rate, the effective activation energy
∆h ∗ can be obtained. This parameter of the Tool-Narayanaswamy-Moynihan model is calculated from
the slope of linear dependence between the logarithm of cooling rate and the fictive temperature [1].
This work compares the results of cyclic experiments performed for various combinations of cooling
(0.5 – 100 K/min) and heating rates (10, 20 or 50 K/min). Obtained values of parameter ∆h ∗ correlate
with the viscosity behavior [2] of the studied pseudobinary chalcogenide glasses - (GeS2)x(Sb2S3)1-x
where x = 0.2 and 0.3.
[1] J. M. Hodge, J. Non-Cryst. Solids, 169, 211, 1994
[2] J. Shanelova, P. Kostal, J. Malek, J. Non-Cryst. Solids, 352, 3952, 2006
The financial support of the Grant agency of Czech Republic afforded under project No. GA
104/07/P106 is gratefully acknowledged.

FROM PROTEIN DYNAMICS TO THERMODYNAMICS BY NMR, MD, AND MOTIONAL
MODELS
Da-Wei Li (1), Scott Showalter (1), Lei Bruschweiler-Li (1), and Rafael Brüschweiler (1)
(1) Department of Chemistry and Biochemistry and National High Magnetic Field Laboratory, Florida
State University, Tallahassee, FL 32306, U.S.A.
Correspondence author: bruschweiler@magnet.fsu.edu
NMR spectroscopy provides a wealth of experimental parameters on protein structure and dynamics
that serve as useful benchmarks to assess progress in molecular mechanics force fields and molecular
dynamics (MD) simulation protocols. Examples will be shown to demonstrate this point [1-4].
Conversely, MD simulations offer insights into certain aspects of protein dynamics that are hard
to obtain by experiment. This concerns the presence of correlated dynamics between various degrees
of freedom, such as pairs of mobile dihedral angles. Such information can then be utilized for the
derivation of entropic measures [5,6] that permit the quantitative translation of experimental protein
dynamics information, represented by NMR order parameters, into configurational entropies [7].
These ideas will be illustrated for different protein systems.
[1] S. A. Showalter, and R. Brüschweiler, J. Chem. Theory Comput., 3, 961, 2007
[2] S. A. Showalter, and R. Brüschweiler, J. Am. Chem. Soc., 129, 4158, 2007
[3] S. A. Showalter, E. Johnson, M. Rance, and R. Brüschweiler, J. Am. Chem. Soc. 129, 14146, 2007
[4] S. A. Showalter, L. Bruschweiler-Li, E. Johnson, F. Zhang, and R. Brüschweiler, J. Am. Chem.
Soc. 130, 6472, 2008
[5] J. Wang, R. Brüschweiler, J. Chem. Theory Comput. 2, 18, 2006
[6] D.-W. Li and R. Brüschweiler, Phys. Rev. Lett. 102, 118108, 2009
[7] D.-W. Li and R. Brüschweiler, J. Am. Chem. Soc. 131, 7226, 2009
Concentration Fluctuations in a binary molecular glass former investigated by X-ray Photon
Correlation Spectroscopy
S. Schramm(1), T. Blochowicz(1), E. Gouirand(1), B. Stühn(1), and Y. Chushkin(2)
(1) Institut für Festkörperphysik, TU Darmstadt, 64289 Darmstadt, Germany
(2) European Synchrotron Radiation Facility, 38043 Grenoble, France
Sebastian.Schramm@physik.tu-darmstadt.de
We investigated concentration fluctuations in the dynamically asymmetric binary glass former Methyl-
THF in oligomeric PMMA by means of X-ray Photon Correlation Spectroscopy (XPCS) in order to
access a more local length scale than by conventional Laser PCS. The weak temperature dependence
of these fluctuations is in contrast to that of the structural relaxation, which can result in an
intersection point of the time constants of both processes. For the present sample this happens at
experimentally accessible time scales and causes a qualitative change of the relaxation behaviour. Far
above Tg, the concentration fluctuations relax by slightly stretched exponential functions and the

corresponding time constants τ show a diffusive wave-vector dependence τ~q -2 , as expected. By
cooling the sample towards Tg, the relaxation-curves become less stretched, and below Tg they even
can be described by so-called compressed exponential functions (steeper than a Debye-process).
Simultaneously the wave vector dependence of τ changes continuously from τ~q -2 to τ~q -1 . These
effects have been reported in the literature for a variety of soft-matter systems out of thermal
equilibrium [1-3], which undergo a so-called jamming transition and are considered to be linked to the
relaxation of internal stress. Our results can be interpreted as a relaxation of concentration fluctuation
in a structurally confined environment by residual degrees of freedom of the small M-THF molecules
below Tg.
[1] L. Cipelletti et al., Faraday <strong>Discussion</strong>s 123 (2003) 237
[2] P. Falus et al., Phys. Rev. Lett. 97 (2006) 66102
[3] C. Caronna et al., Phys. Rev. Lett. 100 (2008) 55702
PROBING NANOSTRUCTURAL ORGANIZATION IN ROOM TEMPERATURE IONIC
LIQUIDS USING OPTICAL KERR EFFECT SPECTROSCOPY
D. Xiao, L. G. Hines, Jr., R. A. Bartsch, and E. L. Quitevis
Department of Chemistry and Biochemistry, Texas Tech University, Lubbock, TX 79409
edward.quitevis@ttu.edu
Room temperature ionic liquids (ILs) based on the 1,3-alkylmethylimidazolium cation ([Cnmim] + ) are
nanostructurally organized into nonpolar domains and ionic networks. We will show how this
nanostructural organization is reflected in the intermolecular dynamics as determined by optical Kerr
effect (OKE) spectroscopy. We observe a change in the dependence of the spectral parameters of the
intermolecular part of the OKE spectra of [Cnmim][NTf2] ILs on alkyl chain length in going from n =2
to n = 3, which is consistent with a change in liquid morphology as predicted by molecular dynamics
(MD) simulations. We will show how the additivity or nonadditivity of the OKE spectra of binary IL
mixtures reveals information on the nature of charge ordering in the ionic networks. Finally, by
studying the OKE spectra of dilute solutions of CS2, CH3CN, and n-pentane in [C5mim][NTf2] as a
function of concentration, we are able to obtain information on the intermolecular vibrational motions
and the solvation of small solute molecules in ILs. These results in concert with X-ray scattering
measurements and MD simulations shed light on the interplay between the structure and
intermolecular dynamics of ILs.
ELLIPSOMETRIC STUDIES OF THE TRANSFORMATION OF ULTRA STABLE
GLASSES INTO LIQUID
Z. Fakhraai(1), G. K. Pribil(2), M.D. Ediger(1)
Department of Chemistry, University of Wisconsin-Madison, Madison, Wisconsin, USA
J.A.Woollam Inc. 645 M Street, Lincoln, NE 68508-2243 USA
fakhraai@chem.wisc.edu
Glasses that are produced by vapor deposition, under certain conditions are more stable than ordinary
aged glasses [1]. Compared to the ordinary glasses of the same material, these glasses have low
enthalpy, high density, and very slow kinetics. Upon heating above the glass transition temperature,
these glasses show anomalous melting behavior and the bulk of the material can stay a glass ten to
twenty degrees above the glass transition temperature. We used ellipsometry to investigate the
structure and melting kinetics of highly stable TNB glasses deposited on a silicon substrate.

Ellipsometry is used to investigate structural differences, such as increase in the density and
anisotropy between highly stable TNB glasses and the normal amorphous material. These glasses are
then heated above the glass transition temperature either by a constant ramp in the temperature or
isothermally to investigate structural changes during melting and to probe the melting surface growth
front [2] observed using other techniques such as SIMS or nano-calorimetry.
[1] S. F. Swallen, K. L. Kearns, M. K. Mapes, Y. S. Kim, R. J. McMahon, M. D. Ediger, T. Wu, L. Yu,
S. Satija, Science, 315, 353,2007.
[2] S. F. Swallen, K. Traynor, R. J. McMahon, M.D. Ediger, T. E. Mates, Phys. Rev. Lett. 102,
065503, 2009,
VITRIFICATION OF SUSPENSION-CULTURED CELLS OF MARCHANTIA
POLYMORPHA
Y. Sugawara and R. Hatanaka
Department of Regulation-Biology, Saitama University, Saitama City, 338-8570 Japan
sugawara@mail.saitama-u.ac.jp
Anhyrobiotic organisms are capable of developing tolerance to extreme desiccation stress.
Vitrification of cells is considered to be one of the most important components in the mechanism of
desiccation tolerance. It is well known that a large amount of sugars, such as trehalose and sucrose,
accumulate in cells during the development of desiccation tolerance in these organisms and that these
sugars play a crucial role in vitrification of the cells. In this study, we tried to induce desiccation
tolerance in suspension-cultured cells of liverwort (Marchantia polymorpha L.) by culturing them in a
medium containing a high concentration of sucrose. With this culture, the cells acquired extreme
desiccation tolerance and more than 80% of the cells survived even after desiccation to a water content
below 0.1 gH2O/gDW. At this water content, glass transition temperature (Tg) of the cells was in the
range of 20 to 30 ℃. The desiccated cells could be preserved at 5℃ without loss of cell survival for 6
months under the condition in which a constant water content was maintained. However, a decrease in
cell survival was observed with a gradual decrease in water content during long-term preservation at 5
℃ on silica gel. These results suggest that some mobile water, which may be involved in cell survival,
remained even in the vitrified cells.
Influence of Mixing Ratio and Cure Temperature on Strength and Fracture Toughness of
Polyurethane Resin made from Liquefied Wood --Attempt on Application of This Resin in
Construction Material--
Takayuki FUMOTO (1)
(1) Department of Civil and Environment Engineering, Faculty of Science and Engineering, Kinki
University, 3-4-1 Kowakae, Higashiosaka, Osaka, 577-8502, Japan
fumoto@civileng.kindai.ac.jp
A polyurethane resin (PU) was made by co-polymerization of polymeric methylene diphenylene
diisocyanate (PMDI) and a liquefied wood (LW) which was processed by heating a mixture of a wood,
polyethylene glycol (PEG) and glycerol[1]. The influence of the ratio of isocyanate to hydroxyl group
([NCO]/[OH]) and cure temperature on strength and fracture toughness of the PU were studied.
Porous block specimens composed from the crushed stone thinly covered with the PU was subjected
to penetration tests.
For specimens conserved at 20 C, a penetration strength of the specimens with [NCO]/[OH] = 0.6 was
less than that value of specimens with [NCO]/[OH] = 1.0, while the strengths of these samples
conserved at 100 C were the same. In addition, the fracture toughness of the specimens increased by a

factor of 2 by conserving the specimens at 100 C. The LW became robbery material, presumably as a
result of condensation reaction, when it was heated and conserved at 100 C.
These results indicate that the unreacted LW exits in the PU when the [NCO]/[OH] is small. The
unreacted LW forms rubber networks when it is heated to 100C, and the rubbery networks fills pore in
the PU. As the result, the strength and toughness increase.
[1]Kurimoto Y, Takeda M, Koizumi A, Yamauchi S, Doi S, Tamura Y, Bioresourse Technology 74(2),
151-157, 2000
EFFECTS OF CHARGE SEPARATION ON PHOTOCURRENT THROUGH DNA FILMS
T.Himeno(1) and A. Yoshimori (2)
(1) Department of Physics, Kyushu University, Fukuoka 812-8581, Japan
(2) Department of Physics, Kyushu University, Fukuoka 812-8581, Japan
t.himeno@cmt.phys.kyushu-u.ac.jp
The charge transfer in DNA is related to a wide range of fields, such as gene injuries, gene repairs,
and device developments using DNA. It attracts attention from many fields. In addition, relaxations of
charge transfer in DNA are interest problems for us.
There are many experiments about the charge transfer in DNA. We try to explain the experimental
results obtained from T.Takada et al.[1] theoretically. We use DNA sequences NI-(A/T)n-(G/C) (NI:
photosensitizer, n: the number of A/T base pairs).
In our model, Hamiltonian of the system is
H≡H (el) +H (i) +H (b)
In previous studies, off-diagonal elements Vmn of the electronic Hamiltonian H (el) have been treated
as a perturbation term. We, however, diagonalize H (el) and treat H (i) P &
t)
, KHamiltonian
P ( t)
of interaction of
( = ∑ '
k′
k
kk ' k
solvents and nucleobasesas a perturbation term, because Vmn is large in DNA. Then we can obtain the
master equation .
Here, Kkk’ is the transfer rate from the k’th state to the kth state. In this equation, we can treat
delocalized states on several bases.
We investigate the charge recombination rate using this model. In addition, we reveal that the
charge recombination rate decreases exponentially with increases in the number of A/T base pairs. The
charge recombination rate depends on reorganization energy of NI. We determine the value of its
reorganization energy which can duplicate the exparimental results[1]. Furthermore, we find that the
charge separation is important for the charge transfer process in DNA.
[1] T.Takada, C.Lin, and T.Majima Angew.Chem.Int.Ed., 46(35), 6681-6683 (2007).
Roles of hydrodynamic interactions in the gel formation of phase-separating colloidal
suspensions
Akira Furukawa, Muneyuki Noguchi, and Hajime Tanaka
Institute of Industrial Science, The University of Tokyo, 4-6-1 Komaba, Meguro-ku, Tokyo 153-8505,
Japan
Gel formation in phase-separating colloidal suspensions has attracted considerable attention not only
from its fundamental importance as an interesting kinetic path to jamming and its relation to glass
transition, but also from applications viewpoints. Gelation is defined as the percolation of colloidal
particles and this percolation threshold has often been discussed on the basis of the concept of
diffusion-limited aggregation (DLA). In a two-dimensional system, however, we demonstrated by
numerical simulations using the fluid particle dynamics (FPD) method that this percolation threshold

is significantly lowered by hydrodynamic interactions between colloidal particles: hydrodynamic
interactions helps gelation. This casts some doubt on the general applicability of the DLA concept to
colloidal gelation. In 3D it is expected that hydrodynamic interactions may be weaken compared to a
2D case, due to an extra dimension for the flow field to escape into. By comparing FPD simulations
properly incorporating thermal noises with Brownian dynamics simulations, we find that even in three
dimensions interparticle hydrodynamic interactions help gelation and shift the gelation threshold
toward the lower colloid volume fraction and the higher effective temperature. The physical
mechanism responsible for this hydrodynamic effect will be discussed on the basis of the
incompressible nature of hydrodynamic flow.
Spatio-temporal structure of the anomalous viscous transport in supercooled liquids
Akira Furukawa and Hajime Tanaka
Institute of Industrial Science, The University of Tokyo, 4-6-1 Komaba, Meguro-ku, Tokyo 153-8505,
Japan
So far the steep increase in the viscosity near the glass transition point has been regarded as the
highlight of the transport anomaly in supercooled liquids. However, we demonstrate here that the
viscosity anomaly has quite a complicated spatio-temporal structure crucial for elucidating the origin
of slow dynamics, on the basis of three-dimensional molecular dynamics simulation: (i) We find that a
distinct crossover from macroscopic to microscopic viscosity takes place at the characteristic
wavelength which grows with an increase in the degree of supercooling. We show a possible link
between the non-locality of the viscosity and dynamic heterogeneity. (ii) Moreover, the shear-stress
autocorrelation function is investigated in details, which provides an important information about
spatio-temporally non-local viscoelastic response. The novel dynamic features of our findings may
call for a physical description beyond a simple mean-field description such as conventional mode
coupling theory.
ESTIMATION OF PHONON DISPERSION RELATION FROM CORRELATION EFFECTS
AMONG THERMAL DISPLACEMENTS OF ATOMS
T. Sakuma (1), N. Isozaki (1), H. Uehara (1), Xianglian (2), H. Takahashi (3), N. Igawa (4), O.
Kamishima (5)
(1) Institute of Applied Beam Science, Ibaraki University, Mito 310-8512, Japan
(2) Department of Physics and Electronic Information, Inner Mongolia University for Nationalities,
Tongliao 028043, China
(3) Institute of Applied Beam Science, Ibaraki University, Hitachi 316-8511, Japan
(4) Quantum Beam Science Directorate, Japan Atomic Energy Agency, Tokai 319-1195, Japan
(5) Department of Physics, Faculty of Engineering, Setsunan University, Neyagawa 572-8508, Japan
sakuma@mx.ibaraki.ac.jp
Neutron powder diffraction measurements have been performed on ionic crystals and semiconductors
at low temperature and room temperature. The oscillatory diffuse scattering intensity was observed at
room temperature. The oscillatory scheme of the diffuse scattering intensity is explained by the
correlation effects among thermal displacements of atoms [1]. The values of the correlation effects
were also obtained by EXAFS measurement. The force constant in crystal is related to correlation
effects and Debye-Waller temperature parameters. The phonon dispersion relation was calculated by
the force constants among atoms [2]. The derivation of phonon dispersion relation is performed with
the values of the correlation effects by neutron diffuse scattering measurements. The force constant of
first nearest neighboring atoms is obtained by EXAFS measurement, whereas the force constants of

first, second and third nearest neighboring atoms are obtained by the analysis of diffuse scattering.
Therefore we would estimate the phonon dispersion relation with a high accuracy by the analysis of
diffuse scattering measurement than the method of EXAFS measurement.
[1] T. Sakuma, Bull. Electrochem., 11, 57, 1995.
[2] O. Kamishima, T. Ishii, H. Maeda and S. Kashino, Jpn. J. Appl. Phys., 36,247, 1997.
STRUCTURE, INTERACTIONS, AND IONIC CONDUCTIVITY OF IONIC LIQUIDS
Aleksandar Matic (1)
(1) Department of Applied Physics, Chalmers University of Technology, SE-41296, Göteborg,
Sweden
matic@chalmers.se
Ionic liquids are attracting considerable interest for use as electrolytes in various electrochemical
applications such as Li-batteries, Graetzel cells and fuel cells. They show many favourable
properties, for example inherently high ionic conductivity and high thermal stability. For
practical applications the ionic liquids have to be incorporated into a membrane and for use in Libatteries
they have to be doped with lithium salts. To develop these lithium conducting
electrolytes, the ion conduction mechanism, the interaction with the membrane material, and
the solvation shell and the structure around the lithium ions are of importance. In this
contribution we report on the structure, interactions and conductivity behaviour of both neat
and Li-salt doped ionic liquids with varying cationic and anionic structure and of polymer
composite ionic liquid membranes. Using Raman spectroscopy, differential scanning
calorimetry and dielectric spectroscopy we investigate the role of structure and side groups of
the cations, size of the anions, Li-salt concentration, and membrane confinement on the glass
transition temperature and the melting point, the ion conductivity, and the Li-ion
coordination number. We find, for instance, that the Li-ion coordination number increases
considerably for low concentrations and that for a given anion the conductivities of the ionic
liquids all fall on a mastercurve when the temperature is scaled by the glass transition
temperature Tg.
The ordering and freezing-in phenomena in the arrangement of the water molecules confined in
1-D channel with crystalline wall.
K. Watanabe(1), M. Tadokoro(2) and M. Oguni(1)
(1) Department of Chemistry, Graduate School of Science and Engineering, Tokyo Institute of
Technology, 2-12-1 O-okayama, Meguro-ku, Tokyo 152-8551, Japan
(2) Faculty of Science, Tokyo University of Science, 1-3 Kagurazaka, Shinjuku-ku, Tokyo 162-8601,
Japan
watanabe.k.ae@m.titech.ac.jp
The adiabatic calorimetry was carried out to examine the low-temperature behavior of channel water
in the crystals which have 1-D cylindrical channels with different pore diameters: sodium silicate Na-
RUB-18 (crystal 1; diameter 1.1 nm), [Ni(cyclam)(H2O)2]3(TMA)2·24H2O (crystal 2; 1.0 nm), and
[M(H2bim)3](TMA)·nH2O (M = Co, Ru, and Cr) (crystal 3, 4, and 5; 1.5 nm). In the crystal 1, the
water molecules of one kind form one-dimensional network of hydrogen bonds with silanol groups,
while those of the other are isolated and form hydrogen bonds with siloxan oxygens. In the crystals 2-
5, the water molecules adjacent to the channel wall form hydrogen bonds firmly at room temperature
but the others located in the central portion of the channel are disordered and behave like a liquid.
Below room temperature, phase transitions were found which were due to the ordering of the channel
water. The crystalline hydrogen-bond network is developed inside the channel with periodic structure
at the low temperatures; this is contrast to that the water molecules in 1.5 nm pores of MCM-41 with
amorphous wall structure do not crystallize. It is indicated that the ordering behavior is attributed to

the confinement within crystalline channels. Glass transitions were also found at around 100-130 K
below the phase transition temperatures in all these compounds. These phenomena will be discussed
taking into consideration the pore size and periodicities of the channel.
CONFOCAL MICROSCOPY EVIDENCE OF A LINK BETWEEN STRUCTURE AND
DYNAMICS IN COLLOIDAL GLASS
M. Leocmach (1), T. Kawasaki (1), C.P. Royall (2), H. Tanaka (1)
(1) Institute of Industrial Science, The University of Tokyo Komaba 4-6-1, Meguro-ku, Tokyo 153-
8505, Japan
(2) The School of Chemistry, University of Bristol, Bristol, BS8 1TS, United Kingdom
A glassy state of matter results if crystallization is avoided upon cooling or increasing density.
However, the physical factors controlling the ease of vitrification and nature of the glass transition
remain elusive. The possibility of a correlation between medium range crystalline ordering and the
dynamic heterogeneity which characterizes the glass transition was brought into light by recent
simulations [1] and 2D driven granular matter experiments [2]. In such systems, the transient slow
regions tend to correspond in space and time to transient crystal-like regions. The local ordering gets
averaged out in large scale experimental measurements. Tracking colloids in real space by confocal
microscopy, we extract each particle coordinates and obtain meaningful medium range statistics. In
particular, we find a good correlation between bond orientational order [3,4] and dynamic
heterogeneity.
[1] T. Kawasaki, T. Araki and H. Tanaka, Phys. Rev. Lett., 99, 21, 215701, 2007
[2] K. Watanabe and H. Tanaka, Phys. Rev. Lett., 100, 15, 158002, 2008
[3] P. Steinhardt, D. Nelson and M. Ronchetti, Phys. Rev. B, 28, 784-805, 1983
[4] W. Lechner and C. Dellago, J. Chem. Phys., 129, 114707, 2008
STRUCTURAL ORIGIN OF SLOW DYNAMICS IN THREE-DIMENSIONAL COLLOIDAL
GLASS FORMERS
Takeshi Kawasaki (1), Hajime Tanaka (1)
(1) Institute of Industrial Science, The University of Tokyo, 4-6-1 Komaba, Meguro-ku, Tokyo 153-
8505, Japan
kawasaki@iis.u-tokyo.ac.jp
A colloidal liquid has played a crucial role in our understanding of glass transition phenomena.
Theoretically, its hard-core nature of the interaction simplifies the physical description.
Experimentally, a large particle size allows us to directly observe the motion of individual particles in
real time and space. It has been established that polydisperse colloidal liquids exhibit all the essential
features of the glass transition phenomena, including dynamic slowing down toward the glass
transition point, decoupling between the local motion inside a cage and escape motion from the cage,
and dynamical heterogeneity. Thus they are now regarded as one of the most ideal model systems for
studying glass transition. Here we study structure and dynamics of three-dimensional polydisperse
colloidal liquids by Brownian dynamics simulations. We find medium-range crystalline order with
hexagonal close packing structure grows in its size and lifetime in a super-cooled liquid state with
increasing the colloid volume fraction. We show that dynamic heterogeneity are strongly correlated
with this structural ordering which suggests its origin is static rather than dynamic at least in this
system as we found in the two dimensional polydisperse colloidal systems[1,2].
[1] T. Kawasaki, T. Araki and H. Tanaka, Phys. Rev. Lett. 99, 215701 (2007).
[2] T. Kawasaki and H. Tanaka, Phys. Rev. Lett. 102, 185701 (2009).

Free energy landscape theory of glass transition
T. Odagaki*, S. Koga † ** and T. Ekimoto**
*School of Science and Engineering, Tokyo Denki University
Saitama 350-0394 Japan
**Department of Physics, Kyushu University, Fukuoka 812-8581 Japan
A unified theoretical framework for understanding dynamic and thermodynamic anomalies of the
glass transition is presented on the basis of the free energy landscape (FEL). Summing up all the fast
modes of constituents, we can define the free energy as a function of the average position of each
constituent. The slow dynamics can then be described by the Langevin equation on the FEL. The FEL
consists of many basins and the physical quantities are given by their average over the basins.
Therefore for a quick observation the average is determined by the initial distribution, which is called
the quenched average, and for a long time observation the average is given by the average over the
equilibrium distribution, which is called the annealed average. As the temperature is reduced for glass
forming materials, the relaxation time becomes longer, and when it becomes longer than the
observation time, the average is changed from the annealed to the quenched, which manifests itself as
the glass transition. Exploiting model landscapes, we obtain the cooling rate dependence of the
entropy whose temperature dependence agrees qualitatively with experiments. We also show that the
fast process is related to the oscillatory relaxation within a basin and its relaxation time is determined
by the curvature of the bottom of the basin, and that the slow relaxation is related to the jumping
motion within a meta-basin and the relaxation is determined by motion among meta-basins. We
discuss relation between the slow relaxation and the phason flips observed in quasicrystals.
* Corresponding author: odagaki@mail.dendai.ac.jp
†Present address: Meiko Gakuen High School, Omuta, Fukuoka 837-0906 Japan
REFINED INTERACTIONS OF CCR5 AMINO-TERMINAL (CCR5-NT) DOMAIN
PEPTIDES WITH THE THIRD HYPERVARIABLE REGION (V3) OF THE HIV ENVELOPE
GLYCOPROTEIN GP120
Α. K. Rizos (1), D. Morikis (2) and E. Krambovitis (3)
(1) University of Crete, Department of Chemistry, and FORTH - IESL, P.O. Box 2208, Heraklion
71003, Crete, Greece
(2) University of California, Riverside, Riverside, CA 92506, USA
(3) Uiniversity of Thessaly, School of Health Sciences, Karditsa, Greece
rizos@chemistry.uoc.gr, rizos@iesl..forth.gr
The human immunodeficiency virus (HIV) has been investigated for its involvement in a number of
complicated interactions with the human immune system. Our work is focusing on the key V3 HIV
domain that appears to be involved in the process of cell entry using chemokine receptors as co
receptors. The co receptor CCR5 is essential to the infective viral particle for transmission from an
infected macrophage to a CD4+ T cell, the main route of infection during the asymptomatic phase. We
have postulated [1] and have also shown by computational modeling at atomic resolution of

electrostatic potentials [2] and in vitro immune cell experiments [3], the ionic nature of the interaction
between the electropositive V3 loop and the highly electronegative CCR5-Nt. We employed light
scattering to investigate the size, shape, dynamics, and interactions of self-associating peptide
complexes formed by V3 peptides, in dilute aqueous solution, in the presence and absence of CCR5-
Nt.
[1] E. Krambovitis, A. Zafiropoulos, S. Baritaki and D. Spandidos, Scand. J. Immunology 59, 231
(2004).
[2] D. Morikis, A. K. Rizos, D. Spandidos and E. Krambovitis, Int. J. Mol. Medicine 19, 343 (2007).
[3] A. Zafiropoulos, S. Baritaki, M. Sioumpara, D. Spandidos and E. Krambovitis, Biochem. Biophys.
Res. Com. 281, 63 (2001).
SOFT VIBRATIONS MAP THE HETEROGENEITIES OF STRUCTURAL RELAXATION
IN MODEL GLASSES
A.Widmer-Cooper (1), V.K.de Souza (2), H.Perry (3), D.R.Reichman (3) and P.Harrowell (2)
(1) Materials Science Division, Lawrence Berkeley National Laboratory, Berkeley CA, USA
(2) School of Chemistry, University of Sydney, Sydney NSW Australia
(3) Department of Chemistry, Columbia University, New York, NY, USA
peter@chem.usyd.edu.au
Slow structural relaxation in supercooled fragile liquids is intimately related with the spatial rarity of
regions at which relaxational motion is possible. This spatial distribution of dynamic heterogeneities
reflects a corresponding heterogeneity in the structure of the particle configurations. We report that the
quasi-localized soft modes of the local potential minima (the inherent structures) provide an excellent
indicator of the ‘hidden’ heterogeneity of the structure that determines the spatial arrangement of long
time dynamic heterogeneities [1]. In a study using constraint networks to model the inherent structures,
we show that both the spatial distribution of these floppy modes and their evolution in time depend
sensitively on how far the structure of the local potential minima are from the point of marginal
mechanical stability [2].
[1] A.Widmer-Cooper, H. Perry, P. Harrowell and D.R.Reichman, Nature Physics, 4, 711, 2008
[2] V.K. de Souza and P. Harrowell, Proc. Nat. Acad. Sci., Early Ed, May 12, 1, 2009
RELAXATION PROCESSES IN ANHYDROUS TREHALOSE GLASSES
Yoon-Hwae Hwang*, Jeong-Ah Seo + , Hyun-Joung Kwon, Dong Myeong Shin, Hyung Kook Kim
Department of Nanomaterials Engineering & BK21 Nano Fusion Technology Division, Pusan
National University, Miryang 627-706, Korea
+ Current address: Laboratoire de Dynamique et Structure des Matériaux Moléculaires, UMR CNRS
8024, Université de Lille 1, UFR de Physique, Bât. P5, 59655 Villeneuve d’Ascq Cedex, France
* Corresponding authors: yhwang@pusan.ac.kr
We studied relaxation processes of anhydrous Trehalose in supercooled and glassy states by using
photon correlation spectroscopy(PCS) and dielectric loss spectroscopy(DLS). In PCS measurements,
we found a compressed-exponential behavior in α-relaxation process at temperatures above 140 o C. In
DLS measurement, however, we observed a stretched exponential behavior of α-relaxation process
and the temperature dependency of α-relaxation times showed crossover at temperatures around the
glass transition temperature[1]. We also observed an unidentified relaxation process in dielectric loss
spectra located between Johari-Goldstein(JG)- and γ-relaxations[2]. In the temperature range where we
observed the compressed exponential relaxtion, we found glycosidic bond structure changes in

trehalose molecules using Raman scattering experiment indicating the observed compressedexponential
relaxation might be related to the intra-molecular(glycosidic bond) structure change.
[1] R. Casalini and C.M. Roland, Phys. Rev. Letts. 102 (2009) 035701
[2] S. Capaccioli, K. Kessairi, D. Prevosto, M. Lucchesi, K.L. Ngai, J. Non-Cryst. Solids 352 (2006)
4643
EFFECTS OF INORGANIC NANOFILLERS AND COMBINATIONS OF THEM ON THE
COMPLEX PERMITTIVITY OF EPOXY-BASED COMPOSITES
R. Kochetov (1), T. Andritsch (1), U. Lafont (2), P.H.F. Morshuis (1), J.J. Smit (1)
(1) Delft University of Technology, Mekelweg 4, 2628 CD, Delft, Netherlands
(2) Delft University of Technology, Julianalaan 136, 2628 BL, Delft, Netherlands
R.Kochetov@tudelft.nl
In this paper, we investigated the influence of nanofiller material and its concentration on dielectric
properties of epoxy-based composite systems. A comparative study is performed between unfilled
base epoxy, the systems containing one type of nanoparticles (silicon dioxide, aluminum oxide or
aluminum nitride) and composites containing a combination of two different fillers inside the host
polymer.
Significant efforts have been devoted to improve the dispersion of nanosized filler in a polymer. The
mechanical dispersion was carried out with ultrasonication and high shear mixing. This was supported
by a chemical method: the surface modification of particles with a silane coupling agent, leading to
enhanced dispersion. The surface chemistry of modified and non-modified nanoparticles was
characterized by a Fourier transformed infrared (FTIR) spectroscopy. The quality of the dispersion
was evaluated with transmission electron microscopy (TEM).
In the present work the dielectric behavior of composite samples is analyzed by using complex
permittivity values, determined by means of dielectric spectroscopy in the frequency range of 0.01 Hz
– 10 MHz at different temperatures. An inspection of the real and imaginary parts of the relative
permittivities of epoxy composites shows that the filler type and concentration has a remarkable effect
and possible explanations for this behavior are given.
DYNAMIC α- AND β− RELAXATIONS IN METALLIC GLASSES
H. Kato (1), T. Ichitsubo (2), J. M. Pelletier (3), J. Saida (4) and A. Inoue (5)
(1) Institute for Materials Research, Tohoku University, Sendai 980-8577, Japan
(2) Department of Materials Science and Engineering, Kyoto University, Kyoto 606-8501, Japan
(3) MATEIS, INSA-Lyon 69621 Villeurbanne Cedex, France
(4) Center for Interdisciplinary Research, Tohoku University, Sendai 980-8578, Japan
(5) President, Tohoku University, Sendai 980-8577, Japan
hikato@imr.tohoku.ac.jp
Dynamic relaxations were investigated in the vicinity of the calorimetric glass transition temperature
(Tg) in typical bulk metallic glasses, e.g. Zr-, Mg-, Pt- and Pd-based alloys. The frequency dependence
of the loss modulus E” measured under the isothermal condition is an asymmetric peak tailing in the
higher frequency region. This indicates that these glasses exhibit the sub-Tg “β-relaxation” as well as
the glass transition “α-relaxation”. When we fit the loss-modulus peak with the sum of the stretched
exponent Kohrausch-Williams-Watts (KWW) functions for the α- and β- relaxations, the thermal
activation energy (Eβ) for the β-relaxation is estimated to be several eV depending on the alloy system,
which is almost the same value for the self atomic diffusion. Thus, the origin of the observed βrelaxation
is considered to be the short-range translational motion of the constituent atoms. If the βrelaxation
occurs in the loosely packed and/or lower elastic isolated region as claimed by Johari [1] or
Ichitsubo [2], we can estimate its volume fraction (vβ) from the intensity of the α- and β-relaxation
peaks. In the case for some typical Zr-based BMGs, vβ is estimated to be about 40 vol% in this

temperature region, which was found to change little with the composition. The relaxation-time
distribution in the vicinity of Tg in the metallic glasses will be discussed in terms of the stretched
exponent, fragility parameter, and difference in the activation energy for the α- and β-relaxations at Tg
in this paper.
[1] J. P. Johari, J. Non-cryst. Solids, 307-310, 317. 2002
[2] T. Ichitsubo et al., PRL 95 (2005) 245501.
OPEN PROBLEMS IN BIOLOGICAL ELECTRON TRANSFER PROCESSES AND
CONNECTIONS WITH MOLECULAR DEVICES
Spiros S. Skourtis
Department of Physics University of Cyprus, PO Box 20537, Nicosia 1678, Cyprus
skourtis@ucy.ac.cy
Biomolecular electron transfer reactions are ubiquitous in biology and they involve a variety of
electron transport mechanisms. We review recent theoretical progress on the effects of conformational
distributions, excited-state polarization, and electron-nuclear dynamics on electron transfer reactions
in different biomolecular systems. Further, we discuss connections between biomolecular electron
transfer and electron transport in small molecule devices.
[1] S.S. Skourtis, J. Lin, and D. N. Beratan In: E. B. Starikov, S. Tanaka, and J. P. Lewis, Editors,
Modern methods for Theoretical Physical Chemistry of Biopolymers, Elsevier (2006), p. 357.
MAGNETODIELECTRIC ANISOTROPY EFFECT
IN THE PDMS FERROMAGNETIC GEL
L.Kubisz 1 , A.Skumiel 2 , E.Pankowski, D.Hojan-Jezierska
1 Department of Biophysics, University of Medical Sciences in Poznań, Poland, kubisz@amu.edu.pl
2 Department of Molecular Acoustics, Institute of Acoustics, Adam Mickiewicz University, Poznań,
Poland
Ferrogel is an assembly of ferromagnetic nanoparticles embedded in a polymer gel. In the
ferrogel, the finely distributed magnetic particles are suspended in the swelling liquid and form a
flexible matrix due to adhesive forces. Polydimethylsiloxane (PDMS) is the a most widely used
silicon base organic polymer because is inert and non-toxic. Addition of chemically stable, non-toxic
and non-carcinogenic ferromagnetic substances such as iron oxide. This results in magnetic and
electric field sensitive materials being applied in controlled drug delivery, artificial muscles and
electromagnetically induced hyperthermia for cancer therapy [1-4].
The mean diameter of magnetic particles of Fe3O4 was determined as equal to 8.87 nm [5].
The presence of conducting metallic particle enhances the effective electrical conductivity of the
PDMS gel (2pSm -1 at 20ºC), which is higher than that of pure PDMS [5,6].
The present paper describes an electric study of magnetic field sensitive PDMS ferrogel.
Possible mechanical deformation of highly elastic PDMS after the application of magnetic uniform
field [7,8] leads to the modification of its electric properties.
Measurements of electric permittivity ε’ were carried out using a homemade cell and the HIOKI
3523-50 LCR HiTESTER in the frequency range of 400 Hz - 5 MHz. To assess anisotropy of ε’,
measurements were carried out for both, electric field E parallel and perpendicular to magnetic
induction B. Measurements were performed at the temperature of 21ºC, in the uniform magnetic field
varying from 0 to 0.5 T, both increasing and decreasing.
The revealed dispersion and induced anisotropy along with hysteresis of ε’ within the
magnetic induction range 0 - 0.50 T, are presumably related to interactions between the external
magnetic field and magnetite particles, which are coupled by adhesion forces to a ferrogel network.

The change in permittivity of ferromaterial on application of homogenous magnetic field, known as
magnetodielectric effect, is an indication of coupled magnetic and elastic order. The effect was found
in the multiferroics systems – composites, which were combination of ferroelectrics and ferromagnetic
materials and ferroliquids.
The magnetodielectric effect observed in the PDMS ferromagnetic gel was temporary.
References
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7. M. Radulescu. 1990 J. Magn. Magn. Mat. 85 144–6
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CONFINEMENT AND INTERFACIAL EFFECTS IN ULTRATHIN POLYMER FILMS
PROBED BY DIELECTRIC SPECTROSCOPY
C. Rotella, S. Napolitano and M. Wübbenhorst
Katholieke Universiteit Leuven, Laboratory for Acoustics and Thermal Physics,
Department of Physics and Astronomy, Celestijnenlaan 200D, B-3001 Leuven, Belgium
cinzia.rotella@fys.kuleuven.be
In ultrathin polymer films physical properties such as the glass transition temperature (Tg) and thus the
cooperative segmental relaxation dynamics are often sensitively altered as compared to the bulk
system [1]. Moreover, the thickness dependence of Tg is strongly influenced by interfacial effects
arising from both attractive interfaces and free surfaces. As a recent example, dielectric relaxation
measurements on freely-standing films of polystyrene (PS) revealed a Tg reduction up to 60 K [2] that
is generally attributed to an enhanced mobility at the free surfaces [3]. However, the postulated
existence of depth gradients in the segmental mobility prompts for the development of experimental
techniques being able to resolve the glass transition dynamics across the film thickness direction [4].
In this paper we discuss the idea and the experimental implementation of a multilayer approach based
on labelled and unlabelled polystyrene. In contrast to previous work using fluorescent labels [5] we are
utilizing probe molecules with high dipole moments (dielectric labels) covalently attached to the
polymer chains. First results are presented and compared with predictions for mobility profiles in thin
films samples.
[1] S. Napolitano, M. Wübbenhorst, J. Phys. Chem. B, 111, 9197, 2007
[2] C. Rotella, S. Napolitano, M. Wübbenhorst, Macromolecules, 42, 1415, 2009
[3] Z. Fakhraai and J. A. Forrest, Science, 319, 600, 2008
[4] P.G. de Gennes, Eur. Phys. J E 2, 201, 2000
[5] C.J. Ellison and J.M. Torkelson, Nat. Mater. 2, 695, 2003
SINGLE MOLECULE PROBING OF POLYMER DYNAMICS IN THE SUPERCOOLED
REGIME: NEW ALGORITHMS TO ANALYSE FLUORESCENCE LIFETIMES AND
LINEAR DICHROISM DATA
G. Hinze (1), Th. Basché (1) and R. Vallée (2)
(1) Institut für Physikalische Chemie, Johannes Gutenberg-Universität Mainz, D-55099 Mainz,
Germany
hinze@uni-mainz.de

(2) Centre de Recherche Paul Pascal (CNRS), 33600 Pessac, France
Fluorescence experiments on single BODIPY molecules embedded in poly(methyl acrylate) have been
performed at various temperatures in the supercooled regime. By using pulsed excitation, fluorescence
lifetime and linear dichroism time trajectories could be recorded at the same time. While the latter
strictly reflects single particle dynamics, the former depends on both, the surrounding and the
chromophore itself. We present new algorithms to analyse the time resolved data without the need of
time binning. The new methods are characterized by a significantly enhanced time resolution to short
times thus allowing to study significantly faster fluctuations of either single molecule reorientation or
fluorescence lifetimes, respectively. Besides the analysis of rotational correlation times and
fluorescence lifetime fluctuations we discuss the geometry of the rotational dynamics as a function of
temperature.
POLYMER DYNAMICS: FROM SYNTHETIC TO BIOLOGICAL MACROMOLECULES
Dieter Richter
Institute for Solid State Research, Research Center Juelich, D-52425 Jülich, Germany
d.richter@fz-juelich.de
During recent years the molecular dynamics of linear polymers has been thoroughly investigated and
by now more complex systems come into focus. After a brief reminder on key results on linear
polymers I will address the effects on confinements on polymer dynamics. We will consider (i) soft
confinement in mesophases of mobile diblock copolymers [1] where surface tension is an important
driver for chain dynamics and (ii) hard confinement where in particular we will discuss the suggested
corset effect which proposes a complete change of the reptation dynamics in confining media [2].
In the second part I discuss neutron spin echo experiments on the interdomain motions in alcohol
dehydrogenase [3] that are essential to enable or to promote biochemical function. The collective
motions are revealed by their coherent form factor and relate to the cleft opening dynamics between
the binding and the catalytic domains enabling thereby the binding and the release of the functional
important cofactor.
[1] R. Lund, L. Willner, M. Monkenbusch, J. Colmenero, D. Richter, to be published
[2] M. Krutyeva, A. Arbe, M. Monkenbusch, J. Martin, C. Migangos, J. Colmenero, D. Richter, to be
published

[3] R. Biehl, B. Hofmann, M. Monkenbusch, P. Falus, S. Preost, R. Merkel, D. Richter, Phys. Rev.
Lett., 101, 138102, 2008
UNIVERSAL CRITICAL-LIKE SCALING OF DYNAMICS IN PLASTIC CRYSTALS
J.C.Martinez-Garcia (1), J.Ll.Tamarit (1), S.J. Rzoska (2), A.Drozd-Rzoska (2), L.C.Pardo (1),
M.Barrio(1)
(1) Department of Physics and Nuclear Engineering, Group of Characterization of Materials, ETSEIB,
Diagonal 647, Universitat Politècnica de Catalunya, Barcelona, Spain
(2) Institute of Physics, Silesian University, ul. Uniwersytecka 4, 40-007 Katowice, Poland
julio.cesar.martinez@upc.edu
Many theoretical models for the glassy dynamics has been proposed so far the impressive changes in
molecular dynamics concerning the extraordinary slowing down in the vitrification process of a
disordered phase on cooling [1-4]. Many of them share the concept of cooperative rearranging regions,
firstly proposed by Adam and Gibbs [1], as the dynamical scaling model [5,6], based on the randomly
diffusion of the free volume which creates random walk clusters of cooperatively rearranging entities.
Within this framework a critical phenomenon relating a hidden phase transition at Tc (below Tg)
−φ
implies the divergence of the relaxation time τ τ , η ∝ ( − C ) T T with a universal scaling
exponentφ → 9 .In this work we apply the DSM model to orientational glasses, obtained from the
quenching of orientationally disordered phases (plastic crystals) via the application of the linearized
derivative-based transformation of dielectric spectroscopy τ(T) data, proposed by the work A.Drozd-
Rzoska et al [7-8].
[1]G.Adam and J.H.Gibbs.J.Chem.Phys 43(1965) 139.
[2]F.Kremer and A.Shonhals (eds), Broad Band Dielectric Sprectroscopy (Springer,Berlin,1988).
[3]J.C.Dyre Rev.Mod.Phys,78, (2006) 953.
[4]H.Tanaka,Phys. Rev. E 62 (2000) 6968.
[5]B.M.Erwin,R.H.Colby J. Non-Cryst. Solids, 225 (2002) 307.
[6]R.H.Colby, Phys. Rev. E 61 (2000) 1783.
[7]A.Drozd-Rzoska and S.J.Rzoska,Phys. Rev. E 73 (2000) 041502.
[8]A.Drozd-Rzoska , S.J.Rzoska, S. Pawlus and J.Ll. Tamarit, Phys. Rev. E 73 (2006) 224205.
ION DYNAMICS IN SOLID POLYELECTROLYTE MATERIALS
Cornelia Cramer (1), Yahya Akgöl (1), Amrtha Bhide (1), Árpád Imre (2) and Monika Schönhoff (1)
(1) Institut für Physikalische Chemie and Sonderforschungsbereich 458, Westfälische Wilhelms-
Universität,
Corrensstraße 28/30, 48149 Münster, Germany
(2) Current Address: Robert Bosch GmbH, P.O. Box 30 02 40, 70442 Stuttgart, Germany
Cramerc@uni-muenster.de
Frequency-dependent conductivities are a valuable tool for studying the ion dynamics on different
time scales. We present and analyze conductivity spectra of two kinds of solid polyelectrolyte
materials, viz. polylectrolyte multilayers (PEM) and polyelectrolyte complexes (PEC). The PEM
spectra were taken at ambient temperature but at various relative humidies. By contrast, the

conductivity of different kinds of dried PEC was studied as a function of temperature. For both kinds
of material classes we show that the MIGRATION concept developed by Funke et al. can be used to
describe the experimental spectra over wide ranges in frequency, indicating that forward-backward
hopping motions of small ions play a vital role in solid polyelectrolyte materials. Apart from these
potentially successful hops, localized motions of charged particles are found to influence the
conductivity spectra as well. Based on the shape of our conductivity spectra and their scaling
properties, we arrive at important conclusions about the microscopic ion dynamics in PEM and PEC
materials.
Thermal properties of ordinary and heavy water confined within mesoporous silica MCM-41
M. Oguni (1), Y. Kanke (1), and A. Nagoe (1)
(1) Department of chemistry, graduate school of science and engineering, Tokyo Institute Technology,
2-12-1 O-okayama, Meguro-ku, Tokyo 152-8551, Japan
Corresponding author: moguni@chem.titech.ac.jp
The thermal properties of the ordinary and heavy water within mesoporous silica MCM-41 were
characterized by an adiabatic calorimetry. It was found that the water in the pore center remained in
the liquid state in the pore diameter below 2.1-2.2 nm while crystallized above 2.3 nm, and that the
interfacial water on the pore wall remained in the disordered arrangement irrespective of the state of
the water in the pore center. The interfacial water showed its glass transition at around 115 K, and the
internal water at around 160 K in the pore diameter below 1.8 nm and around 215 K above 2.1 nm.
The 2.1-2.2 nm is considered as the limiting diameter for the water to remain in the liquid state: Then,
the water seems to display characters of bulk water, indicating that the Tg of bulk water is 215 K but
not 135 or 160 K. All the Tg’s increased by about 5 K by deuterium substitution, similarly to the fusion
temperature. The water showed a heat capacity hump around 233 K and 241 K for H2O and D2O,
respectively, rather independently of the pore size. The difference of 8 K is similar behavior to that in
the temperature of maximum density. This suggests the hump of Cp is the characteristic of structural
change of liquid water such as corresponds to crossing “Widom line” in association with a liquidliquid
transition.
Poly-Ig fragments of beta-connectin from human cardiac muscle: folding, unfolding and
clustering
S. Marchetti (1,2), C.M.C. Gambi (1,2), F. Sbrana (1,5), E. Fratini (3), M. Carlà (1), M. Vassalli (4,5)
B. Tiribilli,(4,5), A. Pacini(6) and A. Toscano(6)
(1) Department of Physics, University of Florence and CNISM Via G. Sansone 1, 50019, Sesto
Fiorentino (Florence), Italy
(2) CRS-Soft Matter (CNR-INFM) University of Rome "La Sapienza", P.le A. Moro 2 , 00185 Rome,
Italy
(3) Department of Chemistry and Consorzio Interuniversitario per lo Sviluppo dei Sistemi a Grande
Interfase (CSGI), University ofFlorence, Via della Lastruccia 3, 50019, Sesto Fiorentino (Florence),
Italy
(4) Complex System Institute of the National Research Council (ISC-CNR), Florence, Italy
(5) CSDC, Department of Physics, University of Florence, Florence, Italy
(6) Department of Anatomy, Histology, and Forensic Medicine, University of Florence, Florence, Italy
corresponding author: marchetti@fi.infn.it
Folding-Unfolding transition and clusters formation of proteins are of wide interest in diverse areas as
biophysics, nanophysics, protein science, biotechnologies and are intimately linked to the pathogenesis
of most neurodegenerative disorders (Parkinson, Alzheimer's). Two specific fragments of betaconnectin
from human cardiac muscle have been investigated in order to understand the intimate
relation between protein-protein interaction and clusters formation. The fragments with elastic

properties are composed by four Ig domains (tetramer) and eight Ig domains (octamer). DLS, SAXS
and AFM imaging studies provide the size and distribution of both fragments.
AFM single molecule force spectroscopy performed on the octamer provides quantitative informations
about the unfolding force and the structural parameters such as the contour length and persistence
length[1].
Moreover, DLS and AFM revealed that the fragment aggregation behavior runs parallel to the
unfolding transition [2].
[1] M.Bohdanecky, Macromolecules, 16, 1483, (1983)
[2] S.Marchetti, F. Sbrana, R. Raccis, L. Lanzi, C.M.C. Gambi, M. Vassalli, B. Tiribilli, A. Pacini and
A. Toscano, Physical Review E, 77, 1, (2008)
DIELECTRIC RELAXATION SPECTROSCOPY OF IONIC LIQUIDS OF LOW VISCOSITY
M.-M. Huang and H. Weingärtner
Physical Chemistry II, Ruhr-Universität Bochum, D-44780 Bochum (Germany)
hermann.weingaertner@rub.de
We have investigated complex dielectric spectra of about 40 ionic liquids of low and moderate
viscosity, mostly at 298 K. The experiments typically cover frequencies from 10 MHz up to 20 GHz,
corresponding to processes on the picosecond-to-nanosecond time scale [1-3]. The spectra show
multimodal behaviour with dispersion/absorption regimes due to diffusive processes on the time scale
of 50 ps to 1 ns, non-diffusive processes near 10-30 ps and evidence for marked contributions beyond
the upper-frequency cut-off of 20 GHz of pour experiments. The dispersion curves reach lowfrequency
plateaus due to quasi-static behaviour. The deduced apparent static permittivities cover a
wide range from εS = 10 for some salts with nonpolar anions to εS ≅ 100 for protic ionic liquids with
OH-terminated alkylammonium cations and polar anions, for example 2-hydroxyethylammonium
lactate. The mechanisms of dielectric relaxation are discussed with regard to results from molecular
dynamics simulations [4].
[1] C. Daguenet, P. J. Dyson, I. Krossing, A. Oleinikova, J. Slattery, C. Wakai, H. Weingärtner, J.
Phys. Chem. B, 110, 12683, 2006.
[2] H. Weingärtner, P. Sasisanker, C. Daguenet, P. J. Dyson, I. Krossing, J. Slattery, P. Schubert, J.
Phys. Chem. B, 111, 4775, 2007.
[3] M.-M. Huang and H. Weingärtner, ChemPhysChem 9, 2172, 2008.
[4] C. Schröder, C. Wakai, H. Weingärtner, O. Steinhauser, J. Chem. Phys., 126, 084511, 2007.
PROTEIN DYNAMICS IN BRILLOUIN LIGHT SCATTERING: THERMAL
DENATURATION OF HEN EGG WHITE LYSOZYME
Svanidze A.V. (1), Lushnikov S.G. (1), Romanov V. P. (2), C. Pruner (3), A.Asenbaum (3)
(1) Ioffe Physical Technical Institute, Politekhnicheskaya 26, St. Petersburg 194021 Russia Laboratory
(2) Saint Petersburg State University, Department of Physics, Ul'yanovskaya 1, Petrodvoretz, 198504
St. Petersburg, Russia
(3) Department for Materials Research and Physics, University of Salzburg, Hellbrunerstasse 34,
Salzburg, Austria
sergey.lushnikov@mail.ioffe.ru
We report results of the Brillouin light scattering studies of the lysozyme solution at heating from 293 K to 355
K. Brillouin scattering from the lysozyme solution is compared with that from the sodium acetate buffer used

to dissolve the lysozyme. Anomalies in the temperature dependences of velocity and damping of hypersound
for the lysozyme solution at thermal denaturation have been revealed [1]. These anomalies are attributable to
phase transformations of the protein in the high-temperature region. It is found also that in the vicinity of 343
K the lysozyme solution becomes opalescent, and the intensity of the Brillouin peaks decreases anomalously
and almost vanishes, to be restored at temperatures above 343 K. No anomalies were observed in Brillouin
scattering for the sodium acetate buffer. The analysis of experimental data revealed a sol-gel transition in the
lysozyme solution near 343 K. A mechanism that correctly describes the behavior of Brillouin light scattering
in the vicinity of the sol-gel transition is suggested [2]. It has been shown that Brillouin light scattering is a
suitable tool for studying the structural evolution of proteins.
[1] A.V. Svanidze, S.G. Lushnikov, Seiji Kojima, JETP Letters 90, 2009, in press
[2] A.V. Svanidze, S. G. Lushnikov, V. P. Romanov, et.al., unpublished.
NANOSTRUCTURE AND CONFINEMENT EFFECS IN SEMI-CRYSTALLINE
POLYMERS
Erisela Nikaj (1), Isabelle Stevenson Royaud (1), Gérard Seytre (1), Laurent David (1)
(1) Université de Lyon, Lyon, F-69003, France ; Université Lyon 1, IMP/LMPB Laboratoire des
Matériaux Polymères et Biomatériaux, Bât ISTIL, 43 bd du 11 Novembre, Villeurbanne, F-69622,
France ; CNRS, UMR5223, Ingénierie des Matériaux Polymères, Villeurbanne, F-69621 , France.
Correspondence author: erisela.nikaj@hotmail.fr
The confinement effects in semi-crystalline poly(ethylene naphthalene-2,6-dicarboxylate) (PEN) were
studied by means of broad band dielectric relaxation spectroscopy (BBDRS) and analyzed in relation
with semi-crystalline morphology. The systems were obtained by cold crystallization at different
crystallization temperatures (Tc) and crystallization times (tc) [1, 2]. Differential scanning calorimetry
(DSC) shows that the crystallinity ratio (Xc) increases when Tc and tc increase, as expected [3]. The
resulting confinement effects increase (the glass transition relaxation is shifted to higher temperatures
or lower frequencies) as the crystallization time increases. Nevertheless the confinement effects
decreased with increasing crystallization temperature. The origin of this anomalous dynamics can be
related to the crystalline lamellar stack morphology, as revealed by small angle X-ray scattering
(SAXS). It can be concluded that the confinement effects of the crystalline phase on the amorphous
phase are less efficient after crystallization in the higher temperature range, resulting in a coarser
microstructure and an amorphous layer thickening. The interface between amorphous phase and
crystalline lamellae is also shown to play a role on the confinement effects.
[1] M. C. García Gutiérrez, D. R. Rueda, F. J. Baltá Calleja, N. Stribeck and R. K. Bayer, Journal of
Materials Science 36 (2001), p. 5739.
[2] M. C. García Gutiérrez, D. R. Rueda, F. J. Baltá Calleja, N. Stribeck and R. K. Bayer, Polymer 44
(2003), p. 451.
[3] A. Nogales, Z. Denchev and T. A. Ezquerra, Macromolecules 33 (2000), p. 9367.

UNIVERSALITY OF JOHARI-GOLDSTEIN RELAXATION
M. Shahin Thayyil(1,2)*, S. Capaccioli(1), D. Prevosto (1), M. Lucchesi (1), P. A. Rolla(1) and K.L.
Ngai (1,3)
(1) CNR-INFM, polyLab & Departimento di Fisica, Universita di Pisa, Italy.
(2) Department of Physics, University of Calicut, India.
(3) Naval Research Laboratory, Washington D.C, USA.
*Correspondence author: shahin@df.unipi.it
Discovery of secondary relaxation in totally rigid molecules by Johari & Goldstein [1] and subsequent
studies [2, 3] gave new insights to the understanding of the glass transition phenomena. We report,
based on broadband dielectric spectroscopy by varying pressure and temperature, the properties of JG
relaxations of rigid dipolar probes in various apolar hosts by choosing systematic increase of size,
different molecular structure, dipole moment and the glass transition temperature. The probes are
halogenated benzenes & naphthalenes, adamantane derivatives, heterocyclic aromatics etc., while the
apolar hosts are alkylbenzenes, decaline, o-terphenyl and oligomers of styrene etc. We could resolve
the true intermolecular JG relaxation for the first time of some well studied flexible low molecular
systems like benzophenone and phthalate derivatives. The elevated pressure experiments in all the
systems studied (rigid & flexible probes) showed exceptional pressure-temperature superposition of
JG and the structural relaxation. We conclude that the JG process is the cause and the structural
relaxation is the effect of the glass transition phenomena.
Reference:
[1] G. P. Johari, M.Goldstein, J. Chem. Phys. 53 (1970) 2372.
[2] K. L. Ngai, M. Paluch, J. Chem. Phys.120 (2004) 857.
[3] K. Kessairi, S. Capaccioli, et al. J. Phys. Chem. B 112 (2008) 4470.
IMPEDANCE ANALYSIS OF AGED ELECTROCHROMIC WO3 THIN FILMS
E. Pehlivan (1), G. A. Niklasson (1), Claes G. Granqvist (1), P. Georen (2) and S. Von Kraemer (2)
(1) Department of Engineering Sciences, The Ångström Laboratory, Uppsala University, P.O. Box
534, SE-751 21 Uppsala, Sweden
(2) ChromoGenics AB, Märstagatan 4, SE-753 23 Uppsala, Sweden
Esat.Pehlivan@Angstrom.uu.se
Long-term ageing of electrochromic WO3 thin films were performed by applying cyclic square wave
potentials. Electrochemical impedance spectroscopy measurements, in the frequency range 0.01Hz to
1 MHz, of the aged films were conducted in a LiClO4/PC electrolyte at various potentials from the
fully colored state to the fully bleached state. The magnitude of the impedance at low frequencies
changed drastically from a few kΩ in the darkest state to 100kΩ in the most bleached state. Equivalent
circuit analysis of the observed data was done to characterize the relaxation parameters. Anomalous
diffusion models, represented by transmission lines, with additional elements representing the
interfaces WO3/electrolyte and WO3/ITO, were used. An increase of the impedance was observed for a
significantly degraded sample.
SIMULATION STUDY OF DIFFERENCES IN COMPOSITION FOR SUPERCOOLED
LIQUIDS ON CU60ZR20TI20 AND CU60ZR30TI10

Hiroyuki Fujii (1), Michio Tokuyama (2)
(1) Graduate school of Tohoku University Aramaki 6-6, Sendai, 980-8579, Japan
(2) World Premier <strong>International</strong> Research Center, Advanced Institute for Materials Research,
Tohoku University, Sendai 980-8577, Japan
Correspondence author: fujii@athena22.wpi-aimr.tohoku.ac.jp
Recently, bulk metallic glasses (BMGs) are of considerable scientific and practical concern [1]. To
evaluate glass formation for BMGs, some indicators of glass forming ability (GFA) are proposed.
These indicators relate with temperature range of supercooled liquid. If a BMG has higher glass
forming ability (GFA), it shows wider temperature region of supercooled liquid. However, no one
answers clearly a question: how to obtain higher GFA. It is essential for GFA to establish composition
rules and to research properties of supercooled liquid of BMGs. In Cu-Zr-Ti system, Cu60Zr30Ti10 has
higher GFA than Cu60Zr20Ti20. It is good opportunity to explore contributions of differences in
composition on properties of supercooled liquids because it helps in finding the above question.
In this work, we have measured the mean-square displacement and the long-time self-diffusion
coefficient (LSDC) of Cu60Zr20Ti20 and Cu60Zr30Ti10 by molecular dynamics simulations [2]. We can
consider that these dynamical properties of Cu60Zr30Ti10 are slower than that of Cu60Zr30Ti10 because of
larger number of Zr having stronger interactions.
Moreover, we compare simulation results of LSDC with Tokuyama theory [3]. We can estimate
singular points from profile of LSDC by using the theory. Singular points of Cu60Zr30Ti10 are lower
than that of Cu60Zr20Ti20. We also normalized dependence of inverse temperature on LSDC against a
singular point, so as to obtain results that LSDC on two systems collapse on the one curve. It means
that dynamics of both systems are same behaviours. It is considered that the singular point includes
many body interactions and curve of LSDC are stretched by differences in singular point. In fact,
simulation results of LSDC have no singular point. However, the singular point in the theory is useful
for normalization of LSDC. We will describe the details in the poster session.
[1] A. L. Greer, Science, 267 (1995) 5206.
[2] H. Fujii, Master’s Thesis, Tohoku University, 2008.
[3] M. Tokuyama, Private communication (2009).
MULTISCALE INTERPRETATION OF THE DIELECTRIC PROPERTIES OF
POLYAMIDE 6 – MONTMORILLONITE NANOCOMPOSITES
Erisela Nikaj (1), Isabelle Stevenson Royaud (1), Gérard Seytre (1), Laurent David (1), E. Espuche (1)
(1) Université de Lyon, Université Lyon 1, UMR CNRS 5223 IMP, Laboratoire des Matériaux
Polymères et des Biomatériaux, Bât. ISTIL, 15, bd. Latarjet F-69622 Villeurbanne Cedex France
Correspondence author: erisela.nikaj@hotmail.fr
The behaviour of blown PA6–montmorillonite nanocomposite films [1] were studied by dielectric
relaxation spectroscopy (DRS) in order to investigate the filler and the drying effect on the molecular
mobility of the polymer chains. The formalism of electric modulus was used to analyze the dielectric
response so as to reduce the influence of permittivity and conductivity at low frequencies. Four
relaxation processes and two Maxwell–Wagner–Sillars (MWS) interfacial polarizations were observed
[2, 3]. It was found that almost all the relaxations were sensitive to water and to filler contents. We
propose an interpretation of the two MWS–relaxations, invoking the effect of ionic species at the
interfaces between the γ–crystalline and the amorphous phases and at the interface between the filler
and the polymer in the case of montmorillonite filled PA6.
[1] E. Picard, A. Vermogen, J. F. Gérard and E. Espuche, Jour. Mem. Sci. 292 (2007), p. 133.
[2] E. Laredo, M. Grimau, F. Sanchez and A. Bello, Macromol. 36 (2003), p. 9840.
[3] A. J. Bur, S. C. Roth and M. McBrearty, Rev. Sci. Instr. 73 (2002), p. 2097.

SPIN-LATTICE RELAXATION DISPERSION IN POLYMERS: INTRACHAIN AND
INTERCHAIN CONTRIBUTIONS, DIPOLAR-INTERACTION COMPONENTS
A. Gubaydullin (1), T. Shakirov (1), N. Fatkullin (1), R. Kimmich (2)
(1) Department of Physics, Kazan State University, Kazan 420008, Tatarstan, Russia
(2) University of Ulm, Sektion Kernresonanzspektroskopie, 89069 Ulm, Germany
A_Gubaydullin@mail.ru
The proton spin-lattice relaxation rate in polymers is composed of inter- and intramolecular
contributions. According to the recent investigations (see Ref. 1, 2) intrachain dipolar interactions
dominate spin-lattice relaxation above about 10 6 Hz, whereas interchain interactions become
significant below 10 6 Hz. Intrachain dipolar interaction of spins was rigorously analyzed by
components representing fluctuations of the Kuhn segment end-to-end vectors and local fluctuations
on a length scale shorter than the root mean square Kuhn segment length. To derive the effective
Hamiltonian for spin-segment coupling, the fluctuations of which reflect non-local chain dynamics,
the Mori–Zwanzig projection operator technique was employed (see Ref. 3). Spin-lattice relaxation
data due to intrachain and interchain interactions were calculated on the basis of the threefold
renormalized Rouse model. Our theoretical results are in a good agreement with the experimental data
presented in Ref. 1, 2.
[1] M. Kehr, N. Fatkullin, R. Kimmich, J. Chem. Phys., 126, 094903, 2007.
[2] M. Kehr, N. Fatkullin, R. Kimmich, J. Chem. Phys., 127, 084911, 2007.
[3] A. Gubaidullin, T. Shakirov, N. Fatkullin, R. Kimmich, Solid State Nuclear Magnetic Resonance,
35, 147 –151, 2009
TEMPERATURE DEPENDENCEOF ELECTRICAL CONDUCTIVITY AND
BIOMEDICALPARAMETERS OF VEINS APPLIED IN CORONARY ARTERY BYPASS
GRAFTING (CABG)
L.Kubisz (1), R.Kalawski (2), D.Hojan-Jezierska (1) A.Mazurek (2), R.Filipiak (2), M.Gauza (1),
(1) Department of Biophysics, University of Medical Sciences, Poznań, Poland
(2)Department of Cardiac Surgery Municipal Hospital, Poznań, Poland
agamon63@wp.pl
First time electric conductivity – temperature relationship (σ-T) has been applied in studies on bone.
Since then, the method has been used in studies on elastin, keratin, collagen, nucleic acids and more
complex biological materials. The method permits the observation of phase transition processes such
as thermal denaturation, glass transition, water release and thermal decomposition, occurring in heated
biological materials.
The most important features in the electric conductivity-temperature relation of vein walls
derive from the major molecular constituents of the tissue, that is collagen and elastin.
Therefore during the analysis of the obtained results electric properties of collagen and elastin
become in the focus of attention. Solid-state collagen and elastin are characterized by
relatively high temperature of denaturation. Their physical properties of collagen and elastin
depend on water content. Their electrical conductivity increases with increasing water content,
whereas activation energy of charge conduction process is reduced.
The aim of this work was to study the effect of temperature on electric conductivity of the vein wall.
Obtained results permitted to determine temperatures of the phase transitions, activation energy of the
charge conduction process.
Sample of vein wall were taken from patients 50-60 years old. Veins were applied in Coronary Artery
Bypass Grafting (CABG) operations. They were burden with any pathological changes. The study on
human vein walls was agreed with the local Ethical Committee.
The electrical conductivity-temperature relationship was determined in the temperature range 295-
520K, with the heating rate 1K/min, in air under atmospheric pressure, applying DC voltage within the
range, where Ohm’s law is obeyed. Peaks and kinks of the electric conductivity - temperature curve
were used to determine the glass transition and denaturation temperatures. Using the Arrhenius plot,

the activation energy of charge conducting process was determined. Next, the correlation between
biophysical and biomedical parameters was tested. On the basis of the performed analysis it was
stated that activation energies determined for veins taken from diabetic patients were significantly
different from activation energies determined for non-diabetic patients.
DIELECTRIC RESPONSE OF ZnO–BASED VARISTOR
C. Tsonos(1), A. Kanapitsas(1), E. Neagu(2), I. Stavrakas(3), C. Anastasiades(3), D. Triantis(3), P.
Pissis(4)
(1)Technological Educational Institute of Lamia, Department of Electronics, 35100 Lamia, Greece
(2)Technical University of Iasi, Department of Physics, Mangeron 67, Iasi 700050, Romania
(3)Technological Educational Institute of Athens, Department of Electronics, Materials Research Lab,
12210 Athens, Greece
(4)Technical University of Athens, Physics Department, Zografou Campus, 15780 Athens, Greece
tsonos@teilam.gr
Zinc Oxide varistors are electronic devices made of polycrystalline ceramics that are mainly used to
limit transient voltage surges. They have a non-linear current-voltage characteristic and they exhibit
significant energy absorption capabilities. Nonohmic properties of such materials are related to the
potential barrier formation at grain boundary while the barrier nature is considered to be Schottky type.
In the present work, the dielectric response of industrially produced ZnO varistor is studied utilizing
Dielectric Relaxation Spectroscopy (DRS) in a wide frequency range 10 -1 – 10 7 Hz and a temperature
range -140 o C up to +40 o C. It is observed that several overlapping loss mechanisms show up, while in
the recent literature up to two loss peaks are mentioned within the corresponding frequency and
temperature range [1]. The analysis of the experimental data has been done by fitting the frequency
spectrum of the imaginary part of complex permittivity ε* by using a sum of Havriliak – Negami
empirical expressions. Isothermal Depolarization Current (IDC) measurements have been done as well
by applying various DC voltages. The experimental measured currents have been approximated with
the Hamon method and by the means of a sum of exponential decaying functions [2]. The
aforementioned varistor has been studied also using Thermally Stimulated Depolarization Current
(TSDC) measurements in the temperature range -140 o C up to +40 o C while applying various DC
polarization voltages. The results of measuring the dielectric response utilizing each of the above
techniques are discussed and compared to those of the others.
[1] Jianying Li, Bo Li, Dengyun Zhai, Shentgao Li, M. A. Alim, J. Phys. D: Appl. Phys.39, 4969,
2006.
[2] E. R. Neagu, R. M. Neagu, Thin Solid Films, 358, 283, 2000.
THERMAL BEHAVIOR OF DRY AND HYDRATED MBCO CROWDED SYSTEMS
S. Giuffrida (1), G. Cottone (1) and L. Cordone (1)
(1) Dipartimento di Scienze Fisiche e Astronomiche, Università degli Studi di Palermo, Via Archirafi
36, I-90123 Palermo, Italy
cottone@fisica.unipa.it

In vivo, proteins are embedded in crowded environments whose properties are different with respect to
in vitro systems. Here we present a FTIR study on the temperature dependence of both protein and
water bands in amorphous carboxymyoglobin (MbCO) matrices, where proteins are both probe
molecule and embedding agent, constituting a model for crowded systems. The study is performed at
different hydration levels and in temperature ranges within 350-20 K interval. The results show that
only interconversion among low tier substates (internal motion not involving protein surface
displacements) are present in dry systems, whose onset is at a very low temperature. A linear
correlation between protein and water dynamics is also present at low temperature, with decoupling
occurring above 200K because of the mobility of water molecules. In hydrated systems, large motions
involving displacement of the protein surface start at the same temperature, and their onset is
connected with CO escape. Our analysis show that the hydration process of MbCO is well described in
term of two sequential processes: in the first step, water addition results in saturation of the
hydrophilic protein sites; further addition of water introduces bulk-like water, weakly bound to the
protein matrix. When only tightly bound water is present the protein shows hindered dynamics and a
remarkable resistance to thermal stresses, despite the absence of biopreserving agents.
EFFECTS OF HYDROGEN BONDS ON THE RELAXATION SCENARIO OF GLASS
FORMERS
R. Bergman 1 , J. Mattsson 1 , H. Jansson 2 , J. Sjöström 1 , J. Swenson 1 , L. Börjesson 1 and P. Jacobsson 1
(1) Department of Applied Physics, Chalmers University of Technology, SE-412 96 Göteborg,
Sweden
(2) Swedish NMR Centre at Göteborg University, SE-405 30 Göteborg, Sweden
Rikard.Bergman@chalmers.se
The relaxation map of OH-bonded glass formers differ from the typical scenario in several ways. For
instance, some otherwise universal scaling properties concerning the role of temperature and volume
have been shown to fail for OH-bonded glass formers [1]. Furthermore, some OH bonded liquids, the
mono-alcohols, even show a unique dielectric relaxation process not observed in other systems [2].
This process is slower than the α-relaxation and its frequency dependence is Debye-like. The physical
nature of this process is not clear but it is believed to be related to some sort of structures formed due
to the hydrogen bonds.
We show results from mainly dielectric relaxation and DSC data on glass forming systems with
varying hydrogen bonding capabilities. Some effects due to hydrogen bonds on the glass transition
dynamics are discussed. For example, we show that the Debye-like process could be present, though
much less pronounced, also in other hydrogen bonded systems.
[1] C.M. Roland et al., Phys. Rev. B, 77 (2008) 012201
[2] B. Jakobsen et al., J. Chem. Phys., 129 (2008) 184502
ELECTRICAL MODELING OF PEI-LiTfSI POLYMER ELECTROLYTES
İ. Bayrak Pehlivan (1,3), G. A. Niklasson (1), R. Marsal (2), C. G. Granqvist (1), and P. Georén
(2)
(1) Department of Engineering Sciences, The Ångström Laboratory, Uppsala University, P.O. Box
534, SE-75121 Uppsala, Sweden
(2) ChromoGenics AB, Märstagatan 4, SE-75323 Uppsala, Sweden
(3) İstanbul Technical University, Department of Physics, Maslak, 34469 İstanbul, Turkey
bayrakilk@itu.edu.tr
Polymer electrolytes containing polyethyleneimine (PEI) and lithium
bis(trifluoromethylsulfonyl)imide (LiTFSI) were investigated by impedance spectroscopy in the

frequency range 10 -3 -10 7 Hz. Impedance spectra were obtained at temperatures between 20 and 70⁰C
for electrolytes with different salt concentrations. The impedance response in the high frequency range
was represented by two different equivalent circuits. The first one includes a conductive Havriliak-
Negami element which represents the ionic conductivity and ion pair relaxation in a single process,
and the second model includes a dielectric Havriliak-Negami element which represents the ion pair
relaxation in parallel with the dc conductivity. Comparison of the two models was done by analyzing
the fitting parameters for different temperatures and salt concentrations. The quality of the fit was
similar or slightly better for the conductive model, despite the fact that it includes one parameter less.
The experimental data follow the Barton-Nakajima-Namikawa (BNN) relation which is an empirical
relation between the DC conductivity, the relaxation strength, and the angular frequency of relaxation.
INFLUENCE OF UNIAXIAL DEFORMATION ON THE LOW Tg COMPONENT
DYNAMICS OF MISCIBLE POLYMER BLENDS
E. Lezak (1,3), A. Alegría (2,3) and J. Colmenero (1, 2, 3)
(1) Donostia <strong>International</strong> Physics Center (DIPC Fundación), Paseo Manuel de Lardizabal 4, 20018
San Sebastián, Spain
(2) Departamento de Física de Materiales UPV/EHU, Apartado 1072, 20072 San Sebastián, Spain
(3) Centro de Física de Materiales (Centro Mixto CSIC-UPV/EHU), Material Physics Center (MPC),
Apartado 1072,
20072 San Sebastián, Spain
scklezae@ehu.es
To achieve new insight into the component segmental dynamics of polymer blends, we have
performed dielectric relaxation experiments on samples subjected uniaxial stretching deformation, at
temperature around the average glass transition temperature, Tg,. In this context, one model system,
polystyrene/poly (vinyl methyl ether) (PS/PVME) blends in miscible state, is studied in PS high
concentration composition (80 wt% of PS). This composition was chosen due to the confinement-like
effect on molecular motions of the dielectrically active component (PVME) caused by high-Tg
component (PS). By means of dielectric spectroscopy in a frequency range 10 0 – 3x10 6 Hz, the PVME
dynamics in the blends has been selectively investigated. The temperature range investigated is from
215 to 340 K. The main relaxation process observed is the relaxation of the PVME segments
constrained by the much less mobile PS chains. Our results evidence that whereas annealing causes
minor effect in segmental dynamics of polymer blends, the dielectric relaxation process is
considerably affected by the uniaxial stretching. These results are rationalized in terms of the strong
suppression of the PVME motions in regions where the PS chains would result highly oriented.
ALL-ATOM SIMULATIONS OF BIOLOGICAL MOLECULES BY MULTICANONICAL
ALGORITHM
M. Bilsel, H. Arkin
Ankara University, Department of Physics Engineering, Ankara, Turkey
holgar@eng.ankara.edu.tr
The conformation space of proteins and peptides presents a complex energy profile consisting of a
tremendous number of local minima separated by energy barriers. Visualization of the whole rugged
landscape covering the entire energy and temperature ranges would be helpful to develop method
allowing one to survey energy surfaces in conformational space. Such a goal can be achieved within
multicanonical approach. Brief discussion of the powerful multicanonical simulation method will be

given. The intermediate steps of the simulation method starting from a given sequence as the input
leading to the folded three dimensional structure and the minimization procedure will be shown.
Attempts to design new algorithms, determination of the topografic structure of energy landscape
and search the low lying stable conformations will be discussed. After that , the simulation results of
an special example, elastin-like polypeptides are presented.
[1] B. A. Berg and T. Celik, Pys. Rev. Lett. 69 (1992) 2292.
[2] F. Yasar, H. Arkin, T. Celik, B. Berg and H. Meirovitch, J. Comp. Chem. 23 (2002) No. 12, 1127.
[3] H. Arkin and T. Celik, Eur. Phys. J. B 30, 577 (2002).
[4] H. Arkin and T. Celik, Int. J. Mod. Phys. C 14(5) (2003)
[5] H. Arkin and M. Bilsel, How Conformational Transitions Depends on Hydrophobicity of Elastin-
Like Polypeptides, submitted.
DIFFERENTIAL AC-CHIP NANOCALORIMETER FOR MEASUREMENT AT LOW
PRESSURE
M. Ahrenberg (1), C. Schick (1), H. Huth (1), K. L. Kearns (2) and M. D. Ediger (2)
(1) Universität Rostock, Institut für Physik, Universitätsplatz 3, 18051 Rostock, Germany
(2) University of Wisconsin-Madison, Dept. Of Chemistry, Madison, Wisconsin 53706
mathias.ahrenberg@uni-rostock.de
We intend to use nanocalorimetry to investigate the formation of extraordinarily stable glasses
prepared by vapor deposition. For that purpose we have built a vapor deposition chamber that will
allow in-situ characterization of vapor-deposited films made from organic molecules. The use of the
nanocalorimeter in the deposition system permits us to produce and in- vestigate stable glasses under
well controlled conditions [1]. Moreover, the developed nanocalorimeter enables us to simultaneously
measure the heat capacity at a particular frequency and the overall enthalpy change upon heating. A
quartz crystal microbalance (QCM) is used to monitor film thickness and rate of deposition. For
conventional DSC experiments on extraordinary stable glasses, the sample thickness must be on the
order of 50 µm. The nanocalorimeter is able to measure films below 100 nm thickness, and therefore,
slower deposition rates can be explored. In this way, we expect to prepare and characterize glasses
with even greater stability than is possible with current techniques.
[1] S. F. Swallen , K. L. Kearns et al, Science 315(5810). 353-356
STRUCTURAL RELAXATION AND VISCOSITY BEHAVIOR IN SELENIUM
SUPERCOOLED MELT
Jiří Málek (1), Roman Svoboda (1), Petr Koštál (1)
(1) Department of Physical Chemistry, Faculty of Chemical Technology, University of Pardubice,
Studentská 573,
Pardubice 532 10, Czech Republic
jiri.malek@upce.cz
Volume and enthalpy relaxation studies have been performed in selenium supercooled melt by
mercury dilatometry [1] and differential scanning calorimetry [2]. For simple temperature jump
experiments, as well as for more complex thermal history the volume and enthalpy relaxation data can
be described by a single set of kinetic parameters for Tool-Naraynaswamy-Moynihan (TNM) model
and for Adam-Gibbs-Scherer (AGS) model. The times required to reach equilibrium for volume and
enthalpy relaxation do not seem to differ significantly, within the limit of experimental uncertainty. A
self-consistent data evaluation shows that at moderate departure from equilibrium volume and
enthalpy in amorphous selenium relax in the same way as expressed by TNM and AGS models. Both
volume and enthalpy change can be interpreted within the same fictive temperature concept [3].
New measurements of viscosity of selenium melt are reported as well as previously published
data from numerous authors which allow to fit the Adam-Gibbs (AG) and the Vogel-Fulcher-Tamman
(VFT) equations with viscosities ranging from 10 -1 to 10 14 Pa.s. The similarity between the

preexponential factor of AG and VFT has been confirmed. The activation energy of viscous flow in
the glass transition range is identical with the effective activation energy for the structural relaxation
process as determined by TNM model. Extensive collection of experimental data allows a detailed
discussion of studied phenomena.
[1] R. Svoboda, P. Pustková, J. Málek, J. Non-Cryst. Solids 352 (2006) 4793.
[2] R. Svoboda, P. Pustková, J. Málek, J. Phys. Chem. Solids 68 (2007) 850.
[3] J. Málek, R. Svoboda, P. Pustková, P. Čičmanec, J. Non-Cryst. Solids 355 (2009) 264.
Financial support for this research from the Czech Science Foundation under grant No. 104/08/1021
is acknowledged.
PHASE TRANSITION IN TETRAGONAL LYSOZYME CRYSTALS: EVIDENCE FROM
AC-NANOCALORIMETRY AND BRILLOUIN LIGHT SCATTERING
A.V. Svanidze (1), H. Huth (2), S.G. Lushnikov (1), C. Schick (2)
(1) A.F. Ioffe Physical Technical Institute, Politekhnicheskaya 26, 194021 St.Petersburg, Russia
(2) University of Rostock, Institute of Physics, Universitatsplatz 3, 18051 Rostock, Germany
svanidze@mail.ioffe.ru
We present results of a study of tetragonal lysozyme crystals by Brillouin light scattering and ACnanocalorimetry
in the temperature range from 295 K to 318 K where a phase transition is expected.
Recently Kobayashi et al. [1] observed an anomalous behavior of the birefringence index of lysozyme
crystals in the vicinity of 307 K. Brillouin scattering in single lysozyme crystals provides information
about the behavior of acoustic phonons in the crystals. The experiment has been done by 6-pass
tandem interferometer Fabry-Perot (Sandercock system) with back-scattering geometry [2].
Complimentary to Brillouin scattering the heat capacity of one lysozyme crystal has been measured by
an AC-chip calorimeter that provides the possibility to measure complex heat capacity of small objects
with pJ/K sensitivity [3]. The used frequency was 20 Hz providing a well defined time scale for the
experiment. During the measurement relative humidity was maintained at about 80 %. The results of
Brillouin light scattering and specific heat capacity show a phase transition in the lysozyme crystals in
the vicinity of 307 K. Our data are in good agreement with the temperature behavior of the
birefringence of the lysozyme crystals [1].
[1] J. Kobayashi, T. Asahi, M. Sakurai, I. Kagomiya, H. Asai and H. Asami, Acta Cryst., A54, 581,
1998
[2] A.V. Svanidze, S.G. Lushnikov, S. Kojima, JETP Letters, 84, 551, 2006
[3] H. Huth, A.A. Minakov, C. Schick, J. Polym. Sci.: Part B: Polym. Phys., 44, 2996, 2006
ION JELLY FILMS CONDUCTIVITY AS STUDIED BY DIELECTRIC SPECTROSCOPY
T. Carvalho (1), A. R. Brás (1), N. Correia (1), R. Igreja (3), C. J. Dias (3), Nuno M.T. Lourenço (2),
Carlos A.M. Afonso (2), S. Barreiros (1), P. Vidinha (1) and M. Dionísio (1)
(1) REQUIMTE, Departamento de Química, Faculdade de Ciências e Tecnologia, Universidade Nova
de Lisboa, 2829-516 Caparica, Portugal
(2) Centro de Química-Física Molecular, Instituto Superior Técnico, Av. Rovisco Pais, 1, 1049-001,
Lisboa, Portugal

(3) Departamento de Ciências dos Materiais—CENIMAT, Faculdade de Ciências e Tecnologia da
Universidade Nova de Lisboa, 2829-516 Caparica, Portugal.
pvidinha@dq.fct.unl.pt; madalena.dionisio@dq.fct.unl.pt
Ion jelly® is a polymer conducting material combining the chemical versatility of ionic liquids (ILs)
with the morphological versatility of a biopolymer, gelatin, which is a widely available, inexpensive
and well studied gelling agent.
The ionic conductivities of several ion jelly films with different cation/anion combination were
measured in the temperature range between 158 and 303 K on the basis of dielectric measurements in
the frequency range between 10 -1 to 10 6 Hz.
It is shown that the conductivity of the ion jelly materials is strongly affected by the ionic liquid used.
Most of the systems tested exhibit very reasonable conductivity values that are of the order of 10 -5 –10 -
4 S cm -1 at room temperature. The usual conductivity pattern observed in disordered conductive
systems is a plateau found at the lowest frequencies, where the conductivity is identical to dc
conductivity (σDC), bending off at higher frequencies into a dispersive regime. The conductivity
frequency dependence of the ion jelly materials conform only partially to this usual profile, since data
are highly influenced by electrode polarization. Such behaviour was only displayed in general for
temperatures below -30ºC.
A new cell with interdigitated electrodes was designed and is being optimized to test the conductivity
in these systems where an accurate control of thickness is difficult to achieve.
Acknowledgement: Fundação para a Ciência e Tecnologia (FCT, Portugal) through projects
PPCDT/BIO/57193/2004, POCI/QUI/57735/2004 and by FEDER is acknowledged. T. Carvalho
acknowledges FCT for a PhD grant SFRH/BD/47088/2008.
Polyamorphism in amorphous ice – macroscopic phase separation
Katrin Winkel (1), Michael S. Elsaesser (2), Erwin Mayer (1), Thomas Loerting (2)
(1) Institute of General, Inorganic and Theoretical Chemistry, University of Innsbruck, Innrain 52a, A-
6020 Innsbruck, Austria
(2) Institute of Physical Chemisty, University of Innsbruck, Innrain 52a, A-6020 Innsbruck, Austria
katrin.winkel@uibk.ac.at
The phenomenon of “polyamorphism” was observed for the first time in amorphous ice by Mishima et
al.[1]. The authors observed an “apparently first order transition” between HDA and low density
amorphous ice LDA [1]. However, the case of a “first order transition” between LDA and HDA is still
under debate, evidence is abundant in the literature both for pro and contra this scenario.
The here presented dilatometry experiments were performed at the highest temperature at which we
can work without crystallization, namely 140 K for decompression of very high density amorphous ice
(VHDA). Going beyond previous studies, we now show the coexistence and macroscopic separation
of HDA and LDA in the small pressure interval 0.06 – 0.08 GPa and 140 K. This is the best evidence
so far for the first-order nature of the HDA → LDA transition.
We speculate that small LDA-clusters occur either at the top or the bottom fraction of the sample and a
phase boundary propagates through the sample when the high density sample transforms to low
density amorphous ice. Several experimental facts, as e.g. the speed at which the phase boundary
propagates, let us assume that we work in the ergodic limit at p ≤ 0.2 GPa and 140 K, and that we
indeed observed a transition between two ultraviscous liquids, namely HDL → LDL, the counterparts
for the amorphous ices HDA and LDA.
[1] O. Mishima, L. D. Calvert, and E. Whalley, Nature, 314, 76, 1985
EFFECT OF WATER CONTENT ON ELECTRICAL CONDUCTIVITY OF FISH SKIN
COLLAGEN

Marlena Gauza, Leszek Kubisz
Department of Biophysics, Poznan University of Medical Sciences, Poland, 61 – 701 Poznan
e-mail: mgauza@ump.edu.pl
Collagen is the major biopolymer of a living organism. Water is an inherent component of collagen
and affects its physical properties and structure [1]. Bovine collagen has long been recognized as a
safe and highly biocompatible material till to discovery of its association with prion transmission.
Therefore collagen hydrolysate obtained from fish skin, as a prion free material, has generated some
considerable interest in medicine and science in recent years. Collagen isolated from fish skin by
hydration [2] seems to maintain its native structure.
Heating of collagen leads to denaturation [3], glass transition and water release, which are reflected in
changes of electrical conductivity σ [4,5]. The release of water, which is essential for its biophysical
properties [6-9], results in the decreased electrical conductivity σ. Water release is a complex process,
because water molecules participate in the structure of collagen macromolecule at different ways. In
the solid state collagen, water is usually divided into three groups: free water, bound water and
structural water [10]. The process of water release from fish skin collagen was studied by means of dc
electrical conductivity measurements carried out at the temperature range 290-510K and the heating
rate 2K/min. The process of free and bound water release was manifested as a peak on the electrical
conductivity-temperature curve between 320-350 K. Further increase in temperature resulted in the
increased electrical conductivity.
Since collagen is the hygroscopic material, the effect of air humidity on electrical conductivity was
observed as well. The higher the relative humidity of air, at which samples were stored, the higher the
peak of electrical conductivity.
[1] V. Sujata Bhat, Biomaterials, Springer, 2002
[2] J.E. Przybylski, K. Siemaszko-Przybylska, Patent 190737 Patent Office RP 2002
[3] V. Samouillan, A. Lamure, E. Maurel, Characterisation of elastin and collagen in aortic
bioprostheses, Med. Biol. Eng. Comput., 38, 226-231, 2000
[4] S. Matsushita, S. Deki, Anomalous behavior of electrical conductivity of solubilized collagen
solutions with thermal denaturation, J. of App. Polymer Sci., Vol. 50 Issue 11, 1969 - 1975, 2003
[5] L. Kubisz, S. Mielcarek, F. Jaroszyk, Differential scanning calorimetry and temperature
dependence of electric conductivity in studies on denaturation process of bone collagen, Int. J. of Biol.
Macromol. 33, 89–93, 2003
[6] H.J.C. Berendsen, Water Structure, Theoretical and Experimental Biophysics, New York Issue 1,
1-11, 1967
[7] J.R. Grigera, Introduction to the Biophysics of Water, Buenos Aires 1976
[8] C. Hazlewood, Physicochemical state of ions and water in living tissues and model systems, Ann.
N. Y. Acad. Sci., 204, 1973
[9] S. Mascarenhas, The electret effect in bone and polymers and the bound-water problem, Ann. N.
Y. Acad. Sci., 238, 1974
[10] S. Nomura, A. Hiltner, J.B. Lando, E. Bear, Interaction of water with native collagen,
Biopolymers, 16, 231-246, 1977
INVENTORY OF LI PATHWAYS IN OXIDES AND SULFIDES FROM ENERGY-SCALED
BOND VALENCE LANDSCAPES
Stefan Adams (1)
(1) Department of Materials Science and Engineering, National University of Singapore, Singapore
117574, Singapore
mseasn@nus.edu.sg
Empirical bond length bond valence relationships can provide insight into the interrelation between
structure of and ion transport in solid electrolytes. Building on our systematic adjustment of bond
valence (BV) parameters to the bond softness, it is shown here how the squared BV mismatch as a
Morse-type potential can be linked to the absolute energy scale [1]. This energy-scaled approach is
then used to analyze the energy landscape of mobile ions and predict ion conduction pathways in
selected oxide glasses as well as all crystalline ternary Lithium oxides and sulfides, for which the

structure is available from the ICSD database. The analysis reveals significant differences to results
from a recent geometric Voronoi–Dirichlet partition based study of cages and channels in crystalline
Lithium oxides by Anurova et al. [2], which are particularly pronounced for the 33 types of ternary
oxides listed in [2] as containing 1D Li pathways: 1D transport channels are observed for 18 of these
structures only. The range of systems investigated is extended to cover all binary to quaternary
Lithium sulfides as well as selected quaternary Lithium oxides focusing on structure types of interest
as Li battery electrode materials.
[1] S. Adams and R. Prasada Rao; Phys. Chem. Chem. Phys., 11, 3210, 2009
[2] N.A. Anurova et al., Solid State Ionics 179 (2008) 2248.
MOISTURE BUFFERING OF FREEZE-DRIED PHARMACEUTICAL PRODUCTS: A
STUDY BY BROADBAND DIELECTRIC SPECTROSCOPY.
I. ERMOLINA, G. SMITH
School of Pharmacy, De Montfort University, The Gateway, Leicester, LE1 9BH, UK
iermolina@dmu.ac.uk
A variety of excipients (including disaccharides) are used routinely in lyophilised product formulation,
to provide a moisture buffering environment and thereby sustain shelf life. We report on a dielectric
spectroscopy study of freeze-dried disaccharides (lactose, trehalose, sucrose and maltose) at various
moisture contents. All four disaccharides revealed two sub-Tg relaxation processes. The faster process
(the rotation of the pendant hydroxyl-methyl groups [1]) was singled out for further analysis by fitting
the Havrialiak-Negami (HN) function to each spectrum. The temperature dependency of the fit
parameters (∆ε, τ, ε∞) were used to calculate values for the Fröhlich parameter, B(T), and activation
energy, ∆H. Previously [2] we suggested that the temperature dependency of the Fröhlich parameter
B(T) is a key parameter to understanding the degree of molecular mobility of the sugar. Here we
examine, in further detail, the impact of moisture on the Fröhlich parameter and speculate on the
importance of the sub-Tg molecular dynamics to the moisture buffering capacity of these
disaccharides. The work further supports the argument that moisture sensitive drugs will be more
stable when freeze-dried with lactose, followed by sucrose/maltose and finally trehalose (with sucrose
being more effective than maltose at the higher moisture contents).
[1] I Ermolina, et al, Non-Cryst Solids, 353, 4485-4491, 2007
[2] G. Smith, I. Ermolina, J. Pharm Pharmacol, Suppl. 1 A-61, 2008
STRUCTURAL PROPERTIES OF MIXED ALKALI BORATE GLASSES BY MOLECULAR
DYNAMICS SIMULATIONS
C.P.E. Varsamis, A. Vegiri and E.I. Kamitsos
Theoretical and Physical Chemistry Institute, National Hellenic Research Foundation, 48 Vassileos
Constantinou Ave., 11635 Athens, Greece
cvars@eie.gr
Structural properties of mixed alkali borate glasses, 0.3[(1-x)Li2O-xM2O]-0.7B2O3 (M=Cs, Na), have
been studied by molecular dynamics simulations at T=300K for several values of the mixing
parameter, x. The short-range order structure was found to consist of borate tetrahedra, BØ4 - , and of
neutral, BØ3, and charged, BØ2O - , triangular borate units [Ø=bridging oxygen atom]. In Li-Cs glasses,
the fraction of BØ4 - was found to decrease from Li to Cs and to exhibit negative deviation from
linearity, but no appreciable changes were detected in the Li-Na system. In mixed glasses, alkali ions
were found to occupy sites similar to those formed in the single alkali borate. However, the Li ioncoordination
environments become better defined and the Li-O interactions strengthen upon alkali
mixing in both systems at the expense of Cs-O and Na-O interactions. These trends were attributed to
formation of dissimilar cation pairs around non-bridging oxygen atoms in mixed glasses, which appear
to constitute the dominant cation configurations. These configurations affect local bonding and
vibrational properties of metal ions in their sites and could provide a structural explanation for the
mixed alkali effect.

DIELECTRIC SPECTROSCOPY OF FAST GLASSY DYNAMICS
M. Köhler (1), P. Lunkenheimer (1), Yu. G. Goncharov (2), and A. Loidl (1)
(1) Experimental Physics V, University of Augsburg, 86135 Augsburg, Germany
(2) Institute of General Physics, Russian Academy of Sciences, 119991 Moscow, Russia
melanie.koehler@physik.uni-augsburg.de
Although the molecular dynamics in the GHz-THz regime is of high relevance for understanding the
glass transition, dielectric data in this region is quite sparse. Here we focus on systematic
investigations of the dielectric response in this region. By studying different closely related molecular
glass formers, we aim at obtaining information on the fast processes that have experienced so much
interest in recent years. One investigated system is the series of the mono-, di-, and trimer of propylene
glycol [1]. They have similar molecular interactions and only differ in molecular size. In addition, we
have investigated the molecular glass former glycerol with dissolved ions of varying concentrations
[2]. This allows us to simultaneously study both, translational AND rotational degrees of freedom by
dielectric spectroscopy. In these systems, molecular size and ion content have a strong impact on the
alpha and slow beta-relaxation dynamics. However, surprisingly the dielectric response in the regime
of the fast processes seems to be only weekly affected. We address important questions like the
consistence with mode coupling theory or the extended coupling model. By these investigations, we
hope to stimulate the discussion about the microscopic origin of the fast beta-process and the boson
peak.
[1] M. Köhler, P. Lunkenheimer, Y. Goncharov, R. Wehn, and A. Loidl, arXiv:0810.5316v1.
[2] M. Köhler, P. Lunkenheimer, and A. Loidl, Eur. Phys. J. E 27, 115 (2008).
Non-Linear Ionic Conductivity Study on Thin Layers of Glass
H. Staesche and B. Roling
Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein-Str., 35032 Marburg, Germany
staesche@staff.uni-marburg.de
Batteries in the form of portable power sources have become omnipresent in our lives and are set to
become even more important. To meet future demands properties of all battery components have to be
improved and optimised. An important role plays the thickness of the electrolyte: in thin layers, even
low voltages result in high electric field strengths. This then gives rise to field-dependent (non-linear)
ionic transport properties resulting in an increase in the ionic conductivity [1]. In the past, experiments
investigating the non-linear behaviour have been carried out using dc methods [2]. However, using
these methods it is not possible to distinguish between an increase due to intrinsic field dependence of
the ionic conductivity and the one due to Joule heating effects [3]. In this study, high-voltage ac
impedance spectroscopy has been used in order to overcome this problem [3]. Analysis of the linear
impedances and of its higher harmonics can help in understanding the conduction processes in
amorphous materials [4].
[1] J. M. Hyde and M. Tomozawa, Phys. Chem. Glasses 27, 147, 1986
[2] J. O. Isard, J. Non-Cryst. Solids, 202, 137, 1996
[3] S. Murugavel and B. Roling, J. Non-Cryst. Solids, 351, 2819, 2005
[4] B. Roling et al, PCCP, 10, 4211, 2008

INFLUENCE OF ELECTRO-THERMAL POLING ON THE SILVER RELEASE OF
ANTIBACTERIAL GLASSES
J. Kruempelmann and B. Roling
Department of Chemistry, University of Marburg, Hans-Meerweinstraße, D-35032 Marburg
kruempej@staff.uni-marburg.de
Phosphate based glasses provide a useful means of delivering the silver ions incorporated into the
network in a controlled manner. This is why they find different applications in healthcare products due
to their antibacterial effect [1] .
We report studies on electrochemical processes in silver doped phosphate based glasses during
electro-thermal poling by means of thermally stimulated polarization depolarization current
measurements, ac impedance spectroscopy and SEM/EDX analyses. In the electrothermal poling
technique a dc voltage is applied to the material for a time interval at a specific temperature [2] . The
applied voltage causes movements of the silver ions and finally leads to the formation of interfacial
layers under the electrodes. When the material is cooled down the surface charges are stored in the
material. For these studies we chose silver doped phosphate glasses to investigate the effect of thermal
poling on the release of silver ions.
[1] V. Simon, C. Albon, S. Simon, Journal of Non-Crystalline Solids 354 (2008) 1751
[2] C.R. Mariappan, B. Roling, Solid State Ionics 179 (2008) 671-677
EFFECTS OF A ZrP FILLER ON THE RELAXATIONAL PROPERTIES OF NAFION
MEMBRANES FOR HYDROGEN FUEL CELLS
A. Paolone (1,2), O. Palumbo (1,3), R. Cantelli (1), M. Casciola (4)
(1) Physics Department, Sapienza University, Piazzale A. Moro 5, 00185, Rome, Italy
(2) Laboratorio Regionale SuperMAT, CNR-INFM, Salerno, Italy
(3) CNISM – Dip. Fisica, Sapienza Università, Piazzale A. Moro 5, I-00185 Roma, Italy
(4) Chemistry Department, University of Perugia, via Elce di Sotto 8, 06123-Perugia, Italy
annalisa.paolone@roma1.infn.it
We report a detailed investigation of the temperature dependence of the dynamic elastic modulus, E,
and of the elastic energy dissipation of a Nafion membrane filled with 10 % of ZrP, which shows
improved electrical properties for PEM fuel cells.[1] The glass transition temperature and the absolute
value of E are affected by the addition of ZrP to Nafion. Moreover the elastic modulus reveals a clear
anisotropy between the plane of the membrane and the perpendicular direction, possibly due to an
alignment of the ZrP platelets. Below room temperature the β relaxation, due to the movement of the
side part of the polymer chain, is observed. The activation energy, Wa, for this motion is higher in the
membrane containing ZrP than in pure Nafion. However, after a heat treatment at 300 °C, Wa in the
ZrP-doped membrane decreases and becomes equal to that of undoped Nafion. This indicates that in
the doped membrane there is an appreciable interaction between ZrP and the side chain of the polymer,
which can be changed by thermal treatments.
[1] G. Alberti and M. Casciola, Annu. Rev. Mater. Res. 33, 129, 2003

STUDY OF ION DIFFUSION COEFFICIENTS IN GELS COMPOSED OF IONIC LIQUIDS
AND NANOPARTICLES
C. Rößer and B. Roling
Department of Chemistry, Philipps-University of Marburg, Hans-Meerwein-Str., 35032 Marburg,
Germany
Roesser2@staff.uni-marburg.de
Ionic liquids (ILs) possess a wide electrochemical window, good chemical and thermal stability, and
very low volatility. Due to its high safety performance ILs are a promising class of electrolytes for
future power sources and electrochemical devices. The gelation of ILs by the addition of nanoparticles
result in interesting properties. These new solid electrolytes show forming ability, transparency and
flexibility, and can be used as electrolytes for high performance dye-sensitized solar cells (DSSCs) [1].
The ionic transport and viscoelastic properties of these nanocomposite ion gels were investigated and
compared with the microstructure. The formation of the gels is controlled by the physical-chemical
properties of the solid-liquid interface. [2,3]
In this work we investigate the influence of the surface chemistry on the ionic transport properties of
these gels. As alternative to silica oxide, we have dispersed silicon nitride nanoparticles in an IL. The
translational self-diffusion coefficient of cations and anions were determined by PFG NMR at
different temperatures. The ionic conductivity calculated from the NMR diffusivities via the Nernst-
Einstein equation can be compared with ac conductivity measurements to provide estimates of ionic
association.
[1] P. Wang, S. M. Zakeeruddin, P. Comte, I. Exnar, and Michael Grätzel, J. Am. Chem. Soc. 125,
1166, 2003
[2] K. Ueno, K. Hata, T. Katakabe, M. Kondoh, and M. Watanabe, J. Phys. Chem. B, 112, 9013, 2008
[3] T. Umecky, Y. Saito, Y. Okumura, S. Maeda, and T. Sakai, J. Phys. Chem. B, 112, 3357, 2008
INTERDENDRIMER INTERACTION IN WATER SOLUTION : A SAXS STUDY
D. Lombardo (1), M. Kiselev (2), P. Calandra (1)
(1) CNR–IPCF, Istituto per i Processi Chimico Fisici - sez. Messina, C.da Papardo Sperone, I-98158,
Messina, Italy.
(2) FLNP, Joint Institute for Nuclear Research, I-141980, Dubna, Russia
lombardo@me.cnr.it
A synchrotron radiation Small Angle X-ray Scattering (SAXS) structural investigation has been
performed on carboxilate terminated poly(amidoamine) PAMAM dendrimers in water solution. The
presence of pronounced interference peaks in the SAXS spectra even in the dilute regime give
evidence of a considerable structural order of electrostatic nature in the system. The long range
intermolecular interaction has been ascribed to the ionisation of the carboxilate terminal groups in the
dendrimers [1]. The experimental inter-dendrimer structure factor S(q), analysed in the framework of
liquid integral equation theory for charged systems in solution, allow the modelling of the effective
interdendrimer interaction potential (Screened Coulombic plus hard-sphere repulsion). The present
analysis, which allow the estimation of the dendrimer effective surface charge Zeff, strongly supports
the finding that structures and interaction of dendrimer is strongly influenced by charge effects [2, 3].
This quantity can be considered as a crucial parameter for the modulation of the degree of structural
organization in solution, suitable for a number of potential applications [4, 5].
References
[1] N. Micali, L. Monsu Scolaro, A. Romeo, D. Lombardo, P. Lesieur, F. Mallamace Phys. Rev. E, 58,
6229, 1998.
[2] F. Mallamace, E. Canetta, D. Lombardo, A. Mazzaglia, A. Romeo, L. Monsù Scolaro, G. Maino
Physica A 304, 235 (2002).
[3] (a) T. Terao, T. Nakayama Macrmolecules 37, 4686, (2004). (b) D.A. Tomalia, A.M.Naylor, W.A.
Goddard. Angew Chem Int Ed. 29:138 (1990)

[4] (a) D. Lombardo, Langmuir 25, 3271 (2009). (b) L. Bonaccorsi, D. Lombardo, A. Longo, E.
Proverbio, A. Triolo. Macrmolecules 42, 1239, (2009)
[5] (a) G. Nisato, R. Ivkov, E.J. Amis. Macromolecules.33, 4172 (2000). (b) M. Ballauff, C.N. Likos.
Angew Chem, Int Ed. 43, 2998 (2004). (c) P.K. Maiti, R. Messina. Macromolecules. 41, 5002 (2008)
Volumetric Glass-to-Liquid Transition in Amorphous Ices up to 0.3 GPa
Michael S. Elsaesser a,* , Markus Seidl a,b,* , Gerhard Zifferer b , Erwin Mayer c , Thomas Loerting a
a Institute of Physical Chemistry, University of Innsbruck, Innrain 52a, A-6020 Innsbruck, Austria
b Department of Physical Chemistry, University of Vienna, Währinger Str. 42, A-1090 Vienna, Austria
c Institute of General, Inorganic and Theoretical Chemistry, University of Innsbruck, Innrain 52a, A-
6020 Innsbruck, Austria
e-mail: thomas.loerting@uibk.ac.at
*these authors contributed equally to this work
Abstract:
Dilatometry experiments on amorphous ices at pressures up to 0.3 GPa are presented. The isobaric
heating curves are followed using powder X-ray diffraction and interpreted in terms of three
competing processes: the glass-to-liquid transition, irreversible relaxation and crystallization. We
demonstrate the reversibility of the glass-to-liquid transition both for low-(LDA) and high-density
amorphous ice (HDA). The onset for the volumetric glass-to-liquid transition in LDA is consistent
with the 1 bar calorimetric data and barely shifts with increasing pressure, whereas in case of HDA it
increases by ≈90 K/GPa and crosses the crystallization line at p≈0.3 GPa. At 0.1 GPa the volumetric
glass-to-liquid transition onset in HDA is found at ≈ 126 K, whereas in LDA it is found ≈ 137 K in the
pressure range up to 0.1 GPa. In case of LDA the glass-to-liquid transition is very weak and becomes
even weaker at increasing pressures so that it is difficult to locate the onset temperature. By contrast,
in case of HDA the onset is easy to detect (unless crystallization precedes the onset). This is consistent
with a “fragile” nature of the high-density liquid and a “strong” nature of the low density liquid. In
addition we demonstrate that depending on preparation history structural defects, which result in early
crystallization, may or may not be present in amorphous samples.
“Doubly” Metastable High Pressure Ice Phases
Marion Bauer a,* , Katrin Winkel a,b,* , Erwin Mayer a , Thomas Loerting b

a Institute of General, Inorganic and Theoretical Chemistry, University of Innsbruck, Innrain 52a, A-
6020 Innsbruck, Austria
b Institute of Physical Chemistry, University of Innsbruck, Innrain 52a, A-6020 Innsbruck, Austria
Abstract:
e-mail: thomas.loerting@uibk.ac.at
We present a study on the nucleation and structural transformation of hexagonal ice at high pressures
up to 1.6 GPa. Using isothermal compression experiments we show that hexagonal ice transforms to
“doubly” metastable phases at high-compression rates, i.e., high-pressure ice phases are observed far
away from their stability regions in the phase diagram. In particular we observe Ice III and Ice V in the
stability field of Ice II and Ice V in the stability field of Ice VI. On the other hand at low compression
rates the thermodynamically stable phase is observed, i.e., the phase expected from the stability region
in the phase diagram. All phases are quenched to 77 K and 1 bar without back-transformation and
analyzed using powder X-ray diffraction. The analysis of the diffractograms shows that at intermediate
compression rates mixtures of ice phases appear. We follow how the composition of the high-pressure
ice phase mixtures changes when changing the temperature and when changing the compression rate.
This analysis allows us to conclude that parallel structural transformation kinetics takes place, where
the “doubly” metastable ice phase is favoured at high compression rates and low temperatures. The
higher the compression rate and the lower the temperature is, the more metastable the phase that
emerges from hexagonal ice. We speculate that it might even be possible to prepare a highly
metastable, amorphous phase by increasing the compression rate beyond the limits of our current setup.
AC CONDUCTIVITY OF PCL/PLA BLEND COMPOSITES WITH CARBON NANOTUBES
E. Laredo (1), A. Bello (1), M. Grimau (1), Y. Zhang (2), D. Wu (2)
(1)Universidad Simón Bolívar, Apartado 89000, Caracas 1080, Venezuela
(2) Yangzhou University, Jiangsu 225002, PR China
elaredo@usb.ve
Electrical conductivity, σ(f), of nanocomposites made of Poly(ε-caprolactone)/polylactide (70/30)
immiscible blend charged with functionalized multiwall carbon nanotubes was studied in a wide
frequency range (10 -3 ≤f ≤10 7 Hz). In this material it has been shown that a selective localization of
the MWCNT exists in the semi-crystalline PCL matrix and on the interphase of the two blend
components [1]. The AC conductivity variation as a function of the nanotubes weight concentration, p,
(0 < p< 2%) showed the existence of a percolation threshold, pc = 0.98%. For p>pc, two zones were
found, a frequency independent region f < fc, and at higher frequencies an f s dependence, with
exponent s varying from 1 to 0.472 as p increases. The dependence of σDC with (p-pc) and with –p -1/3 ,
allowed the determination of the critical exponent, t, which is indicative of the dimension of the
percolative system. The existence of tunneling transport of charge carriers before the infinite cluster
necessary for percolation is formed is demonstrated [2]. The polarity of both blend components made
the analysis complex due to the presence of relaxation modes in the frequency window whose
contribution had to be carefully evaluated.
[1] D. Wu, Y. Zhang, M. Zhang and W. Yu, Biomacromolecules, 10, 417, 2009

[2] A. Linares, J. C. Canalda, M. E. Cagiao, M.C. Garcia-Gutierrez, A. Nogales, I. Martin-Gullón, J.
Vera and T. Ezquerra, Macromolecules, 41, 7090, 2008.
Influence of the interfacial polarization relaxations in conducting composite films based on
polyaniline: application of Maxwell-Wagner-Hanai effective medium theory
C. Vanga Bouanga a , K. Fatyeyeva b , J.-P. Adohi c , M. Tabellout a
a Laboratoire de Physique de l’Etat Condensé, UMR CNRS 6087, Université du Maine, Avenue
Olivier Messiaen, 72085 Le Mans cedex 9, France
b Laboratoire "Polymères, Biopolymères et Surfaces", FRE 3101, CNRS Université de Rouen, Bd.
Maurice de Broglie, 76821 Mont Saint Aignan cedex, France
c UFR-SSMT, Université de Cocody, 22 B.P 582 Abidjan 22, Ivory Coast
E-mail: christele.vanga_bouanga.etu@univ-lemans.fr
The present study is focused on the preparation and characterization of the conducting
composites based on the matrix polymer - polyamide-6 (PA-6), and polyaniline (PANI) as the
conducting polymer. PANI attracts much attention due to its good chemical stability under the
environmental conditions and due to its high electrical conductivity. Different techniques were used
such as dielectric relaxation spectroscopy (DRS), atomic force microscopy (AFM) as well as effective
medium theory. This theory plays an important role in the modelling of the physical properties of
composite materials.
The composite PA-6/PANI films were chemically prepared by in-situ aniline polymerization
in the presence of the polymer matrix. It was established that pure polymer matrix and the PA-6/PANI
composites demonstrate different dielectric behaviour. Carried dielectric measurements (from 0.1 Hz
to 1 MHz) for PA-6/PANI composite films have shown two relaxation peaks attributed to the
interfacial polarization phenomena. The dielectric relaxation mechanism in the composite film was
explained based on Maxwell-Wagner polarization relaxation theory and AFM investigations. The high
frequency dielectric relaxation (at about 10 2 Hz) was attributed to the interfacial polarization effects
and the lower one (at about 10 5 Hz) was due to the heterogeneity of the composite PANI containing
layer. The system was modelled using Maxwell-Wagner-Hanaï mixture equation and the phase
parameters were calculated. The found parameter values were found in good agreement with
experimental data, thus validating the proposed model. The performed dielectric measurements have
shown that the dielectric response of the composite film was strongly influenced by the PANI
concentration in the composite film.

Keywords: dielectric relaxation spectroscopy; polyamide-6; polyaniline; composite
EFFECT OF PRESSURE AND COMPOSITION ON THE SEGMENTAL DYNAMICS OF
POLYUREA
D. Fragiadakis, C. M. Roland
Naval Research Laboratory, Code 6120, Washington DC 20375-5342, USA
daniel.fragiadakis.ctr@nrl.navy.mil
By applying elastomer coatings to hard substrates, one can obtain significant increases in blast and
impact resistance. The mechanism for this improvement is complex and incompletely understood.
However, an important contribution seems to be the large energy dissipation during the transition from
the rubbery to the glassy state, which occurs during impact when the polyurea is subjected to both very
high deformation rate and locally elevated pressure. Polyurea, formed by reacting diisocyanates with
polyamines, is an attractive polymer for use in impact-resistant coatings. We study the effect of
pressure and of stoichiometry, i.e. the ratio of isocyanate to amine, on the viscoelastic properties of a
series of polyureas.
Varying the stoichiometry results in very significant differences in the mechanical properties of the
material. However, the segmental relaxation of the soft segments, which controls the impact-induced
glass transition, shows more modest changes. With increasing amount of isocyanate, segmental
relaxation times slightly increase. This slowing down becomes more pronounced with increasing
pressure, indicating an increase in activation volume. The relaxation times obey the thermodynamic
scaling law τ = f(TV γ ); although the exponent γ decreases slightly with increasing isocyanate fraction,
the relaxation times collapse on the same master curve independent of stoichiometry.
Mechanical relaxations in bulk metallic glasses : is there any beta relaxation ?
J.M. PELLETIER and C. GAUTHIER
Mateis, UMR 5510, Bat. B. Pascal, INSA-Lyon, France
Molecular of amorphous materials has been the subject of a lot of works, both from an experimental or
a theoretical point of view. It is well known that mechanical relaxations are observed when a sample is
submitted to a mechanical stress or to an electric field. Depending on the molecular architecture, the
number of relaxations may change. In polymers, the main relaxation is preceded by secondary
relaxations, especially the beta secondary relaxation, which corresponds to localized movements. In
oxide glasses, situation is not so clear. And in bulk metallic glasses ?
This presentation will address mechanical relaxations appearing in bulk metallic glasses, especially
common features and differences of these phenomena compared to those occurring in other
amorphous alloys (polymers, oxide glasses). One of the difficulties is that the beta relaxation, which is
clearly detected in polymers, for instance, is not so evident in bulk metallic glasses. Nevertheless,
physical models developed to explain the phenomena in other materials may be applied in BMG.

Jean-marc.pelletier@insa-lyon.fr
SCALING OF THE STRUCTURAL RELAXATION IN FRAGILE AND STRONG
GLASSFORMING LIQUIDS
A. Le Grand, C. Dreyfus, C. Bousquet and R.M. Pick
I.M.P.M.C., Université Pierre et Marie Curie-Paris 6 and CNRS-UMR 7590, Paris, France
catherine.dreyfus@impmc.jussieu.fr
A scaling law for the alpha relaxation time, tau, involving the ratio of a density-dependent energy to
the thermal energy, has been found to hold in many fragile glass-forming liquids. This scaling has
been recently linked to a local quantity, nloc(d,T) relating the variation of the alpha relaxation time
with density, d, to its variation with temperature, T. In many fragile liquids, the variation of nloc(d,T)
is weak enough to take it as constant over the experimental temperature and density domain. We show
that simulated liquid silica has an opposite behavior; close to Tg, nloc is negative for moderate
densities and exhibits a significant variation with d and T, reaching positive values for higher
temperature and/or densities. Moreover, those variations linearly correlate to a measure of the bonding
properties of the liquid.
NMR METHODS BASED ON DIFFUSION TENSOR MEASUREMENTS TO STUDY
CARTILAGE FEATURES AND AGING
Cesare E. M. Gruber (1), S. Capuani (1,2), T. Gili (1,3) and B. Maraviglia (1,3)
(1) Physics Department Sapienza University of Rome, Rome Italy
(2) INFM-CNR SOFT, Physics Department Sapienza University of Rome, Rome Italy
(3) MarbiLab, Enrico Fermi Center, Rome, Italy
silvia.capuani@roma1.infn.it
NMR represents a powerful tool to investigate, non-invasively, water diffusion in living systems.
Specifically, Diffusion-Tensor-Imaging (DTI) [1] is a quite recent NMR technique which is
especially sensitive to anisotropic molecular diffusion. DTI method provides parametric maps
where pixel intensity is proportional either to mean diffusivity (MD) or to fractional anisotropy
(FA, i.e. the degree of media anisotropy). Quantitative measurements of MD and FA allow
biological tissue morphology to be characterized on the base of its water molecular diffusion
features. We report DTI measurements on bovine cartilage samples to characterize cartilage
aging due to dehydration process. The experiments were performed at 9.4T magnetic field
strength using a microimaging probe. Images resolution were 60x60µm 2 . NMR data are in
accord to polarised light microscopy and scanning electron microscopy data, recognizing
variation of collagen fiber alignments in different cartilage zones [2]. FA and MD assume
different values as function of both the dehydration time and cartilage zones microstructure.
These studies can help the understanding of relationships between cartilage ageing and
osteoartitic diseases.
[1] P.J. Basser, J. Mattiello and D. LeBihan, J. Mag. Res. B 103, 247, 1994.
[2] X. Denga, M. Farley, M. T. Nieminena, M. Grayb, and D. Burstein. Magn. Res. Img., 25,168, 2007
DIELECTRICAL BEHAVIOUR OF Li2O-ZnO-P2O5 GLASSES
L. Pavic (1), A. Mogus – Milankovic (1), S. T. Reis (2) and D. E. Day (2)
(1) Rudjer Boskovic Institute, Department of Chemistry, Bijenicka cesta 54, 10000 Zagreb, Croatia

(2) Missouri University of Science and Technology, Rolla, MO 65401, USA
Luka.Pavic@irb.hr
Structural and dielectrical properties of xLi2O-(40-x)ZnO-60P2O5 glasses, (0 ≤x≤ 40), in mol%, have
been investigated by DTA, Raman and Impedance Spectroscopy in the frequency range from 0.01 Hz
to 4 MHz and temperature range from 298 to 473 K.
The systematic change in the variety of properties at 20 mol% Li2O is an after effect of changes in the
nature of the oxygen bonds in glass network [1]. The Raman spectra show predominantly
metaphosphate structure with barely detectable pyrophosphate units in all investigated glasses.
The dielectric permittivity and dielectric strength [2] (∆ε = εs – ε∞) as a function of Li2O content,
measured at lower temperatures, show a minimum at 20 mol% whereas linearly increase at higher
temperatures. This suggests that the dielectric properties are directly related to the thermally
stimulated mobility of Li + ions in the high temperature region. However, the anomaly observed at
lower temperatures for glass containing 20 mol% Li2O coincides with the minimum in the glass
transition temperature, Tg, and glass forming tendency, (∆Ts= Tx-Tg). These alterations in physical
properties of lithium zinc phosphate glassses are related to the discrete restructuring in glass network
due to the changes in the nature of the oxygen bonds [3].
[1] R. K. Brow, J. Non-Cryst. Solids 263&264, 1, 2000
[2] D. L. Sidebottom, Phys. Rev. B 61, 14507, 2000
[3] A. Mogus-Milankovic et al.; J. Non-Cryst. Solids (2009) accepted for publication
ADVANCED NUCLEAR MAGNETIC RESONANCE METHODS TO CHARACTERIZE
WATER DIFFUSION IN BONE MARROW
S. De Santis (1,2) and S. Capuani (1,2)
(1) Physics Department, “Sapienza” University of Rome, P.zle A. Moro 5, 00185 Rome, Italy
(2) INFM-CNR SOFT, “Sapienza” University of Rome, P.zle A. Moro 5, 00185 Rome, Italy
silvia.capuani @roma1.infn.it
NMR signal which describes water diffusion in biological systems, is often found to deviate from the
conventional mono-exponential decay: S(b)=S(0)exp(-bD) [1], where D is the diffusion coefficient
and b depends on the spins diffusing time and on diffusion gradient strength. Due to the interaction
between water molecules and the environment, a stretched exponential form for the signal decay is
found: S(b)=S(0)exp(-Ab γ ) [2], where γ is the stretching parameter which also defines the non linear
2 γ
dependence of the mean squared displacement of diffusing spins to the diffusion time r () t ∝ t . We
investigated water diffusion behaviour in calf bone marrow at high magnetic field (9.4T), using
diffusion weighted sequences at different b values . Bovines’ age was chosen in the range between 8
and 24 months in order to investigate diffusion behaviour at different water/fat ratios. We found a
dependence of the magnitude of the stretching parameter γ to the water content and to the water
compartmentalization.
Our results demonstrate that γ values may provide complementary useful information about diffusion
behaviour of water to better describe the complex fat-water interface system and to improve bonemarrow
pathologies diagnosis.
[1] P.J. Basser, J. Mattiello and D. LeBihan, J. Mag. Res. B 103, 247, 1994
[2] M. G. Hall, T. R. Barrick, Magn. Res. Med. 59, 447, 2008
DYNAMIC CROSSOVER OF WATER RELAXATION IN CRYOPROTECTANT
MIXTURES AT VERY HIGH PRESSURE
S. Ancherbak* (1), S. Capaccioli (1), D. Prevosto (1), Shahin M. Thayyil (1), P.A. Rolla (1), N.
Shinyashiki (2)
(1) CNR-INFM, polyLab & Dipartimento di Fisica, Universita di Pisa, Italy

(2) Department of Physics, Tokai UniVersity, Hiratsuka, Kanagawa 259-1292, Japan
*Correspondence author: ancherbak@df.unipi.it
Broad-band dielectric measurements for water-fructose mixtures with water concentrations 20.0,
26.0 and 30.0 wt% and water-polyethylene glycol (PEG400 and PEG600) mixtures (both 35% wt.)
were carried out in the frequency range of 10 mHz to 10 MHz, in the temperature range from 140
K to 300K and pressure range from 0.1 MPa to 6 MPa. In all the systems two relaxation processes,
the structural α- process at lower frequency and a fast secondary ν process (due to water) at higher
frequency, were observed, as already reported in previous studies [1]. The fast ν relaxation time,
related to water, showed a marked crossover from a Vogel-Fulcher temperature behaviour to an
Arrhenius one on cooling, resembling the Fragile to Strong transition already postulated for
confined and bulk water [2]. At odds with the current theoretical predictions [3], this crossover is
not occurring at constant time or temperature, but it is stronlgy dependent on pressure and it occurs
always in correspondence with the calorimetric glass transition of the mixtures or, in other terms,
when the structural relaxation time τα exceeds 1000 s. Both the glass transition temperature Tg and
the activation energy of the ν process are increasing with pressure, but their ratio is not constant (it
increases too), so the timescale separation at Tg between the slow and fast processes is increasing
with pressure. The evidences suggest a local and peculiar character of the ν process related to the
hydrogen-bonding mechanism.
References:
[1] S. Capaccioli, K. L. Ngai, N. Shinyashiki, J. Phys. Chem. B, 53 (1970) 2372.
[2] L. Liu et al., Phys. Rev. Lett. 95, 117802 (2005).
[3] P. Kumar, G. Franzese, H.E. Stanley, Phys. Rev. Lett. 100, 105701 (2008).
PROBING VISCOELASTIC PROPERTIES OF MODEL GLASSY INTERFACES SHEARED
BETWEEN A BEADS LAYER AND AN ULTRASONIC RESONATOR
J. Léopoldès (1), X. Jia (1)
(1) Laboratoire de Physique des Matériaux divisés et Interfaces, Université Paris Est, CNRS UMR
8108,Citée Descartes, 77454 Marne la Vallée cedex 2, France
julien.leopoldes@univ-mlv/fr
From wet sand to the eye cornea, liquid systems confined into small volumes are ubiquitous
in nature and are known to alter friction and adhesion at a solid-solid interface [1-4]. Moreover the
mechanical properties and stability of thin films are of paramount importance for a number of
applications requiring specific nanometric coatings such as optical reflectors or dielectric stacks. It is
then natural to ask whether the properties of confined liquids are similar to their bulk counterpart. But
conventional mechanical testing is not adapted for thin films investigation and specific metrology is
needed. In this study, we describe another approach to probe the viscoelastic properties of thin films
by using a conventional QCM. To this end, we deposit gently a layer of spherical bead (glass) on the
top of different films of thickness h ~ 1 - 100 nm coated on the surface of the ultrasonic resonator. The

esulting shifts of resonance frequency and inverse of quality factor can be related directly to the
elastic modulus and viscous dissipation of the films. We discuss different ageing morphologies
corresponding to various thin films used as model glassy interfaces.
[1] M. Urbakh, J. Klafter, D. Gourdon, J.N. Israelachvili, Nature 430, 525 (2004)
[2] G. He, M.H. Muser, M.O. Robbins, Science 284, 1650 (1999)
[3] L. Bocquet, E. Charlaix, S. Ciliberto and J. Crassous, Nature 396, 735 (1998)
[4] Th. Brunet, X. Jia and P. Mills, Phys. Rev. Lett. 101, 138001 (2008)
RELAXATION DYNAMICS AND EXCESS ENTROPY IN ROOM TEMPERATURE IONIC
LIQUIDS
Cinzia Chiappe, Marco Malvaldi
Dipartimento di Chimica e Chimica Industriale, via Risorgimento 35, 56126 Pisa
marco@dcci.unipi.it
The relaxation dynamics in a model room temperature ionic liquid (methyl-methyl imidazolium
chloride [mmim][cl]) is studied with Molecular Dynamics calculations and integral equation theory,
extending previous works on the structure of RTILs[1,2]. The differential diffusion and of the cage
correlation functions of the liquid are calculated and interpreted with the help of excess entropy
function, approximated as the two-body contribution. It is found that the diffusion scales with excess
entropy following a Rosenfeld-type equation, and that the entropy is able to predict the anomalous
cation/anion diffusion ratio in quantitative agreement with MD calculations.The cage relaxation times
τn (times needed for an ion to lose n counterions of its nearest-neighbor cage) are found to follow too a
Rosenfeld-type equation. Finally, the contribution of higher-order distribution functions (three,...,n
particle distribution functions) to the excess entropy as a function of temperature is studied in order to
understand to which extent the higher order organization, such as the cation-cation stacking, affects
the dynamics.
[1] M.Malvaldi,S.Bruzzone, and C.Chiappe, Phys. Chem. Chem. Phys., 41, 5576, 2007.
[2] S. Bruzzone, M. Malvaldi and C. Chiappe, J. Chem. Phys., 129, 074509, 2008.
MOLECULAR DYNAMICS AND STRUCTURE IN DIBLOCK COPOLYMERS STUDIED
BY NMR AND BROADBAND DIELECTRIC SPECTROSCOPY
J. Jenczyk, M. Makrocka-Rydzyk, A. Wypych, S. Głowinkowski, S. Jurga *
Department of Macromolecular Physics, Faculty of Physics, Adam Mickiewicz University,
Umultowska 85, 61-614 Poznań, Poland.
* zfmak@amu.edu.pl
Block copolymers are under great research interest due to their current and potential applications.
Properties of these systems depend on individual blocks characteristics and on the interaction between
the components[1]. We have investigated two nearly symmetric poly(styrene-b-isporene) diblock
copolymers: PS(11500)-b-PI(10500)→SI1, PS(45000)-b-PI(46000)→SI2. NMR and BDS studies
were applied to characterize molecular motions in copolymers and their neat components. It appeared
that the flexible polyisoprene (PI) and stiff polystyrene (PS) blocks in copolymer influence one
another in terms of molecular dynamics. As a result the increase of the glass transition temperatures

(Tg) for PI chains and decrease of Tg for PS chains for both copolymers was observed [2]. Moreover,
there is a substantial broadening in the distribution of relaxation times connected with the glass
transition process in copolymers in comparison with neat components and it is more pronounced for
the copolymer of higher molecular weight. It is assumed that these changes result from both type
chains mutual interactions, since PS blocks make spatial confinement for PI chains motion, whereas
the moving PI chains act as plasticizer for PS blocks. The size of PS domains were determined by
NMR spin diffusion experiment. Obtained values compare well with other measurements [3,4].
[1] I.W. Hamley Developments in Block Copolymer Science and Technology (2004) John Wiley&Sons,
Ltd.
[2] J. Jenczyk, M. Makrocka-Rydzyk, A. Wypych, S. Głowinkowski, M. Radosz, S. Jurga J. Non
Cryst. Sol. (2009), accepted for publication.
[3] B. Cott Pinheiro, K. I. Winey Macromolecules 31 (1998) 4447-4456
[4] J. Denault, B. Morese-Seguela, J. Prud’homme Macromolecules 23 (1990) 4658-4670
Acknowledgements:
This work is supported by 6th Framework Programme under SoftComp Grant No 502235-2 and
research grant No N N202 128536 (Poland).
A. Wypych expresses her appreciation to the Ministry of Science and Higher Education in Poland for
a Postdoctoral Fellowship (POL-POSTDOC III).
DYNAMIC ARREST IN MULTICOMPONENT GLASS FORMING ALLOYS
Alexander Bartsch (1), Klaus Rätzke (1), Andreas Meyer (2), and Franz Faupel (1) *
(1) Institut für Materialwissenschaft - Materialverbunde, Technische Fakultät, Christian-Albrechts-
Universität Kiel, Kaiserstr. 2, D-24143 Kiel, Germany
(2) Institut für Materialphysik im Weltraum, Deutsches Zentrum für Luft- und Raumfahrt (DLR),
51170 Köln
*e-mail: ff@tf.uni-kiel.de
Metallic glasses are currently among the most actively studied metallic materials. Apart from their
many novel applicable properties, metallic glasses have also been in the focus of research advancing
our understanding of liquids and of glasses in general. Here, we report radiotracer diffusivities in
multicomponent Pd and Zr based melts including the slow components Pd and Zr, which are most
important for glass formation but have not yet been accessible. While in Pd43Cu27Ni10P20 a very strong
decoupling over 4 orders of magnitude is observed between the diffusivity of Pd and of the smaller
components exactly at the critical temperature Tc of the mode coupling theory, no decoupling is seen
for Pd diffusion and viscous flow. The Stokes-Einstein relation holds in the whole range investigated
encompassing more than 14 orders of magnitude suggesting the formation of a slow subsystem as a
key to glass formation. In Zr46.75Ti8.25Cu7,5Ni10Be27.5, the Stokes-Einstein equation as a whole even
breaks down in the equilibrium melt, and only holds for Zr which is still decoupeld from diffusion of
the lighter elements about 50 K above the melting temperature. This shows that a slow Zr subsystem
prevails in the equilibrium melt.
INVESTIGATION OF THE SOLID STATE MUTAROTATION OF D-GLUCOSE
N. Dujardin, J-F. Willart, E. Dudognon, A. Hédoux, Y. Guinet, L. Paccou, M. Descamps.
Laboratory of Dynamic and Structure of Molecular Materials, University of Lille 1, France
jean-francois.willart@univ-lille1.fr

We show that crystalline α-glucose and crystalline β-glucose can be amorphized and vitrified directly
in the solid state by mechanical milling [1, 2]. Contrary to the usual thermal quench of the liquid this
solid state amorphization route does not involve any mutarotation giving rise to anomerically pure
amorphous glucose. This possibility offers an exceptional opportunity to investigate the mutarotation
in the solid state. In particular, we have studied the kinetics of mutarotation at several temperatures so
as to identify a possible coupling between the phenomenon of mutarotation (local process) and the
slow structural relaxations characteristic of the glassy state (cooperative process), in other words a
possible coupling between the chemical and physical stability. The investigations are performed by Xray
diffraction, differential scanning calorimetry and Raman spectroscopy.
[1] N. Dujardin, J. F. Willart, E. Dudognon, A. Hédoux, Y. Guinet, L. Paccou, B. Chazallon and M.
Descamps, Solid State Communications 148 (2008), p. 78.
[2] N. Dujardin, J. F. Willart, E. Dudognon, F. Danède and M. Descamps, J. Pharm. Sci. Submitted
(2009).
A QUEST FOR A GROWING LENGTH SCALE IN SUPERCOOLED LIQUIDS
Christiane Alba-Simionesco (1,2), Cécile Dalle-Ferrier (1,2), Stefan Eibl (2,3)
(1)Laboratoire Léon Brillouin, unité mixte CEA-CNRS, Saclay,France
(2)Laboratoire de Chimie-Physique, Université Paris-Sud, France
(3) Institut laue Langevin, Grenoble France
Correspondence author: christiane.Alba-Simionesco@cea.fr
MOLECULAR DYNAMICS OF LINEAR AND DENDRIMER-LIKE STAR-BRANCHED
POLYSTYRENES AS SEEN BY DIELECTRIC AND NMR SPECRTROSCOPIES
A. Wypych (1), M. Makrocka-Rydzyk (1), E. Szcześniak (1), S. Jurga* (1) and A. Hirao (2), T.
Watanabe (2).
(1) Department of Macromolecular Physics, Faculty of Physics, Adam Mickiewicz University,
Umultowska 85, 61-614 Poznań, Poland.
(2) Graduate School of Science and Engineering, Tokyo Institute of Technology,
H-127, 2-12-1, Ohokayama, Meguro-ku, Tokyo 152-8552, Japan.
* zfmak@amu.edu.pl
Dendrimer-like star-branched polymers have recently appeared as a new class of
hyperbranched polymers. These materials are synthesized by means of living anionic polymerization
[1] or atom transfer radical polymerization [ 2 ]. Their structure with monomer units branching out from
a center cord comprises several layers (so-called generations). The material under study is a starbranched
polystyrene of third generation [3]. Broadband Dielectric and 13 C NMR Spectroscopies were
employed to examine the influence of the morphologic state of linear and dendritic polystyrenes on
their molecular dynamics. The analysis of the temperature behavior of dielectric data indicates an
existence of three motional processes denoted by α, β and γ in order of decreasing temperature. The α
relaxation is related to the dynamic of glass transition, the β -relaxation was assigned to a motion of
the phenyl rings, while the γ relaxation was attributed to the local motions of the methylene units

(present due to tail-to-tail or head-to-head sequences). A broadening of the distribution of relaxation
times in the polymer of dendritic structure with respect to the linear one was observed.
[ 1 ] W.A. Braunecker, K. Matyjaszewski, Prog. Polym. Sci., 32, 93, 2007.
[ 2 ] B.Lepoittevin, R. Matmour, R. Francis, D.Taton, Y.Gnanou, Macromolecules, 38, 3120, 2005.
[3] A. Deffieux, M. Schappacher, A. Hirao, T. Watanabe, J. Am. Chem. Soc., 130 (17), 5670, 2008.
Acknowledgements: This work is supported by 6th Framework Programme under SoftComp Grant No
502235-2 and research grant No N N202 128536 (Poland). A. Wypych expresses her appreciation to
the Ministry of Science and Higher Education in Poland for a Postdoctoral Fellowship (POL-
POSTDOC III).
TRANSFORMATION OF ULTRASTABLE GLASSES ABOVE Tg
S.F. Swallen, Z. Fakhraai, M.D. Ediger
Department of Chemistry, University of Wisconsin-Madison, Madison, Wisconsin, USA
swallen@chem.wisc.edu
The stability of glasses can be increased by aging, but only to a small extent due to very slow
relaxation rates below Tg. We have shown that highly stable molecular glasses can be quickly
prepared by appropriate control of physical vapor deposition conditions. These materials have low
enthalpy, high density, and very slow kinetics, even compared to conventionally aged glasses. We
report depth-profiling measurements of isotopically labeled multilayer thin films of two molecular
glasses, IMC and TNB, which give detailed information on the glass-to-liquid transformation process
during annealing near Tg. Growth fronts are observed to propagate from the film surfaces, giving rise
to a supercooled liquid. The stable glass ahead of the front shows no measurable motion for times
exceeding the supercooled liquid τα by a factor of 1000. These results are in excellent agreement with
transformation times determined by calorimetry and light scattering. This highly heterogeneous
transformation mechanism can not be described by conventional models of the glass transition which
assume homogeneous relaxation processes.
RHEOLOGY STUDIES OF MOLECULAR DYNAMICS IN THERMOPLASTIC OLEFIN
POLYMERS
M. Makrocka-Rydzyk, G. Nowaczyk, S. Głowinkowski, S. Jurga *
Department of Macromolecular Physics, Faculty of Physics, Adam Mickiewicz University,
Umultowska 85, 61-614 Poznań, Poland
* zfmak@amu.edu.pl
Understanding of the influence of polymer chain modification on structure and molecular
motions is essential for polymer engineering chemistry. New substances synthesized from polymers of
different properties may show properties intermediate between those of the initial products. The
materials used in this study were ethylene/norbornene copolymers made by Ticona (Germany).
Rheological studies of molecular dynamics have been performed for copolymers having 35 and 51
molar percentage of norbornene. The analysis of data reveals the existence of three relaxations: the
primary (α) and two secondary (β and γ) processes [1]. The α-process is associated with segmental
motions and its motional rate follows the Vogel-Fulcher-Tammann equation, indicating cooperative
nature of the motions involved in this process. The secondary processes β and γ are connected with the
local motions of ethylene and norbornene groups, respectively, and their motional rates follow the
Arrhenius relation. Moreover, the β one was recognized as Johari-Goldstein process acting as a driving
force for the motions associated with the primary process. An increase of norbornene content in

copolymer slows down molecular motions of both norbornene fragments as well as whole chains. In
consequence it causes a shift of these relaxation processes into higher temperatures. The motional
parameters for processes mentioned above were estimated using the Havriliak-Negami formalism.
[1] M. Makrocka-Rydzyk, B. Orozbaev, G. Nowaczyk, S. Głowinkowski, S. Jurga, Acta Phys Pol A
2005, 108, 211.
Acknowledgements: This work is supported by 6th Framework Programme under SoftComp Grant No
502235-2 and research grant No N N202 128536 (Poland).
SINGLE-PARTICLE AND COLLECTIVE DYNAMICS OF PROTEIN HYDRATION
WATER.
MOLECULAR DYNAMICS SIMULATIONS AND NEUTRON SCATTERING INSIGHTS
V. Conti Nibali (1), G. D’Angelo (1), A. Paciaroni (2), C. Petrillo (2), F. Sacchetti (2), M. Tarek (3), U.
Wanderlingh (1).
(1) Dipartimento di Fisica, Universita di Messina,I-98166 S. Agata (Messina), Italy
(2) Dipartimento di Fisica, Universita di Perugia, I-06123 Perugia, Italy
(3) Reactivitè des Systemes Moleculaires Complexes, Nancy University, CNRS, France
vcontinibali@unime.it
Protein hydration water is important for protein structure and stability, and inluences the dynamics of
the protein molecule as a whole. As a step toward understanding the key role of water, we characterize
water single particle and collective density fluctuations in Maltose Binding Protein (MBP) crystals by
means of an analysis based on molecular dynamics simulations.
Moreover, we present an extensive comparison to neutron scattering experiments, in which protein
hydration water has shown to exhibit dynamical features quite different from bulk water, with a
behaviour reminescent of glassy systems.
SPECTROSCOPIC STUDIES OF PHOSPHOCHOLINE DMPC/GEMINI SURFACTANT
SYSTEM
K. Szpotkowski, A. Wypych, M. Kozak, S. Jurga*
Departament of Macromolecular Physics, Faculty of Physics, Adam Mickiewicz University,
Umultowska 85, 61-614 Poznań, Poland
*zfmak@amu.edu.pl
Phospholipids are structural basis of biological membranes, with structures strongly dependent on
temperature and additions, such as cholesterol and surfactants [1]. Gemini surfactants are a new
generation amphiphilic molecules, which contain two monomer surfactant molecule linked by a spacer.
This group of surfactants has special properties and potential applications in many areas [2]. Gemini
surfactant molecule intercalates between zwiterionic phospolipid molecules and causes a change of
surface charges which disturb in turn a bilayer structure [3].
Aqueous suspension of 1,2-dimyrilstoyl-sn-glycero-3-phosphocholine (DMPC) with different
concentration of the surfactant 1,1’-(1,4-butane) bis 3-decyloxymethylimidazolium chloride (GEM-
IK1) has been investigated by Broadband Dielectric Spectroscopy and Fourier Transform Infrared
Spectroscopy.
Dielectric spectroscopy in frequency range from 10 6 Hz to 10 9 Hz was used to study a polar part of
DMPC phospholipid. The observed small step in the dependence of dielectric constant vs. temperature
is connected with a transition from gel to liquid crystalline phase, in accordance with temperature
dependencies of the stretching bands of phosphate and carbonyl groups detected by FTIR. Two
characteristic bands from IR spectra, corresponding to symmetric and antisymetric vibrations of
methyl groups, were used do detect changes in the non-polar part of phospholipids bilayer.
Our results show, that the temperatures of the observed main- and pre– transitions` decrease with an
increase of the surfactant concentration.
[1] J. Katsaras, T. Gutberlet (Eds.), Springer- Verlag, Berlin – Heidelberg, 2001.

[2] Mingqi Ao, Guiying Xu, Yanyan Zhu, Yan Bai, Journal of Colloid and Interface Science 326
(2008) 490–495.
[3] D. Uhrikowa, G. Rapp, P. Balgavy. Bioelectrochemistry 58 (2002) 87-95.
Acknowledgements: This work is supported by 6th Framework Programme under SoftComp Grant No
502235-2 and research grant No N202 248935 (Poland). A. Wypych expresses her appreciation to the
Ministry of Science and Higher Education in Poland for a Postdoctoral Fellowship (POL-POSTDOC
III).
THE INVESTIGATION OF THE IONIC GELATION PROCESS IN AQUEOUS AMIDATED
LOW METHOXYL PECTIN SOLUTIONS
M. Dobies, G. Nowaczyk, K. Szpotkowski, S. Jurga*
Department of Macromolecular Physics, Faculty of Physics, Adam Mickiewicz University,
Umultowska 85, 61-614 Poznań, Poland.
*zfmak@amu.edu.pl
Amidated low methoxyl pectins (ALMP) belong to the family of heteropolysaccharides which are
widely used in food industry as textural ingredients because of their thickening and gel-forming
properties. They are also useful in medical application as colon-specific drug delivery systems [1, 2].
The chemical structure of ALMP polysaccharides mainly consists of α (1-4) linked D-galacturonic
acid residues in which some of the carboxyl groups are substituted with methyl esters (< 50%) and
amide groups. ALMP form gels by intermolecular associations induced by addition to aqueous
solutions of ALMP multivalent metal cations, which act as a bridge between pairs of carboxyl groups
of different pectin chains (the egg-box mechanism) [3, 4]. In addition, amide groups along the ALMP
chain give rise to association through hydrogen bonding.
The 1 H NMR relaxometry and diffusometry in combination with the FTIR spectroscopy and
rheometry were applied to study the calcium-induced gelation of 1% w/w aqueous ALMP solutions
and physicochemical mechanisms responsible for gel network formation. The results of our studies
show that at the same concentration of calcium cations the gel network of amidated LM pectin is
stronger than that previously noted for the non-amidated LM pectin [5]. It confirms that the hydrogen
bonds (between block of amide residues belonging to different pectin chains) play significant role in
junction zones creation of LMPA gel networks.
Acknowledgements: The authors wish to acknowledge the financial support of the 6 th Framework
Programme under SoftComp Grant No. 502235-2.
[1] S. E. Hill, D.A. Ledward, J.R., Mitchell (Ed), Functional Properties of Food Macromolecules,
Aspen Publishers, Inc, pp 169-175, 1998
[2] L. Liu, M. L. Fishman, J. Kost, K. Hicks, Biomaterials 24, 3333, 2003
[3] G. T. Grant, E. R. Morris, D.A. Rees, P. J. C. Smith, and D. Thom, FEBS Lett., 32, 195, 1973
[4] I. Braccini and S. Perez, Biomacromolecules, 2, 1089, 2001
[5] M. Dobies, S. Kuśmia, S. Jurga, Acta Phys. Polon., 108, 33, 2005
IN SITU RAMAN SCATTERING OF SILICA GLASS UNDER HIGH PRESSURE AT HIGH
AND LOW FREQUENCIES.
T.Deschamps, C. Martinet, C.Coussa, B.Champagnon
Laboratoire de Physico-Chimie des Matériaux Luminescents
10, rue A.M. Ampère, 69622 Villeurbanne cedex France
deschamps@pcml.univ-lyon1.fr

We report in situ Raman measurements on vitreous silica under high-pressure and ambient
temperature. We recorded both high and low frequencies spectra and focused our attention on the
elastic behaviour of this glass between 0 and 8 GPa , more precisely on the compressibility anomaly
before 3 GPa [1]. Our results show a rapid shift toward higher frequencies of the main Raman band
around 3 GPa wich suggests a fast decrease of the mean intertetrahedral Si-O-Si angle. The narrowing
of this band and the collapse of the Boson peak (at 50 cm -1 ) intensity during compression play in
favour of a structural homogeneisation at different scales: at short scale, intertetrahedral angle
distribution is narrowed and at nanometric scale, the contrast of elastic heterogeneities decreases under
pressure [2].
[1]P.W.Bridgman, Proc.Amer.Acad.Arts Sci. 76, 55 (1948)
[2] E.Duval, A.Boukenter, B.Champagnon, Phys. Rev. Lett, 56, 2052, (1986)
MOLECULAR DYNAMICS IN GRAFTED POLYDIMETHYLSILOXANES STUDIED BY
NMR, BROADBAND DIELECTRIC SPECTROSCOPY AND RHEOLOGY
S. Jurga*(1), M. Jancelewicz (1), W. Waszkowiak (1), A.Wypych (1), M. Rydzyk (1), H. Maciejewski
(2).
(1) Department of Macromolecular Physics, Faculty of Physics, Adam Mickiewicz University,
Umultowska 85,
61-614 Poznan, Poland.
(2) Poznan Science and Technology Park, Rubiez 46, 61-612 Poznan, Poland.
*zfmak@amu.edu.pl
Molecular dynamics of linear and grafted polydimethylsiloxanes (PDMS) was investigated using
NMR, Broadband Dielectric Spectroscopy and Rheology, whereas their thermal behavior was
determined by DSC. The linear PDMS is partially crystalline, while the structure of its grafted
copolymers depends on the type of a modifier. An incorporation of the following side chains: (a) (-
C7H15), (b) (-CH2)3-O-CH2-(CHOCH2), (c) (-C16H33) and (d) (-CH2)3-(OCH2CH2)7-OCH3 to the PDMS
backbone influences morphology and molecular dynamics of PDMS. It was found that PDMS
copolymers grafted by side chains of the type: (a) or (b) have amorphous structure, whereas an
incorporation of the (c) and (d) modifiers leads to the semicrystalline morphology formed probably by
an arrangement of the grafted long side chains.
NMR measurements made possible to distinguish two relaxation processes: rotation of methyl groups
around the Si-C bond (low temperature process) and segmental motions of the main chain (αrelaxation
- high temperature process), dielectric and rheology studies in turn revealed segmental chain
motions of polymer backbone as well as slow motions due to polymer chain dynamics (normal mode)
for all investigated PDMS samples.
Acknowledgements: This work is supported by 6th Framework Programme under SoftComp Grant No
502235-2. A. Wypych expresses her appreciation to the Ministry of Science and Higher Education in
Poland for a Postdoctoral Fellowship
(POL-POSTDOC III).

NONLINEAR SUSCEPTIBILITY MEASUREMENTS IN A SUPERCOOLED LIQUID
CLOSE TO Tg : EVIDENCE OF A CRITICAL BEHAVIOR
C. Thibierge (1), C. Brun (1), F. Ladieu (1), D. L’Hôte (1), G. Biroli (2), J.-P. Bouchaud (1,3)
(1) Service de Physique de l’Etat Condensé (CNRS/MIPPU/URA 2464), DSM/IRAMIS/SPEC CEA
Saclay, F-91191 Gif-sur-Yvette Cedex, France
(2) Institut de Physique Théorique, CEA, (CNRS URA 2306), 91191 Gif-sur-Yvette, France
(3) Science & Finance, Capital Fund Management, 6, Bd. Haussmann, 75009 Paris, France
denis.lhote@cea.fr
The possible existence of a growing correlation length associated with the strong increase of relaxation
times of glass-formers close to the glass transition is still a major open question in glass physics [1-7].
It has been recently proposed that the ac nonlinear susceptibility of a supercooled liquid close to the
glass transition temperature Tg would be a probe of dynamical correlations [6-7]. As for spin glasses,
where the nonlinear susceptibility diverges at the transition, this quantity is tailored to reveal the
“hidden” critical behavior of the glass transition. We have developed a high sensitivity experimental
device to measure the nonlinear dielectric susceptibility of an insulating material at finite frequency
[8]. It measures the third harmonics of the current flowing out of a capacitor with the supercooled
liquid as the dielectric layer. It is based on a bridge with two capacitors, and reaches a sensitivity
better than 10 -7 (ratio of third to first harmonics).
Our first results on supercooled glycerol will be presented. They clearly reveal the growing of the
correlations close to the glass transition, thus reinforcing the picture of an underlying critical nature of
the glass transition.
[1] G. Adam and J. H. Gibbs, J. Chem. Phys. 43, 139 (1965).
[2] P. G. Debenedetti, Metastable Liquids, Concepts and Principles, Princeton University Press,
Princeton, 1996.
[3] L. Berthier, G. Biroli, J.-P. Bouchaud, L. Cipelletti, D. El Masri, D. L’Hôte, F. Ladieu, M. Pierno,
Science 310, 1797 (2005).
[4] C. Bennemann, C. Donati, J. Baschnagel, S. C. Glotzer, Nature 399, 246 (1999).
[5] C. Dalle-Ferrier, C. Thibierge, C. Alba-Simionesco, L. Berthier, G. Biroli, J.-P. Bouchaud, F.
Ladieu, D. L’Hôte, and G. Tarjus, Phys. Rev. E76, 041510 (2007).
[6] J.-P. Bouchaud and G. Biroli, Phys. Rev. B 72, 064204 (2005).
[7] M. Tarzia, G. Biroli, A. Lefèvre and J.-P. Bouchaud, Preprint arXiv:0812.3514 (2008).
[8] C. Thibierge, D. L’Hôte, F. Ladieu, and R. Tourbot, Rev. Sci. Inst. 79, 103905 (2008).
THE PRIMARY AND SECONDARY RELAXATION BEHAVIORS IN SEVERAL
INORGANIC GLASS FORMERS
Yuanzheng Yue(1,2), Lina Hu (2), Lasse Hornbøll (1)
(1) Section of Chemistry, Aalborg University, Denmark
(2) Key laboratory of Liquid Structure and Heredity of Materials, Shandong University, China
yy@bio.aau.dk
By applying the hyperquenching – annealing – calorimetry approach, we study both primary and
secondary relaxation behaviours of inorganic glasses with different fragilities. To do so, we choose the
following three glass formers as objects of this study: GeO2 glass (strong system), basaltic glass
(intermediately fragile system) and La-based metallic glass (fragile system). We demonstrate the
fundamental differences in enthalpy relaxation between the three glass systems. We show that the
manner of enthalpy relaxation in hyperquenched (HQ) glasses (glasses far from equilibrium) is linked
to the α- and β-relaxations. The correlative degree between the secondary and the primary relaxations
is closely associated with the liquid fragility. We have found that, unlike the HQ basaltic and metallic
glasses, the HQ GeO2 glass relaxes in a manner that all the secondary relaxation units contribute to the
primary relaxation. By analyzing dynamic properties of the secondary relaxation, we have identified
the typical feature of the Johari-Goldstein (JG) relaxation in the HQ GeO2 glass, i.e., the relationship
observed between the activation energy Eβ and the glass transition temperature Tg well agrees with that
typical for the JG relaxation. Besides, the characteristic secondary relaxation time of the GeO2 glass at

Tg is found to be about 10 seconds, larger than that of relatively fragile glasses. These results imply
that the JG peak in strong glasses is hidden by the α peak in the dielectric loss curves. The close
relationship between Eβ and Tg is also observed in the secondary relaxation in hyperquenched
La55Al25Ni20 ribbons. By a survey of experimental data related to sub-Tg relaxation dynamics of other
metallic glass systems, the general correlation Eβ=26.1RTg is found, which indicates that JG
relaxations are intrinsic in metallic glass formers. By analyzing on the average relaxation time of JG
motion,τ JG, and the crossover time in the coupling model, tc, we discuss why the excess wing, rather
than the JG peak (or shoulder), is generally present in metallic glass systems.
[1] L. Hornboll and Y.Z. Yue, J. Non-Cryst. Solids, 354, 350, 2008
[2]L. N. Hu and Y. Z. Yue, J. Phys. Chem. B, 112, 9053, 2008
COMPARISON BETWEEN MOLECULAR MOBILITIES AND MISCIBILITY OF BLENDS
AND DIBLOCK COPOLYMERS OF POLY(LACTIDE) AND POLY(ε-CAPROLACTONE)
M. Grimau , E. Laredo , A. Bello , D. Newman and A.J. Müller
Universidad Simón Bolívar, Caracas, Venezuela.
mgrimau@usb.ve
The miscibility and molecular mobilities of poly(D,L-lactide)/poly(ε-caprolactone) blends and poly(Llactide)-b-poly(ε-caprolactone)
diblock copolymers in a wide composition range were studied by
thermally stimulated depolarization currents techniques (TSDC) following both local and segmental
mobilities. [1, 2]. Whilst PDLLA/PCL blends show similar dielectric spectra as those given by the
homopolymer indicating only a certain degree of miscibility with a PCL rich phase, the diblock
copolymers show a complex behaviour with several segmental modes in the wide interval between
the two Tg’s of the homopolymers (∆Tg = 123 K). The compositional dependence of the glass
transitions detected in the copolymers is predicted by the self-concentration model for miscible blends
with a large Tg contrast, where the dynamic concentration fluctuations are originated by chain
connectivity. In the blends, the temperature shifts of the PCL segmental mobility as a function of
composition are much weaker as compared to the copolymer, showing only the existence of a limited
rigidization of PDLLA on PCL. Another difference is the crystallinity degree of the components of
both materials, which is higher for both PLLA and PCL in the block copolymer.
[1] D. Newman, E. Laredo, A. Bello, A. Grillo, J.L. Feijoo and A. Müller, Macromolecules.
DOI:10.1021/ma9007303
[2] E. Laredo, N. Prutsky,, A. Bello, M. Grimau, R.V. Castillo, A. Müller and Ph. Dubois, Eur. Phys.
J. E, 23, 295, 2007
DISCOVERY OF A NEW CRYSTALLINE PHASE OF IBUPROFEN
E. Dudognon ( 1 ), F. Danède ( 1 ), M. Descamps ( 1 ) and N. T. Correia (2)
(1) LDSMM, UMR CNRS 8024 - BAT P5, Université de Lille 1, 59655 Villeneuve d'Ascq, France
(2) REQUIMTE, Departamento de Química, Faculdade de Ciências e Tecnologia, Universidade Nova
de Lisboa, 2829-516 Caparica, Portugal
emeline.dudognon@univ-lille1.fr
The manipulation of the crystallization behavior of substances is an important issue in pharmaceutical
industry. The search for polymorphic varieties recently became a topic of major interest as the nonconventional
crystalline forms may have enhanced therapeutic activity. This work reports the
discovery of a polymorphic crystalline form of the active pharmaceutical ingredient: IBUPROFEN.
Indeed, in addition to the well-known conventional crystalline phase I, we observed for the first time,

y both differential scanning calorimetry and X-ray powder diffraction, the development of another
crystalline phase II which melts at lower temperature and is thus of lower stability. Its appearance,
conditioned by a quench of the liquid at very low temperatures, emphasizes the occurrence of a
nucleation process far below Tg. The discovery of this metastable form of presumably much higher
solubility may be interesting for drug formulation.
Acknowledgement: Financial support to Fundação para a Ciência e Tecnologia (FCT, Portugal)
through the project PTDC/CTM/64288/2006 and the Pessoa partnership Hubert Curien is
acknowledged.
BIOPROTECTIVE SUGARS : INSIGHTS FROM MOLECULAR DYNAMICS
SIMULATIONS
A. Lerbret, F. Affouard, A. Hédoux, Y. Guinet and M. Descamps.
Laboratoire de Dynamique et Structure des Matériaux Moléculaires, UMR CNRS 8024, Université
Lille I, 59655 Villeneuve d’Ascq, France
Correspondence author: frederic.affouard@univ-lille1.fr
Disaccharides such as trehalose have received a huge interest over the past few decades for their
preservation capabilities of biosystems such as cells, vaccines, or therapeutic proteins. Indeed, they
can be added to biologically active solutions to overcome the limited stability range of proteins (in pH,
in temperature, in salt concentration, etc.). However, the molecular mechanisms at the origin of the
superior capabilities of trehalose and, more generally, of the biopreservation phenomenon itself still
remain unclear. Several hypotheses (glass transition temperature, water molecules replacement,
hydrogen bonding destructuring effect, preferential excluded volume,…) have been proposed, but
none of them can be considered as fully accepted. In order to better understand the physical properties
of disaccharides and their influence on the protein stability we have performed a Molecular Dynamics
(MD) investigation of hen egg-white lysozyme in presence of three homologous disaccharides:
trehalose, sucrose and maltose. Vibrational properties in the low frequency spectral range [0 - 350] cm -
1 and the structural organization of the sugar/water solvent surrounding were mainly analyzed. This
study confirms that the hydrogen bonds (HB) network of water is highly dependent on the presence of
sugars and contributes to the stabilization of lysozyme. The privileged interaction of trehalose with
water is confirmed below a threshold weight sugar concentration of about 50 %.
IMIDAZOLIUM BASED IONIC LIQUIDS UNDER HIGH PRESSURE – A DIELECTRIC
SPECTROSCOPY STUDY
M.Mierzwa(1), S.Pawlus(1), A. Rivera-Calzada(2) and M.Paluch(1)
(1) A. Chelkowski Institute of Physics, University of Silesia, ul. Uniwersytecka 4, 40-007 Katowice,
Poland,
(2) GFMC, Dpto. Física Aplicada 3, Universidad Complutense de Madrid, Spain
Correspondence author: michal.mierzwa@us.edu.pl
We have investigated the dynamics of room temperature ionic liquids based on the 1-butyl-3-methyl
imidazolium cation using dielectric relaxation in the broad frequency, temperature and pressure
ranges. The process connected to ionic conductivity as well as the relaxations typical for glassformers
were observed in modulus representation. The features and origin of those processes are discussed in
comparison with conventional molecular glasses.
CONFINEMENT SIZE EFFECT IN DYNAMICS OF CLUSTERS OF LOW-MOLECULAR-
WEIGHT MOLECULES ENCAPSULATED IN CARBON NANOTUBES – COMPUTER
SIMULATION STUDY
Z. Dendzik, K. Górny and Z. Gburski

Institute of Physics, University of Silesia, Uniwersytecka 4, 40-007 Katowice, Poland
dendzik@us.edu.pl
Molecular systems embedded in carbon nanotubes reveals interesting properties [1-2] and are studied
not only for fundamental reasons, but also for their potential importance in practical applications as
chemical biosensors, nanoelectronic devices, field emission displays or energy storage [3-5]. We
performed all atoms molecular dynamics simulations of clusters of low-molecular-weight molecules
confined in single-walled carbon nanotubes to study the confinement size effect on the dipolar
relaxation of the studied clusters.
[1] I.A. Kolesnikov, J.M. Zanotti, C.K. Loong, P. Thiyagarajan, A.P. Moravsky, R.O. Loutfy and C.J.
Burnham, Phys. Rev. Lett. 93, 035503, 2004
[2] J. Zhao, A. Buldum, J. Han and J.P. Lu, Nanotechnology 13, 195, 2002
[3] A. Dillon, K. Jones, T. Bekkedahl, C. Kiang, D. Bethune and M. Heben, Nature 386, 377, 1997
[4] P. Chen, X. Wu, J. Lin and K. Tan, Science 285, 91, 1999
[5] J. Lu and J. Han, Int. J. High Speed Electron. Syst. 9, 101, 1998
DIPOLAR RELAXATION OF MOLECULAR SYSTEMS CONFINED IN POROUS SILICA –
MD STUDY
Z. Dendzik, K. Górny, W. Gwizdała and Z. Gburski
Institute of Physics, University of Silesia, Uniwersytecka 4, 40-007 Katowice, Poland
dendzik@us.edu.pl
Behavior of molecules in nanoscale confinement is of great interest to biology, geology and materials
science and reveals features not observed in bulk systems [1-4]. The characteristic of the dipolar
relaxation process in nanoscale confinement is an outcome of a couterbalance between interaction
between host and guest systems and the change in the length scale of the cooperatively rearranging
regions imposed by the geometrical constraints. We have carried out fully atomistic molecular
dynamics simulation to study dipolar relaxation of propylene glycol molecules confined in porous
silica and discussed the effect of confinement on the relaxation time and the shape of the relaxation
spectra.
[1] U. Raviv and J. Klein, Nature 413, 51, 2001
[2] K. Morishige and K. Kawano, J. Chem. Phys. 110, 4867, 1999
[3] S. Mitra, R. Mukhopadhyay, I.Tsukushi and S. Ikeda, J. Phys.:Condens. Matter 13, 8455, 2001
[4] P. Pissis, D. Daoukaki-Diamanti, L. Apekis and C. Christodoulides, J. Phys.: Condens. Matter 6,
L325, 1994
DENSITY -TEMPERATURE DEPENDANCY OF STRUCTURAL RELAXATION IN
FRAGILE AND STRONG GLASSFORMING LIQUIDS
A. Le Grand(1), C. Dreyfus(1), R. Pick(1), J. Gapinski(2), A. Pakowski(2), W.Steffen(3)
(1)I.M.P.M.C., Université Pierre et Marie Curie-Paris 6 and CNRS-UMR 7590, Paris, France
(2)Institute of Physics, A.Mickiewicz University, Poznan, Poland
(3)Max-Planck-Institut fur Polymerforschung, Postfach 3148, 55021 Mainz, Germany
catherine.dreyfus@impmc.jussieu.fr
The depolarised light scattering spectrum of a supercooled liquid over a large frequency domain was
determined by H.Z. Cummins and al. during their seminal study of CKN. Using the same technique,
some of us showed, through a study of supercooled o-terphenyl under variable density and
temperature that this depolarized dynamics was governed by a relaxation times that can be expressed
as the ratio of the density at some power n, here equal to 4, to the absolute temperature. Using either

light scattering or dielectric techniques, the preceding result has been then found to hold for a great
number of fragile glassforming liquids, the parameter n usually ranging from 3.5 to 8. We have later
generalised the preceding notion, expressing the relaxation time through a local quantity, nloc, which in
principle depends on temperature and density but equals the constant n when the former result is valid.
Through the study of simulated liquid SiO2, we have shown that nloc linearly correlates with a
parameter which describes a local orientational order between neighbouring Si atoms; this order
largely changing with temperature.
PHYSICAL AND CHEMICAL PROPERTIES OF CHALCOGENIDE GLASSES VIA AB
INITIO MOLECULAR DYNAMICS SIMULATIONS
Sébastien Le Roux, Sébastien Blaineau and Philippe Jund
Institut Charles Gerhardt Montpellier - UMR 5253 CNRS-UM2-ENSCM-UM1
Equipe Physicochimie des Matériaux Désordonnés et Poreux
Place Eugène Bataillon CC03, 34095 Montpellier Cedex 5, France.
pjund@univ-montp2.fr
With the use of DFT-based molecular dynamics simulations we study the physical and chemical
properties of amorphous germanium disulfide (GeS$_2$) as well as of sodium doped glasses. We
focus on the structural, dynamical and electronic properties of these chalcogenide glasses.
From the radial distribution function we find nearest neighbor distances almost identical to the
experimental values and the static structure factor is extremely close to its experimental counterpart.
Furthermore,we obtain the correct distribution of corner and edge-sharing tetrahedra in our amorphous
samples, and we find homopolar Ge-Ge and S-S bonds. Concerning the dynamical characteristics we
make an in-depth analysis of the Vibrational Density of States (VDOS), in order to determine the
microscopic origin of the vibrational modes found experimentally.Finally we calculate the Electronic
Density of States (EDOS) which is in good agreement with its experimental counterpart. We also
study the atomic charges, and analyze the impact of the local environment on the charge transfers
between the atoms.
Concerning the sodium doped glasses we show that a new feature appears in the static structure factor
above a threshold Na concentration, which is the signature of a non homogeneous distribution of the
ions inside the glassy matrix.
SLOW DYNAMICS, AGING AND CRYSTALLIZATION OF CONCENTRATED
MULTIARM STARS
E. Stiakakis 1 , A. Wilk 2 , J. Kohlbrecher D. Vlassopoulos 1 and G. Petekidis 1
(1) IESL-FORTH and Department of Materials Science and Technology,
Heraklion, Crete, Greece
(2) PSI, Villigen, Switzerland
georgp@iesl.forth.gr
Multiarm star polymers are model systems with intermediate colloid to polymer-like character
exhibiting rich phase behaviour, internal relaxations and flow properties. However a puzzling open
question is the lack of experimental proof for the existence of crystalline states in contradiction to
theoretical predictions. Here we present unambiguous experimental evidence, via multispeckle
dynamic light scattering (MSDLS) and small angle neutron scattering (SANS) for the crystallization

of concentrated solutions of 128 arm stars in an intermediate quality solvent. MSDLS revealed an
unexpected speed up of the star self diffusion during ageing of the glassy state attributed to the
formation of looser cages due to slow crystallization. Following the same protocol, SANS
measurements demonstrated the appearance of Bragg spots in 2D images and main peak S(q) values
significantly higher than 2.85, the Hansen-Verlett criterion for crystal formation, establishing a
pathway for multiarm star crystallization.
GENERALIZED ENTROPY THEORY OF GLASS-FORMATION: COMPARISON WITH
EXPERIMENT
Karl F. Freed 1 , Evgeny B. Stukalin 1 , Jack F. Douglas 2
(1) James Franck Institute, University of Chicago, Chicago, IL 60637
(2) Polymers Division, NIST, Gaithesburg, MD
freed@uchicago.edu
Computations of the configurational entropy using the lattice cluster theory are combined with the
Adam-Gibbs theory to provide predictions for a variety of properties of glass formers, including the
fragility, the characteristic temperatures (onset, crossover, glass transition, Kauzmann, and Vogel
temperatures), and the characteristic pressures (for glass formation at constant temperature). The
predictions are compared quantitatively with available experiment, while many quantitative
predictions remain to be tested with new experiments. The systems studied are poly(α-olefins), where
predictions are given for the dependence of all properties on molar mass, and the predicted trends
accord qualitatively with observations for polystyrene. The theory contains four empirical parameters:
the nearest neighbor energy and cell volume are fit to equation of state data for polypropylene, and the
two bending energies are fit using the glass transition temperatures of polyethylene and polypropylene.
The results demonstrate that the generalized entropy theory provides a quantitative representation of
the properties of glass-formers.
MOLECULAR MOBILITY OF GLASSY POLYMERS IN MULTILAYER GEOMETRY :
INFLUENCE OF THE LAYER THICKNESS REDUCTION ON DEFORMATION AND
CALORIMETRIC BEHAVIOURS.
L. Delbreilh 1 , K. Arabeche 1 , S. Scholtyssek 2 , J.-M. Saiter 1 , G.H. Michler 2 , R. Adhikari 3 , A. Hiltner 4 , E.
Baer 4
(1) Polymères, Biopolymères et Surfaces, Equipe LECAP, Université de Rouen, UMR FRE 3101,
Université de Rouen, 76801 Saint Etienne du Rouvray, France.
(2) Department of Engineering, Martin-Luther University Halle-Wittenberg, D-06099 Halle, Germany
(3) Central Department of Chemistry, Tribhuvan University, Kirtipur, Kathmandu, Nepal
(4) Department of Macromolecular Science, Case Western Reserve University, Cleveland, Ohio
44106-7202, USA
laurent.delbreilh@univ-rouen.fr
The materials investigated in this work are multilayered films comprising tens to thousands of
alternating layers of two immiscible polymers, Bisphenol A Polycarbonate (PC) and polymethylmethacrylate
(PMMA) fabricated by layer multiplying coextrusion technique. On these samples we
carried out combined studies using uniaxial tensile testing, morphology observations (TEM and AFM)
and calorimetric measurements at the glass transition. From the calorimetric measurements, the
molecular mobility in each polymer was found to be altered in entirely different ways as the thickness
of each component became thinner than 125 nm whereby the polymers exist as two dimensional layers
under those conditions. PC obviously exhibited a confinement effect with a drastic decrease in the
characteristic length at the glass transition (ξ) [1,2] while few modification was observed for PMMA.
For 12 nm layer thickness, a large evolution of cooperative characteristic length for both polymers
produces a merging of both behaviors. In this thickness range, despite of the very different relaxation
behavior between PC and PMMA in bulk conditions [3], the molecular mobility of both materials

increases to reach similar properties. This effect has been identified in the deformation behavior of the
multilayered films; for layers thinner than 250 nm, the specimens deform as one single material and no
more as a combination of two separated polymers.
References
[1] G., Gibbs J.H., « On the temperature dependence of cooperative relaxation properties in glassforming
liquids », J. Chem. Phys., 43 139, 1965.
[2] E.Donth ,Characteristic length of the glass transition , J. Polym. Sci., Part B: Polym. Phys. 34,
2881, 1996.
[3] H.H. Kausch, Intrinsic Molecular Mobility and Toughness of Polymer, Springer, 62-109, 2005.
LOW-TEMPERATURE STRUCTURAL RELAXATIONS IN ORGANIC SOLIDS:
OBSERVATION VIA SMS AND THERMAL CYCLING
I. Yu. Eremchev (1), A.V. Naumov (1), Yu. G. Vainer (1), L. Kador (2)
(1) Institute for spectroscopy, RAS, Troitsk, Moscow Reg., 142190, Russia
(2) University of Bayreuth, Institute of Physics and BIMF, D-95440 Bayreuth, Germany
eremchev@isan.troitsk.ru
In our work we investigated slow structural relaxation processes in disordered solids (amorphous
polyisobutylene and polycrystalline ortho-dichlorobenzene) via single-molecule spectroscopy. The
main idea is that spectra of single chromophore molecules inserted into samples are very sensitive to
parameters of local environment. The time behaviors of spectra were recorded at temperatures
between 4.5 K and 7 K. In order to observe structural rearrangements over a broader temperature
range, we used the thermal-cycling technique. We heated the sample quickly (during 10-50s) up to the
desired temperature, kept it at this temperature for about 10 minutes, and then quickly cooled it down
to the original temperature. We found outstanding cases of structural modifications in local
environment of impurity molecules after cycles (changes of parameters of low-energy excitations -
tunneling two level systems and low-frequency vibration modes). Values of changed low-energy
excitation parameters were estimated. Moreover temperature dependence of slow structural processes
efficiency in polyisobutylene in wide temperature range (from 4.5 K to the temperature of glasstransition)
was experimentally estimated (we averaged data over several hundreds of observed time
behaviors of single-molecule spectra for each temperature point).
This work was supported by DFG, SFB 481, RFBR (07-02-00206, 08-02-00147). A.N. thanks CRDF
(BRHE), and a Grant of the President of Russia.
RELAXATION AND DIFFUSION-VISCOSITY DECOUPLING IN SUPERCOOLED AND
GLASSY POLYOL AQUEOUS SOLUTIONS
M. P. Longinotti (1,2), J. Trejo González (1), J. Gelman Constantín (1) and H. R. Corti (1, 2, 3)
(1) Instituto de Química Física de los Materiales, Medio Ambiente y Energía (INQUIMAE). Facultad
de Ciencias Exactas y Naturales, Universidad de Buenos Aires. Pabellón 2, Ciudad Universitaria
(1428), Buenos Aires, Argentina.
(2) Consejo Nacional de Investigaciones Científicas y Técnicas (CONICET). Argentina.
(3) Departamento de Física de la Materia Condensada, Comisión Nacional de Energía Atómica,
Buenos Aires, Argentina.
longinot@qi.fcen.uba.ar
Tracer and self-diffusion have been widely studied in one component supercooled liquids [1,2].
However, few studies have been performed in more complex systems, such as water-polyol mixtures,
which are the most interesting systems for technological applications, such as cryopreservation. In this
work we have analysed the diffusion viscosity dependence of ionic and neutral solutes in supercooled
sucrose, trehalose and glycerol aqueous solutions, along with the dielectric relaxation in related
systems.

We meassured the molar conductivity of several electrolytes and the diffusion of ferrocene-methanol,
using electrochemical techniques, over a wide viscosity range.
It was observed that for the ionic solutes: NaCl, KCl, CsCl, Bu4NBr and MgCl2, the molar
conductivity viscosity dependence cannot be described by the classical hydrodynamic model (Walden
Rule) well above the glass transition temperature (Tg) [3]. This behaviour was explained by the
presence of structural microheterogeneities in the solution.The diffusion of the neutral probe in
supercooled sucrose and glycerol aqueous solutions was well described by the classical hydrodynamic
model (Stokes- Einstein equation) at small Tg/T values, while close to Tg diffusion decouples from
viscosity. The critical temperatures at which diffusion decouples from viscosity were compared with
the temperatures at which α and β relaxation processes bifurcate.
[1] R. R. Blackburn, C-Y. Wang and M. D. Ediger. J. Phys Chem. 100, 18249-18257, 1996.
[2] M. K. Mapes, S. F. Swallen and M. D. Ediger. J. Phys. Chem. B 110, 507-511, 2006.
[3] M. P. Longinotti and H. R. Corti. J. Phys. Chem. B 113, 5500-5507, 2009.
Equivalence between Spontaneous and Shear-Induced Relaxations in Suspensions of Charge-
Stabilized Vesicles near the Glass Transition
Sándalo Roldán-Vargas 1 , J. de Vicente 1 , Ramon Barnadas- Rodríguez 2,3 , Manuel Quesada-Pérez 4 , Joan
Estelrich 2 , and José Callejas-Fernández 1
1 Grupo de Física de Fluidos y Biocoloides, Departamento de Física Aplicada,
Universidad de Granada, E-18071 Granada, Spain.
2 Departament de Fisicoquímica, Facultat de Farmàcia, Universitat de Barcelona, E-
08028 Barcelona, Catalonia, Spain.
3 Centre d'Estudis en Biofísica, Facultat de Medicina, Universitat Autònoma de
Barcelona, E-08193 Cerdanyola del Vallès Bellaterra, Barcelona, Catalonia, Spain.
4 Departamento de Física, Escuela Politécnica Superior de Linares, Universidad de Jaén,
Linares, E-23700 Jaén, Spain.

To investigate the glass transition phenomenon (GT), one of the reference systems amenable to
experimentation is a suspension of mesoscopic particles whose interaction is solely mediated by a
repulsive potential. While close to the glassy state their microscopic structure does not reveal a
significant difference with that associated to a normal liquid, these systems behave as solids since they
can sustain shear stress. Thus, their macroscopic liquid-to-solid transition is connected to the
microscopic ergodic-to-nonergodic transition, suggesting that macroscale elasticity arises from
microscale structural arrest. So far, the slowing down of the relaxation dynamics of these glassy
colloidal systems has been studied extensively by light scattering and rheological measurements. As a
result, the relaxations of both the spontaneous and shear-induced fluctuations have been interpreted as
manifestations of structural relaxation processes. However, the quantitative correspondence between
these processes has only been investigated vaguely on real systems.
Accordingly, in this work we present experimental evidence for the equivalence between time and
frequency domain relaxations of spontaneous and shear-induced fluctuations in suspensions of charge-
stabilized mesoscopic vesicles near the GT. Moreover, the choice of our experimental system also
obeys at a biological interest since recently vesicles suspensions have contributed to a better
understanding of complex processes involving cellular phenomena. To elucidate the origin of the glass
transition phenomenon in these systems, our study provides a close interplay between light scattering
and rheological measurements accounted for by a mode-coupling formalism.
Acknowledgements
The authors are grateful to “MCINN” (Projects No. MAT2006-12918-C05-01 -02, and -05 and MAT-
2006-13646-C03-03), ERDF Funds, and “Junta de Andalucía” (Project P07-FQM-02496) for financial
support.
Reference List
[1] D.D. Lasic, Liposomes: From Physics to Applications, Elsevier /Amsterdam (1991).
[2] P.N. Pusey and W. van Megen, Physica A 157: 705 (1989).
[3] A. Moussaïd and P.N. Pusey, Physical Rev. E 60: 5670 (1999).
[4] K.N.Pham et al., Physical Rev. E 69: 011503 (2004).

[5] W. Götze and L. Sjögren, Rep. Prog. Phys. 55: 241 (1992).
[6] W. Kob, Course 5: Supercooled Liquids, the Glass Transition, and Computer
Simulations, Les Houches, Springer Berlin / Heidelberg (2003).
[7] T. G. Mason and D.A. Weitz, Phys. Rev. Lett. 75, 2770 (1995).
LOW-TEMPERATURE DYNAMICS OF AMORPHOUS POLYMER CONFINED IN A THIN
FILM: STUDY BY SINGLE-MOLECULE SPECTROSCOPY
Yu.G. Vainer (1), A.V. Naumov (1), Ya. Sobolev (1), L. Kador (2)
(1) Institute for spectroscopy RAS, Troitsk, Moscow reg., 142190, Russia
(2) Institute of Physics and BIMF, University of Bayreuth, D-95440 Bayreuth, Germany
vainer@isan.troitsk.ru
Low-temperature dynamics of thin films of amorphous polyisobutylene weakly doped with fluorescent
chromophore molecules of tetra-tert-butylterrylene has been studied at 4.5 K via single-molecule
spectroscopy. The temporal behavior of individual optical spectral lines of single chromophore
molecules in films of thicknesses between 10 and 300 nm was observed and analyzed. It was found
that with decreasing of film thickness the number and amplitudes of frequency jumps and drifts in
individual optical spectra of single chromophores are more and more increased, reflecting the complex
and random character of dynamics of polymer confined in thin film. The possible mechanisms of the
observed dynamical properties of polymer confined in a thin film are discussed.
The work was supported by DFG, SFB, RFBR (07-02-00206, 08-02-00147). A.N. acknowledges
CRDF and Grant of the President of Russia.
Interfacial relaxation Dynamics in nanocomposite materials
D. Prevosto 1 , M. Labardi 1 , S. Capaccioli 2 , M. Lucchesi 1,2 , E. Passaglia 3 , K. Nguyen 2 , M. Bertoldo 1 , S.
Coiai 3,4 , M. Scatto 4 , A. Saiter 6 , L. Delbreilh 6 , F. Ciardelli 1,4 , P.A. Rolla 1,2
(1)CNR-INFM polylab, L.go B. Pontecorvo 3, 56127 Pisa;
(2) Department of Phyics,University of Pisa, L.go B. Pontecorvo 3, 56127 Pisa;
(3) ICCOM-CNR Pisa section c/o Department of Chem. and Ind. Chem., via Risorgimento 35, 56126
Pisa, Italy;
(4) Centro Italiano Packaging, Via delle Industrie 25/8, 30175 Venezia, Italy;
(5) Department of Chemistry and Industrial Chemistry, University of Pisa, via Risorgimento 35, 56126
Pisa, Italy;
(6) LECAP, Institut des Matériaux de Rouen. Université de Rouen Av. de l'Université BP 12, 76801
Saint Etienne du Rouvray, France.
prevosto@df.unipi.it
The investigation of polymer properties at interfaces is of large interest in nanostructured and confined
systems. In fact, in such cases properties of the interfacial portion of the material determine the bulk
averaged macroscopic ones. In polymer-clay nanocomposite the large variation of dynamic and
mechanical behaviour of material at interface is exploited to obtain new bulk properties. I will present
results of relaxation dynamics in nanocomposites derived by polyolefin functionalized with a dipolar
group. Samples with different clay loading have been prepared and their dynamics has been
characterized by dielectric spectroscopy. Samples were also prepared with the residue material
obtained by an extraction procedure [1]. By such investigation we evidenced the different role of
confinement and interfacial interactions in nanocomposites. Finally, I will present some preliminary
results on the application of a local dielectric spectroscopy technique based on a AFM [2,3]. Such

technique allows the investigation of relaxation dynamics on sample surface with lateral resolution of
the order of tens of nanometer. Support from ‘Nanopack’ FIRB 2003 D. D. 2186 grant RBNE03R78E
and INFM Seed Project 2008 are acknowledged.
[1] E. Passaglia, D. Prevosto, et al., European Polymer Journal, 44, 1296, 2008.
[2] P.S. Crider, M.R. Majewski, at al., Appl. Phys. Lett. 91, 013102, 2007.
[3] M. Lucchesi, D. Prevosto, et al., J. Appl. Phys. 105, 054301, 2009.
SECONDARY RELAXATION IN POLYMER MELTS AND BLENDS: INSIGHT FROM
MOLECULAR DYNAMICS SIMULATIONS
Dmitry Bedrov(1) and Grant D. Smith (1)
(1) Department of Materials Science & Engineering, University of Utah, 122 S. Central Campus Dr.,
Rm 304, Salt Lake City, Utah, 84112, USA.
Correspondence author: d.bedrov@utah.edu
Investigation of the mechanisms and the importance of secondary (β-relaxation) processes in
segmental relaxation of polymers have been conducted using extensive molecular dynamics (MD)
simulations of chemically realistic melts and model miscible blends. Both the α- and β- relaxation
processes of backbone segments were resolved in the time window accessible to MD simulations.
Mechanistically we found that the β-relaxation process in pure polymer melts of 1,4-polybutadiene
can be associated with large-scale conformational motions corresponding to all or nearly all dihedrals
visiting each conformational state. Both the α- and β-relaxation processes in the pure melts are
operative at all temperatures including high temperatures. Moreover, at high temperatures the βrelaxation
process dominates the segmental relaxation. The observed segmental relaxation
mechanisms in pure melts were found to have important consequences for segmental relaxation of
component polymers in miscible polymer blends. This effect was found to be particularly important
for the lower Tg component of the blends.
MORPHOLOGY AND DYNAMICAL BEHAVIOUR OF GRAFTED COPOLYMERS
S. Etienne (1,2), J. M. Hiver (1), M. Billy (3), A. Jonquières (3), R. Clément (3), Isabelle Stevenson
Royaud (4), E. Nikaj (4), G. Seytre (4), L. David (4)
(1) Laboratoire de Physique des Matériaux, UMR CNRS 7556, Ecole Nationale Supérieure des Mines,
Nancy Université, Parc de Saurupt, 54042 Nancy, France
(2) EEIGM, Nancy Université, 6 rue Bastien Lepage, 54010 Nancy, France
(3) Laboratoire de Chimie Physique Macromoléculaire, UMR CNRS 7568, Nancy Université, Ecole
Nationale Supérieure des Industries Chimiques, 1 rue Grandville, BP20451, 54001 Nancy Cedex,
France
(4) Université de Lyon, Université Lyon 1, UMR CNRS 5223 IMP, Laboratoire des Matériaux
Polymères et des Biomatériaux, Bât. ISTIL, 15, bd. Latarjet F-69622 Villeurbanne Cedex France
Correspondence author: erisela.nikaj@hotmail.fr
We investigated the coupling of the motions between the main chain (cellulose acetate) and the lateral
chains (poly(methyl(diethylene glycol)methacrylate)) in grafted copolymers obtained by controlled
radical polymerization [1]. The effects of two structural parameters were studied separately, namely: (i)
the number of grafted chains on the main chain and (ii) the length of the grafted moieties. The
molecular mobility was assessed by Low Frequency Mechanical Spectroscopy and Broadband
Dielectric Spectroscopy. The effects of the chemical structure of the copolymers and the
microstructure at the nanoscale, as investigated by Small and Wide Angle X-ray Scattering, were

discussed. It can be concluded that the presence of grafted moieties induces a cooperative dynamics in
the copolymers, reflecting the molecular confinement effects associated to the attachment of the
mobile grafts onto the rigid backbone. The cooperative features of the motions of the grafted
segments are in turn related to the controlled structure of the copolymers (density and length of the
grafts) [2].
[1] M. Billy, Nouveaux copolymères dérivés d'esters cellulosiques par polymérisation radicalaire
contrôlée, Institut National Polytechnique de Lorraine, Ecole Nationale Supérieure des Industries
Chimiques, Nancy (2008).
[2] S. Etienne, L. David, M. Mitov, P. Sixou and K. L. Ngai, Macromolecules 28 (1995), p. 5758.
DIELECTRIC AND CALORIMETRIC MEASUREMENTS OF THE COOPERATIVE
CHARACTERISTIC LENGTH AT DYNAMIC GLASS TRANSITION IN AMORPHOUS
POLYMERS.
H. Couderc, A. Saiter, K. Arabeche, L. Delbreilh, J.-M. Saiter.
Polymères, Biopolymères et Surfaces, Equipe LECAP, Université de Rouen, UMR FRE 3101,
Université de Rouen, 76801 Saint Etienne du Rouvray, France.
laurent.delbreilh@univ-rouen.fr
In the Cooperative Rearranging Region (CRR) concept [1], the glass forming liquid is divided into
independently relaxing sub-systems, called CRR.
The use of Temperature Modulated DSC allows to calculate the CRR volume Vα, by the calculation of
two particular parameters : Tα, the dynamic glass transition temperature, and δT the standard deviation
of the C” peak Gaussian fit, equalized by Donth to the temperature fluctuation on an average CRR [2].
The δT quantity is also characteristic from the relaxation time distribution width [2].
It is interesting to characterize the CRR volume variation against temperature in the liquid state. We
can obtain this characteristic by varying the heat flow frequency applied to the sample in TM-DSC.
The CRR volume decrease with the increase of the dynamic glass transition temperature, produces a
widening of the C” peak [3] but the allowed frequency range is very low.
TM-DSC and dielectric spectroscopy (DS) both measure complex quantities and show several
common features in the glass transition manifestation. The loss peak width is also characteristic from
relaxation time distribution width [4], and we see a widening of the loss peak with increasing the
dynamic glass transition temperature with a very large allowed frequency range.
We show that the quantity Vα, taking δT as the standard deviation of the ε’’ peak, shows a continuous
variation against temperature with the TM – DSC values.
References
[1] G., Gibbs J.H., « On the temperature dependence of cooperative relaxation properties in glassforming
liquids », J. Chem. Phys., 43 139, 1965.
[2] Donth E., « The Glass transition, Relaxation Dynamics in Liquid and Disordered Materials »,
Springer, Berlin, Germany, 2001.
[3] Reading M., Hourston D.J., « Modulated-Temperature Differential Scanning Calorimetry :
Theoritical and Practical Applications in Polymer Characterisation », Springer, Dordrecht,
Netherlands, 2006.
[4] Kremer F., Schönhals A., « Broadband Dielectric Spectroscopy », Springer, Berlin, Germany 2003.
THE TEMPERATURE DEPENDENCE OF FREE VOLUME EVALUATIONS IN A
POLYMER (PVME).
Dušan Račko (1,4), Sara Capponi (1,2), Fernando Alvarez (2,3), Juan Colmenero (1,2,3) and Josef
Bartoš (4)
(1) Donostia <strong>International</strong> Physics Centre, Paseo Manuel de Lardizabal 4, 20018 San Sebastián, Spain

(2) Departamento de Física de Materiales, Universidad del País Vasco (UPV/EHU), Apartado 1072,
20080 San Sebastián, Spain
(3) Centro de Física de Materiales (CSIC-UPV) – Materials Physics Center MPC, Apartado 1072,
20080 San Sebastián, Spain
(4) Polymer Institute, the Slovak Academy of Sciences, 842 36 Bratislava, Slovak Republic
dusan_racko@ehu.es
We investigated the free volume microstructure in a model polymer system – poly (vinyl methylether)
(PVME). At first, the polymer condensed phase was prepared by molecular dynamics simulations
(MD) through a wide temperature range between 250 – 400 K. The density in the supercooled region
corresponded to the experimental density with deviation δ = ±0.7%. The free volume was obtained by
a direct computational approach, by probing the simulated structures. The free volume microstructure
is found percolated over the whole temperature range for a probe of the ortho-Positronioum (o-Ps)
particle RP = 0.53 Å. The maximum of the cavity number distribution moves between 0.7 - 0.8 Å in
the supercooled and glassy region, and shifts to 0.9 - 1.0 Å in liquid phase. The percolated structure
was divided into a distribution of individual sub-cavities though connected through bottlenecks [1]. By
excluding certain cavity threshold the cavity sizes, observed in another direct method for the free
volume determination – the positronium annihilation (PALS), have been obtained [2,3]. A geometrical
analysis on these cavities showed increasing elongation and irregularities of cavities with temperature.
The radial distribution of the cavities showed structured features for the small cavities sampled by
small probes. The total number of cavities dropped with temperature, while the number of large
cavities is almost constant over the investigated temperature range, with the number density of holes K
~ 1 x 10 -3 Å -3 . This supports model for the free volume fraction in the PALS.
[1] D. Račko, S. Capponi, F. Alvarez, J. Colmenero and J. Bartoš, J. Chem Phys, 2009 submitted
[2] D. Račko, R. Chelli, G. Cardini, J. Bartoš and S. Califano, Eur Phys J D, 32, 289, 2005
[3] D. Račko, R. Chelli, G. Cardini, S. Califano, J. Bartoš, Theor Chem Acc 118, 443, 2007
STUDY OF DEUTERIUM ISOTOPE EFFECT IN LIQUID CRYSTAL CBOOA-d17 BY 13 C
HIGH-RESOLUTION NMR
S. Hagiwara and H. Fujimori
Graduate School of Integrated Basic Sciences, Nihon University, Sakurajosui, Setagaya-ku, Tokyo
156-8550, Japan
fujimori@chs.nihon-u.ac.jp
A liquid-crystalline phase is a medium that exhibits both the mobility of a liquid and the anisotropy of
a crystal. The interaction between molecules is one of the important roles in the formation of liquid
crystalline phase. 4-Octyloxy-N-(4-cyanobenzylidene)aniline (CBOOA) and the chain-deuterated
analog of CBOOA (CBOOA-d17) has the thermotropic phase sequence, isotropic liquid (I) - nematic
(N) - smectic Ad (SAd) - crystal (C), on lowering the temperature at atmospheric pressure. The I-N
phase transition temperature is reduced to 3.4 K by the deuteration. In this study, high-resolution 13 C
NMR experiments were performed in SAd, N, and I phases of CBOOA and CBOOA-d17. The spinlattice
relaxation times (T1) for each carbon atoms in molecules were measured to discuss the
difference of molecular interactions between CBOOA and CBOOA-d17.
STABILIZATION PROCESSES OF META-STABLE CRYSTALLINE PHASES IN 2,5-
DICHLOROTHIOPHENE
N. Tanimoto and H. Fujimori

Graduate School of Integrated Basic Sciences, Nihon University, Sakurajosui, Setagaya-ku, Tokyo
156-8550, Japan
fujimori@chs.nihon-u.ac.jp
2,5-dichlorothiophene has three crystalline phases, two meta-stable crystalline phases and the moststable
one. In the most-stable crystalline phase a glass transition is observed at 138 K [1]. The
interesting property is found by nuclear quadrupole resonance (NQR) that the meta-stable crystalline
phases havs more orderly than the most-stable one [2]. In this study the relaxation processes from the
meta-stable crystalline phase to the meta-stable one and from the meta-stable one to the stable one
were investigated by tracking the enthalpy relaxation for a long time under the constant temperature
using by differential scanning calorimetry (DSC). The results were discussed using by Avrami
equation, 1-C = exp(-Zt n ), where C is the transformed fraction, n Avrami index, and Z the overall
crystallization rate constant.
[1] H. Fujimori, K. Matsuda, A. Todoroki, T. Asaji, and M. Oguni, J. Non-Cryst. Solids, 352, 4790,
2006.
[2] S. Minoshima, H. Fujimori, and T. Asaji (unpublished).
DSC STUDY OF WATER CONFINED IN MESOPOROUS SILICA AND ORGANOSILICA
K. Oodo, T. Masuda, and H. Fujimori
Graduate School of Integrated Basic Sciences, Nihon University, Sakurajosui, Setagaya-ku, Tokyo
156-8550, Japan
fujimori@chs.nihon-u.ac.jp
Recently, the structural and dynamic properties of water confined within porous silica have been
subject of considerable interests. The melting point of bulk water at atmospheric pressure is 273.15 K,
however, the one of water confined within the silica pores decreases with decreasing the pore diameter
[1]. The interaction between water and the silica walls plays an important role in the pore. In this study,
differential scanning calorimetry (DSC) measurements were performed for water confined within
mesoporous silica TMPS-4 and TMPS-4M (modified TMPS-4 by 3-aminopropyltriethoxysilane)
which have highly ordered cylindrical channels.
Acknowledgements: We would like to thank Taiyo Kagaku Co., Ltd. for supplying us TMPS.
[1] Y. Nishioka and H. Fujimori, Complex Systems, 363, 2008.
THERMAL BEHAVIOR OF NaCl AQUEOUS SOLUTION CONFINED WITHIN SILICA
PORES
Y. Nishioka, S. Hagiwara, and H. Fujimori
Graduate School of Integrated Basic Sciences, Nihon University, Sakurajosui, Setagaya-ku, Tokyo
156-8550, Japan
fujimori@chs.nihon-u.ac.jp
Differential scanning calorimetry (DSC) measurements of NaCl aqueous solution, confined within
mesoporous silica of pore diameter 1.4-7.1 nm, were performed. The freezing point of water within
the pores decreased with decreasing pore diameter. The glass transition was observed, and the
temperature was not dependent on pore diameter and NaCl concentration in aqueous solution.

INFLUENCE OF INDUCED POLARIZTION ON PREDICTION OF DYNAMICS OF IONIC
LIQUIDS FROM MOLECULAR DYNAMICS SIMULATIONS.
Dmitry Bedrov(1,2) and Oleg Borodin (1,2)
(1) Department of Materials Science & Engineering, University of Utah, 122 S. Central Campus Dr.,
Rm 304, Salt Lake City, Utah, 84112, USA.
(2) Wasatch Molecular Inc., 2141 Saint Mary’s Dr., Salt Lake City, Utah, 84108, USA
Correspondence author: d.bedrov@utah.edu
A transferable, quantum chemistry-based polarizable force field has been developed and validated in
molecular dynamics (MD) simulations a wide range of ionic liquids (ILs). Inclusion of the induced
polarization effects provides unprecedented accuracy in description of thermophysical and dynamical
properties of thirty ILs investigated. MD simulations predict self-diffusion coefficients with am
average 23% deviation from experimental data. However, simulations without inclusion of induced
polarization effects (with non-polarizable force field) predict dynamics, which are at least factor of
two slower than experimental values. We investigate structural and dynamical correlations in ILs and
attempt to obtain a mechanistic understanding of influence of polarization effects on dynamics in ILs.
We also discuss attempts to develop non-polarizable force fields that would be able to predict accurate
dynamics of ILs from MD simulations.
RELAXATION DYNAMICS OF WATER IN THE AQUEOUS MIXTURES OF PROPYLENE
GLYCOL OLIGOMERS AT AMBIENT AND ELEVATED PRESSURE
K. Grzybowska (1), M. Paluch (1), A. Grzybowski (1), S. Pawlus (1), S. Ancherbak (2), D. Prevosto
(2), S. Capaccioli (2)
(1) Institute of Physics, University of Silesia, ul. Uniwersytecka 4, 40-007 Katowice, Poland
(2) Dipartimento di Fisica, Università di Pisa and CNR-INFM, PolyLab, Largo B. Pontecorvo 3, I-
56127, Pisa
The properties of supercooled water can be indirectly studied in aqueous mixtures of substances which
prevent ice crystal formation by modifying the hydrogen bonding dynamics of water. Ones of the most
common cryoprotectants are propylene glycol oligomers (PGO). We will present results of systematic
dielectric studies of molecular dynamics of water mixtures of PGO at ambient pressure, depending on
molecular weight of PGO and amount of water in the solution. Moreover, we will show unique results
of measurements of water mixture of PGO 400 with 26wt% concentration of H2O performed in the
broad pressure range (up to 1.8 GPa). We will especially focus on the effect of pressure on the
dynamic crossover of the ν relaxation process (reflecting dynamics of water molecules), which is
observed near the glass transition of the mixture. A similar intriguing change of dynamics from VFT
to Arrhenius behavior has been established for water in confined systems [1]. We will compare the
dynamic crossover properties for water in aqueous mixture of PGO 400 with those for water in
confined geometry.
[1] Li Liu, Sow-Hsin Chen, Antonio Faraone, Chun-Wan Yen, and Chung-Yuan Mou, Phys. Rev.
Lett., 95, 117802 (2005).
Glass and glass-like transitions in pure ethanol
B. Kabtoul and M. A. Ramos

Laboratorio de Bajas Temperaturas, Departamento de Física de la Materia Condensada, Universidad
Autónoma de Madrid, 28049 Madrid
bisher.kabtoul@uam.es
Besides being a well-known chemical substance in daily life, ethanol has been considered to be a
model system in order to study different kinds of disorder in condensed-matter phases. In fact, it has
been found [1-4] that ethanol can present 4 different monoclinic crystalline phases, a bcc plastic
crystal (PC), a glass (amorphous) phase, and a glassy crystal or ODC (Orientationally-Disordered
Crystal) phase, obtained by quenching the former PC phase below its “glass-like” transition
temperature.
In this work, we present new calorimetric and thermodynamic measurements for the glass transition of
differently obtained glasses (with different thermal histories). Both glass and glass-like (ODC−PC)
transitions are studied and discussed in this work. Astonishingly, both the standard glass transition and
that dynamical freezing of the PC into the ODC are found [2] to occur exactly at the same temperature
(Tg ≈ 97 K) and with comparable discontinuities in the specific heat and thermal-history dependences.
Furthermore, the ODC of ethanol shows the same universal behavior [3] in low-temperature properties
and low-frequency dynamics as the conventional glass, hence the alternative use of the name “glassy
crystal”.
The heat capacity measurements were conducted in the temperature range 1.5 K – 300 K, using a
homemade low-temperature calorimetric set-up [5] for three different experimental cells to better
study the thermal history effect on obtaining the various phases of ethanol. We have found [6] that
there are at least three important factors influencing the glass-forming ability of liquid ethanol, which
account for the discrepancies about critical cooling rates found in the literature: (i) possible water
content; (ii) mechanical details of the experimental cell which may drive heterogeneous crystallization;
(iii) previous thermal history of ethanol, so that some memory of orientational or positional order may
unexpectedly persist in the liquid state! As a rule, ethanol-glass formation is improved by: (i) a small
amount of water impurity; (ii) a smooth, flat and clean experimental environment, devoid of
nucleation centers; (iii) heating the liquid ethanol above 250 K.
[1] O. Haida, H. Suga, S. Seki. J. Chem. Thermodyn. 9, 1133 (1977).
[2] M. A. Ramos et. al., Phys. Rev. Lett. 78, 82 (1997).
[3] C. Talón, M. A. Ramos, S. Vieira, Phys. Rev. B 66, 012201 (2002).
[4] M. A. Ramos et. al., J. Non‐Cryst. Solids 352, 4769 (2006).
[5] E. Pérez‐Enciso and M. A. Ramos, Termochimica Acta 461, 50 (2007).
[6] B. Kabtoul, R.J. Jiménez‐Riobóo, M. A. Ramos, Philosophical Magazine 88, 4197 (2008).
A QUESTION ABOUT THEORETICAL GROUNDS FOR THE THERMODYNAMIC
SCALING
A. Grzybowski (1), M. Paluch (1), and K. Grzybowska (1)
(1) Institute of Physics, University of Silesia, Uniwersytecka 4, 40-007 Katowice, Poland
andrzej.grzybowski@us.edu.pl
In search of an universal description for thermodynamic and dynamic properties of viscous liquids
within the framework of the thermodynamic scaling idea, we have established that some equation of
state derived from the repulsive part of the generalized Lennard-Jones potential on the assumption of
the thermodynamic scaling validity can be successfully applied to describe isothermal volumetric data
for several glass-forming liquids. However, the scaling exponents γ evaluated from the fitting
procedure for each tested material have turned out at least 2 times larger than those earlier found from
relaxation data. This significant discrepancy indicates that the appealing idea of thermodynamic
scaling, which has been recently intensively explored, requires more efforts to find a satisfying
theoretical grounds for it. We intend to discuss this problem taking into account experimental and
simulation data.

ON THE PRESSURE EFFECT ON FRAGILITY OF GLASS-FORMING SYSTEMS
S. Capaccioli* (1), D. Prevosto (1), Shahin M. Thayyil (1), S. Ancherbak (1), M. Lucchesi (1) P.A.
Rolla (1)
(1) CNR-INFM, polyLab & Dipartimento di Fisica, Universita di Pisa, Italy
*Correspondence author: capacci@df.unipi.it
It was recently [1] shown that for most systems the structural dynamics can be expressed as a function
of a single parameter Γ=ρ n /T, taking into account all the density and temperature effect : in fact a
master-plot for all the relaxation time obtained at difefrent T and P τα(T,P) is often obtained vs. Γ.
Additionally the parameter Γ controls the shape of the structural relaxation [2], the separation between
α and β relaxation and other important static and thermodynamic quantities. The parameter Γ
originates by the power law dependence of the intermolecular repulsive potential [3]. This result has a
direct implication on the steepness index or “fragility”, defined as m=∂log(τα)/∂(Tg/T)⏐T=Tg. Actually,
when the density scaling parameter Γ rules, the isochoric fragility of that system is a constant.
Moroever, as mP= mV(1+nαPTg), it turns out that the isobaric fragility mP(P) is a slightly decreasing
function of pressure for common glass-formers [1]. The only exceptions are hydrogen-bonded systems,
whose fragility strongly increases with pressure, with a transition from intermediate to fragile behavior
maybe related to some change of the hydrogen bonding degree. We report here dielectric spectroscopy
studies over a broad range of temperature and pressure on some of them (e.g., propylene glycol
oligomers), where mP increased more than 40% up to 7 kbar and the isochoric fragility mV is changing.
The experiment was extended to the molten salt CKN and in a plastic crystal. In all these systems,
where fragility is strongly affected by pressure, the density scaling and the shape of the structural
relaxation were not controlled by Γ. The mechanism of relaxation is maybe quite different at low and
high pressure in these systems.
References:
[1] R. Casalini, C.M. Roland, Phys. Rev. B, 71, 014210 (2005).
[2] K. L. Ngai, R. Casalini, S. Capaccioli, M. Paluch, and C. M. Roland, J. Phys. Chem. B 109, 17356
(2005).
[3] D. Coslovich and C. M. Roland, J. Chem. Phys. 130, 014508 (2009)
INFLUENCE OF COMPOSITION AND THERMAL TREATMENT ON THE MOLECULAR
DYNAMICS OF PEO/PLLA BLENDS
A.R. Brás (1), P. Malik (2), C. Rodrigues (1), J. Mano (2), M. Dionísio (1)
(1) REQUIMTE, Departamento de Química, Faculdade de Ciências e Tecnologia, Universidade Nova
de Lisboa, 2829-516 Caparica, Portugal
(2) 3B’s Research Group – Biomaterials, Biodegradables and Biomimetics, Campus de Gualtar, 4710-
057, Braga, Portugal
madalena.dionisio@dq.fct.unl.pt
Poly(L-lactic acid) (PLLA) and Poly(ethylene oxide) (PEO) blends with 95/5, 90/10, 85/15 and 70/30
composition in weight, have been studied by Differential Scanning Calorimetry (DSC) and Dielectric
Relaxation Spectroscopy (DRS).

All blends were found to have semi-crystalline PLLA by comparing the heat of crystallization and the
heat of fusion of the PLLA fraction as quantified by DSC. Moreover, the relaxation process detected
by DRS, associated to the PLLA dynamic glass transition in the blends, shifts to lower
frequencies/higher temperatures as compared with the completely amorphous PLLA.
In blends containing less than 15% weight as the PEO weight % increases the glass transition detected
increases. On the other hand the melting endotherm is almost unchanged for PLLA fraction.
Concerning PEO fraction no melting endotherm could be detected, by DSC and a relaxation process
most likely related to the α-relaxation of PEO was observed by DRS. More, under cooling this process
becames extinguished due to non-isothermal crystallization.
In blends with 30 weight % PEO no accurate PLLA crystallization temperatures could be determined
because of overlap of the PEO melting peak and the PLLA crystallization exotherm; also, no clear
glass transition could be distinguished. Only the melting of both PEO and PLLA fraction emerged
clear.
Acknowledgement: Financial support to Fundação para a Ciência e Tecnologia (FCT, Portugal)
through the project PTDC/CTM/64288/2006 and POCTI/FIS/61621/2004 is acknowledged. A. R. Brás
acknowledges FCT for a PhD grant SFRH/BD/23829/2005.
SURFACE EFFECTS ON THE MOLECULAR DYNAMICS OF A NEMATIC LIQUID
CRYSTAL CONFINED TO MOLECULAR SIEVES
A.R. Brás (1), S. Frunza (2), I.M. Fonseca (1), A. Corma (3), L. Frunza (2), M. Dionísio (1) and A.
Schönhals (4)
(1) REQUIMTE, Departamento de Química, Faculdade de Ciências e Tecnologia, Universidade Nova
de Lisboa, 2829-516 Caparica, Portugal
(2) National Institute of Materials Physics, R-077125 Magurele, Romania
(3) Instituto de Tecnologia Química (UPV-CSIC), Universidad Politécnica de Valência, Spain
(4) BAM Federal Institute of Materials Research and Testing, Unter den Eichen 87, D-12205 Berlin,
Germany
ana.bras@dq.fct.unl.pt
Broadband dielectric spectroscopy was applied to investigate the dynamics of E7 molecules confined
to pores of MCM-41 and SBA-15 molecular sieves which have the same chemical composition and a
hexagonal structure of cylindrical pores. The pore diameter varies from 2.8 to 6.8 nm. From TGA
measurements a filling degree of about 55 wt-%.was estimated. The low values of filling degree were
chosen to study the molecular mobility of the E7 molecules adsorbed in a surface layer at the pore
walls.
To analyze interactions of E7 with the pore wall, FTIR measurements were carried. The spectra show
two well separated regions for the CN-stretching vibration: one located in the wave number range
characteristic for bulk E7 slightly broadened and another shifted to higher wave numbers which is
related to E7 molecules interacting by hydrogen bonding via the CN group of E7 and the hydroxyl
groups of the molecular sieves.
Dielectric measurements revealed two new relaxations which are not present in the bulk. These
relaxation processes, designated as I and S, have a strongly reduced molecular mobility compared with
the bulk, process S having the slowest dynamics (located at higher temperatures). By comparison with
cyanobiphenyl-aerosil composites having high silica densities, where an additional process relative to
the bulk was observed, the I process was assigned to cyanobiphenyl molecules forming a layer
anchored at the surface of the aerosil. The second relaxation peak, S, was associated to molecules

forming a surface layer at inner surface of the pore walls. The simultaneous detection of both inner
and outer surface related processes in a LC confined is to our knowledge reported for the first time.
Acknowledgements: FCT through project PTDC/CTM/64288/2006 and for a PhD grant
SFRH/BD/23829/2005.
HIGH AND LOW FREQUENCY DYNAMICS IN GLYCEROL AND GLYCEROL –WATER
MIXTURES
Puzenko Alexander(1) , * , Segev Ido(1) and Feldman Yuri(1)
(1)Department of Applied Physics, The Hebrew University of Jerusalem, Givat Ram,91904 Jerusalem,
Israel
* Correspondent author: puzal@vms.huji.ac.il
Understanding the liquid-glass transition and its related dynamics is one of the more important and
challenging problems in modern soft condensed matter physics. Glycerol and its mixtures with water
are hydrogen-bonded (H-bonded) liquids, which are widely used as models to study the cooperative
dynamics and also glass transition phenomena in complex liquids.
The typical dielectric spectra of glass formers display dielectric dispersion in an extremely broad
frequency range. The α process, corresponding to slow cooperative relaxations, the excess wing (or βprocess)
[1,2] , "fast processes" [1,3,4] and Boson Peak (BP) [5,6,7], corresponding to an excess of the
vibration density of states at frequencies around ω BP ≈1
THz .
Recently a new phenomenological relationship for complex dielectric permittivity was proposed in
order to provide a comprehensive fitting of our "low frequency" experimental data both for
conductivity, main process and excess wing [8, 9]. In this presentation we consider a
phenomenological model capable to describe the "high frequency" Boson Peak. These two models
provide insight to the nature of coupling between he fast process and the one at the low frequencies.
[1]P. Lunkenhimer, U. Schneider, R. Brand and A. Loidl Contemporary Physics, 41,1,15-36 (2000).
[2]K. L. Ngai, M. Shahin Thayyil, S. Capaccioli Critical Issues of Current Research on the Dynamics
Leading to Glass Transition J. Phys. Chem. B,77,5085-5088(2008).
[3]T. Franosch, W. Götze, M. R. Mayr, and A. P. Singh, Physical Review E, 55 (3), 3183-3190
(1997).
[4]V. N. Novikov and A. P. Sokolov, Nature, 431, 961-963 (2004).
[5]M. I. Klinger and V. Halpern, Journal of Non-Crystalline Solids, 345-346, 239-241 (2004).
[6]T. S. Grigera, V. Martı´n-Mayor, G. Parisi and P. Verrocchio, Nature, 422, 289-292 (2003).
[7]V.N. Novikov, Journal of Non-Crystalline Solids, 235-237, 196-202 (1998).
[8]A. Puzenko, Y. Hayashi, Ya.E. Ryabov, I. Balin, Yu. Feldman, U. Kaatze, and R. Behrends,
Journal of Phyical ChemistryB, 109, 6031-6035, (2005).
[9]A. Puzenko, Y. Hayashi, and Yu. Feldman, Journal of Non-Crystalline Solids, 353, 4518-
4522 (2007).

ELECTROSTATIC ANALYSIS OF PROTEIN-PROTEIN INTERACTIONS
D. Morikis
Department of Bioengineering, University of California, Riverside, CA 92521, USA
dmorikis@engr.ucr.edu
We report a high-throughput computational protocol for the study of electrostatic contributions in
protein-protein interactions. Electrostatics drives the long-range recognition between proteins with
excess of opposite net charge and contributes to local interactions at the binding interface. Our
protocol involves: (i) the generation of computational alanine scans to delineate the contribution of
each ionizable amino acid in the formation of a protein complex; (ii) the calculation of electrostatic
potentials, using the Poisson-Boltzmann method; (iii) the calculation of electrostatic free energies of
association, including solvation effects; (iv) clustering analysis of the spatial distributions of
electrostatic potentials and cluster classification according to the electrostatic free energies; and (v)
visualization plots of electrostatic potentials, clustering, free energies, and amino acid distances from
the binding interface. We report applications of the protocol in a variety of protein complexes and we
present comparisons to experimental data. We also report the predictive value of the protocol for the
effects of single or multiple mutations on the capability of single proteins to form complexes. Finally,
we report electrostatic analyses of immune system regulators with long modular structures of repeated
structural motifs with diverse electrostatic properties, and we make correlations to binding and
function, and, in some instances, to autoimmune diseases.
WHAT IS THE GLACIAL STATE OF n-BUTANOL?
M. A. Ramos (1), M. Hassaine (1), A. I. Krivchikov (2) and R.J. Jiménez-Riobóo (3)
(1) Laboratorio de Bajas Temperaturas, Departamento de Física de la Materia Condensada,
Universidad Autónoma de Madrid, 28049 Madrid, Spain
(2) B. Verkin Institute for Low Temperature Physics and Engineering of NAS Ukraine, Kharkov
61103, Ukraine
(3) Instituto de Ciencia de Materiales de Madrid, Consejo Superior de Investigaciones Científicas
(ICMM-CSIC), Cantoblanco, 28049 Madrid, Spain
miguel.ramos@uam.es
The first polyamorphic transition for a molecular glass-forming liquid was reported to occur in
triphenyl phosphite (TPP) by Kivelson and co-workers [1]. They observed a new solid phase denoted
as “glacial phase” or glacial state, obtained by a first-order, exothermic transformation from the
supercooled-liquid state of TPP. More recently, the same case of a new solid phase (presumably
amorphous) was reported by B.V. Bol’shakov and A. G. Dzhonson [2] in n-butanol at ambient
pressure. Under isothermal conditions in the range 130−160 K, the supercooled liquid transformed
gradually into a white or slightly opalescent solid phase, that they and other authors have identified as
the same glacial state. Although several experimental works have been published on TPP and, to a
lesser extent, on n-butanol phases, the very nature of this new glacial state remains controversial.
With the aim of shedding light on these debated issues, we have investigated through non-commercial
calorimetry and elasto-acoustic Brillouin experiments the phase diagram of n-butanol, and have
measured the specific heat and the thermal conductivity in a wide low-temperature range for its three
different states, namely glass, crystal and “glacial” states. Our experimental results show that the
obtained glacial state is not an homogenous, amorphous state, but rather a mixture of two different
coexisting phases, very likely [3] the (frustrated) stable crystal and a disordered phase.
[1] A. Ha, I. Cohen, X. Zhao, M. Lee and D. Kivelson, J. Phys. Chem., 100, 1, 1996
[2] B.V. Bol’shakov and A.G. Dzhonson, Dokl. Phys. Chem., 393, 318, 2003; J. Non-Cryst. Solids,
351, 444, 2005
[3] A. Wypych, Y. Guinet and A. Hédoux, Phys. Rev. B, 76, 144202, 2007

ANOMALOUS CONCENTRATION DEPENDENCE OF STRUCTURAL AND WATER
RELAXATIONS IN AQUEOUS SOLUTIONS.
J. Sjöström, J. Mattsson, R. Bergman and J. Swenson
Department of Applied Physics, Chalmers University of Technology, SE-412 96 Göteborg, Sweden
johan.sjostrom@chalmers.se
The hydrogen bonding interplay between water and other organic molecules control many material
properties which are important both in nature and in a wide range of technological applications. Many
macroscopic properties of H-bonded liquids are linked to the structural relaxation. To investigate the
effects of H-bonding on the dynamics of complex materials, we focus on the structural relaxation and
the secondary relaxation of water in binary aqueous mixtures. When decreasing the H-bonding ability
for a family of liquids, the concentration dependence of the structural relaxation time changes from a
monotonic behaviour, as usually seen in mixed glass formers, to a remarkably non-monotonic
variation. This anomalous behaviour suggests significant structural changes with composition. We
quantitatively describe this phenomenon as a competition between two effects: (i) a H-bond induced
formation of effective relaxing entities and (ii) a plasticizing effect due to the existence of "free" water.
However, irrespectively of the different concentration dependence of the structural relaxations, we
show that the water relaxations in the glassy state exhibit both qualitatively and even quantitatively
similar behaviour.
CAPILLARY FLOW OF POLYMERS IN GEOMETRICAL NANOCONFINEMENT
A. Serghei, and T.P. Russell
Department of Polymer Science and Engineering, University of Massachusetts Amherst, USA
serghei@polysci.umass.edu
Ordered arrays of parallel cylindrical nanopores (with a narrow pore size distribution and diameters
down to ~ 10 nm) are used as templates to investigate the capillary flow of polymers in 2D
geometrical nano-confinement. Several aspects are investigated. (1) The velocity of the capillary flow
is measured for different pore sizes to assess possible changes in the polymer viscosity, particularly in
the case when the pore radius becomes comparable to (or even smaller than) the radius of gyration of
the polymer chains. (2) The segmental dynamics of the polymer chains (corresponding to the dynamic
glass transition) is directly measured – via Broadband Dielectric Spectroscopy - during the capillary
flow into the nanopores. The results are compared to the glassy dynamics of the polymer in the bulk.
(3) Flourescence microscopy is used to give evidence for a nanometric thin precursor film preceding
the capillary flow.
DIELECTRIC AND STRUCTURAL CHARACTERIZATION OF STARCH AND ITS
BLENDS WITH POLY(L-LACTIDE)
A. Bello , E. Laredo , R. Pezzoli , D. Newman and A.J. Müller
Universidad Simón Bolívar, Apartado 89000, Caracas 1080, Venezuela
abello@usb.ve

In this work, semi-crystalline native and amorphous transformed samples of Cassava starch and its
blends with poly(L-Lactide) have been studied by WAXS and thermally stimulated depolarization
currents,TSDC. In the dielectric spectra of native starch, an α mode located at temperatures which
increase throughout the drying process, is associated to the dynamic glass transition of the amorphous
phase in the granules [1]. The transformed starch showed a bimodal glass transition which also shifts
to higher temperatures as the humidity content decreases. This is attributed to a heterogeneous
amorphous phase with different degrees of rigidity due to the granule disruption during the
transformation process. The effect of humidity on the local and segmental modes and the
retrogradation of transformed starch was followed. Similar studies were performed in the
Starch/PLLA blends with different compositions. They are found to be immiscible but certain chain
interactions affect the local mobilities. Activation parameters are determined and their variation with
moisture content. The WAXS results show the nucleating effect of the starch component over the
PLLA as the isothermal crystallization is faster and more efficient as the content of starch increases.
[1] E. Laredo, D. Newman, A. Bello, A.J. Müller, European Polymer Journal, 45, 1506, 2009
NEW DIELECTRIC AND THERMODYNAMIC APPROACH TO ANALYZE THE
OSMOTIC DEHYDRATION OF APPLE
Castro-Giráldez M, Fito P.J., Chenoll, C.1, Fito P.
(Institute of Food Engineering for Development. Universidad Politécnica de Valencia. Spain.
pedfisu@tal.upv.es
Candying of fruit is a common operation in the industry of sweets, pastries and others. In this
operation, the kinetic control is very important in order to preserve the quality and safety of the
product. Non-destructive techniques to control the fruit candying, as microwaves and radio frequency
signal technologies, could be an opportunity to improve the quality and safety properties of the
products. One option to understand the behaviour involved in the fruit dehydration could be analyzing
the dielectric spectra in the range of 0.1 to 20 GHz of samples dehydrated at different treatment times.
Fruits were dehydrated in a sucrose solution of 65º Brix, at 180, 360, 480, 660, 1453, 1590, 1735,
1915, 4320 minutes, at 30ºC. Before and after treatments, mass, volume, water activity, soluble solids
content and dielectric spectra were measured in each sample.
Mass loss and volume gained curves show the effects of water and soluble solids diffusion and the
compression and relaxation phenomena. Water activity and mechanical behaviour could be correlated
with the dielectric properties at different frequencies. Estimating those effects it is possible to predict
the dehydration level, the final sugar content and other properties related with the final quality and
safety.
FUNCTIONAL IONIC MEMBRANES
Monica Olvera de la Cruz (1,2) and Graziano Vernizzi (1)
(1) Materials Science and Eng., Northwestern University, Evanston Il 60091
(2) Chemistry, Northwestern University, Evanston Il 60091
m-olvera@northwestern.edu
Cationic-anionic co-assemblies of oppositely charged amphiphile respond rapidly to external stimuli
including pH and salt concentration variations. These ionic co-assemblies often form vesicles. We

show that electrostatic interactions lead to buckling into icosahedral faceted structures. This novel
electrostatics driven faceting mechanism breaks icosahedral symmetry and rotational symmetry due to
different arrangements of the charged components amongst the facets [1]. We will discuss the
symmetries that ionic heterogeneities break in various ionic assemblies and their associated functions.
[1] G. Vernizzi and M. Olvera de la Cruz Proc. Natl. Acad. Sci. USA, 104 (47) 18382-86 (2007).
SPATIAL AND TEMPORAL CORRELATION IN A SUPERCOOLED LIQUID: ATOMIC
LEVEL STRESSES AND GREEN-KUBO EXPRESSION FOR VISCOSITY
V. A. Levashov (1), T. Egami (1,2,3), and J. R. Morris (1,3)
(1) Department of Physics and Astronomy, University of Tennessee, TN 37996, USA
(2) Department of Materials Science and Engineering, University of Tennessee, TN 37996, USA
(3) Oak Ridge National Laboratory, Oak Ridge, TN 37831, USA
levashov@utk.edu
The concept of atomic level stresses is useful in establishing a bridge between the microscopic and
macroscopic behaviors of liquids and glasses. In particular, Green-Kubo expression for viscosity can
directly be expressed in terms of the space and time correlations among atomic level stresses. Using
MD simulations we studied space/time dependence of atomic level stress-stress correlation functions
in a simple liquid/glass. We found that the correlations extend well beyond third neighbors over large
times even at high temperatures. Even though they are oscillatory and partially cancel out when
integrated over distances, the presence of such extended correlation is surprising, and implies hidden
effects, such as the size effect of simulation, in evaluating viscosity. The distance dependence of the
same-time correlation function resembles, in general, behavior of the pair density function. The
correlation is significantly altered by the propagation of longitudinal and transverse sound waves and
their attenuation. We show that the rapid increase in viscosity below the crossover temperature is
caused by increases in correlation in both space and time. This work was supported by the Department
of Energy, Office of Basic Energy Sciences.
CONTROLLING THE GLASS TRANSITION TEMPERATURE IN THE CHARGE DENSITY
WAVE SUPERSTRUCTURE
D. Starešinić (1), D. Dominko (1), K. Biljaković (1), M. Jakšić (2), Z. Siketić (2), P. Lunkenheimer (3),
and A. Loidl (3)
(1) Institute of Physics, P.O.B. 304, HR-10001 Zagreb, Croatia
(2) Institute Ruđer Bošković, Bijenička 54, HR-10000 Zagreb, Croatia
(3) Experimental Physics V, University of Augsburg, D-86135 Augsburg, Germany
damirs@ifs.hr
The family of glasses includes nowadays numerous systems which are very far from the supercooled
liquids. Even such exotic systems as the charge density wave (CDW) superstructures occurring in
quasi one-dimensional crystals demonstrate multiple phenomena typical for glasses [1,2]. The disorder
in these glasses is introduced on the superstructure level through the pinning of CDW to the crystalline
defects which breaks the CDW in the domains of the coherent phase. The viscosity of the relative
motion of the domains is controlled through the screening by the residual free carriers excited over the
CDW gap. The glass transition occurs at a temperature Tg at which there is less then one free carrier
per domain and the screening is no longer effective [1].
We have varied the domain sizes in the CDW system o-TaS3 over two orders of magnitude through the
defects created by proton irradiation. The dielectric spectroscopy on irradiated samples shows the
decrease of the amplitude and the microscopic relaxation time of α process, while the activation
energy increases. The corresponding increase of Tg is related to the irradiation dose, and consequently
to the domain size, in the activated manner. It follows closely the temperature dependence of the free
carrier density thus corroborating the freezing criterion for CDW glass. We have demonstrated that Tg

is closely related to the domain size in CDW glasses, which might contribute to the understanding of
the glass phenomenology in general.
[1] D. Starešinić et al. Phys. Rev. B, 65, 165109, 2002; ibid, Phys. Rev. B, 69, 113102, 2004
[2] K. Biljaković, Phys. Rev. Lett., 96, 039603, 2006
THERMODYNAMIC VS DYNAMIC STABILITY OF PROTEINS IN SACCHARIDE GLASS:
RESOLUTION OF A LONGSTANDING QUESTION
M.T. Cicerone (1), J. Johnson (1) and M.J. Pikal (2)
(1) National Institute of Standards and Technology, 100 Bureau Drive, MailStop 8543, Maryland,
USA 20899
(2) University of Connecticut, Pharmacy School, Room 429 69 North Eagleville Road, Unit
3092 Storrs, Connecticut 06269
cicerone@nist.gov
Sugar-based glasses have long been known to stabilize proteins against aggregation and chemical
degradation; however, it has been an open question as to whether the stability arises primarily from
thermodynamic or dynamic considerations. Several years ago we demonstrated a striking correlation
between β relaxation (as measured by mean-squared displacement from neutron backscattering) and
stability of model proteins [1]. Here we report on significant extensions of that work, and use the
quantitative relationship between dynamics (α and β relaxation) and protein stability in many systems
to show conclusively that, in general, thermodynamic stabilization of proteins by sugar-based glass is
not an important stabilizing mechanism.
[1] M. T. Cicerone and C. L. Soles, Biophys J., 86, 3836, 2004
GLASS PHENOMENOLOGY IN CHARGE DENSITY WAVE SYSTEMS
D. Dominko (1), D. Starešinić (1), K. Biljaković (1), M. Jakšić (2), Z. Siketić (2), P. Lunkenheimer (3),
A. Loidl (3), J.C. Lasjaunias (4), and P. Monceau (4)
(1) Institute of Physics, P.O.B. 304, HR-10001 Zagreb, Croatia
(2) Institute Ruđer Bošković, Bijenička 54, HR-10000 Zagreb, Croatia
(3) Experimental Physics V, University of Augsburg, D-86135 Augsburg, Germany
(4) Institut Neel, CNRS, BP 166X, F-38042 Grenoble, France
ddominko@ifs.hr
The charge density wave (CDW) superstructure occurs in many quasi one-dimensional crystals and it
is known for numerous glass-like phenomena. The dielectric response of CDW systems is very similar
to that one of canonical glasses, with the high frequency resonance, α process which freezes at a finite
temperature Tg and β process splitting from α process and remaining below Tg [1]. Thermal capacity
(cp) of CDW systems demonstrates the peak in cp/T 3 and the contribution from low energy excitations
(LEEs), as well as very long time relaxation and ageing [2]. Defects restrict the CDW phase coherence
to the domains of the µm size whose interaction depends the screening by free carriers. The theory of
CDW phase dynamics shows that the three processes in the dielectric response represent the acousticlike
oscillations within the domain, the cooperative dynamics of the domains and the local dynamics
of topological phase defects (solitons). The “Boson peak” in CDW corresponds to the contribution of
the acoustic-like phase excitations (phasons) and the LEEs the contribution of solitons. The
measurements on irradiated and doped samples corroborate these conclusions. This striking similarity
of the CDW and canonical glasses and the well established CDW microscopic picture impose the
CDW systems as a toy model for the glass phenomenology.
[1] D. Starešinić et al. Phys. Rev. B, 65, 165109, 2002; ibid, Phys. Rev. B, 69, 113102, 2004
[2] K. Biljaković, Phys. Rev. Lett., 96, 039603, 2006

PHASE EXCITATIONS IN CHARGE DENSITY WAVE SYSTEMS VERSUS BOSON PEAK
AND TLS IN GLASSES
K. Biljaković (1), D. Starešinić (1), J.C. Lasjaunias (2), and P. Monceau (2)
(1) Institute of Physics, P.O.B. 304, Hr-10001 Zagreb, Croatia
(2) Institut Neel, CNRS, BP 166X, F-38042 Grenoble, France
katica@ifs.hr
The dynamics of charge density waves (CDW) is described by the temporal changes of the amplitude
and the phase of the complex order parameter. The low energy degrees of freedom are phase excitations
– phasons. They are acoustic-like and therefore govern the low-frequency CDW response. The well
known CDW pinning is characterized by the resonant response at GHz frequencies. Screening by free
carriers is tightly bound with the deformation of CDW and gives the criterion for freezing at Tg [1]. The
dynamics of the dielectric glass transition strongly resembles the scenario of the freezing in supercooled
liquids [2]. The glassy phenomenology is completed with low-energy excitations (LEE), the peak in heat
capacity (Cp/T 3 ), long-time energy relaxation and aging found at low-T. In this new class of glass
relevant degrees of freedom concern the CDW superstructure on the characteristic scales of the size of
the phase coherence length (lϕ~µm). As the lattice distortion associated with the CDW can be thought of
as being a “frozen” phonon, we discuss its possible manifestations in relation with the phenomenology
of Boson peak in glasses as the freezing of incomplete softening of superstructural mode near glass
transition temperature. Some very well understood aspects of the microscopic picture in CDW systems
and the parallels we draw with glass forming systems might be of mutual interest for both fields.
[1] D. Starešinić, this conference
[2] K. Biljaković et al., Physica B, 404, 456, 2009

ANOMALOUS THICKNESS EFFECTS AND DIELECTRIC RELAXATION BEHAVIOUR
IN ULTRATHIN FILMS OF I-PMMA/CLAY NANOCOMPOSITES
M.Wübbenhorst (1), T.A. Tran (2), Y. Grohens (2),
(1) Department of Physics and Astronomy, Katholieke Universiteit Leuven, Celestijnenlaan 200D,
Leuven, 3001, Belgium
(2) Laboratoire Polymeres, Proprietes aux Interfaces et Composites (L2PIC), Centre de Recherche BP
92116, Rue de Saint Maude, 56321 Lorient Cedex, France.
wubbenhorst@fys.kuleuven.be
The effects of nanometer confinement on the glass transition dynamics of amorphous polymers have
widely been studied in the past years. Two particularly important systems are ultrathin films and
nanocomposities, which typically show reductions or elevations in the glass transition temperature
depending on the strength of the polymer/solid interactions. This paper is devoted to a systematic
study of the cooperative and local dynamics in ultrathin films of isotactic poly(methyl methacrylate)
containing organophilic montmorillonite (Cloisite 15A) by broadband dielectric relaxation
spectroscopy (BDRS).
Films prepared by spin-casting from a polymer solution in chloroform with up to 35 wt% cloisite
revealed a highly discontinuous dependence of the film thickness on the clay concentration. Similar
discontinuities were found for glass transition temperature showing a maximum Tg-increase by 20K
for a clay content of 12 wt%, as well as for the thermal activation parameters of the dielectric betaprocess.
The results are discussed in terms of a filler-induced coil-rod conformation transition in i-
PMMA together with the existence of reduced mobility layers at the polymer/solid interfaces.
CHAIN FOLDING AND DIFFUSION IN MONODISPERSE LONG N-ALKANES BY SOLID-
STATE NMR
Giuseppe Grasso(1) and Jeremy J. Titman(2)
(1) Dipartimento di Scienze Chimiche, Università di Catania, Viale Andrea Doria 6, 95125 Catania,
Italy.
(2) School of Chemistry, University of Nottingham, University Park, Nottingham, NG7 2RD, UK.
Studies of crystallization and morphology in semi-crystalline polymers are often complicated by
poly-dispersity, and for this reason mono-disperse normal alkanes have often been used as models for
polyethylene. For mature crystals, the lamella thickness is an integer fraction of the chain length,
indicating the formation of so-called “integer-folded” structures. In this talk we describe the use of
solid-state NMR to study long mono-disperse n-alkanes in order to establish morphological details [1].
The size of the folded segment of the alkane chain in the once-folded form of C246H494 has been
measured directly by NMR and shown to contain an average of 8 ± 2 carbon atoms at 293 K. This
tight fold is in contrast to the looser fold obtained indirectly for similar samples in earlier NMR work,
but in good agreement with the picture provided by SAXS and LAM Raman spectroscopy studies.
The recovery after saturation of the carbon-13 magnetization associated with the all-trans carbon-13
peak has also been measured. The behavior as a function of recovery time has been compared with
simple simulations which model the combined effects of chain diffusion and spin-lattice relaxation.
These results suggest that at short times the mechanism for the magnetization recovery involves the
alkane chain diffusing around the fold with the methyl groups constrained from entering the crystal
through the opposite surface of the lamella, in line with the conclusions of Yao et al. [2].
[1] G. Grasso and J. J. Titman Macromolecules, in press, 2009.
[2] Y.-F. Yao, R. Graf, H. W. Spiess and S. Rastogi, Macromolecules, 41, 2514, 2008.

EXPERIMENTAL EVIDENCE BY NEUTRON SPECTROSCOPY FOR THE ORIGIN OF
THE DYNAMIC TRANSITION
F. Mezei (1,2), M. Russina (3), P. Falus (4), B. Farago (4), B. Frick (4), G. Chen (1), P.W. Fenimore
(1), H. Frauenfelde (2) and B.H. McMahon (1)
(1) Los Alamos National Laboratory, Los Alamos, NM 87545, USA
(2) Research Institute for Soild State Physics, 1121 Budapest, Konkoly Thege ut 29-33, Hungary
(3) Helmholtz-Zentrum-Berlin, Glienicker str 100, 14109 Berlin, Germany
(4) Institute Laue-Langevin, BP 156, F-38042 Grenoble Cedex 9, France
mezei@lanl.gov
The marked crossover in the temperature dependence of the mean square displacement of atoms in
hydrated proteins around 200 K, the so called “dynamic transition” has been originally observed by
Mössbauer spectroscopy and by “elastic window” neutron backscattering spectroscopy. Its origin
remained controversial over the past decades. We have extended its exploration by a detailed study of
the whole quasielastic and inelastic neutron scattering spectra over the exceptionally broad energy
transfer domain of 50 neV to 20 meV. This was achieved by the combination of TOF, backscattering
and NSE experiments in both H2O and D2O hydrated myoglobin. We have found unambiguous
evidence that this phenomenon is caused by the temperature dependence of a relaxation process spread
over several orders of magnitude in time, which reveals all neutron scattering signature properties of
the canonical β relaxation process observed in the vicinity conventional glass transitions. The
similarity is reciprocal, we have also shown that if analyzed the same way as protein data have been,
the quasielastic scattering on glasses show archetypical dynamic transition too. These observations
unambiguously exclude some recently proposed mechanisms for the dynamic transition, (such as
softening of the elastic constants or fragile to strong cross-over in the alpha relaxation), while they are
consistent with the temperature dependence of the beta fluctuations recently explored over the large in
myoglobin samples of different degrees of hydration by dielectric relaxation experiments. It is
significant, that in the present neutron spectroscopic study we were able to cover similarly large
frequency range than dielectric relaxation measurements and also achieve some overlap in frequency
between the two sets of data. We have adopted a model independent approach to the analysis of the
neutron data, also taking advantage of the large dynamic range covered. At the same time, this has
revealed the inherent prohibitive ambiguities of the use of model fitting procedures in the study of the
complex protein dynamics covering many orders of magnitude in time.
GEL-LIKE MECHANICAL REINFORCEMENT IN POLYMER NANOCOMPOSITES
Pinar Akcora (1), Sanat K. Kumar (2)
(1) University of Missouri, Laffarre Hall W2018 Columbia, MO 65211, USA
(2) Columbia University, New York, NY 10027 USA
akcorap@missouri.edu
We have recently shown that the self-assembly of polymer grafted nanoparticles can be achieved by
varying the brush grafting density and chain lengths of matrix and brush. The mechanical behavior of
these nanocomposites with various states of particle dispersion has been explored using x-ray photon
correlation spectroscopy and rheology. Nanoscale and macroscopic dynamic measurements show that
mechanical reinforcement results from the percolated and also strongly entangled brushes forming
strong networks. Particle dynamics within various nanostructures and their corresponding macroscopic
dynamics will be discussed through their shear stress relaxations.

ANALOGIES BETWEEN THE DIELECTRIC PROPERTIES OF SOME AgI-BASED IONIC
GLASSES AND THEIR MECHANICAL RESPONSE AT ULTRASONIC FREQUENCIES
A. Mandanici, M. Cutroni, M. Federico
Dipartimento di Fisica, Università di Messina, 98166 Messina, Italy
cutroni@unime.it
The dynamical response of silver iodide-silver borate glasses and silver iodide-silver molybdate
glasses has been studied in a wide frequency range from mHz to GHz down to low temperatures and
analyzed in terms of frequency dependent conductivity, complex permittivity and electric modulus.
The observed dynamical features have been compared with the mechanical properties of the same
materials as revealed by measurement of acoustic attenuation and longitudinal sound velocity at
ultrasonic frequencies [1]. The results have been discussed considering complementary information
provided by recent EXAFS and thermal expansion measurements [2].
[1] M. Cutroni, A. Mandanici, A. Raimondo, A. Sanson, Physics and Chemistry of Glasses - European
Journal of Glass Science and Technology, Part B, 47, 388, 2006; A. Mandanici, A. Raimondo, M.
Cutroni, M. Federico, F. Rocca,
Materials Science and Engineering A, in press.
[2] A. Mandanici, A. Raimondo, M. Cutroni, M. A. Ramos, J. G. Rodrigo, S. Vieira, C. Armellini, F.
Rocca,
J. Chem. Phys., 130, 204508, 2009.
DIELECTRIC AND ELECTRICAL PROPERTIES INVESTIGATION OF POLYAMIDE/
POLYANILINE COMPOSITE FILMS
D. Mezdour (1, 2), M. Tabellout (1) and S. Sahli (2)
(1) Laboratoire de Physique de l’Etat Condensé, UMR CNRS 6087, Université du Maine, Avenue
Olivier Messiaen, 72085 Le Mans cedex, France
Dmezdour@univ-lemans.fr
(2) Laboratoire de Microsystèmes et Instrumentation, Département d’électronique, Faculté des
Sciences de l’Ingénieur, Université Mentouri , Route d’Ain el Bey 25000, Constantine, Algérie
Reducing filler concentration by the elaboration of new composite materials represents a technological
interest since an excessive amount may affect other properties of the materials such as mechanical and
optical properties [1]. Surface conductive composites were chemically prepared at room temperature
by in situ polymerization of aniline inside polyamide films. The obtained composites which can be
applied for antistatic devices, consist of polyamide 6 (PA-6) polymer films containing conductive
Polyaniline (PANI) particles. Dielectric properties measured in the frequency range of 10 -2 to 10 7 Hz
are reported and the frequency behaviour of dielectric permittivity was investigated as a function of
Polyaniline (PANI) concentration. The experimental permittivity value was found to increase
continuously with PANI content. The drastic change in the electrical conductivity beyond a threshold
concentration was observed on surface potential decay curves. Scanning electron microscope images
suggest that the network structure became denser with increasing PANI content, originating a slightly
improved electrical conductivity proven by charge decay on film surfaces. The low PANI content
films exhibit a relatively high surface conductivity allowing the possibility to tune the electrical
conductivity of the polyamide composites according to desired utilization technology [2].
[1] X. Jing and W. Zhao, J. Mat. Sci. Lett., 19, 377, 2000
[2] V. Singh, S. Mohan, G. Singh, P. C. Pandey and R. Prakash, Sensors and Actuators, B 132, 99,
2008

DESIGNING ION-CONTAINING POLYMERS FOR FACILE ION TRANSPORT
Ralph H. Colby, Wenjuan Liu and Michael J. Janik
Materials Science and Engineering, Penn State University, University Park, PA, 16802
Correspondence author: rhc@plmsc.psu.edu
We use ab initio quantum chemical calculations at 0 K in vacuum to characterize ion interactions and
ion solvation by various functional groups on ion-containing polymers. Of primary interest are singleion
conducting ionomers, potentially useful for actuators and for battery membranes. Simple ideas for
estimating the ion interactions and solvation at practical temperatures and dielectric constants are
presented that indicate the rank ordering observed at 0 K in vacuum should be preserved. Hence, such
ab initio calculations are useful for screening the plethora of combinations of polymer-ion, counterion
and polar functional groups, to decide which are worthy of synthesis for new ionomers. The results
provide estimates of parameters for a simple four-state model for counterions in ion-containing
polymers: free ions, isolated ion pairs, triple ions and quadrupoles. We show some examples of how
ab initio calculations can be used to understand experimental observations of dielectric constant, glass
transition temperature and conductivity of polymerized ionic liquids with ionic liquid counterions.
ELASTIC INSTABILITIES IN POLYMER FILMS TO MAKE SELF-STRUCTURED
SURFACES
S. Desprez (1), B. Kolaric (2), and P. Damman (2),
(1) Materia Nova, Interfaces and Complex Fluids unit, 1 avenue Copernic B-7000 Mons (Belgium)
(2) Laboratory of Interfaces and Complex Fluids, University of Mons, 20 place du parc B-7000 Mons
(Belgium)
sylvain.desprez@materianova.be
Upon compression, thin and rigid elastic membranes supported on a soft elastic solid spontaneously
deviate from their flat geometry by forming regular wrinkle patterns. A wide variety of such
mechanical instabilities can be found in natural systems, either at the macroscopic or at the
microscopic scales. Wrinkles on the surface of the skin, specific structures of vegetables or the
mechanism of closure in carnivorous plants [1] are some examples among so many others. Here we
report experiments performed on multilayer systems: supported polymer/metal or PDMS/modified
PDMS bilayer [2, 3]. Wrinkle patterns geometry depends on layers thicknesses and elastic modulus
and on the applied compression rate. If classical sinusoidal profile can be reach for small compression
rates, large deformations lead to the focalization of strain in folders. Such wrinkles patterns were used
to generate super-hydrophobic surfaces. Wrinkle patterns have furthermore a great potential in
biological, adhesion, nanofluidic and even in photonic applications. Indeed, cycloid or hemispheric
wrinkles profiles are expected to be used to focus light on photovoltaic devices. Furthermore,
wrinkling seems to be an interesting way to produce switchable optical cavity by using stimuloresponsive
polymer materials.
[1] Y. Forterre, J.Skotheim, J. Dumais, L. Mahadevan, Nature, 433, 421, 2005.
[2] H. Vandeparre, J. Léopoldès, C. Poulard, S. Desprez, G. Derue, C. Gay, P. Damman, .PRL 99,
188302, 2007.
[3] H. Vandeparre, P. Damman, PRL 101, 124301, 2008.
SECONDARY RELAXATIONS IN ETHYLCYCLOHEXANE ABOVE AND BELOW THE
CALORIMETRIC GLASS TRANSITION TEMPERATURE
A. Mandanici, M. Cutroni
Dipartimento di Fisica, Università di Messina, 98166 Messina, Italy

andrea.mandanici@unime.it
Different relaxation processes in ethylcyclohexane (ECH) have been revealed by high resolution
dielectric spectroscopy [1] and mechanical spectroscopy [2] above and below the glass transition
temperature, Tg [3]. While the dielectric β-relaxation observed in the glassy phase of ECH could have
an intramolecular origin [1,4], a trace of the Johari-Goldstein relaxation can be found from the
analysis of the ultrasonic attenuation profiles [5]. In addition, two secondary relaxations, γ and χ,
slower than the α-relaxation, have been observed in the liquid above Tg. Interestingly, very similar
activation parameters characterize the low-temperature β-process and the high-temperature χ-process,
in ECH as well as in different materials having structural similarities with the ethylcyclohexane
molecule. Thus the β-process could correspond to some intramolecular mode that in the case of ECH
apparently persists in the liquid state at slow relaxation times which exceed those of the α-process.
[1] A. Mandanici, W. Huang, M. Cutroni, R. Richert, J. Chem. Phys. 128, 124505, 2008.
[2] A. Mandanici, M. Cutroni, J. Phys. Chem. B, 111, 10999, 2007.
[3] A. Mandanici, M. Cutroni, A. Triolo, V. Rodriguez-Mora, Miguel Angel Ramos, J. Chem. Phys.,
125, 54514, 2006.
[4] A. Mandanici, W. Huang, M. Cutroni, R. Richert, Philosophical Magazine, 88, 3961, 2008.
[5] A. Mandanici, M. Cutroni, Materials Science and Engineering A, in press.
DISCOVERY OF A NEW CRYSTALLINE PHASE OF IBUPROFEN
E. Dudognon ( 1 ), F. Danède ( 1 ), M. Descamps ( 1 ) and N. T. Correia (2)
(1) LDSMM, UMR CNRS 8024 - BAT P5, Université de Lille 1, 59655 Villeneuve d'Ascq, France
(2) REQUIMTE, Departamento de Química, Faculdade de Ciências e Tecnologia, Universidade Nova
de Lisboa, 2829-516 Caparica, Portugal
emeline.dudognon@univ-lille1.fr
The manipulation of the crystallization behavior of substances is an important issue in pharmaceutical
industry. The search for polymorphic varieties recently became a topic of major interest as the nonconventional
crystalline forms may have enhanced therapeutic activity. This work reports the
discovery of a polymorphic crystalline form of the active pharmaceutical ingredient: IBUPROFEN.
Indeed, in addition to the well-known conventional crystalline phase I, we observed for the first time,
by both differential scanning calorimetry and X-ray powder diffraction, the development of another
crystalline phase II which melts at lower temperature and is thus of lower stability. Its appearance,
conditioned by a quench of the liquid at very low temperatures, emphasizes the occurrence of a
nucleation process far below Tg. The discovery of this metastable form of presumably much higher
solubility may be interesting for drug formulation.
Acknowledgement: Financial support to Fundação para a Ciência e Tecnologia (FCT, Portugal)
through the project PTDC/CTM/64288/2006 and the Pessoa partnership Hubert Curien is
acknowledged.
POSITRON ANNIHILATION RESPONSE AND THE RELAXATION DYNAMICS FROM
BROADBAND DIELECTRIC SPECTROSCOPY AND NUCLEAR MAGNETIC
RESONANCE: 1,4 – POLY (BUTADIENE)
J. Bartoš (1), O.Šauša (2), G.A.Schwartz (3), A.Alegría (3,4), J.M.Alberdi (4), J.Krištiak (2) and
J.Colmenero (3,4,5)
(1) Polymer Institute of SAS, Dúbravská cesta 9, SK - 842 36 Bratislava, Slovak Republic
(2) Institute of Physics of SAS, Dúbravská cesta 9, SK - 842 28 Bratislava, Slovak Republic
(3) Centro de Fisica de Materiales, Centro Mixto CSIC - UPV/EHU, Edificio Korta, 20018 San
Sebastián, Spain
(4) Departamento de Fisica de Materiales, UPV/EHU, Apdo 1072, 20080 San Sebastián, Spain

(5) Donostia <strong>International</strong> Physics Center, P 0 M.deLardizabal 4, 20018 San Sebastián, Spain
upolbrts@savba.sk
We report phenomenological analyses of the annihilation behaviour of the ortho-positronium (o-Ps)
from positron annihilation lifetime spectroscopy (PALS) and the dynamic behaviour over a very wide
temperature and frequency range on a prototypical amorphous polymer glass-former: cis- trans -1,4 -
poly(butadiene). The dielectric spectra have been evaluated in two ways: i ) the main spectral feature
of the structural relaxation by using the Havriliak – Negami (HN) function being close to the use of
the standard peak maximum analysis and ii ) the total spectrum by using the Williams - Watts (WW)
ansatz. Analysis of τ 3 −T
plot reveals the three characteristic PALS temperatures: T
PALS
g ,
T
PALS
b1
= 1.
18Tg
and T
PALS
b2
= 1.
44Tg
. A number of relationships between both the o-Ps annihilation
and the relaxation parameters have been found. The onset of the plateau at Tb2 occurs when τ 3 reaches
the relaxation time of the main process from the peak maximum analysis. It is approximately related to
a crossover of the structural relaxation time τα (T ) from non - Arrhenius to Arrhenius character from
the coupled BDS and NMR data. Next, the slighter bend effect at Tb1coincides with a deviation of the
secondary effective β - relaxation in the BDS spectra from a low–T Arrhenius behavior suggesting the
same origin of both the phenomena. Finally, both the databases can be described by using the two -
order parameter (TOP) model in a consistent way.
High-Frequency Dielectric Loss of Hydrogen-Bonding Glass Formers
Ryusuke Nozaki and Masahiro Nakanishi
Department of Physics, Faculty of Science
Hokkaido University, Sapporo 060-0810, Japan
It is commonly recognized that glass-forming materials has hierarchical dynamics with the glass
transition. Recent understanding for the materials strongly supports existence of the structural alpha
process, the Johari-Goldstein beta (JG-beta) process and the Boson peak. These processes can be
observed by means of dielectric spectroscopy if the materials are polar. It is well known that there is a
dielectric loss minimum between the first two processes and the Boson peak. Since characteristic
times for the first two processes have temperature dependence while that for the Boson peak
essentially doesn't depend on temperature, behavior of the loss minimum varies with decreasing
temperature. Slightly above the glass transition temperature Tg, the minimum has steep slopes in both
the higher and the lower frequency sides. As temperature decreases, bottom of the minimum becomes
deeper and the steepness of the slope in the low frequency side decreases. Finally, far below Tg,
dielectrics loss with very weak frequency dependence appears in an extremely wide frequency range
up to the microwave frequency region. Recently, this high frequency dielectric loss of the glass
formers is of great interest for many scientists because origin of the loss is considered to be very
important to understand not only the glass transition phenomena but also the disordered system such
as glassy state.
Hydrogen-bonding materials such as sugar alcohols have been extensively investigated by means of
dielectric spectroscopy. Behaviors for the alpha process, the JG-beta process and the Boson peak
especially in sugar alcohols are well investigated because we can systematically control the glass
transition parameters such as the glass transition temperature and the fragility index by changing the
molecular weight. In this study, we have performed the complex permittivity measurements for
several hydrogen bonding materials including the sugar alcohols especially paying attention to the
high frequency dielectric loss. In order to access the small loss in an extremely wide frequency range
including the microwave frequencies, we have developed new dielectric test fixtures. <strong>Discussion</strong> will
be made on the loss behavior from the view points of the high frequency tail of the JG-beta process
and the nearly constant loss (NCL).

LOW-ENERGY VIBRATIONAL EXCITATIONS IN DISORDERED SOLIDS:
STUDY BY SINGLE-MOLECULE SPECTROSCOPY
A.V. Naumov (1), Yu.G.Vainer (1), L.Kador (2)
(1) Institute for spectroscopy RAS, Troitsk, Moscow reg., 142190, Russia
(2) Institute of Physics and BIMF, University of Bayreuth, D-95440 Bayreuth, Germany
naumov@isan.troitsk.ru
We overview new experimental possibilities for studying the low-temperature vibrational dynamics of
disordered solids on a microscopic level. Analysis of individual temperature dependences of linewidth
for many single impurity molecules (SMs) measured at T = 5÷40 K allows to determine the values
frequencies of vibrational modes in local environment of SMs. It was found that these frequencies are
distributed in a broad region from a few up to a few tens of wavenumbers (i.e. in the region of the
Boson peak). The experimental data demonstrated a temporal stability of vibrational mode parameters
in time scale of a few hours both for polymer and molecular glass. The comparative analysis of the
local vibration frequency distributions measured via SMS and a Boson peak as measured by inelastic
neutron scattering, by Raman scattering, and by nuclear inelastic scattering revealed close agreement
between different types of data. It demonstrates the direct relationship between the Boson peak and
local vibrations inherent to glasses. An important result is that doping the matrices with a small
amount of neutral nonpolar chromophores, whose chemical composition is similar to that of the matrix
molecules, does not affect the observed vibrational dynamics significantly.
The work was supported by DFG, SFB, RFBR (07-02-00206, 08-02-00147). A.N. acknowledges
CRDF and Grant of the President of Russia.
HEAT CAPACITY STUDY OF FORMATION MECHAISM OF POLAR NANOREGION IN
PEROVSKITE-TYPE RELAXORS
Hitoshi Kawaji (1), Yosuke Moriya (2) and Tooru Atake (2)
(1) Materials and Strucutures Laboratory, Tokyo Institute of Technology, 4259 Nagatusta-cho,
Midori-ku, Yokohama, Japan
(2) Department of Chemical System Engneering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku,
Tokyo, Japan
(3) General Safty Management Center, Tokyo Institute of Technology, 2-12-1 Ookayama, Meguro-ku,
Tokyo, Japan
kawaji@msl.titech.ac.jp
Relaxors is a group of dielectrics, which show a large broad peak in the dielectric constant with
frequency dependent dispersion extending in wide temperature range, and have attracted much
attention besides conventional paraelectrics, ferroelectrics, and antiferroelectrics. In relaxors, the polar
region grows only up to nanometer size with decreasing the temperature and freezes with random
orientations within the paraelectric matrix. However, very few calorimetric studies have been reported
for the relaxors, and we started thermodynamic studies on this group of compounds. A heat capacity
anomaly due to the formation of polar nanoregion was found in typical relaxors Pb(Mg1/3Nb2/3)O3
(PMN), Pb(Mg1/3Ta2/3)O3 (PMT) [1], and Pb(Zn1/3Nb2/3)O3 (PZN). We also extended the study to
another type of relaxor such as Pb(Sc1/2Ta1/2)O3 (PST) and Pb(In1/2Nb1/2)O3 (PIN), in which the
dielectric property changes from the ferroelectric to relaxor with decreasing the degree of ordering of
B-site cations. In addition, thermodynamic properties of some relaxor-ferroelectrics solid solutions
such as PMN–PbTiO3(PT) and PZN-PT have been studied. The results indicate that the increase of PT
content facilitates a long range polar order. The mechanism of the growth and freezing of the polar
nanoregion will be discussed.
[1] Y. Moriya, H. Kawaji, T. Tojo, and T. Atake, Phys. Rev. Lett., 90, 205901, 2003.

The Mixed Mobile Ion Effect in Ag-Na Metaphosphate Glasses; a diffraction, reverse Monte
Carlo and bond valence study
A. Hall (1), J. Swenson (2) and St. Adams (3)
(1) Department of Material Science and Engineering, National University of Singapore, Singapore
117574
(2) Department of Applied Physics, Chalmers University of Technology, 412 96 Göteborg, Sweden
(3) Department of Material Science and Engineering, National University of Singapore, Singapore
117574
msejah@nus.edu.sg
The mixed mobile ion effect (MMIE) is one of many fenomena that must be understood before a
general theory of ionic conductionity in glasses can be formed. A general understanding of the MMIE
as a blocking effect has risen in the past decade, but there is still more to learn.
We have studied the mixed Ag-Na metaphosphate glass system which, by its extraordinarily weak
MMIE, is an interesting contrast to the otherwise studied strong MMIE systems. The structure, studied
by neutron and X-ray diffraction and subsequently modelled by reverse Monte Carlo, shows a
remarkable likeness between AgPO3, NaPO3 and the mixed compositions. In all glass compositions,
Ag and Na have the same oxygen distances in the first coordination shell. In fact, the difference in
experimental structure factors can all be ascribed the different scattering cross sections of Ag and
Na.[1] Furthermore, a study of the bond valence (BV) landscapes in this system shows a striking
corrrelation between the ionic pathways of Ag and Na, regardles of the Ag/Na ratio.[2] The similar
prefered environment and the coinciding pathways suggest that the MMIE in this system is suppresed
as the two types of ions may participate in a cooperative hopping process.
[1] A. Hall, J. Swenson, C. Karlsson et al., J. Phys.: Condens. Matter 19, 415115 (2007).
[2] A. Hall, J. Swenson, S. Adams et al., Phys. Rev. Lett. 101, 195901 (2008).
Study of Supercooled Orientationally Disordered Binary Solid Solutions -III:
cyclohexanol + cycloheptanol and neopentanol + neopentylglycol
Geeta Singh and L. P. Singh
Abstract
As part of the ongoing study on the supercooled orietationally disordered binary solid
solutions, dielectric spectroscopy and differential scanning calorimetry (DSC) investigations
on two remarkable two-component (H-) bonded sytem i. e. neopentanol-neopentylglycol
(NPOL-NPGOL) is reported.In this binary system NPOL-NPGOL, where the phase-I of NPOL
forms a continuous solid solution with the phase-I of NPGOL. This solid phase has been
investigated at low temperatures at several concentrations. Depending upon the
concentration, this phase reveal a glass transition, and a pronounced relaxation process
associated with it, identifiable with the so called α-process characteristic of single component
orientationally disordered crystal. The dielectric spectra is found to follow the Havriliak-
Negami (HN) equation. In addition, two sub-Tg processes are found which are designated as
β- & γ- processes respectively. In both binary systems, the β- process may be identified with
Johari-Goldstein (JG) or βJG process as it is found to follow the predictions of the coupling
model proposed by Ngai. However, the identification of the γ- process with internal degrees

of freedom are fraught with some problems in the interpretation of the experimental data that
are high-lighted.
MICROSCOPIC DYNAMICS AND ELASTICITY AT THE GLASS TRANSITION: INSIGHTS
FROM SOFT COLLOIDAL DISPERSIONS
G. Romeo 1 , L. Imperiali 1 , A.F. Nieves 2 , D. Acierno 1 and D. A. Weitz 3
1
CR-INSTM Tecnologie di trasformazione di materiali polimerici e compositi, UDR di Napoli.
Dipartimento di Ingegneria dei Materiali e della Produzione, Università Federico II, P.le
Piazzale V. Tecchio 80, 80125 Napoli
2 School of Physics 837 State Street, Georgia institute of technology, Atlanta, Georgia.
3 School of engineering and applied sciences, Harvard university, Cambridge,
Massachussets.
ABSTRACT
We investigate the microscopic dynamics of compressible colloidal particles as function of
concentration through dynamic light scattering and confocal microscopy experiments. In analogy with
hard sphere (HS) colloidal systems, we find that the particles display liquid, supercooled liquid or
glassy dynamics, depending on volume fraction. In the present case, however caging effects are
observed for particle volume fractions higher than one, i.e. when the particles are compressed.
Differently from HS systems we can map the dynamics in terms of the inter-particle repulsive
potential. The frequency dependence of the viscoelastic moduli G' and G'' obtained from
microrheology agrees with the results obtained from bulk rheology. However the absolute values of
the moduli obtained from one point microrheology are smaller than those measured by standard
rheology, such difference increasing with volume fraction. We conjecture that such difference may
arise from spatial density heterogeneities. Finally we find that heterogeneous dynamics, described by a
non Gaussian distribution of the displacements, play a major role in the under-cooled liquid in
proximity of the relaxation time.
Molecular cooperativity in the dynamics of glass forming systems: A new insight
L. Hong 1 , P. D. Gujrati 1 , V.N. Novikov 2 , A.P. Sokolov 1
1
Department of Polymer Science, The University of kron, Akron, OH 44325, USA
2
Institute of Automation & Electrometry, Russ.Ac.Sciences, Novosibirsk 630090, Russia
Abstract
The mechanism behind the steep slowing down of molecular motions upon approaching the glass
transition remains a great puzzle. Most of the models relate this mechanism to the cooperativity in
molecular motion. In this work we estimate the cooperativity length scale for many glass-forming
systems from the collective vibrations (the so-called boson peak). We demonstrate that directly
correlates to the dependence of structural relaxation on volume. This dependence presents only one
part of the mechanism of slowing down the structural relaxation. Our analysis reveals that another part,
the purely thermal variation of the structural relaxation (at constant volume), does not correlate to

molecular cooperativity. These results call for a conceptually new approach to the analysis of the
mechanism of the glass transition.
RELAXATION OF A RING POLYMER TRAPPED IN AN ARRAY OF OBSTACLES IN
TWO DIMENSIONS
Katsumi Hagita (1), and Hiroshi Takano (2)
(1) Department of Applied Physics, National Defense Academy, 1-10-20, Hashirimizu, Yokosuka,
239-8686, JAPAN
(2) Faculty of Science and Technology, Keio University, 3-14-1, Hiyoshi, Kouhoku-ku, Yokohama,
223-8522, JAPAN
Correspondence author: hagita@nda.ac.jp
Monte Carlo simulations of a ring polymer trapped in an array of obstacles in two dimensions are
performed by using the bond fluctuation model [1]. Recently, behaviors of a ring polymer with the
trivial knot in a melt has been attracted much interest due to recent progress of synthetic method of
cyclic polymers. It is believed that ring polymers in a melt do not entangle with each other because of
entropic effect. On the other hand, linear polymer chains in a melt entangle with each other. According
to the reptation theory [2], a linear polymer chain in a melt behaves as that in an imaginary “tube”
representing the surrounding polymers. The “tube” moves along itself and both ends of the “tube”
move randomly. In the case that surrounding polymers are replaced by fixed obstacles, a similar
behavior of a linear chain is observed. For the case of a ring polymer in the presence of obstacles in
two dimensions, it is expected that a “temporary edge” of a ring polymer is created due to obstacles
and the “temporary edge” moves randomly in an array of obstacles.
[1] I. Carmesin and K. Kremer: Macromolecules, 21, 2819, 1988.
[2] P. G. de Gennes: Scaling Concepts in Polymer Physics (Cornell University Press, Ithaca, 1984).
Low temperature phase transitions of interfacial water.
Connection to protein dynamics.
J.-M. Zanotti 1 , P. Judeinstein 2 , J. Farrington 3 , S. Greenbaum 3 and M.C. Bellissent-Funel 1
1 Laboratoire Léon Brillouin (CEA-CNRS), CEA Saclay, 91191 Gif-sur-Yvette Cedex, France
2 ICMMO, (UMR CNRS 8182), Université Paris-Sud, 91405 Orsay, France
3 Dept. of Physics and Astronomy, Hunter College of CUNY, New-York, NY 10065, USA
We are considering water adsorbed as a monolayer on Vycor, a porous silica glass. The interfacial
water molecules interact with the substrate through hydrogen bonding with the numerous silanol (Si-
OH) groups present all over the surface. The water molecule dynamics has been decomposed in terms
of purely rotational and translational contributions that both exhibit peculiar temperature dependence
[1]. In particular, a combined calorimetric, diffraction, high resolution quasi-elastic and inelastic
neutron scattering study shows that interfacial water experiences several low temperature phase
transitions.
The connections of these findings to protein dynamics, in particular to the protein dynamical transition
around 220 K [2, 3] is discussed. We propose a mechanism, at the molecular level, for the contribution
of water. In particular, from complementary neutron and 2 H NMR spectroscopies, we identify the key
importance of rotational motion [4] of the hydration water as a source of configurational entropy
triggering (i) the 220 K protein dynamical crossover but also (ii) a much less intense and scarcely
reported protein dynamical crossover, associated to a calorimetric glass transition around 150 K.
[1] J.-M. Zanotti, M.-C. Bellissent-Funel and S.-H. Chen, Europhys. Lett., 71, 91 (2005).

[2] W. Doster, S. Cusack, and W. Petry, Nature, 337: 754 (1989).
[3] M. Ferrand, A. J. Dianoux, W. Petry, and G. Zaccai, Proc. Natl. Acad. Sci. USA. 90, 9668 (1993).
[4] J.-M. Zanotti, G. Gibrat, M. C. Bellissent-Funel. Physical Chemistry Chemical Physics, 10, 4865-
4870 (2008).
MICROWAVE HEATING IN SLOW MOTION
Ranko Richert
Department of Chemistry and Biochemistry, Arizona State University, Tempe, AZ 85287, USA
ranko@asu.edu
Dielectric relaxation measurements in the 0.1 Hz - 50 kHz range are performed on viscous liquids
using fields E as high as 450 kV/cm. At these fields, configurational modes of supercooled liquids
absorb energy from the external field, as in microwave heating, but at much lower frequencies where
time resolved experiments are possible. The study focuses on the time scales and relevant heat
capacities involved in energy transfer from the configurational to vibrational modes. Detection of the
dielectric properties, e.g. tanδ, is employed to measure the configurational (or fictive) temperatures as
a function of frequency and of the time that energy absorption is occurring. Therefore, this highly
nonlinear (in E) technique generates the equivalent of four time correlation functions.
The following results have been obtained from these experiments and the associated modelling: Both
dielectric and thermal relaxation times in simple liquids are heterogeneous, with their relaxation time
constant being locally correlated [1]. This 'reverse calorimetry' facilitates the measurement of the
configurational contribution Cp,cfg to the total excess heat capacity Cp,exc, which turns out to vary
systematically with fragility [2]. The relaxation time scale of the configurational temperatures (τT)
relative to the times of the dielectric modes (τD) that had been absorbing the energy is a matter of the
type of liquid. For simple liquids we find τT = τD [3], many monohydroxy alcohols are characterized
by τT > τD. The results are analogous to those derived from
dynamic heat capacity methods, but with a reversed direction of enegy flow.
[1] R. Richert, S. Weinstein, Phys. Rev. Lett. 97, 095703 (2006)
[2] L.-M. Wang, R. Richert, Phys. Rev. Lett. 99, 185701 (2007)
[3] W. Huang, R. Richert, J. Phys. Chem. B 112, 9909 (2008)
[4] W. Huang, R. Richert, J. Chem. Phys. 130, 194509 (2009)
Influence of Nanoparticles on the Amplitude of Molecular Motions and the Fragility a Model
Glass-Forming Polymer Melt
Jack F. Douglas 1 and Francis W. Starr 2
(1) Polymers Division, NIST, Gaithersburg, MD USA 20899, USA
(2) Department of Physics, Wesleyan University, Middletown, CT 06459, USA
jack.douglas@nist.gov
We investigate the impact of the addition of nanoparticles on both the fast and slow dynamics of
model polymer melts by molecular dynamics. The fast dynamics is characterized by the Debye-Waller
factor (the average mean square particle displacement at a characteristic time in the caged particle
motion regime) and the slow structural relaxation is characterized by the coherent intermediate
scattering function, S(q,t). Our study explores how both the polymer-particle and nanoparticle volume

fraction change the amplitude of the high frequency molecular motions relative to the reference
condition of a pure melt and the strength of the temperature dependence of the structural relaxation
time (defining the fragility of glass formation, as well as the glass transition temperature). Substantial
variations of the Debye-Waller factor are observed and we test the effectiveness of the Buchenau
relation linking the Debye-Waller factor to the long time structural relaxation time. We also consider
how the presence of nanoparticles in the polymer melts influence the fragility of glass formation
where a range of criteria are utilized to define fragility. Appreciable changes of fragility are observed,
these changes being dependent on the nanoparticle concentration and particle-polymer interaction.
Generalized Entropy Theory of Glass-Formation: Molecular Model of Fragility
Jack F. Douglas 1 , Jacek Dudowicz 2 , Karl F. Freed 2
(1) Polymers Division, NIST, Gaithersburg, MD USA 20899
(2) James Franck Institute, University of Chicago, Chicago, IL 60637
jack.douglas@nist.gov
Considerable evidence supports the idea of Gibbs and DiMarzio that glass-formation arises when the
configurational entropy of a liquid becomes critically small and the subsequent arguments by Adam
and Gibbs (AG) that quantitatively relate the configurational entropy to the rate of long wavelength
structural relaxation. We revisit this classical entropy theory of glass-formation using a minimal lattice
model of the thermodynamics of polymer melts that incorporates monomer structure, the different
rigidities of the polymer chain backbone and side-groups, compressibility effects, and van der Waals
interactions. Based on a combination of the AG theory and our general thermodynamic theory, we
analytically calculate the characteristic temperatures of glass-formation describing the onset of the
glass-formation (TA), a crossover temperature (TI or Tc) separating high and low temperature regimes
of glass-formation, the glass transition temperature (Tg), which is defined by a Lindemann softening
criterion, and the temperature T0 where the configurational entropy extrapolates to zero.
Experimentally established trends in the fragility of polymer melts with respect to variations in
monomer structure and pressure are interpreted within our theory in terms of the accompanying
changes in chain packing efficiency. We briefly compare the entropy theory predictions to molecular
dynamics simulations for model fragile and strong polymeric fluids.
TIMESCALES OF MECHANICALLY STIMULATED GLASSES
L. Grassia, A. D’Amore
Department of Aerospace and Mechanical Engineering, The Second University of Naples – SUN –
81031, Aversa (CE), Italy
alberto.damore@unina2.it
We have recently reported that the phenomenological intricacies of mechanically stimulated glasses
can be reliably predicted by linking the modified KAHR equation with the constitutive equation for
linear viscoelastic materials written in the reduced time domain [1,2]. The model requires the
knowledge of the “linear” shear and bulk relaxation functions, the factors that alter the responses
timescales being encrypted into the definition of the reduced (or material) time. It was shown
analytically that the dimensionless bulk compliance coincides with the memory function appearing in

the modified KAHR equation, so that it can be extracted directly from the experimental PVT data.
Now the modelling approach is extended to the case of large strains in order to account for the volume
variation due to the deviatoric components of the stress tensor. It is assumed that the relaxation times
of mechanically stimulated glasses depend on the specific volume and the fictive temperature
(namely: ). This approach comes from the recent findings by Roland et al. [3] concerning the scaling
rules of relaxation time above T
g
for many glass-formers. The model allows us managing the shear
stresses-induced nonlinearity of glasses.
[1] L. Grassia, A. D’Amore, J. Rheol., 53, 339, 2009
[2] L. Grassia, A. D’Amore, J. Polym. Sci. Part B: Polym. Phys., 47, 724, 2009
[3] C. M Roland, S. Hensel-Bielowka, M. Paluch, R. Casalini, Rep. Prog. in Phys., 68, 1405, 2005
EFFECT OF STRUCTURAL RELAXATION ON THE LOW TEMPERATURE HEAT
CAPACITY OF GLASSY ALLOYS
A. Uchida (1), H. Kawaji (1), T. Atake (1), M. Fukuhara (2), H. Kimura (2) and A. Inoue (2)
(1) Materials and Structures Laboratory, Tokyo Institute of Technology, 4259 Nagatsuta-cho, Midoriku,
Yokohama, Japan
(2) Institute for Materials Research, Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai, Japan
uchida.a.aa@m.titech.ac.jp
Glassy alloy are important functional materials and much attention has been recently paid on the
variety of applications. We have measured the heat capacity of glassy ribbon and rod samples of
Zr0.55Al0.10Ni0.05Cu0.30 glassy alloy prepared by rapid and rather slow quenching, respectively
[1,2], and found the difference in the low temperature heat capacity. In the present study, the heat
capacity of the glassy rod samples and glassy ribbon samples annealed under different conditions was
compared with each other to clarify the effect of structural relaxation. The heat capacity of the ribbon
sample decreased in the whole temperature region with increasing the annealing temperature. This
result indicates that the excess heat capacity is attributed to the softness of the lattice vibrations in the
as-prepared glassy ribbon sample and the structural relaxation causes the hardening of the lattice
vibrations. The relationship between the lattice vibration properties and the local structure of the
samples will be discussed.
[1] Y. Moriya, T. Yoshida, H. Kawaji, T. Atake, M. Fukuhara, H. Kimura, and A. Inoue, Ceramic
Trans. 198, 117 2008.
[2] Y. Moriya, T. Yoshida, H. Kawaji, T. Atake, M. Fukuhara, H. Kimura, and A. Inoue, Mater. Sci.
Eng. B 148, 207 2008.
The Solubility of non-Polar Compounds in Water: Insights from Simple and form Detailed
Models
Pablo G. Debenedetti
Department of Chemical Engineering
Princeton University
Princeton, NJ 08544
USA
The solubility of non-polar compounds in water is of interest for both practical and theoretical reasons
(e.g., ultimate fate of pollutants; theory of hydrophobicity). A spherically-symmetric model with two
characteristic length scales displays water-like solvation thermodynamics, including non-monotonic
temperature dependence of hard sphere solubility, and cold unfolding of apolar chains [1]. Replica
exchange molecular dynamics is used to calculate the solubility of n-alkane chains up to C20 in water
[2]. The calculations reveal nearly exponential decrease in solubility with carbon number. A free

energy landscape analysis of chain conformations reveals remarkable similarities between ideal gas
and solvated landscapes, suggesting that solvated chain conformations up to C22 are driven primarily
by ideal gas statistics.
[1] S.V. Buldyrev, P. Kumar, P.G. Debenedetti, P.J. Rossky and H.E. Stanley, Proc. Nat’l. Acad. Sci.
USA, 104, 20177, 2007.
[2] A.L. Ferguson, P.G. Debenedetti and A.Z. Panagiotopoulos, J. Phys. Chem. B, 113, 6405, 2009.
NEUTRON SCATTERING STUDY OF THE DYNAMICS OF A POLYMER MELT UNDER
NANOSCOPIC CONFINEMENT
M. Krutyeva (1), J. Martin (2), A. Arbe (3), J. Colmenero (3,4,5), C. Mijangos (2), M. Monkenbusch
(1), D. Richter (1)
(1) Institut für Festkörperforschung, Forschungszentrum Jülich, Postfach 1913, 52425 Jülich,
Germany
(2) Instituto de Ciencia y Tecnología de Polímeros, CSIC, Madrid, Spain
(3) Centro de Física de Materiales (CSIC-UPV/EHU) – Materials Physics Center (MPC), San
Sebastián, Spain
(4) Departamento de Física de Materiales UPV/EHU, San Sebastián, Spain
(5) Donostia <strong>International</strong> Physics Center, San Sebastián, Spain
m.krutyeva@fz-juelich.de
According to recent NMR experiments confinement have a drastic effect on the dynamics of polymer
chain in the melt. Recent NMR data were described in terms of the so called corset effect which is
predicted to change the mesoscopically sized tube confinement in polymer melts to a lateral
confinement on the level of the chain diameter [1]. This phenomenon was argued to arise from the
strong collectivity of the chain motion. Neutron scattering accesses dynamical properties with
space/time resolution. For polymer dynamics, this allows separating different dynamical regimes for
different length scales [2]. First neutron scattering experiments have been performed using
backscattering and time-of flight spectrometers. These instruments allow to explore the time window
from ps to a few ns and length scales from a few nanometers down to some tenth of a nanometer. An
anisotropic slowing down of the dynamics is observed under confinement, this effect being more
pronounced in the direction perpendicular to the pore axis. The observed slowing down of the
molecular displacements perpendicular to the pore axis affects about ~10% of the segments. This
effect could be attributed to the interactions between the pore walls and polymer segments within an
~1 nm layer. To answer the question whether the additional confinement effects arise at larger length
scales will need further investigations. In this work we have estimated a minimum possible value of
the tube diameter of ~1.5 nm from our results in the time-of-flight and backscattering window. We
expect that future neutron spin-echo experiments addressing the dynamics at larger length scales will
tell whether there exists a change of chain confinement beyond the tube diameter in the pores.
[1] N. Fatkullin, R. Kimmich, E. Fischer, C. Mattea, U. Beginn, M. Kroutieva, N. J. Phys. 6, 46 (2004)
[2] D. Richter, M. Monkenbusch, A. Arbe, J. Colmenero, Adv. Polym. Sci. 174, 1 (2005)
A KINETIC MODEL FOR THE ENZYMATIC HYDROLYSIS OF CELLULOSE
Christina L. Ting (1) and Zhen-Gang Wang (2)
(1) Biochemistry and Molecular Biophysics, California Institute of Technology, Pasadena, CA 91125
(2) Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena,
CA 91125
zgw@caltech.edu

There is considerable current interest in the economical production of ethanol from cellulosic biomass
on commercial scale. A key step in the process is the enzymatic hydrolysis of the polysaccharide
chains that are tightly bound to the cellulose crystal. We develop a mechanochemical model for the
hydrolysis kinetics by the cellulase, a two-domain enzyme connected by a peptide linker, as it extracts
and breaks down the polyscchraide chain from a crystalline substrate. We consider two random
walkers, representing the catalytic domain (CD) and the carbohydrate binding module (CBM), whose
rates for stepping are biased by the coupling through the linker and the energy required to lift the
cellulose polymer from the crystalline surface. Our results show that the linker length and stiffness
play a critical role in the cooperative action of the CD and CBM domains and that, for a given linker
length, the steady state hydrolysis shows a maximum at some intermediate linker stiffness. The
maximum hydrolysis rate corresponds to a transition of the linker from a compressed to an extended
conformation, where the system exhibits maximum fluctuation as measured by the variance of the
separation distance between the two domains and the dispersion around the mean hydrolysis speed. In
the range of experimentally known values of the parameters of our model, improving the intrinsic
hydrolytic activity of the CD leads to proportional increase in the overall hydrolysis rate.
Oligopeptide Self-Assembly: Insights from Experiments and Simulations
Phanourios Tamamis and Georgios Archontis
Department of Physics, University of Cyprus, PO20537, CY1678, Nicosia, Cyprus
Studies of peptide aggregation provide general insights on biomolecular self-assembly and can guide
technological applications. We have employed implicit-solvent replica-exchange simulations to study
the self-assembly of two classes of peptides; (i) the diphenylalanine peptide (FF), which assembles,
into three-dimensional crystals or hollow nanotubes and the triphenylalanine peptide, which forms
nanoplates, and (ii) the peptides NSGAITIG and GAITIG from the adenovirus fiber shaft, which form
amyloid fibers.
The FF peptides assemble into three-dimensional crystals or hollow nanotubes and the FFF peptides
into nanoplates rich in β-sheet content. In the simulations the peptides form aggregates, which contain
open or ring-like peptide networks, as well as elementary and network-containing structures with βsheet
characteristics. The charged termini of neighbor peptides are involved in hydrogen-bonding
interactions and their aromatic side-chains form “T-shaped” contacts, as in the FF crystals. These
interactions may assist the FF and FFF self-assembly at the early stage, or also stabilize the mature
nanostructures. The FFF peptides have higher network propensities and increased aggregate stabilities
with respect to FF, which can be interpreted energetically.
The NSGAITIG and GAITIG peptides form experimentally amyloid-like fibrils. In the simulations,
the peptides assemble readily into β-sheet conformations. The structural properties of these
conformations and the stabilizing interactions will be discussed.
Molecular Recognition of the Complement Component C3c by Inhibitors Based on Compstatin:
Insights from Molecular Dynamics Simulations.
Phanourios Tamamis and Georgios Archontis
Department of Physics, University of Cyprus, PO20537, CY1678, Nicosia, Cyprus
The 13-residue cyclic peptide compstatin prevents the proteolytic activation of complement
component C3 by binding to the C3-chain, and constitutes a promising candidate for the therapeutic

treatment of unregulated complement activation. Compstatin has the sequence Ile1-Cys2-Val3-Val4-
Gln5-Asp6-Trp7-Gly8-His9-His10-Arg11-Cys12-Thr13-NH2, and is maintained in a cyclic
conformation via the disulfide bridge Cys2-Cys12. Structural (NMR) studies have shown that the
dominant peptide conformation in solution corresponds to a random coil, with the backbone segment
Gln5-Gly8 in a type-I β-turn conformation and the terminal residues Ile1-Val3 and Cys12-Thr13 in a
hydrophobic cluster. Mutational studies have shown that residues of the 5-8 β-turn and the
hydrophobic cluster are critical for activity, even though certain point mutations can be tolerated,
provided they preserve the chemical properties (V3L, Q5N). Recent X-ray studies have shown that the
more active double mutant Ac-V4W/H9A-NH2 (W4A9) binds to C3c (a proteolytic fragment of C3)
in a different conformation. In the present work we study by all-atom MD simulations the properties
of three compstatin derivatives, both in solution and in the complex with C3c. We focus on a native
analog that is acetylated (Ac) at the N-terminal, the more active double mutant W4A9 and the inactive
single mutant Ac-Q5G-NH2. The differences among the conformational properties and interactions of
the three compounds in solution and in the complex will be discussed in connection with their
differences in activity.
DIELECTRIC RELAXATION OF 4-CYANO-4-N-PENTYLBIPHENYL (5CB) MESOGENS
CONFINED BETWEEN GRAPHENE WALLS – COMPUTER SIMULATION
W. Gwizdała, Z. Gburski
Institute of Physics, University of Silesia, Uniwersytecka 4, 40-007, Katowice, Poland
zgburski@us.edu.pl
The dielectric loss spectrum of a thin film of mesogenic molecules 5CB confined between graphene
walls has been calculated using molecular dynamics (MD) technique. The spatial ordering of 5CB
layer persists at higher temperature, well above the nematic-isotropic phase transition temperature of a
bulk 5CB sample (unconfined). This property might be of some importance, when it comes to consider
the future applications of graphene based optoelectronics. Several additional observables of 5CB
molecule were also calculated: radial distribution function, linear and angular velocity autocorrelation
functions, mean square displacement, second rank order parameter - in order to set ground for the
physical interpretation and modeling of obtained spectra.
NEW TECHNIQUE TO OBTAIN ISOTHERMS OF SALTED MEAT USING DIELECTRIC
SPECTROSCOPY
Castro-Giráldez M, Fito P.J., Chenoll, C., Fito P.
(Institute of Food Engineering for Development. Universidad Politécnica de Valencia. Spain.
pedfisu@tal.upv.es

Salting is one of the most traditional preservation methods employed at food industry. One of its main
problems is the difficulty to control the simultaneous water and NaCl fluxes into the product
throughout processes. Usually after salting, meat products suffer a drying process. In this process,
meat losses water, until a safe level is reached. During drying, relationships between the main
components in meat vary, changing the meat properties.
Dielectric properties of salted porcine meat are strongly related to its structure and composition:
moisture, water activity, salt and fat content [1]. As consequence, dielectric properties measurement
appears as a promising method in non-destructive and on-line control of drying processes in salted
meat industry.
The aim of this study was to obtain the desorption isotherms from raw and salted longissimus dorsi
pork samples until different NaCl content. The dielectric spectra were measured before and after the
drying process. Moisture and salt content, water activity and sample volume were also measured.
Dielectric spectra were measured in the frequency range 200 MHz-20 GHz by a coaxial probe (HP
85070E) connected to a Network Analyzer (HP E8362B).
The salted meat isotherms show a salt saturation point at water activity of 0.75. For aw0,75. For high frequencies a
significant relationship between ε’’ and aw was obtained. For low frequencies the salt content in the
meat liquid phase may be well correlated with ε’’. These two conditions allow calculating the amount
of water and salt adsorbed by the solid matrix.
Keywords: dielectric spectroscopy, salting process, dielectric properties, sorption isotherms
Evidence of Dynamic Crossover Phenomena in Water and Its Relation to the Liquid-Liquid
Critical Point: Experiments and MD Simulations
Sow-Hsin Chen*, Y Zhang, M Lagi, P Baglioni
Water distinguishes itself with an exotic phase behaviour. Besides the existence of 15 crystalline
polymorphs, it is a pure substance that first exhibits the so-called polyamorphism: the existence of two
distinct glass forms, the low-density amorphous ice (LDA) and the high-density amorphous ice (HDA).
Furthermore, its thermodynamic response functions, such as the isobaric thermal expansion coefficient
and the isobaric specific heat, show a tendency of divergence at moderately supercooled state at
ambient pressure. One possible explanation of these anomalies is based on the hypothesis that in the
deeply supercooled state there exists two structurally distinct liquids, the low-density liquid (LDL) and
the high-density liquid (HDL). They are respectively the thermodynamic extensions of the LDA and
HDA into the liquid state. Thus in this deeply supercooled state, there should be a coexistence line
between LDL and HDL which ends at a second liquid-liquid critical point (LLCP) at some elevated
pressure. The diverging behaviour of the thermodynamic response functions can be attributed to the
crossing of the Widom line, the line of the maximum correlation length above the LLCP in the one
phase region. However, the experimental evidence of the existence of the LLCP is so far unclear. We
use neutron scattering to directly measure the equation of state of deeply supercooled D2O confined in
mesoporous silica material, namely the density as a function of temperature and pressure ρ(P, T). The
combination of the measured isobaric density profile and the evaluated isobaric thermal expansion
coefficient allow us to track the Widom line and locate its end point (Tc = 195 ± 5 K, Pc = 2250 ± 250
bar, with a critical density of ρc = 1.09 ± 0.01 g/cm 3 ).
In a recent Quasi-Elastic Neutron Scattering experiment on water (H2O) confined in a Portland cement
paste, we find that this 3-D confined water shows a dynamic crossover phenomenon at TL = 227 ± 5 K.
The DSC heat-flow scan upon cooling and an independent measurement of specific heat at constant
pressure of confined water in silica gel show a prominent peak at the same temperature. We further
demonstrate with MD simulations that the dynamic crossover phenomenon in confined water is an
intrinsic property of bulk water, and is not due to the confinement effect. We can attribute the peaking
of specific heat as the result of the crossing of the Widom line also. Consequently, a coherent picture
of the anomalous properties of supercooled and glassy water begins to emerge.

PROTEIN DYNAMICS IN HARD CONFINEMENT: DIELECTRIC RELAXATIONS AND
PICOSECOND HYDROGEN FLUCTUATIONS
A. Cupane and G. SchiròDept. of Physical and Astronomical Sciences, University of Palermo, I-90123
Palermo, Italy
cupane@fisica.unipa.it
The comprehension of the dynamical behavior of water and proteins in confined geometries and near
solid surfaces is of utmost importance in biological physics, since most of the water in living
organisms is closely associated with different kinds of biomolecules or with intracellular assemblies.
Here we report the results of experimental studies on the dynamics of a protein in confined geometry,
i.e. encapsulated in a porous silica matrix, at low hydration levels. The samples of encapsulated
proteins have been left aging in order to reach a condition where only few water layers surround the
proteins. In order to enhance the specific effect of confinement in the silica host, we compared this
system with another one (i.e. hydrated powder) where proteins are confined by other proteins. Met-
Myoglobin (met−Mb) has been chosen here as a model of globular protein.
Using elastic neutron scattering we investigated the temperature dependence of the mean square
displacements of non-exchangeable hydrogen atoms of sol-gel encapsulated met-Mb. In order to
clarify the effect of hydration the study is extended to samples at 0.2, 0.3 and 0.5 [gr water]/[gr protein]
and comparison is made with met-Mb powders at the same average hydration and with a dry powder
sample. Our data show a relevant reduction of average local dynamics, as suggested by the reduction
of hydrogen atoms mean square displacements, and a clear perturbation in the relaxation properties of
water. It is very interesting that even in these extremely confined conditions, protein dynamics at high
temperature (i.e. above the solvent dependent dynamical transition) is clearly dependent on hydration
level, as it has been shown in this work for the first time. Moreover, the effect of confinement is at his
maximum when the hydration corresponds to a complete first shell of water molecules on protein
surface.
A dielectric spectroscopy investigation on the same systems helped to clarify the effect of
encapsulation on protein dynamics. The comparison between the data relative to the two different
systems indicates that geometrical confinement within the silica matrix plays a crucial role in proteinwater
dielectric relaxations, the effect of sol-gel encapsulation being essentially a suppression of
cooperative relaxations that involve the coherence/cooperativity of solvent motions and solventcoupled
protein dynamics. We also provide direct evidence that protein relaxations inside the gel
depend on the hydration level and are “slaved” to the solvent α-relaxation.
[1] G. Schirò, M. Sclafani, C. Caronna, F. Natali, M. Plazanet and A. Cupane, Chem. Phys. 345, 259,
2008
[2] G. Schirò, M. Sclafani, C. Caronna, F. Natali, M. Plazanet and A. Cupane , Eur. Biophys. J. 37,
543, 2008
[3] G. Schirò, A. Cupane, E. Vitrano and F. Bruni, J. Phys. Chem. B, 2009, in press.
Thermosensitive Triblock Copolymers
Anna-Lena Kjøniksen, Kaizheng Zhu, Bo Nyström*
Department of Chemistry, University of Oslo, P.O. Box 1033 Blindern, N-0315 Oslo, Norway.
Aqueous solutions of methoxy-poly(ethylene glycol)-block-poly(N-isopropylamide)-block-poly(4styrenesulfonic
acid sodium), MPEG-b-PNIPAAM-b-PSSS, charged triblock copolymers has been
studied in the presence of different amounts of salt (NaCl). The block copolymer consists of a

hydrophilic MPEG group, a PNIPAAM group, which is thermoresponsive and becomes hydrophobic
at elevated temperatures, and a charged PSSS group. We have studied three different triblock
copolymers where the length of the PINPAAM group is varied while the lengths of the other groups
are kept constant. Turbidity measurements show that only the sample with the longest PNIPAAM
group becomes turbid when the sample is heated, and the turbidity of this sample increases when NaCl
is added to the solution. Dynamic light scattering experiments demonstrate that even though some of
the samples do not become turbid, there are temperature sensitive aggregates formed in the solutions.
The aggregation behavior of the sample with the shortest PNIPAAM block only changes slightly when
the temperature and salt concentration is varied, but as the length of the PNIPAAM chain is increased
the samples becomes much more sensitive to changes in temperature and NaCl concentration.
Salt-Induced Aggregation of Silver Nanoparticles in Aqueous Solutions of Cellulose Derivatives
Loan T. T. Trinh*, Kaizheng Zhu, Anna-Lena Kjøniksen, Bo Nyström
Department of Chemistry, University of Oslo, P.O. Box 1033 Blindern, N-0315 Oslo, Norway.
The effect of the addition of polymers on the salt-induced aggregation of silver suspensions
has been studied. The amount of adsorbed polymer and the thickness of the adsorbed layer is found to
play a decisive role in steric stabilization of the silver suspensions. The effect of polymer
hydrophobicity on the adsorption of the polymer onto the citrate-covered silver surfaces has also been
investigated. DLS has been used to study the effect of adsorbed polymers on the salt-induced
aggregation of silver suspensions. The sample of HM-2-HEC pre-coated silver particles in presence of
salt is incredible stabile, whereas the stabilization of the systems is very poor when either HEC or
HM-1-HEC was adsorbed on the silver particles. This interesting result is probably due to the degree
of hydrophobicity of the hydrophobic moieties which was grafted onto the polymer backbone. To
compliment the finding from the DLS experiments, absorbance measurements by UV-spectroscopy
were executed to gain a better understanding of the effect of adsorbed polymer on the aggregation
process, and how this affects the plasmon resonance peaks.

TRANSPORT PROPERTIES OF MOLECULAR AND IONIC LIQUIDS USING A SCALING
CONCEPT
Thermodynamic scaling and transport properties of molecular and ionic liquids
A.S. Pensado (1,2), M.J.P. Comuñas (1), E.R. López (1), A.A.H. Pádua (2), J. Fernández (1)
(1)Laboratorio de Propiedades Termofísicas, Universidad de Santiago de Compostela, Spain
(2)Thermodynamique et Interactions Moléculaires, FRE3099, Université Blaise Pascal, Clermont-
Ferrand, CNRS, France.
josefa.fernandez@usc.es
Establishing quantitative relations between relaxation phenomena and transport properties, and the
underlying molecular interactions is a key factor towards a fundamental understanding of the dynamic
properties of the liquid state. Roland, Casalini and other authors found that relaxation times and
viscosity can be expressed as a unique function of Tv γ , where T is the temperature, v is the molar
volume and γ a state-independent scaling exponent. A study of the dependence of the scaling
parameter on molecular structure, deduced from high-pressure viscosity data, is presented for different
classes of compounds, represented through a choice of molecules or ions of different sizes and with
diverse dominants in their intermolecular interactions. In addition, a possible generalization of this
thermodynamic scaling to other transport properties, such as electrical conductivity or ion diffusion
coefficients for ionic liquids, is presented. For the electrical conductivity the same scaling parameter
obtained from viscosity values remains valid, whereas the self-diffusion coefficients can also be
expressed in terms of a scaling parameter, but here the values of γ are slightly different from those
obtained from viscosities or relaxation times.
NON-DEBYE EXCESS HEAT CAPACITIES AND BOSON PEAKS ON ALKALI BORATE
GLASSES
Y. Matsuda (1), M. Kawashima (1), K. Kaneda (1), Y. Yamamura (1), S. Yasuzuka (1), K. Saito (1), H.
Kawaji (2),
T. Atake (2) and S. Kojima (1)
(1) Graduate School of Pure and Applied Sciences, Univ. of Tsukuba, Tsukuba, Ibaraki 305-8573,
Japan
(2) Materials and Structures Laboratory, Tokyo Institute of Technology, Midori-ku, Yokohama 226-
8503, Japan
s-matsuda@ims.tsukuba.ac.jp
The low energy excitation in disordered materials is one of the current topics of condensed matter
physics. This excess excitation compared to the Debye model for crystalline counterparts relates to the
anomaly of low-temperature excess heat capacitiy in 5- 10 K, which is generally observed as a bump
in Cp /T 3 , called boson peak. Despite the progress in this field, the origin of the boson peak still
remains an open question. The alkali borate glasses are an attractive system to study since their
physical properties such as stretched exponentiality [1] and fragility [2] drastically vary with the alkali
compositions. In this study, the low temperature heat capacities of binary alkali borate glasses, R2O-
B2O3 (R is alkali metal), with different compositions have been measured and presented in Cp /T 3 . The
Raman spectra [3] have been also measured for comparison. The results for Li2O-B2O3 show that
although the boson peak intensities and temperatures drastically change with lithium composition, the
shapes themselves remain the same for all of the compositions. In the presentation, the compositional
variations of the boson peaks will be discussed on the basis of the microscopic structural changes,
especially the coordination changes of boron atoms.
[1] Y. Matsuda, Y. Fukawa, M. Kawashima, M. Mamiya and S. Kojima, Solid State Ionics, 179 (2008)
2424.
[2] Y. Matsuda, Y. Fukawa, Y. Ike, M. Kodama and S. Kojima, J. Phys. Soc. Jpn, 77 (2008) 084602.
[3] S. Kojima, V. N. Novikov and M. Kodama, J. Chem. Phys., 113 (2000) 6344.

Thermal poling-induced amorphous-to-amorphous transitions in germanate glasses *
G. Guimbretiere, E.I. Kamitsos and D. Palles
Theoretical and Physical Chemistry Institute, National Hellenic Research Foundation, 48 Vassileos
Constantinou Ave., 11635 Athens, Greece
guimbretiere@eie.gr
The tetrahedral germanium sites in v-GeO2 can easily transform into octahedral sites by application of
pressure or by addition of alkali metal oxide (M2O). This structural transition is accompanied by
changes in germanate rings statistic; when pressure is applied to v-GeO2 there is initially an increase in
the population of small rings followed by the creation of higher-coordinated germanate species. M2O
induces similar structural changes including the formation of non-bridging oxygen atoms at high M2O
contents. We report here that thermal poling, i.e. application of a high electrostatic field bellow glass
transition, can also induce amorphous-to-amorphous transitions in germanate glasses. The possibility
to explore amorphous germanates with different concentrations of small rings and higher coordinated
germanate species, than those obtained by pressure or M2O addition, is of interests for understanding
correlations between local structure and macroscopic physical properties in germanate glasses. The
thermal poling-induced polyamorphism in v-GeO2 is discussed on the basis of micro-Raman spectral
measurements.
* Support by EC Grant No. MTKD-CT-2006-042301.
Comparison of Dielectric Relaxation Behavior of Supercooled Polyhydric Alcohols
M. Nakanishi and R. Nozaki
Department of Physics, Faculty of Science, Hokkaido University, Sapporo 060-0810, Japan
nakanishi@dielectrics.sci.hokudai.ac.jp
We report the dielectric relaxation behavior of supercooled polyhydric alcohols. Sugar alcohols are
one of polyhydric alcohols, and consist of a linear backbone chain with OH groups attached to every
carbon atoms. In previous works, a systematic change of the α relaxation process according to the
chain length has been reported [1, 2]. In the case of sugar alcohols, however, the number of carbon
atoms ( Nc ) is always equal to that of OH groups ( NOH ). Therefore we can’t distinguish the difference
of the effect to the α relaxation between Nc and NOH. In order to solve this problem, we examine the
1,2,6-hexanetriol with a broadband dielectric spectroscopy. In this material, Nc is equal to that of
sorbitol and NOH is equal to that of glycerol. Our experimental results show that temperature
dependence of the α relaxation time is similar to that of glycerol rather than sorbitol. This results
suggest NOH is responsible for the α relaxation. On the other hand, the Kirkwood g-factors with regard
to dipole moment of OH group show similar manner for all of the polyhydric alcohols examined here.
This result suggests that the structure of hydrogen bonding network of polyhydric alcohols is
essentially the same, and this feature is considered to be one of the origin of the systematic nature.
[1] A. Döß, M. Paluch, H. Sillescu, and G. Hinze, Phys. Rev. Lett., 88, 095701, 2002
[2] A. Minoguchi, K. Kitai, and R. Nozaki, Phys. Rev. E, 68, 031501, 2003
DISENTANGLING THE β-RELAXATION IN THE BYNARY SYSTEM CYCLOHEPTANOL-
CYCLOOCTANOL
J. C. Martinez-Garcia (1), J.Ll.Tamarit (1), L.C. Pardo (1), M. Barrio(1) and N. Veglio(1)
(1) Grup de Caracterització de Materials, ETSEIB, Department of Physics and Nuclear Engineering,
Diagonal 647,

08028 Barcelona, Universitat Politècnica de Catalunya, Barcelona, Spain
Correspondence author: jose.luis.tamarit@upc.edu
The low-molecular weight cyclic alcohols, such CnH2n-1OH, n=5,6,7,8 are pseudoglobular molecules
showing orientationally disordered (OD) phases that, by fast cooling, can give rise to orientational
glasses (OG). In addition, such molecules display ring molecular puckered conformations, the number
of which increases with the number of carbons involved in the ring, as well as axial and equatorial
conformations of the polar OH group [1,2]. Broadband dielectric spectroscopy (BDS) studies for both
cycloheptanol (C7) and cyclooctanol (C8) compounds have revealed the existence of β- and γrelaxation,
in addition to the ubiquitous α-relaxation associated to the intrinsic orientational disorder.
The OD simple cubic mixed crystals formed between C7 and C8 were characterized as OG formers for
the whole concentration range [3]. A recent BDS study on several mixtures seems to reveal the lack of
the β-relaxation for the mixed crystals [4], which would indicate the suppression of the ring
conformations for the OD mixed crystals. In this work, new low-temperature BDS experiments have
been done in order to demonstrate that in fact β-relaxation is still there, but the overlapping with the αrelaxation
makes it difficult to disentangle and a deep data analysis is required.
[1] R. Brand, P. Lunkenheimer, A. Loidl, J. Chem. Phys. 116 (2002) 10386.
[2] D. L. Leslye-Pelecky and N. O. Birge, Phys. Rev. Lett 72 (1994) 1232.
[3] M. A. Rute, J. Salud, P. Negrier, D. O. Lopez, J. Ll. Tamarit, R. Puertas, M. Barrio, D. Mondieig, J.
Phys. Chem. B 107 (2003) 5914.
[4] L. P. Singh and S. S. N. Murthy, J. Phys. Chem. B 112 (2008) 2606.
The coupling between hydration-water and protein dynamics
as assessed by neutron scattering
and perdeuteration of a globular, an intrinsically unfolded and a membrane protein
K. Wood 1, 2 , F.-X. Gallat 1, 2 , D. Tobias 3 , G. Zaccai 2 , M. Weik 1
1. Institut de Biologie Structurale CEA-CNRS-UJF, 41 rue Jules Horowitz, 38027 Grenoble Cedex 1,
France
2. Institut Laue-Langevin, 6 rue Jules Horowitz, B.P. 156, 38042 Grenoble Cedex 9, France
3. Department of Chemistry, University of California, Irvine, California, USA
The thin film of water around proteins, their hydration water, is vital to the macromolecule’s
biological activity. Without hydration water, proteins would not only be incorrectly folded but also
lack the conformational flexibility that animates their 3D structures and brings them to life.
Consequently, protein dynamics is thought to be slaved to hydration-water dynamics. One way of
exploring the coupling exploits so-called dynamical transitions, characteristic changes in atomic
fluctuations that appear in both water and proteins at certain cryo-temperatures. Do both dynamical
transition temperatures coincide? In other words, does a transition in the water trigger one in the
protein at the same temperature? If the coupling is indeed tight, one would assume so. We combined
incoherent neutron scattering experiments and MD simulations on a soluble protein and on a
biological membrane to gain insight into the dynamical coupling between protein and hydration-water
dynamical transitions. The experimental trick played to directly access the water transition was

perdeuteration of the protein, which almost completely masked the protein’s contribution to the
neutron scattering signal. In the case of the soluble maltose-binding protein (MBP), a hydration-water
transition was observed at 220 K, coinciding with the dynamical transition of the protein [1]. The latter
was measured on a hydrogenated MBP sample hydrated in D2O. MD simulations reproduced the
coincidence of transitions and revealed that both originate from the onset of translational diffusion of
water molecules at the protein’s surface. The combination of neutron scattering, perdeuteration and
MD simulations, carried out on the same protein, paints a coherent picture in which the dynamics of
soluble proteins and their hydration-water are strongly coupled. The observation is in sharp contrast
with the case of the purple membrane (PM), a biological membrane composed of the protein
bacteriorhodopsin (BR) and several lipid species. The hydration-water transition and the membrane
transition appeared at temperatures that differ by 50 K [2], suggesting that the dynamics of membrane
proteins is controlled by their lipid environment, rather than by the membrane hydration water.
Preliminary experiments on the intrinsically unfolded protein tau suggest that protein flexibility is
increased with respect to globular and membrane proteins.
[1] Wood, K., Frolich, A., Paciaroni, A., Moulin, M., Hartlein, M., Zaccai, G., Tobias, D. J. & Weik,
M., J Am Chem Soc 130, 4586 (2008).
[2] Wood, K., Plazanet, M., Gabel, F., Kessler, B., Oesterhelt, D., Tobias, D. J., Zaccai, G. & Weik,
M., Proc Natl Acad Sci U S A. 104, 18049 (2007).
AGING OF THE JOHARI-GOLDSTEIN BETA RELAXATION IN SORBITOL AND
XYLITOL
Robert Leheny (1)
(1) Dept. of Physics & Astronomy, Johns Hopkins University, 3400 N. Charles St.Baltimore, MD
21218, USA
*leheny@pha.jhu.edu
We present dielectric susceptibility studies of the Johari-Goldstein beta relaxations in the molecular
glassformers sorbitol and xylitol following quenches through the glass transition. For both liquids, the
magnitude of the relaxation displays a dependence on the time since the quench, or aging time, that is
quantitatively very similar to the age dependence of the alpha peak frequency; however, the Johari-
Goldstein relaxation time remains essentially constant during aging. Hence, one cannot sensibly assign
a fictive temperature to the Johari- Goldstein relaxation. This behavior contrasts with that of liquids
lacking distinct Johari-Goldstein peaks for which the excess wing of the alpha peak tracks the main
part of the peak during aging in a way that enables the assignment of a single fictive temperature to the
entire spectrum. We will discuss the consequences of this observation for microscopic pictures of the
Johari-Goldstein relaxation and the excess wing and further will discuss the potential utility of the
aging behavior as a criterion for categorizing Johari-Goldstein relaxations.
RELAXATION IN SILICATES MELTS: A BRILLOUIN SCATTERING STUDY UP TO 2630 K
P. Richet (1), Y.Bottinga (1), D. Vo-Thanh (1) and A. Polian (2)
(1) Physique des Minéraux et des Magmas, Institut de Physique du Globe de Paris,
4 place Jussieu, 75005 Paris, France
(2) Physique des Milieux Condensés, Université Pierre et Marie Curie, Campus Boucicaut,

Bâtiment 15, 140 rue de Lourmel, 75015 Paris
The compressibility of liquids owes it great theoretical importance to the fact that it directly reflects
the interplay of interatomic forces at work under pressure. For silicate melts, the compressibility it also
of great practical interest as physical and thermodynamic properties of magmas should be known up to
pressures of tens of GPa. Even at room pressure, however, determination of silicate melt
compressibilities is made difficult not only by the high temperatures to be considered, but also by
structural relaxation that results in frequency dependent properties. But relaxation represents in itself
another useful of information since it is of course related to the temperature- and pressure-induced
structural changes that take place in the melt.
Liquids of the system CaO-MgO-Al2O3-SiO2 have great industrial and geological importance. Hence,
they represent valuable model systems to investigate, through compressibility determinations, the
connection between dynamical and physical properties of glass-forming melts. In this study, we will
first present Brillouin scattering experiments on 10 compositions up to 2630 K, at GHz frequencies,
and compare the results obtained with literature ultrasonic measurements made at MHz frequencies on
the same melts. We will then discuss these results in terms of melt structure, which is rather well
known, and of thermodynamic properties, which have also been extensively investigated. Particular
attention will be paid to the role of Al coordination changes and to correlations between the properties
of glasses, at low temperatures, and those of melts above the glass transition.
Confinement effect in SiO2/AgI nanostructured composites
A. Pradel*, P. Yot, S. Albert, N. Frolet, M. Ribes
Institut Charles Gerhardt Montpellier, UMR 5253 CNRS-UM2-ENSCM-UM1, Equipe Physicochimie
des Matériaux Désordonnés et Poreux (PMDP), CC 1503, Université Montpellier 2, Place E. Bataillon,
34095 Montpellier Cedex 5, France
Some thirty years ago, it was shown for the first time that the conductivity of an ionic conductor could
be greatly improved by several orders of magnitude when it was associated with an insulating phase.
About thirty five years ago, C.C. Liang reported that composites made of LiI and Al2O3 have higher
ionic conductivity than that of pure LiI by two orders of magnitude [1]. More recently, it was shown
that the increase in conductivity was even larger when the insulating phase was a mesoporous material.
Strong dependence between the conductivity, the size of the pores and the quantity of conductor in the
composites was reported [2].
* apradel@lpmc.univ-montp2.fr

With the aim to study such a phenomenon, an investigation of SiO2/AgI composites was carried out.
The chosen SiO2 matrix was a commercial nanoporous glass from Corning (Vycor® 7930). The
composites were obtained by insertion of the conductive phase, i.e. AgI, by electrocrystallisation or
after thermal treatment and sintering. A new, very performing sintering technique, i.e. the Spark
Plasma Sintering-SPS, was tested.
The conductivity of the composites was measured by impedance spectroscopy. Several other
techniques such as X-ray diffraction, scanning electron microscopy coupled with energy dispersive
spectroscopy, Hg intrusion were also used to correlate the variation in conductivity with
microstructure and synthesis conditions.
While no increase in conductivity due to the mixing effect could be observed in these composites,
another interesting phenomenon was observed i.e. a hysteresis phenomenon with temperature for the
transition from β-AgI to α-AgI. The strongest effect was observed for the composite prepared by
electrocrystallisation. In this case, the phase transition appeared at about 405 K while the phase
transition α↔β AgI occurs at 420 K. Upon cooling the transition was observed at even lower
temperature (≈ 360 K).
Keywords: nanostructured composites, glass, ion conductor, structure, conductivity
UNIVERSALITY OF THE MIXED GLASS FORMER EFFECT?
THE EXAMPLE OF CHALCOGENIDE GLASSES
Annie Pradel* and Michel Ribes
Institut Charles Gerhardt Montpellier, UMR 5253 CNRS-UM2-ENSCM-UM1, Equipe Physicochimie
des Matériaux Désordonnés et Poreux (PMDP), CC 1503, Université Montpellier 2, Place E. Bataillon,
34095 Montpellier Cedex 5, France.
*annie.pradel@univ-montp2.fr
At the opposite of the famous mixed alkali effect (MAE) which corresponds to a decrease in
conductivity when an alkali ion is replaced by another one, the total amount of alkali being constant,
the “mixed glass former effect” (MGFE) corresponds to an increase in conductivity. In this case, the
network former is replaced by another, the total modifier content being constant. This effect was first
observed in borophosphate glasses and related to the appearance of BPO4 entities [1].
In order to investigate the phenomenon and check whether it was as universal as the MAE is, four
families of chalcogenide glasses were investigated. Three of them correspond to compositions where a
classical MGFE could be expected i.e. xLi2S-(1-x)[(1-y)SiS2-yGeS2], x = 0.3, 0.5 [2-4] and 0 < y < 1;
0.5Li2S-0.5[(1-y)SiS2-yAl2S3], 0 < y < 0.5 [5]; 0.5Na2S-xSnS2-(1-x)GeS2, 0

[2] V. K. Deshpande et al., Materials Research Bulletin, 23 (1988) 379-384.
[3] A. Pradel et al., Chemistry of Materials, 10 (1998) 2162-2166.
[4] A. Pradel et al., Journal of Physics: Condensed Matter, 15 (2003) S1561-S1571.
[5] V. K. Deshpande et al., Solid State Ionics, 28 (1988) 756-761.
[6] B. Barrau, Thesis Université Science et Technique du Languedoc 1983.
[7] B. Carette et al., Solid State Ionics, 9/10 (1983) 735-738.
ABSTRACT
Influence of Conversion and Crosslinking on the Tg Depression in Nanopores
Sindee L. Simon
Department of Chemical Engineering
Texas Tech University
Lubbock, TX 79409-3121
The effects of nanoconfinement on the glass transition phenomena of polymeric and low
molecular weight glass forming materials have been extensively investigated in the literature, and the
glass transition temperature (Tg) is generally depressed relative to the bulk unless strong interactions at
an interface are present. On the other hand, the Tg depression of materials synthesized under
nanoconfinement has not been well studied, nor has the influence of conversion and crosslinking been
characterized. To this end, we examine the trimerization reaction of monofunctional and difunctional
cyanate esters in nanopores to form a low molecular cyanurate and a crosslinked polycyanurate,
respectively. For the monofunctional reactant, there is no possibility for the intracyclization side
reactions that can occur in the difunctional system.
Using differential scanning calorimetry (DSC), we find a Tg depresssion for both of the
reactants and their products; the magnitude of the depression increases with increasing conversion and
with increasing crosslink density and, in this system, seems to be related to the size of the molecule
being confined relative to the confinement size. In addition to the Tg depression, the trimerization
reaction is accelerated relative to the bulk when the reactants are confined in nanopores. The origin
of the reactivity enhancement is not due to an increase in the intracyclization reaction since this

eaction cannot occur for the monofunctional reactant. Rather, we hypothesize that the enhanced
reactivity arises from an enhancement in collision efficiency due to the proximity of the surface.
DIRECT MEASUREMENT OF ENHANCED MOLECULAR MOBILITY DURING THE
ACTIVE DEFORMATION OF POLYMER GLASSES.
M.D. Ediger (1), Hau-Nan Lee (1), R. A. Riggleman (2), and J. J. de Pablo (2)
(1) Department of Chemistry, University of Wisconsin-Madison, Madison, WI 53706 USA
(2) Department of Chemical and Biological Engineering, University of Wisconsin-Madison, Madison,
WI 53706 USA
ediger@chem.wisc.edu
We use an optical photobleaching technique to quantitatively measure changes in molecular mobility
during the active deformation of polymer glasses. For PMMA, segmental mobility increases by up to
a factor of 1000 during uni-axial tensile creep. While the Eyring model can describe the increase in
mobility at low stress, it fails to describe mobility after flow onset. In this regime, mobility is strongly
accelerated and the distribution of relaxation times narrows significantly, indicating a more
homogeneous ensemble of local environments. At even larger stresses, in the strain-hardening regime,
mobility decreases with increasing stress. Consistent with the view that stress-induced mobility allows
plastic flow in polymer glasses, we observe a strong correlation between strain rate and segmental
mobility during single-step creep; more complicated deformations break this correlation. Coarsegrained
molecular dynamics simulations reproduce all the qualitative features of the experimental
measurements. The simulations reveal that “enhanced mobility” is a conceptually reasonable
description of the behaviour observed in simulation and experiments.
DIELECTRIC AND NEUTRON SPECTROSCOPY ON LIQUID CRYSTALS CONFINED TO
NANOPORES
L: Frunza (1), S. Frunza (1), B. Frick (2), R. Zorn (3) and A. Schoenhals (4)
(1) National Institute of Material Physics, R-077125 Magurele, Romania
(2) Institut Laue-Langevin (ILL), BP 156, F-38042 Grenoble Cedex 9, France
(3) Forschungszentrum Jülich, IFF, D-52425 Jülich, Germany
(4) BAM Federal Institute for Materials Research and Testing, D-12205 Berlin, Germany
Andreas.Schoenhals@BAM.de
The liquid crystals (LC) E7 and 8CB were studied in the confinement by nanopores of the molecular
sieve Al-MCM-41 (Si/Al=60) with a mean pore diameter of 3 nm. Dielectric spectroscopy shows that
for the confined systems one relaxation process is observed. Its characteristic relaxation time is much
lower compared to that of the bulk. No signature of the phase transition characteristics of the bulk LC
is detected. The temperature dependence of the relaxation time of this relaxation process shows
similarities to glassy dynamics. Moreover excess contributions to the vibrational densities of state (the
‘boson peak’ which is a characteristic feature of glassy behavior) were found by inelastic neutron
scattering (INS) using the time-of-flight (TOF) spectrometer IN6 at the ILL. For the confined systems
the contribution to the Boson-Peak is reduced at low frequencies as it is also found for confined
conventional glass forming systems. In addition elastic scans were carried out at the backscattering
spectrometer (BS) IN10 at ILL. Also these measurements show the signature of a glass transition.
Broadband INS was carried out by combining TOF (IN6, ILL) and BS (IN10, ILL; SPHERES, JCNS).
The obtained data are compared in detail with the dielectric results.

DENSITY CHANGES RESULTING FROM CRYSTALLIZATION OF METALLIC GLASSES
C.V. Thompson (1,3), Y. Li (2,3) Q. Guo(3) , and J. A. Kalb (1,4)
(1) Department of Materials Science and Engineering, Massachusetts Institute of Technology (MIT),
Cambridge, Massachusetts 02139, USA.
(2)
Department of Materials Science and Engineering, National University of Singapore, 7 Engineering
Drive 1, Singapore 117576.
(3)
Singapore-MIT Alliance, 4 Engineering Drive 3, Singapore 117576.
(4) Present address: Intel Corporation, Santa Clara, CA 95054, USA
cthomp@mit.edu
We have made systematic deflection measurements using arrays of micro-cantilevers to determine the
density change resulting from crystallization for a range of Cu-Zr thin film alloy compositions created
using a combinatorial-deposition method [1]. This experimental approach allows separate
measurements for many compositions, allowing property determination with high compositional
resolution. We find a clear correlation between glass-forming ability and the density change upon
crystallization. Three distinct peaks in the density change were found to correlate with specific
maxima in the critical thickness for glass formation. The implications of these results in terms of
suppression of crystal nucleation and the structure of the amorphous phases will be discussed.
[1] Y. Li, Q. Guo, J.A. Kalb, and C.V. Thompson, Science 322 (2008) 1816.
MAGNETICALLY TUNABLE ELECTRIC RELAXATIONS AND DYNAMICALLY
ENHANCED MAGNETODIELECTRIC EFFECT IN La-DOPED BiMnO3
Y. H. Jeong
Department of Physics, Pohang Univ. of Science and Technology, Pohang 790-784, Korea
yhj@postech.ac.kr
Multiferroic materials, where ferroelectricity and magnetism coexist, have been actively studied. This
class of materials would offer a large application potential for new devices taking advantage of two
coupled degrees of freedom based on local off-centered distortion and electron spin. Although most
often the magnetic state in coexistence with ferroelectricity is antiferromagnetic, BiMnO3 is an
interesting exception with the simultaneous existence of ferromagnetism and ferroelectricity. However,
the transition temperatures are in great disparity with TFE = 770 K and TFM = 105 K, and consequently
its ME coupling is not large. We propose that disorder be used as a means for inducing an overlap of
the magnetic and electric phase transitions in multiferroic materials and thus enhancing the interproperty
coupling.
In order to implement the idea BiMnO3 is modified with disorder via La doping. 20% Ladoped
BiMnO3(BLMO) in thin film form remains in a ferromagnetic phase below 100 K, but displays
a disorder-broadened ferroelectric transition below 150 K overlapping with the magnetic one. The
electric polarization reaches 12 µC/cm 2 , nearly 200 times the BiMnO3 value, at low temperatures. This
new magnetic ferroelectrics shows an immensely enhanced magnetodielectric effect in the transition
region with maximum 45% at 9 T, which is more than a 70-fold increase from the maximum value of
the pure compound. In addition, BLMO shows similar dielectric relaxation behaviors as found in
many relaxor ferroelectrics. What is most distinct for this system is that the electric relaxation
characteristics are tunable with a magnetic field. It is demonstrated that the magnetodielectric effect is
dynamically enhanced due to this novel phenomenon of magnetic field controlled electric relaxations.
THERMODYNAMIC PROPERTIES OF SPIN LIQUID STATES AND SPIN GLASS
STATES IN MOLECULAR COMPOUNDS
Y. Nakazawa , S. Yamashita and T. Yamamoto

Deparatment of Chemistry, Graduate School of Science, Osaka University, Machikaneyama 1-1,
Toyonaka, Osaka 560-0043, JAPAN
nakazawa@chem.sci.osaka-u.ac.jp
In the case of a planer antiferromagnetic triangular lattice consisting of S=1/2 spins, the geometric
frustration prohibits the formation of ordering and therefore a liquid-like ground state is expected [1].
By our single crystal relaxation calorimetry measurements for dimer-based organic charge transfer
salts of κ-(BEDT-TTF)2Cu2(CN)3 and EtMe3Sb[Pd(dmit)2]2 down to the dilution temperatures, a Tlinear
heat capacity similar to thoses of metallic systems was clearly observed. The electronic heat
capacity coefficient (γ) was found to be about 15-20 mJK -2 mol -1 . The degeneration of energy states
given by a frustrated quantum spins give a gap-less excitations from the ground state like a Fermi
liquid state in usual metals [2]. The present thermodynamic result seems to be consistent with the
Fermionic excitation as was suggested by the RVB like senario. We also studied the thermodynamic
properties of a two-dimensional networked system of large anisotropic spins in metal complex systems.
The coexistence of Ising-like nature of spin in a complex, frustration in spin arrangements, and large
activation energy for spin-reversing process give an interesting freezing behavior in spin correlations
at low-temperatures region [3]. The details of thermodynamic data obtained by the relaxation method
are discussed.
[1] P.W. Anderson, Mater. Res. Bull. 8, 153 , 1973
[2] S. Yamashita et. al., Nature Physics, 4, 459, 2008
[3] S. Yamashita et al. J. Phys.Soc. Jpn 77, 073708, 2008
LOCALIZED RELAXATION IN A GLASS, DIELECTRIC RELAXATION STRENGTH AND
ITS MIMICRY WITH GLASS-SOFTENING THERMODYNAMICS
J. K. Vij (1), G. Power(1) and G. P. Johari (2)
(1) Trinity College University of Dublin, Dublin 2, IrelandInstitute Laue-Langevin, BP 156, F-38042
Grenoble Cedex 9, France
(2) McMaster University, Hamilton, Ontario, Canada
jvij@tcd.ie
The dielectric permittivity and loss spectra of the glassy state of 5-methyl-2-hexanol obtained by
quenching it from the liquid state has been studied. In one experiment, the spectra were studied at
different temperatures as the quenched sample was heated at 0.1 K/min from 105.3 to 160.5 K. In the
second experiment, the quenched sample was heated from 77 to 131.6 K and kept at that temperature
for 14.6 ks. The relaxation rate, fm,β the dielectric relaxation strength, ∆εβ, and the distribution of
relaxation time parameters, α and β for the Johari–Goldstein process were determined. ∆εβ initially
decreased on increasing the temperature, reached aminimum value at ~145.6 K, and then increased.
The plot of fm,β against the reciprocal temperature decreased in slope and at ~140 K became linear. We
find that fm,β increases on structural relaxation. In the course of the annealing at 131.6 K, ∆εβ of the
quenched sample decreased with time, approaching a plateau value. It is described by an equation,
∆εβ(t) = ∆εβ(t→∞) + [∆εβ(t = 0) – ∆εβ(t→∞)] exp[–(t/τ)], where t is the time, and (τ=3.5 ks) is the
characteristic time. A consideration of dielectric permittivity arising from small-angle motions of all
molecules, which has been suggested as an alternative mechanism for the localized motions seen as β
relaxation, indicates that this mechanism is inconsistent with the known increase in the equilibrium
permittivity on cooling. We also show a correspondence in the plot of ∆εβ against temperature with
those of H, S and V of a glass spontaneously relaxing at T < Tg.

The role of heat capacity in arguments for a new glassformer paradigm.
C. Austen Angell,
Dept. of Chemistry and Biochemistry,
Arizona State University, Tempe, AZ 85287-1604
Heat capacity measurements can provide a powerful probe of both energetic and kinetic processes in
condensed matter systems 1 , and with the right expertise can be made with great precision. In this
contribution we use heat capacity measurements provided by different practitioners of the laboratory
art 1, 2 3 (aided by computer simulation studies (that provide data at temperatures where all known
calorimeters would be vaporized 4 ) to lay out a pattern of heat capacity behavior for glassformers that
is a challenge to theory 5 . At one end of the temperature range, focused on strong liquids of the familiar
silica type, we find heat “excess” capacity behavior reminiscent of (but smeared from) the lambda
transition in metallic alloys 6 , and C-60 7 , where glass-like transitions are also found, and where the
disordering kinetics above Tg also exhibit Arrhenius behavior until the disordering is complete. The
peak heat capacity is associated with the fragile-to-strong transition for these liquids 8 . In the middle
we find systems with liquid-liquid transitions which usually crystallize 3, 9 , and at the other end we find
the familiar fragile molecular glassformers where the heat capacity behavior looks more like the
mirror image of a lambda transition except that the sudden decrease (now at the low temperature
extreme) is entirely kinetic in character (viz. the glass transition). However, in this case the only
theoretical model that can fully describe the form of excess heat capacity 10 , requires that the ordering
process be terminated by a first order transition to the glassy state at a temperature somewhat below
Tg. Accordingly the process would not normally be observable. An unexpected route to a new low
entropy glass state, which may be related to the hidden phase, has recently been discovered by the
Ediger group 11 . This phenomenology and its significance, form the subject of another symposium at
this meeting.
References
1. Atake, T., J. Chem. Thermodynamics 2009, 41, 1-10.
2. Yamamuro, O.; Takahara, S.; Inaba, A.; Matsuo, T.; Suga, H., J. Phys. Cond. Matt. 1994, 6,
L169-L172.
3. Mizukami, M. Hanaya, M. Oguni, M., J. Phys. Chem. B 1999, 103, 4078-4088.
4. Scheidler, P.; Kob, W.; Latz, A. Horbach, J.; Binder, K., Phys. Rev. B 2005, 63, 104204.
5. Angell, C. A., Journal of Non-Crystalline Solids 2008, 354, 4703-4712
6. Gschwend, K.; Sato, H.; Kikuchi, R.; Iwasaki, H.; Maniwa, H., J. Chem. Phys. 1979, 71, 2844-2852.
7. Atake, T.; Tanaka, T.; Kawaji, H. Chemical Physics Lett. 1992, 196, 321-324.
8. Saika-Voivod, I.; Poole, P. H.; Sciortino, F.,. Nature 2001, 412, (6846), 514-517.
9. Angell, C. A., Science 2008, 319, 582-587.
10. Matyushov, D. V.; Angell, C. A., T. Journal of Chemical Physics 2005, 123, (3), -.
11. Swallen, S. F.; Kearns, K. L.; Mapes, M. K.; Kim, Y. S.; McMahon, R. J.; Wu, T.; Yu, L.; Ediger,
M. D., Science 2007, 315, 354-356.
Diffusion and relaxation in a monohydroxy alcohol
R. Gainaru (1), C. Gainaru (1), S. Schildmann (1), R. Böhmer (1)
(1) Experimentelle Physik III, T.U. Dortmund, 44227 Dortmund, Germany
catalin.gainaru@uni-dortmund.de
Viscous monohydroxy alcohols, also water, exhibit in their dielectric spectra the so called Debye
process [1]. This relaxational feature corresponds to degrees of freedom which are about 100 times
slower than those giving rise to the structural rearrangements (α-process). In spite of numerous
experimental investigations, the nature of these slow “superstructure” relaxation modes is not agreed

upon, although it is clear that they are to be related with the presence of hydrogen bonds. In particular,
the research in this field needs to address whether the aliphatic protons and those participating in an Hbond
network can be distinguished, for instance on the basis of their structural and dynamical
properties.
As a step in this direction we performed field-gradient diffusion NMR experiments on 2-ethyl-1hexanol.
The diffusion coefficients, obtained for a range of temperatures, are discussed together with
those obtained from broad-band dielectric spectroscopy. In addition, spin-lattice relaxation times were
measured to check if this dielectrically strongly active Debye process carries also a specific NMR
signature.
[1] L-M. Wang, R. Richert, J. Chem. Phys., 121, 11170, 2004
A DIELECTRIC STUDY OF THE OLIGOMER-TO-POLYMER TRANSITION IN
PROPYLENE GLYCOL CHAINS
C. Gainaru (1), R. Böhmer (1)
(1) Fakultät für Physik, TU Dortmund, 44221 Dortmund, Germany
The polymer dynamics sets in at times longer than those characterizing the structural rearrangements
and the delay between the α-process (monomer dynamics) and the slowest relaxation mode (the
reorientation of the overall chain) increases with the chain length. For long, but non-entangled chains,
the thoroughly investigated polymer dynamics is well described by the Rouse theory [1]. However,
there is only little information regarding the dynamics of short chains [2,3]. Using dielectric
spectroscopy we present the evolution of the dielectric response including both the α- and the polymer
dynamics when the molecular size of polypropylene glycol (PPG) is systematically changed from one
to a few hundred monomers. For PPG, as for some other polymers, a large dipole moment is formed
along their chain by the superposition of the individual monomeric contributions. This end-to-end
dipole moment provides a strong coupling to the electric field, making the dielectric technique best
suited for the investigation of the overall chain dynamics. We discuss the influence of the molecular
size upon the local dynamics (α-process) and upon the strength and time scale of the chain’s dielectric
response.
[1] P.E. Rouse, J. Chem. Phys., 21, 1272, 1953
[2] S. Kariyo, C. Gainaru, H. Schick, A. Brodin, V.N Novikov and E.A. Rössler, Phys. Rev. Lett., 97,
207803, 2006
[3] Y. Ding, A. Kisliuk and A.P. Sokolov, Macromolecules, 37, 161, 2004
A `GRANOCENTRIC’ VIEW OF RANDOM PACKING: EXPERIMENTS AND THEORY
Maxime Clusel, Eric. I. Corwin, Alexander J. Siemens and Jasna Brujic
New York University, Center for Soft Matter Research, Department of Physics,
4 Washington Place, New York NY 10003, USA
jb2929@nyu.edu
Packing problems are everywhere, ranging from oil extraction through porous rocks to grain storage in
silos and the compaction of pharmaceutical powders into tablets. At a given density, particulate
systems pack into a mechanically stable and amorphous jammed state. Theoretical frameworks have
explored a connection between this jammed state and the
glass transition, a thermodynamics of jamming, as well as geometric modeling of random packings.
Nevertheless, a simple underlying mechanism for the random assembly of athermal particles,
analogous to crystalline ordering, remains unknown. Here we use three-dimensional measurements of
polydisperse packings of emulsion droplets to build a simple statistical model in which the complexity
of the global packing is distilled into a local stochastic process [1]. From the perspective of a single
particle the packing problem is reduced to the random formation of nearest neighbours, followed by a

choice of contacts among them. The two key parameters in the model, the available space around a
particle and the ratio of
contacts to neighbours, are directly obtained from experiments. Remarkably, we demonstrate that this
“granocentric” view captures the properties of the polydisperse emulsion packing, ranging from the
microscopic distributions of nearest neighbours and contacts to local density fluctuations and all the
way to the global packing density. Further applications to monodisperse and bidisperse systems
quantitatively agree with previously measured trends in global density. This model therefore reveals a
general principle of organization for random packing and lays the foundations for a theory of jammed
matter.
[1] M. Clusel, E. I. Corwin, A. Siemens, J. Brujic, Nature, xx, yyyy, 2009 (June)
A COMPARATIVE ASSESSMENT OF COMMONLY-USED CALORIMETRIC
METHODOLOGIES TO ASSESS STRUCTURAL RELAXATION TIMES OF AMORPHOUS
PHARMACEUTICAL SOLIDS – APPROACHES BASED ON CONFIGURATIONAL
ENTROPY, ENTHALPY RECOVERY, AND ENTHALPY RELAXATION
D.P. Miller
Novartis Pharmaceuticals Corporation, 150 Industrial Road, San Carlos, CA 94070, USA
dan.miller@novartis.com
Over the last 20 years, the assessment of characteristic relaxation times of amorphous solids has
become more commonplace in the pharmaceutical industry. Though several analytical tools are
available to measure relaxation phenomena (e.g., dielectric spectroscopy, thermally stimulated current,
dilatometry), calorimetric methodologies are the most widely used approaches, likely due to the
widespread availability of differential scanning calorimeters in modern physical characterization
laboratories. Calorimetric methodologies can be categorized under three main approaches – those
based on configurational entropy, enthalpy recovery, and enthalpy relaxation. Work in our and other
laboratories has indicated significant differences in the relaxation times determined using the enthalpy-
and entropy-based approaches. With the intent of improving our understanding of the origin of these
differences, this work will involve a comparison of these approaches, using as model systems several
amorphous pharmaceutical solids that would be expected to differ in their extent of hydrogen bonding,
glass transition behavior, molecular weight, and other physicochemical properties.
Characterization of Amorphous Ice Structures via Transformation Processes
H. Schober (1), M.M. Koza (1), and M. Müller (2)
(1) Institut Laue Langevin, 6 Rue Jules Horowitz, F-38042 GRENOBLE, France
(2) GKSS Forschungszentrum Geesthacht GmbH, Max-Planck-Straße 1, 21502 Geesthacht, Germany
schober@ill.fr
The phenomenon of amorphous polymorphism, i.e. the existence of more than one amorphous
structure in a single substance, is closely related to amorphous solid water. We have tried to establish
by the application of diffraction, small angle scattering techniques and inelastic spectroscopy

systematic dependences of the amorphous ice properties upon the thermodynamic conditions at which
they are formed. Furthermore, we have performed extensive time resolved measurements following
the transformation kinetics of vHDA, HDA and other high—density amorphous structures into LDA.
These studies were performed at 0 GPa at different T in the range of 80 K to 30 K. Our results
indicate that the manifold of amorphous ice structures is due to a complex kinetics of their
preparation process [1]. All amorphous structures of intermediate density in respect to LDA and
vHDA revealed to be of heterogeneous character at a spatial scale of some nanometers. There is a
characteristic and systematic dependence of the kinetic properties on the formation conditions of the
amorphous structures. Indeed, only vHDA and LDA are rather homogeneous structures.
I will equally present some results obtained for water in cellulose. The recorded elastic and inelastic
signals indicate the gradual dynamic arrest of the water over a large temperature interval into an
amorphous form reminiscent of LDA. This result is interesting in the context of discussions revolving
around the dynamic cross-over in glassy systems.
[1] M.M.Koza et al., J.Phys. :Cond.Matter 15, 321, (2003); Phys.Rev.Lett. 94, 12556, (2005); J.Non-
Cryst.Solids 352, 4988, (2006); J.Appl.Cryst. 40, s517, (2007)
Diffusion Anomalies and Arrested Dynamics for Hydration Water
FRANCISCO DE LOS SANTOS (University of Granada)
We present a simple Hamiltonian model that reproduces the basic properties
of liquid water and that, by parameters tuning, reproduces various of the
scenarios that have been proposed to rationalized water anomalies. By means of
extensive Monte Carlo simulations, we show results on the ordering of the hydrogen
bonds and the diffusion coefficient over a significant region of the phase
diagram. We discuss the possible relation of the diffusion anomaly to the
existence of a liquid-liquid critical point at low temperatures and some
nonequilibrium phenomena at low temperatures, possibly related to the appearence
of a density minimum.
ANALYSIS OF THE STABILITY OF VAPOR DEPOSITED THIN FILM ORGANIC
GLASSES: CASE OF TOLUENE
J. Rodriguez-Viejo (1,2), E. Leon-Gutierrez (1), G.Garcia (1), M.T. Clavaguera-Mora (1)
(1) Group of Nanomaterials and Microsystems. Department of Physics, Unversitat Autònoma de
Barcelona, Bellaterra 08193, Spain
(2) MATGAS Research Centre, Campus UAB, Bellaterra 08193, Spain
javirod@vega.uab.es

Contrary to previous thinking it has been recently shown that bulk samples of organic glasses grown
by vapor deposition at temperatures around 0.85 Tg exhibit an extremely high thermodynamic and
kinetic stability, which is manifested in a lower fictive temperature and a higher onset temperature of
the overshoot of the heat capacity, compared to glasses conventionally cooled from the liquid [1,2].
We have recently developed a new experimental setup [3] that allows for in-situ heat capacity
measurements of a variety of organic glassy thin films grown directly from the vapor phase at
temperatures above 77 K. The measurement device installed inside an ultrahigh vacuum chamber
consists of a pair of identical membrane-based nanocalorimeters with embedded heater/sensors to
impose predefined temperature variations. We use the quasi-adiabatic differential method developed
by Allen et al. [4] that permits a direct measure of the heat capacity of the thin films as a function of
the temperature at heating rates of the order of 10 4 -10 5 K/s. In this presentation we will discuss on the
influence of different parameters such as deposition temperature, growth rate and film thickness, on
the stability of vapor deposited toluene glasses. We will stress the importance of the free surface on
the properties of the thinnest films.
[1] S. F. Swallen, K. L. Kearns, M. K. Mapes, Y. S. Kim, R. J. McMahon, M. D.Ediger, T. Wu, L. Yu,
S. Satija, Science 315, 353-356 2007.
[2] K. Ishii, H. Nakayama, S. Hirabayashi, R. Moriyamaet, Chem. Phys. Lett. 459, 109–112, 2008.
[3] E. Leon-Gutierrez, G. Garcia, A. F. Lopeandia, J. Fraxedas, M. T. Clavaguera-Mora, J. Rodriguez-
Viejo, J. Chem. Phys. 129, 181101, 2008.
[4] M. Y. Efremov, E. A. Olson, M. Zhang, Z. Zhang, L. H. Allen, Phys. Rev. Lett. 91, 085703, 2003.
Modeling the configurational entropy of supercooled liquids
Dmitry V, Matyushov,
Dept. of Chemistry/Physics,
Arizona State University, Tempe, AZ-85287 USA
We discuss two issues of current interest in the theories of low-temperature glass-formers: (i) the lowtemperature
portion of the configurational entropy and (ii) a model of relaxation avoiding reliance on
the Adam-Gibbs scenario of cooperatively rearranging regions. We first present an exact solution for
the enumeration function of the fluid of dipolar hard spheres and show how the Stillinger’s [1]
requirement of a divergent derivative on the approach to the ideal glass transition makes the
enumeration function non-Gaussian. The effective width of the distribution of landscape minima then
gains approximately linear scaling with temperature. Simulations allow to drive the system of dipolar
spheres nearly to the point of ideal glass transition which is avoided via a first-order liquid-liquid
phase transition [2]. The temperature dependence of the width in the distribution of landscape minima
is also employed in the picture of glass thermodynamics in terms of excitations above the ground state
of an ideal glass. This model fits well the existing data for the excess entropy and heat capacity of
structural glass-formers on approach to the glass transition. The main distinction between fragile and
strong liquids appears in terms of an order of magnitude difference in the Gaussian width of their
excitation energies. The model predicts that fragile liquids will release the excess of their
configurational entropy by a liquid-liquid phase transition at a temperature falling between the
laboratory glass transition and the Kauzmann temperature. The dynamic model is formulated in terms
of activated transitions over the energy barrier instead of the reliance on the configurational entropy as
the driving force of the dynamics, as in the Adam-Gibbs picture. A relation for the relaxation time is
derived [3] in which configurational/excess heat capacity rather than the configurational entropy
controls the temperature dependence of the relaxation time. Relaxation data for several laboratory
glass-formers fall on one common line when analyzed with the new equation, while producing quite
distinct slopes in the standard Adam-Gibbs formalism.
[1] F. H. Stillinger, J. Chem. Phys. 88 (1988) 7818.
[2] D. V. Matyushov, Phys. Rev. E 76 (2007) 011511.

[3] D. V. Matyushov and C. A. Angell, J. Chem. Phys. 128 (2007) 144505.
COMPONENTS OF DIELECTRIC CONSTANTS OF IONIC LIQUIDS
Ekaterina I Izgorodina (1) and Douglas R MacFarlane (1)
(1) School of Chemistry, Monash University, Wellington Rd, Clayton, Melbourne VIC 3800,
Australia
Katya.Izgorodina@sci.monash.edu.au
In this study ab initio-based methods were used to calculate electronic polarizability and dipole
moment of ions comprising ionic liquids [1]. The test set consisted of a number of anions and cations
routinely used in the ionic liquid field. As expected, in the first approximation electronic polarizability
volume turned out to be proportional to the ion volume, also calculated by means of ab initio theory.
For ionic liquid ions this means that their electronic polarizabilities are at least an order of magnitude
larger than those of traditional molecular solvents like water and DMSO. On this basis it may seem
surprising that most of ionic liquids actually possess modest dielectric constants, falling the narrow
range between 10 and 15. The lower than first expected dielectric constants of ionic liquids has been
explored in this work via explicit calculations of the electronic and orientation polarization
contributions to the dielectric constant using the Clausius-Mossotti equation and the Onsager theory
for polar dielectric materials. We determined that the electronic polarization contribution to the
dielectric constant was rather small (between 1.9 and 2.2) and comparable to that of traditional
molecular solvents. These findings were explained by the interplay between two quantities, increasing
electronic polarizability of ions and decreasing number of ions present in the unit volume; although
electronic polarizability is usually relatively large for ionic liquid ions, due to their size there are fewer
ions present per unit volume (by a factor of 10 compared to traditional molecular solvents). For ionic
liquids consisting of ions with zero (e.g. BF4) or negligible (e.g. NTf2) dipole moments the calculated
orientation polarization does not contribute enough to account for the whole of the measured values of
the dielectric constants. We suggest that in ionic liquids an additional type of polarization, “ionic
polarization”, originating from small movements of the centre of the charge on the ions might be
present. According to our estimations, this ionic polarization contribution to the dielectric constant
could be rather significant (between 8 and 10 for some ionic liquids).
[1] E. I. Izgorodina, M. Forsyth and D. R. MacFarlane, Phys. Chem. Chem. Phys., 11, 2452, 2009.
RELAXATION PROCESSES IN A SERIES OF 1-ALKYL-3-METHYLIMIDAZOLIUM
HEXAFLUORO-PHOSPHATE
O. Russina (1), M. Beiner (2) and A. Triolo (1)
(1) Istituto Processi Chimico-Fisici, Consiglio Nazionale delle Ricerche, Messina, Italy
(2) Department of Physics, Martin-Luther-University Halle-Wittenberg, Halle, Germany
triolo@me.cnr.it
We report on the complex relaxation map of a series of room temperature ionic liquids that are
characterised by the [PF6] anion and the 1-alkyl-3-methylimidazolium cation (with alkyl=butyl, hexyl
and octyl).
Together with structural information derived from X-ray and neutron scattering experiments, we will
present new data sets on the relaxation processes in an important class of salts.
On the basis of rheological, dielectric and neutron spin echo data, we will present information on the
primary process in these salts and on the existence of secondary processes whose nature will be
investigated as a function of the alkyl chain length.

MOLECULAR COOPERATIVITY IN THE DYNAMICS OF GLASS FORMING SYSTEMS:
A NEW INSIGHT
L. Hong (1), P. D. Gujrati (1), V.N. Novikov (2), A.P. Sokolov (1)
(1) Department of Polymer Science, The University of kron, Akron, OH 44325, USA
(2) Institute of Automation & Electrometry, Russ.Ac.Sciences, Novosibirsk 630090, Russia
alexei@uakron.edu
The mechanism behind the steep slowing down of molecular motions upon approaching the glass
transition remains a great puzzle. Most of the models relate this mechanism to the cooperativity in
molecular motion. In this work we estimate the cooperativity length scale for many glass-forming
systems from the collective vibrations (the so-called boson peak). We demonstrate that cooperativity
length directly correlates to the dependence of structural relaxation on volume. This dependence
presents only one part of the mechanism of slowing down the structural relaxation. Our analysis
reveals that another part, the purely thermal variation of the structural relaxation (at constant volume),
does not correlate to molecular cooperativity. These results call for a conceptually new approach to the
analysis of the mechanism of the glass transition.
NEW INSIGHT INTO THE LIQUID-LIQUID TRANSITION IN SUPERCOOLED YTTRIUM
ALUMINATES.
Paul F. McMillan (1), Martin C. Wilding (2) and Mark Wilson (3)
(1) Christopher Ingold Laboratories, Department of Chemistry, University College London, 20
Gordon Street London WC1H 0AJ, United Kingdom
(2.) Institute of Mathematical and Physical Sciences, Aberystwyth University, Aberystwyth, SY23
3BZ, United Kingdom.
(3.) Physical and Theoretical Chemistry Laboratory, University of Oxford, Oxford, OX1, 3QZ, United
Kingdom.
Correspondence author: mbw@aber.ac.uk
The direct observation of the first order transition between supercooled yttrium aluminate liquids of
identical composition was first made by Aasland and McMillan in 1994. Since then there has been a
series of studies focussing on the structure of glasses produced in this system and their thermodynamic
properties. These studies have however failed to convince a sceptical audience. Although there are
many reasons to suspect that the yttrium aluminate system is polyamorphic, there are features of this
system that contrast with other candidates for polyamorphism. For example, the liquid-liquid transition
occurs at ambient pressure and more conventional phase-separation would be expected in this system.
Furthermore the formation of high- and low-density amorphous forms of yttrium-aluminates is
complicated by the presence of crystals which means that the low-density-form has yet to be isolated.
Recently it has been possible to study Y2O3-Al2O3 liquids directly without the need to interpret
diffraction or thermodynamics data obtained from glass. Containerless techniques can be used in
combination with X-ray scattering to evaluate the structure of stable yttrium aluminate liquids and
metastable supercooled liquids. A combined small and wide-angle X-ray study shows unequivocally
the rise and fall of the small angle signal as the liquid-liquid transition is approached, the wide angle
signal, collected simultaneously shows shifts in the first peak in the diffraction pattern suggesting

change sin intermediate range order. High energy X-ray diffraction studies on stable yttrium aluminate
liquids suggest that the intermediate-range ordering changes in the clustering of Y-O and Al-O
polyhedra are a characteristic of yttrium aluminate liquids that is not reflected in other rare earth
aluminates.
Inelastic neutron scattering data and Raman scattering data have been collected on a series of glasses.
As with the diffraction data, the changes in the vibrational density of states are subtle rather than
dramatic. The inelastic neutron scattering spectrum is featureless but broadly agrees with the data
obtained from Raman measurements and from calculation. The subtle changes in density of states is
consistent with the rheological differences between high- and low-density liquids having and origin
the in YOx-AlOx clusters or domains suggested by X-ray scattering.
MIXED GLASS FORMER EFFECTS IN ALKALI OXY- AND THIO-BORATE GLASSES
Steve W. Martin(1), Randilynn Christensen(1), Christian Bischoff(1), Michael Haynes(1), Garrett
Olson(1), Dirk Larink(1,6), Valeri Petkov(2), Sebastien Le Roux(2), Xinwei Wu(3), Ruediger
Dieckmann(3), Aleksandar Matic(4), Andreas Hall(4), Philipp Maas(5), Christian Mueller(5), Michael
Schuch(5)
(1) Department of Materials Science and Engineering, Iowa State University, Ames, IA, 50011, USA
(2) Department of Physics, Central Michigan University, Mt. Pleasant, MI, 48859, USA
(3) Department of Materials Science & Engineering, Cornell University, Cornell, NY 14853, USA
(4) Department of Applied Physics, Chalmers UNiversity of Technology, S-41296 Gothenburg,
Sweden
(5) Technische Universitaet Ilmenau, Fakultaet fuer Mathematik und Naturwissenschaften, 10 05 65,
98684 Ilmenau, Germany
(6) Institut für Physikalische Chemi, Universitat Münster, Münster D-48149, Germany
swmartin@iastate.edu
Significant progress has been made in developing increasingly accurate models of the structure and
properties of glass forming systems. The most progress has been made on simply constituted single
glass-former systems to which has been added a single modifying oxide (or sulfide). Such systems
include the enormously studied alkali silicate, borate, and phosphate glasses. Detailed understanding is
now available on how the network glass structure, such as SiO2, is modified through the addition of
the modifier. Less understood, but growing significantly in interest, are multi-component, so-called
mixed glass-former glass systems where there are (typically) two glass-formers that compete for the
modifying oxide (or sulfide). In this talk, a review will be made of some of the progress that is now
being made on a few of the more thoroughly studied mixed-glass former systems. This study is part of
an NSF sponsored Materials World Network research program that is investigating the specific
question of the mixed glass-former enhancement (and reduction) of the alkali ion conduction as one
glass former is substituted for another while the mole fraction of the modifying oxide or sulfide is held
constant. Specific examples of this effect in mixed oxy-borosilicate and oxy- and thio-boro-phosphate
glasses will be reviewed and discussed.
Influence of temperature, pressure and volume on the low frequency relaxation process in liquid
crystals
Stanislaw Urban (1), C.M. Roland (2), R. Bogoslovov (2), R. Casalini (2) and J. Czub (1)
(1) Institute of Physics, Jagiellonian University, Reymonta 4, 30-059 Krakow, Poland
(2) Naval Research Laboratory, Code 6120, Washington DC 20375-5342, USA
Liquid crystals (LCs) are the state of matter placed between the isotropic liquid and the crystalline
state. The building molecules have strongly anisotropic shapes (rod-like in most cases). This leads

to the interaction potential that consists of the distant-dependent and orientation-dependent parts.
Rotational dynamics of molecules around the principal inertia axes falls into different frequency
regions. Especially the rotations of molecules around the short axes (the low frequency, l.f.,
relaxation process) are strongly hindered by the potential barrier and are coupled to the
fluctuations of the centers of mass. This flip-flop motion exhibits therefore a considerable
temperature, pressure and volume dependence. The results of studies of the l.f. relaxation process
at different thermodynamic conditions (isobaric, isothermal and isochoric) will be presented [1-6].
The scaling law proposed for glass-formers [7,8] was successfully applied to the l.f. relaxation
times determined for the liquid-like (nematic, smectic A and C) as well as for the crystal-like
(smectic E) LC phases [4,5,6]. A material constant related to the steepness of the intermolecular
repulsive potential was determined.
References:
[1] S. Urban and A. Würflinger, "Dielectric properties of liquid crystals under high pressure", in
Advances in Chemical Physics, Edited by I. Prigogine and S. A. Rice, John Viley & Sons, New
York, vol. 98, 143-216 (1997).
[2] S. Urban and A. Würflinger, “Influence of pressure on the dielectric properties of liquid
crystals”, in Nonlinear Dielectric Phenomena in Complex Liquids, S. J. Rzoska and V. P.
Zhelezny (eds.), 2004 Kluwer Academic Publishers, pp. 211-220.
[3] A. Würflinger and S. Urban, „Dielectric Relaxation Processes in Condensed Matter
Under Pressure”, in Relaxation Phenomena, W. Haase an S. Wróbel, editors, Springer,
2003, ch. 1.4, pp. 71-88.
[4] S. Urban and A. Würflinger, “Thermodynamical scaling of the low frequency
relaxation time in liquid crystals”, Phys. Rev. E, 72, 021707(4) (2005).
[5] S. Urban, C.M. Roland, J. Czub and K. Skrzypek, „Thermodynamic analysis of the
low frequency relaxation time in the smectic A and C phases of a liquid crystal”,
J. Chem. Phys., 127, 094901 (2007).
[6] R.B. Bogoslovov, C.M. Roland, J. Czub and S. Urban, “Interaction potential in
nematogenic 6CHBT”, J. Phys. Chem. B 112, 16008-16011 (2008).
[7] R. Casalini and C. M. Roland, “Thermodynamical scaling of the glass transition
dynamics”, Phys. Rev. E 69, 062501 (2004).
[8] C M Roland, S Hensel-Bielowka, M Paluch and R Casalini, “Supercooled dynamics
of glass-forming liquids and polymers under hydrostatic pressure”, Rep. Prog. Phys. 68,
1405–1478 (2005).
SLOW SOLVATION AND HETEROGENEOUS DYNAMICS IN IONIC LIQUIDS
S. Arzhantsev, H. Jin, X. Li, D. Roy, and M. Maroncelli
Department of Chemistry, The Pennsylvania State University, University Park PA 16802, USA
maroncelli@psu.edu
We have been using electronic spectroscopy and molecular dynamics simulations to explore the nature
of solvation and simple chemical reactions in ionic liquids. Our work, and that of many other groups,
has shown that equilibrium solvation in ILs is often surprisingly similar to that found in highly dipolar
organic solvents. Dynamically, however, ILs are distinctive. In contrast to the situation in
conventional room-temperature solvents, where solute-solvent interactions usually relax on a 1-10 ps
time scale, complete relaxation in room temperature ionic liquids typically requires several
nanoseconds. The solvation response in these liquids is broadly distributed in time, extending from
the 100 fs range out to tens of nanoseconds. This slow and broadly distributed solvation response has
a pronounced retarding effect on solvent-controlled processes and it gives rise to heterogeneous
kinetics for chemical reactions and other processes that occur on picosecond and nanosecond time

scales. Heterogeneity is manifest in both non-exponential and excitation-wavelength dependent
kinetics of excited-state reactions. I will provide an overview of what is currently known about
solvation and kinetics in ionic liquids and present some of our recent experimental and computational
results on this topic.
DYNAMICS OF IONIC LIQUIDS, SUPERCOOLING AND IONIC CONDUCTIVITY
A. Rivera-Calzada
GFMC, Facultad de Físicas, Universidad Complutense de Madrid, Madrid 28040, Spain.
Alberto.Rivera@fis.ucm.es
We study the dynamics of several (room temperature) Ionic Liquids (IL), based mainly on the 1-butyl-
3-methylimidazolium cation, which can be supercooled and reach the glass transition decreasing
temperature [1,2]. When their dynamics are probed by means of dielectric spectroscopy, the electric
spectra are dominated by the translational contribution, showing a typical ionic conductor behavior.
However, the glassy behavior is evidenced in the VFT dependence of the dc ionic conductivity, as
well as in the secondary relaxations observed below Tg [3]. Characteristic orientational times obtained
by depolarized light scattering experiments τα are the same as the translational ones τM, indicating a
strong rotational/ translational coupling above Tg [4]. The glassy nature of the IL is also evidenced
when hydrostatic pressure is applied to them. The IL 1-butyl-1-methylpyrrolidinium
bis[oxalato]borate, shows the same qualitative and quantitative dynamic behavior as molecular glass
formers under pressure, reaching the glass transition at different temperatures applying pressure, with
τM following the pressure-equivalent VFT equation. Also, we find pressure-temperature superposition,
indicating that the supercooled dynamics are governed by the translational-rotational characteristic
time τM = τα [5].
[1] P. Wasserscheid, T. Welton, Ionic Liquids in Synthesis, Wiley-VCH (2003)
[2] Angell et al., J. Phys. Chem. B 107, 6170 (2003)
[3] A. Rivera, E. A. Rössler, PRB 73, 212201 (2006)
[4] A. Rivera, A. Brodin, A. Pugachev, E. A. Rössler, JCP 126, 114503 (2007)
[5] A. Rivera-Calzada, K. Kamisnki, C. Leon, M. Paluch, J. Phys. Chem. B 112, 3110 (2008)
HIGHER ORDER FREQUENCY-FLUCTUATION CORRELATION FUNCTIONS
MEASURED BY 3D-IR SPECTRSOCOPY: APPLICATION TO WATER
Sean Garrett-Roe and Peter Hamm
Institute of Physical Chemistry, University of Zurich, Zurich, Switzerland
phamm@pci.uzh.ch
We will present 3D-IR spectra of the OD vibration of isotopically substituted liquid water. The
frequency of the OD vibration is a sensitive probe of its immediate surrounding; as such nonlinear
vibrational spectroscopic methods, in particular 2D-IR spectroscopy, are commonly used to elucidate
the ultrafast hydrogen-bond dynamics of water. The statistics of the OD frequency fluctuations is
profoundly non-Gaussian. In this case, 3D-IR spectroscopy can provide additional non-trivial
information not contained in 2D-IR spectroscopy. In particular, 3D-IR spectroscopy is a sensitive
measure of three-time-point frequency fluctuation correlation functions (FFCF), which characterizes
the stochastic process of hydrogen-bond breaking and making more thoroughly than just the two-time
point FFCF typically extracted from 2D-IR spectroscopy. We will discuss the theoretical background
of 3D-IR spectroscopy [1-3], and present first experimental results on water.
[1] P. Hamm, J. Chem. Phys., 124, 124506, 2006
[2] S. Garrett-Roe, P. Hamm, J. Chem. Phys., 128, 104507, 2008
[3] S. Garrett-Roe, P. Hamm, Acc. Chem. Res. 2009, available online

Heterogeneous deformation and shear band melting in metallic glasses
A.R. Yavari*
Euronano SIMaP-CNRS, Institut Polytechnique de Grenoble, St-Martin-d'Hères, 38402, France
Metallic glasses possess exceptionally high mechanical strength and elastic limit (resilience).
However, plastic deformation in metallic glasses at room temperature occurs via heterogeneous
deformation. This deformation is localized in shear bands only tens of nanometers thick in which
elastic energy is converted to heat via local heavy deformation leading to temperature rise, free
volume generation, shear softening and often catastrophic failure without significant macroscopic
plasticity. How this plays at the level of the atomic structure- short and medium range order – is not
clear.
Following the deformation and temperature rise occurring in time scales of the order of nanoseconds
in such thin bands in real time is nearly impossible but examination of shear offsets (shear steps) that
result from such slip can provide valuable information and clues concerning the underlying
mechanisms.
Real space pair distribution (PDF) derived from high precision x-ray diffraction data can also reveal
the effects of deformation on the atomic structure of metallic glasses. Preliminary results indicate that
the local atomic structure of metallic glasses remains unchanged in the first nearest neighbor (nn)
shell, whereas it is modified in the second and higher neighboring atomic shells, suggesting that
deformation does not affect the short range order (SRO) but it does modify the medium range order
and the interconnection between the basic clusters of atoms that serve as the building blocks of the
structures.
*Corresponding author: euronano@minatec.inpg.fr

DIFFUSIVITY AND IONICITY OF ROOM TEMPERATURE IONIC LIQUIDS
Masayoshi Watanabe
Department of Chemistry and Biotechnology, Yokohama National University, Yokohama 240-8501,
Japan
mwatanab@ynu.ac.jp
Room temperature ionic liquids (RTILs) are liquids, consisting of entirely of ions, and their important
properties, e.g., such as their negligible vapor pressure, are considered to result from the ionic nature.
However, we do not know how ionic the RTILs are. The ionic nature of the RTILs (“ionicity”) was is
defined in this study as the molar conductivity ratio (Λimp/ΛNMR) [1], calculated from the molar
conductivity measured by the electrochemical impedance method (Λimp) and that estimated by use of
pulse-field-gradient spin-echo NMR ionic self-diffusion coefficients and the Nernst-Einstein relation
(ΛNMR). A series of the studies has presented quantitative results of the ionic diffusivity and the
ionicity [2]. The Λimp/ΛNMR well illustrates the degree of cation-anion aggregation in the RTILs at
equilibrium, which can be explained by the effects of anionic donor and cationic acceptor abilities for
the RTILs having different anionic and cationic backbone structures with fixed counter parts, and by
the inductive and dispersive forces for the various alkyl chain lengths in the cations. The liquid-state
dynamics is controlled by a subtle balance between the electrostatic and other intermolecular forces.
[1] A. Noda, K. Hayamizu, M. Watanabe, J. Phys. Chem. B, 105, 4603, 2001
[2] H. Tokuda, M. Watanabe et al., J. Phys. Chem. B, 108, 16593, 2004; 109, 6103, 2005; 110, 2833,
2006; 110, 19593, 2006
NEW INSIGHT INTO THE METAL TO NONMETAL TRANSITION IN FLUID ALKALI
METALS BY NEUTRON INELASTIC SMALL ANGLE SCATTERING
W.-C. Pilgrim(1), F. Demmel (2), and Daniel Szubrin (1,3)
(1) Physical Chemistry, Univ Marburg, Hans-Meerwein-Strasse, Germany
(2) ISIS, Rutherford Appleton Laboratory, Chilton, Oxfordshire, U.K.
(3) ILL, 6, rue Jules Horowitz Grenoble, France
pilgrim@mailer.uni-marburg.de
It is well known that liquid alkali metals suffer a Metal to Nonmetal-Transition at sufficiently low
density if they are continuously expanded with increasing temperature and pressure. However, the
structural and dynamical consequences of this transition are still not fully understood. The generally
accepted view is that the conduction electrons localize at about twice the critical density, due to a
breakdown of the electronic screening which otherwise shields the strong coulomb forces from the
ionic cores. As a consequence, the system forms molecular aggregates where the electrons are
localized in interatomic bonds. However, there is now theoretical and also experimental evidence that
the actual breakdown of the conduction electron system sets in at considerably higher density, i.e. at
lower temperature and pressure. From structural data obtained from in accurate x-ray investigations it
is concluded that the instability of the electron system leads to attractive forces between equally
charged negative ions due to the formation of a negative dielectric constant in the fluid. Another view
however, favours the segregation into a p- and T-dependent equilibrium mixture of metallic and nonmetallic
domains if the stability limit of the electron system is approached.
Inelastic scattering of neutrons at low momentum transfer is at moment the only technique to
unambiguously unravel the real processes on microscopic time- and lengths scales and to distinguish
between the proposed mechanisms. BRISP is a new instrument installed at the ILL in Grenoble and
perfectly suited for this task. It is the only neutron spectrometer worldwide allowing to measure
spectra in the lower Q- range. We have just started a series of experiments on this instrument in order
to investigate the microscopic processes around the proposed transition range in liquid Rubidium.

Multiple glass transitions in star polymer mixtures
E. Zaccarelli(1), C. Mayer(1), F. Sciortino(1), P. Tartaglia(2), C.N. Likos(3), H. L\"owen(3), E.
Stiakakis(4), A. Munam(5), M. Gauthier(5), N. Hadjichristidis(6), H. Iatrou(6), D. Vlassopoulos(4)
(1) Dipartimento di Fisica and CNR-INFM-SOFT, UniVersita` di Roma La Sapienza, Piazzale Aldo
Moro 2,
I-00185 Rome, Italy
(2) Dipartimento di Fisica and CNR-INFM-SMC, UniVersita` di Roma La Sapienza, Piazzale Aldo
Moro 2,
I-00185 Rome, Italy
(3) Institut fu¨r Theoretische Physik II: Weiche Materie, Heinrich-Heine-UniVersita¨t
Du¨sseldorf, UniVersita¨tsstrasse 1, D-40225 Duesseldorf, Germany
(4) FO.R.T.H., Institute of Electronic Structure and Laser, GR-71110 Heraklion, Crete, Greece
(5) Department of Chemistry, Institute for Polymer Research, University of Waterloo, ON, N2L 3G1,
Canada
(6)University of Athens, Department of Chemistry, GR-15771 Athens, Greece
Correspondence author: emanuela.zaccarelli@phys.uniroma1.it
The glass transition in binary mixtures of star polymers is studied by rheological measurements, mode
coupling theory and extensive molecular dynamics computer simulations. In particular, we have
explored vitrification in the parameter space of size asymmetry δ and concentration f2 of the small star
polymers at fixed concentration of the large ones. Depending on the choice of parameters, different
glassy states are identified: a single glass of big polymers at low δ and low f2, a double glass at high δ
and low f2, and a novel double glass at high f2 and high δ which is characterized by a strong
localization of the small particles[1,2]. We identify this as an asymmetric glassy state, which is
characterized by strongly anisotropically distorted cages, bearing similarities to those of hard-sphere
glasses under shear. The anisotropy is induced by the presence of soft additives. This phenomenon
seems to be generic to soft colloids and its origins lie in the penetrability of the constituent particles.
Thus, a new route opens for the rational design of soft particles with desired tunable rheological
properties.
[1] C. Mayer, E. Zaccarelli, E. Stiakakis, C. N. Likos, F. Sciortino, A. Munam, M. Gauthier, N.
Hadjichristidis, H. Iatrou, P. Tartaglia, H. Löwen and D. Vlassopoulos Nature Materials 7, 780-784
(2008).
[2] C. Mayer, F. Sciortino, C. N. Likos, P. Tartaglia, H. Löwen, E. Zaccarelli Macromolecules 42,
423-434 (2009)
REPULSIVE AND ATTRACTIVE GLASSES REVISITED
Wilson Poon (university of Edinburgh)
We report simulations of glassy arrest in hard-core particles with short-range interparticle attraction.
Previous experiments, theory and simulations suggest that in this kind of system, two qualitatively
distinct kinds of glasses exist, dominated respectively by repulsion and attraction. It is thought that in
the former, particles are trapped ‘topologically', by nearest-neighbor cages, while in the latter, nonergodicity
is due to interparticle ‘bonds'. Subsequent experiments and simulations have suggested that
bond breaking destabilizes attractive glasses, but the long-term fate of these arrested states remains
unknown. By running simulations to times a few orders of magnitude longer than those reached by
previous experiments or simulations, we show that arrest in an attractive glass is, in the long run, also
topological. Nevertheless, it is still possible to distinguish between ‘non-bonded' and `bonded'
repulsive glassy states. We study the melting of bonded repulsive glasses into a hitherto unknown
‘dense gel' state, which is distinct from dense, ergodic fluids. We propose a new ‘state diagram' for

concentrated attractive particles, and discuss the relevance of our results in the light of recent
rheological measurements in colloid-polymer mixtures.
Glassy dynamics and charge transport in ionic liquids
F. Kremer, J. R. Sangoro, C. Iacob, and J. Kärger
Institute of Experimental Physics I, University of Leipzig, Linnéstr. 5, 04103, Leipzig, Germany
kremer@physik.uni-leipzig.de
Charge transport and glassy dynamics of a variety of glass-forming ionic liquids (ILs) are investigated
in a wide frequency and temperature range by means of Broadband Dielectric Spectroscopy(BDS),
Pulsed Field Gradient Nuclear Magnetic Resonance (PFG NMR), ac Calorimetry, Differential
Scanning Calorimetry and Rheology. The dielectric spectra are dominated – on the low-frequency side
– by electrode polarization effects while, for higher frequencies, charge transport in a disordered
matrix is the underlying physical mechanism. While the absolute values of dc conductivity and
viscosity vary over more than 11 decades with temperature and upon systematic structural variation of
the ILs, quantitative agreement is found between the characteristic frequency of charge transport and
the structural α-relaxation. This is discussed within the framework of the concept of dynamic glass
transition driven hopping traced back to Einstein, Einstein-Smoluchowski, and Maxwell relations [2].
A novel approach is applied to extract diffusion coefficients from BDS spectra in quantitative
agreement with PFG NMR values but in a much broader range. It becomes possible to extract from the
dielectric spectra separately the number density and the mobilities of the charge carriers and the type
of their thermal activation. It is shown that the observed Vogel-Fulcher-Tammann (VFT) dependence
of the dc conductivity can be traced back to a similar temperature dependence of the mobility while
for the number density an Arrhenius-type thermal activation is found [2].
[1] J. R. Sangoro, C. Iacob, A. Serghei, C. Friedrich, F. Kremer, Phys. Chem. Chem. Phys. 11, 913
2009
[2] J. R. Sangoro, A. Serghei, S. Naumov, P. Galvosas, J. Kärger, C. Wespe, F. Bordusa, and F.
Kremer, Phys. Rev. E 77, 051202 2008
Diffusion in ionic liquids as studied by broadband dielectric spectroscopy
J. R. Sangoro, C. Iacob, S. Naumov, J. Kärger, and F. Kremer
Institute of Experimental Physics I, University of Leipzig, Linnéstr. 5, 04103, Leipzig, Germany
sangoro@physik.uni-leipzig.de
Diffusion coefficient in glass-forming ionic liquids (ILs) is investigated in a wide frequency and
temperature range by means of broadband dielectric spectroscopy (BDS) and pulsed field gradient
nuclear magnetic resonance (PFG NMR). It is experimentally shown that in the time-scale
characterising the cross-over from sub-diffusive to diffusive ion dynamics, the hopping lengths are of
the order of molecular diameters determined from quantum-chemical calculations. This provides a
direct means – via Einstein-Smoluchowski relation – to determine diffusion coefficient by BDS over
more than 8 decades unambiguously and in quantitative agreement with independent PFG NMR
measurements [1,2]. Unprecedented possibilities in the study of charge transport and dynamic glass
transition are thus opened.
[1] J. R. Sangoro, A. Serghei, S. Naumov, P. Galvosas, J. Kärger, C. Wespe, F.Bordusa, and F.
Kremer, Phys. Rev. E 77, 051202 2008; J. R. Sangoro et al, J. Chem. Phys. 128, 214509 2008 ; J. R.
Sangoro et al., Macromolecules, 42(5) 1648-1651 2009.
[2] J. R. Sangoro, C. Iacob, H. Rexhausen, V. Strehmel, J. Hunger, R. Buchner, S. Naumov, J. Kärger,
and F. Kremer 2009. Submitted to: Angewandte Chemie Int. Ed.

PROTON SOLID STATE NMR AND AC CHIP CALORIMETRIC STUDY OF PMMA
MONOLAYER ABSORBED ON THE SINICA NANOPARTICLES
Qiang Gu, Yang Liu, Xiaoliang Wang, Wei Jiang, Dongshan Zhou and Gi Xue
Department of Polymer Science and Engineering, School of Chemistry and Chemical Engineering,
State Key Laboratory of Co-ordination Chemistry, Nanjing National Laboratory of Microstructures,
Nanjing University, Nanjing, 210093, China
dzhou@nju.edu.cn, xuegi@nju.edu.cn
Study the glass transition and mobility of the layer in direct contact with the nano-particles is usually
most important to understand the corresponding properties of the polymer nano-composite as a whole.
Because of any specific or non-specific interaction or confining effect, the dynamics of the attached
chain can be either enhanced or suppressed [1, 2]. However, there lacks highly selective method to
study the attached layer only owning to the extreme trace amount. Here, we prepared nano-particles
covered by PMMA monolayer in average and use sensitive proton solid state NMR and AC chip
calorimeter to investigate the mobility and glass transition of PMMA. Multi-pluse dipole dephasing
technique enables us to selectively investigate the dynamics of rigid (or mobile) chains by filtering the
magnetism of the mobile (or rigid) chains [3]. We find that the PMMA monolayer absorbed on the
silica nano-particles (~20nm) show increased mobility than that of the multilayer and the bulk. With
sensitive AC chip calorimeter, we also find that the glass transition of PMMA is lower than that of
multilayer. The agreement between NMR and calorimetric results in this system drives us to testify its
validity in other systems, particularly, polymers with stronger constrained mobility.
[1] F. Mammeri, L. Rozes, E. Le Bourhis, and C. Sanchez C, J. Europ. Ceram. Soc., 26, 267, 2006.
[2] B. J. Ash, L. S. Schadler, R. W. Siegel, Mater. Lett., 55, 83, 2002.
[3] X. Wang, Q. Gu, Q. Sun, D. Zhou, P. Sun, G. Xue., Macromolecules, 40, 9018, 2007.
PROBING LOCAL DIELECTRIC RESPONSE AND CORRELATION FUNCTIONS IN POLYMER GLASS
N. E. Israeloff and H. Oukris
Dept. of Physics, Northeastern University, Boston, MA 02115
Corresponding author : n.israeloff@neu.edu
Nanodielectric spectroscopy techniques based on scanning probe microscopy are used to study
nanoscale time-dependent dielectric responses and fluctuations in poly vinyl acetate near its glass
transition. Spatio-temporal correlation functions of the noise are compared with dielectric relaxation
functions both in equilibrium and during aging following rapid quenches through the glass transition.
In the latter case fluctuation-dissipation-relation (FDR) violations are found and analyzed. Analysis of
higher order spatio-temporal correlation functions will be discussed.
CORRELATED MOTION IN COLLOIDAL GLASSES
Eric R. Weeks (1) and Scott V. Franklin (2)
(1) Physics Dept., Emory University, Atlanta, GA 30322, USA
(2) Physics Dept., Rochester Institute of Technology, Rochester, NY 14623-5603
weeks@physics.emory.edu
We use a confocal microscope to examine the motion of individual particles in a dense colloidal
suspension. Close to the glass transition, particle motion is strongly spatially correlated. The
correlations decay exponentially with particle separation, yielding a dynamic length scale of O(2-4 σ)
(in terms of particle diameter σ) [1]. This length scale grows modestly as the glass transition is

approached. Further, the correlated motion exhibits a strong spatial dependence on the pair correlation
function g(r). Motion within glassy samples is weakly correlated, but with a larger spatial scale for this
correlation. We additionally compare χ4 for liquids and glasses.
[1] E. R. Weeks, J. C. Crocker and D. A. Weitz, J. Phys.: Cond. Mat., 19, 205131, 2007.
IONIC LIQUIDS AND IONIC LIQUID/WATER MIXTURES STUDIED BY TERAHERTZ
TIME-DOMAIN SPECTROSCOPY
Kohji Yamamoto (1), Masahiko Tani (2) and Masanori Hangyo (3)
(1) Research Center for Development of Far-Infrared Region, University of Fukui, Fukui, 910-8507
Japan
PRESTO, Japan Science and Technology Agency, 4-1-8 Honcho Kawaguchi, Saitama 332-0012,
Japan
(2) Research Center for Development of Far-Infrared Region, University of Fukui, Fukui, 910-8507
Japan
(3) Institute of Laser Engineering, Osaka University, 2-6 Yamadaoka, Suita, Osaka 565-0871, Japan
Correspondence author: kohji@fir.u-fukui.ac.jp
We have investigated low-frequency dielectric spectra of imidazolium ionic liquids and 1-butyl-3methylimidazolium
(BMIm + ) tetrafluoroborate (BF4 - )/water mixtures using the terahertz time-domain
spectroscopy (THz-TDS). The ionic liquids show structured lineshapes of complex dielectric spectra
in the THz region. The structured lineshapes of the ionic liquids reflect the low-frequency motions of
interion vibrations and indicate that the ionic liquids in the liquid phase have local structures similar to
their solid-phase structures [1]. The component-resolved THz dielectric spectra of BMImBF4 in
mixtures are similar with those of pure BMImBF4. An analogous trend is observed for water.
Therefore, it is suggested that BMImBF4 water mixtures are not fully mixed in a microscopic scale but
form microscopic domains of the ionic liquid and water separately.
[1] K. Yamamoto, M. Tani, and Masanori Hangyo, J. Phys. Chem. B, 111, 4854, 2007
LOCAL ELASTIC HETEROGENEITIES AND LOW FREQUENCY VIBRATIONAL
DYNAMICS IN GLASSES.
Giovanna D'Angelo
Dipartimento di Fisica, Università di Messina, 98166 S. Agata (Messina), Italy
gdangelo@unime.it
The elasticity of a series of oxide glasses has been locally changed by inserting alkaline ions making
bonds of different strength with the oxygenated anionic groups of the glassy matrix. Their presence
individuates regions of structural inhomogeneities on the mesoscopic scale, corresponding to looser
packing zones. Raman scattering measurements are used to study the changes of the low frequency
vibrational dynamics following the hardening of the glassy structure. A linear correlation between the
boson peak frequency and the transverse sound velocity is evidenced, suggesting a mainly transverse
character of the low energy excess vibrational modes in glasses. This study is complemented by
inelastic neutron scattering and low temperature specific heat measurements and the photon-phonon
coupling coefficients are evaluated.
An extension of the present study to biological systems is also discussed.
ION TRANSPORT FEATURES AND INTERMEDIATE-RANGE ORDERING IN GLASSES
E. Bychkov
LPCA, UMR CNRS 8101, Université du Littoral, 59140 Dunkerque, France

ychkov@univ-littoral.fr
Despite significant progress achieved in theoretical understanding and experimental verification of ion
transport properties in disordered solids, there are still open questions related to the influence of
intermediate-range ordering and mobile species distribution in the glass network on transport
phenomena. Drastically different ion transport regimes in glasses over a large composition range
covering several orders of magnitude in the mobile ion content, as well as mixed cation or mixed
anion effects belong to this topic. I will concentrate my attention on a relatively rare phenomenon,
degenerated mixed cation effect, found for several Ag/Cu chalcogenide and chalcohalide glass
families using conductivity measurements, 110 Ag and 64 Cu tracer diffusion [1,2]. High-energy x-ray
scattering and pulsed neutron diffraction data provide reliable results on local and intermediate-range
ordering in these glasses, which allows macroscopic transport properties and structural features on
microscopic level to be related.
[1] A. Bolotov et al., Solid State Ionics 113-115 (1998) 697.
[2] E. Bychkov, Defect Diff. Forum 194-199 (2001) 909.
THERMAL PROPERTIES OF NANOCONFINED WATER AND ICE IN VYCOR AND
MCM-41
E. Tombari (1), C. Ferrari (1), G. Salvetti (1) and F. Mallamace (2)
(1) Istituto per i Processi Chimico-Fisici del CNR, via G. Moruzzi 1, 56124 Pisa, Italy
(2) Dipartimento di Fisica and CNISM, Università di Messina, Vill. S. Agata, C.P. 55, 98166 Messina,
Italy
tombari@ipcf.cnr.it
Studies of nanoconfined water are performed with an expectation that it would help in revealing the
behavior of bulk supercooled water in its unaccessible temperature range [1]. The thermal properties
of water and ice in 4 nm pores of Vycor, for different water pore filling, and in 1.4, 1.8 nm and 2.4 nm
pores of MCM-41 were measured in the temperature interval from110 K to 280 K, both during
cooling and heating. The apparent specific heat, Cp,app, and the real and imaginary components of the
dynamic specific heat, Cp’ and Cp”, were measured simultaneously by means of temperature
modulated scanning calorimetry [2], where a temperature modulation period of 300 s and 1 K peak to
peak amplitude was superposed to the normal temperature scanning of 12 K/h. A variety of behaviors
of crystallization exotherms and melting endotherms in function of the pore dimension of MCM-41
and in function of the pore filling in Vycor have been observed in the Cp,app of confined water on
cooling and heating, respectively. In all studies the dynamic specific heat components, Cp’ and Cp”,
show no indications of relaxations which are typically expected in presence of glass transitions. The
water in nanopores has a thermodynamic behavior strongly dependent from the diameter and filling
factor of the pores, i.e., the thickness of the water layer covering the internal pore surface.
[1] P.G. Debenedetti and H.E. Stanley, Physics Today, 56, 40, 2003.
[2] G. Salvetti, C. Cardelli, C. Ferrari, E. Tombari, Thermochimica Acta, 364, 11, 2000.
WATER MOBILITY AND GLASS TRANSITION IN LOW-MOISTURE BIOPROTECTANT
SUGARS
A. Cesàro (1), F. Sussich (1), S. Di Fonzo (2), C. Masciovecchio (2)
(1) Lab. Phys. Macromol. Chem., Univ. Trieste, Via Giorgieri 1, Trieste, Italy
(2) Sincrotrone Trieste, Strada Statale 14 km 163.5, Area Science Park, I-34012 Trieste, Italy
cesaro@units.it
Changes in physico-chemical properties in low-moisture amorphous and crystalline sugars are
presented and discussed in view of their role in several bio-technological fields [1]. Data mainly refer
to conventional calorimetric glass transition determination and Brillouin scattering in the UV region in

comparison with other literature data on trehalose and similar sugars [2-4]. The discussion of these
data underline that quite a few peculiarities can be ascribed to the structural-dynamic properties of
trehalose [5]. The emphasis is on interpretation at molecular level of the interplay of water in the
dehydration processes of sugar matrices.
[1] A. Cesàro, O. De Giacomo, and F. Sussich, Food Chemistry 106, 1318, 2008.
[2] D. Kilburn, et al. Nature Materials 5, 632, 2006.
[3] A. Cesàro, Nature Materials 5, 593, 2006.
[4] Di Fonzo, S. et al,. J. Phys. Chem. A 111 , 12577, 2007.
[5] F. Sussich and A. Cesàro, Carbohydr. Res. 343, 2667, 2008.
Correlations between Relaxation Dynamics and Stability in Glassy Pharmaceutical Systems:
The Impact of Annealing
Michael J. Pikal, School of Pharmacy, University of Connecticut, Storrs, CT-USA
The objective of these studies was to investigate the impact of heat treatment (annealing) on the
molecular mobility and pharmaceutical stability of freeze-dried materials. We subject the dried sample
to temperatures above ambient but below the glass transition temperature (Tg) for times on the order of
a few hours. Enthalpy relaxation times and other measures of mobility are determined, and stability
studies are conducted by storing samples at selected temperatures above ambient but well below Tg for
times on the order of months. Samples are assayed for degradation by HPLC assay, and rate constants
for degradation are evaluated. Example systems include decarboxylation in the antibiotic, moxalactam
di-sodium, formation of a cylic diketopiperazine in saccharide formulations of aspartame, dimerization
in saccharide formulations of sodium Ethacrynate (ECA), and aggregation in saccharide formulations
of an IgG1 monoclonal antibody. Protein (secondary) structure was characterized by FTIR on both
“fresh” and annealed samples. Enthalpy recovery and global mobility were studied with DSC and the
thermal activity monitor (TAM), respectively, and free volume was estimated based on density
measurements. Fast, local mobility was studied with neutron backscattering and with 13 C solid state
NMR. We find annealing has no effect on protein structure in the solid state, as measured by FTIR.
However, as expected, annealing decreases global mobility, and annealed samples exhibited better
pharmaceutical stability. Further, in spite of increases in degradation products during annealing, the
annealed samples showed less total degradation after about 1 month storage at ≈ 50°C. Thus, not only
is the degradation rate decreased by annealing, but the overall purity after storage is also improved. In
general, maximum enthalpy recovery, maximum (calorimetric) structural relaxation time, and
minimum fictive temperature were observed after annealing at about Tg-15 o C, and in those cases
where sufficient data were obtained, the minimum in degradation rate also occurred at Tg-15. While
annealing decreased global mobility, and increased density, both of which correlate with the observed
impact of annealing on stability, annealing had little or no effect on local mobility as measured by
neutron backscattering or 13 C solid state NMR relaxation times. This observation is quite unexpected
in view of the fact that we have several examples of formulation variations in stability being better
correlated with local dynamics than with global dynamics.
THIN FILM NETWORK GLASSES TO BE USED AS ION-CONDUCTING MEMBRANES
G. Schmitz, R. Abouzari, F. Berkemeier, G. Greiwe, T. Stockhoff
Institute of Material Physics, Westfälische Wilhelms-Universität, Wihelm-Klemm-Str. 10, 48149
Münster, Germany
gschmitz@uni-muenster.de
We explored the potential function of thin film borate and silicate network glasses as ion-conducting
membranes. Lacking crystalline anisotropies, amorphous materials can be deposited as homogeneous

films with almost perfect interfaces. We utilized this advantage to reduce the thickness of membranes
down to a few nanometers and studied the particular properties with decreasing thickness.
Conductivity and ionic transport across the membranes were quantified by impedance spectroscopy
and tested in thin film model batteries. Local chemical and structural analysis was performed by TEM
and atom probe tomography. It is demonstrated that the ionic conductivity of sputter-deposited Liborate
films increases by two to three orders of magnitude in comparison to the bulk glass that served
as sputter target, while thin films of silicate glass just reproduce the performance of the respective bulk
[1]. Furthermore, Li-borate glass films show a distinguished finite-size effect in conductivity.
Decreasing the thickness of the membranes from 100 nm down to about 7 nm, the specific
conductivity is shown to increase by three orders of magnitude [2]. Exploiting this effect, the absolute
conductivity across the membrane would be way sufficient to be used in an all-solid state battery.
[1] F. Berkemeier, M. R. Abouzari, G. Schmitz, Ionics, 15, 241 (2009).
[2] F. Berkemeier, M.S. Abouzari, G. Schmitz, Phys. Rev. B 76, 024205 (2007).
STABLE STRUCTURES IN SUPERCOOLED LIQUIDS: REFINING OUR INTUITION
CONCERNING SHAPE AND DISORDER
U. R. Pedersen (1), T. B. Schrøder (1), J. C. Dyre (1), T. S. Hudson (2) and P. Harrowell (2)
(1) Department of Science, DNRF Centre “Glass and Time”, IMFUFA, Roskilde University, Roskilde,
Denmark
(2) School of Chemistry, University of Sydney, Sydney NSW Australia
peter@chem.usyd.edu.au
The observation that liquids are disordered, while undisputed, is quite ambiguous. The term ‘disorder’
leaves unspecified exactly what order is missing and, therefore, what order may remain. Often, order
is implicitly associated with that of simple close packed crystals, despite the fact that most glassforming
materials form more complex crystals with many particles per unit cell. In this talk we shall
review some key ideas in the description of structures, simple and complex, and then apply them to the
results of extensive simulations of three model glass formers: a non-associating binary alloy proposed
by Wahnström, an associating binary alloy proposed by Kob and Andersen and a model of o-terphenyl
proposed by Lewis and Wahnström. In each case the supercooled liquid is observed to eventually
crystallise. Structural motifs, taken from the respective crystals, are used to develop descriptions of the
structural fluctuations in the metastable liquids and to establish the structural identity of the local
quenched potential minima (the inherent structures) that make up the low energy wing of inherent
structure density of states. We present a number of insights gained from these studies concerning the
role of short range and medium range order in stabilizing liquid structure, the difference between those
structures that slow down relaxation and those that nucleate crystallization and how good is our
intuition concerning the relationship between particle shape and glass forming ability.
MHZ-GHZ COHERENT ACOUSTIC WAVE STUDY OF GLASS-FORMING LIQUIDS
Keith A. Nelson
Department of Chemistry, MIT, Cambridge, MA 02139, USA
kanelson@mit.edu
We have developed methods for pulsed optical excitation of frequency-selected shear and longitudinal
acoustic waves throughout much of the MHz-GHz ranges and used the methods for study of
supercooled liquids. MHz acoustic waves are selected by wavevector through the use of crossed
excitation pulses whose interference defines the acoustic wavelength. GHz acoustic waves are selected

y frequency which is determined by the repetition rate of a timed sequence of optical pulses. The
methods have been used separately [1,2] to examine supercooled liquid behaviour in each frequency
range. Comprehensive use of the methods to map out structural relaxation dynamics across the
combined frequency ranges, and collaborative extension of the coverage to include far lower
frequency ranges probed by other methods [3], will be discussed.
[1] D. H. Torchinsky, J. A. Johnson, and K. A. Nelson, J. Chem. Phys., 130, 064502, 2009
[2] T. Pezeril, C. Klieber, S. Andrieu, and K. A. Nelson, Phys. Rev. Lett., 102, 107402, 2009
[3] C. Maggi, B. Jakobsen, T. Christensen, N. B. Olsen, J. C. Dyre, J. Phys, Chem. B, 112, 16320,
2008.
COHERENT MHZ SHEAR AND LONGITUDINAL ACOUSTIC PHONONS IN
SUPERCOOLED LIQUIDS
Jeremy A. Johnson, Darius H. Torchinsky, and Keith A. Nelson
Department of Chemistry, MIT, Cambridge, MA, USA
jeremyj@mit.edu
Recent advances in the depolarized impulsive stimulated Brillouin scattering technique [1] have made
available megahertz-frequency shear acoustic waves. In tandem with polarized impulsive stimulated
light scattering measurements [2], this allows previously inaccessible direct comparison of the shear
and longitudinal structural relaxation dynamics in the MHz frequency range. We present such
comparisons for the glass formers triphenyl phosphite and polyphenyl ether (Santovac 5) along with
tests of mode coupling theory predictions.
[1] D. H. Torchinsky, J. A. Johnson, and K. A. Nelson, J. Chem. Phys. 130, 064502, 2009.
[2] Y. Yang, and K. A. Nelson, J. Chem. Phys. 103, 7722, 1995.
THE LOW TEMPERATURE ENDOTHERM IN POLY(ETHYLENE TEREPHTHALATE):
PARTIAL MELTING AND RIGID AMORPHOUS FRACTION DEVITRIFICATION
M.C. Righetti (1), M.L. Di Lorenzo (2), E. Tombari (1), M. Angiuli (1)
(1) Istituto per i Processi Chimico-Fisici (CNR) – Area della Ricerca CNR – Via G. Moruzzi, 1, 56124
Pisa, Italy
(2) Istituto di Chimica e Tecnologia dei Polimeri (CNR) – Via Campi Flegrei 34, 80078 Pozzuoli
(NA), Italy
righetti@ipcf.cnr.it
A detailed investigation of the low temperature endotherm of poly(ethylene terephthalate) performed
by temperature-modulated differential scanning calorimetry is presented [1]. The origin of the small
endotherm, generally observed a few degrees above the crystallization temperature in PET and many
other polymers, is a widely discussed matter. The most frequent interpretation considers it as the result
of partial fusion with superposition of a recrystallization process, even if it has also been proposed that
it can originate from enthalpic recovery connected to mobilization of the rigid amorphous fraction. In
an attempt to resolve the question, a new method for the interpretation of the modulated heat-flow-rate
curve resulting from a temperature modulation program is here proposed. The procedure consists in
the analysis of the initial points of the steady-state heat-flow-rate signals in the heating and cooling
semi-periods, being the temperature modulation performed with a sawtooth profile. The study showed
that multiple processes, involving both the crystalline and the rigid amorphous fraction, overlap in the
temperature range in which the low temperature endotherm is observed. The origin of the endotherm
under investigation was found to be connected with both partial fusion of the crystalline portions and
enthalpy recovery subsequent to structural relaxation of the rigid amorphous fraction. An estimation of
the relative percentages of the two different processes is presented and discussed.

[1] M.C. Righetti, M.L. Di Lorenzo, E. Tombari, M. Angiuli, J. Phys. Chem. B, 112, 4233, 2008.
There is considerable interest in understanding the behavior of polymeric glasses and polymer
nanocomposites at multiple length scales, particularly under active deformation. Over the past two
years, we have used a combination of Monte Carlo and molecular dynamics simulations to examine
the local and global thermophysical properties of several coarse grain models of polymeric and
nanocomposite glasses both at rest and under constant stress or constant strain rate deformation. Our
simulations and recent experimental studies have demonstrated that an applied stress can lead to a
decrease in the segmental relaxation times by several orders of magnitude. Many questions regarding
the origins of these behaviors that remain unanswered. Our simulations of an entangled polymer glass
and a nanocomposite glass suggest that nanoparticles impart mechanical reinforcement onto the
polymer, requiring larger stresses to achieve the same deformation. In both materials, the dynamics
correlate well with the instantaneous strain rate, although there are situations where this correlation
breaks down. Our trends with the dynamics during creep agree very well with recent experiments on a
pure polymer glass. Finally, we examine how the entanglement network in the polymer is affected by
the presence of the nanoparticles. We find a significant number of network bridges between the
nanoparticles that become increasingly pronounced as the materials are deformed.
Following entanglements formation in a disentangled polymer melt
Sanjay Rastogi
Department of Materials
Loughborough University, Leicestershire LE11 3TU
England (UK)
e-mail: s.rastogi@lboro.ac.uk
One particular class of linear polyethylene is the ultra high molecular weight polyethylene
(UHMWPE) where the molar mass of the polyethylene is over 1 x 10 6 g/mol whereas the molar mass
of polyethylene is generally between 50,000-300,000 g/mol. UHMWPE has excellent physical and
mechanical properties [1] such as high abrasion resistance, high impact toughness, good corrosion,
chemical resistance, resistance to cyclic fatigue and resistance to radiation. Consequently, UHMWPE
finds use in highly demanding applications, as for example artificial hip prosthesis materials [2],
cordages, bullet resistance vests, helmets and others. However, one of the major draw-back of
UHMWPE is its poor processability. After processing UHMWPE, the final product possesses fusion
defects or grain boundaries which lead to poor mechanical performance.
Here we show that when synthesized under controlled conditions [3] it is feasible to obtain
high modulus – high strength polyethylene tapes below the melting point of the polymer [4].
Mechanical deformation of these high molar mass polymers strongly depends on the topological
constraints residing in the amorphous region of the semi-crystalline polymer [5], so is the melting
behavior of the thus synthesized polymer [6] and the resultant melt [7], where chains tend to entangle
with time [8].
[1]. Encyclopaedia of Polymer Science and Engineering; John Wiley & Sons: New York, 1985, 6, 495.
[2]. S. Li, A.H. Burstein, Bone and Joint Surg., 1994, 76A, 1080.

[3]. Process for the preparation of a shaped part of an ultra high molecular weight polyethylene;
application number: US2006142521 (A1) — 2006-06-29 ; S. Rastogi, K. Garkhail, R. Duchateau, G.
Gruter, D. Lippits
[4]. Polyethylene film with high tensile strength and high tensile energy to break; application owned
by Teijin Aramid; WO2009007045 (A1); 2009-01-14; AP de Weijer; M Peters; H van De Hee; S
Rastogi; B Wang.
[5]. Segmental Mobility in the Non-crystalline Regions of Semicrystalline Polymers and its
Implications on Melting; S Rastogi, Y Yao, DR. Lippits, GWH Höhne, R Graf, HW Spiess, PJ
Lemstra; Macromolecular Rapid Communications 30 (9-10) 2009, pp 826-839
[6]. Melting Kinetics in Polymers; DR Lippits, S Rastogi and GWH Höhne, Physical Review Letters,
96, 2006, p 218303..
[7]. Heterogeneity in polymer melts from melting of polymer crystals; S Rastogi, DR Lippits, G Peters,
R Graf, Y Yefeng, H Spiess, Nature Materials 2005, 4, 635-641
[8]. The formation of entanglements in an initially disentangled polymer melts; DR Lippits, S Rastogi,
S Talebi, C. Bailly, Macromolecules 2006, (39) 8882 – 8885.
DYNAMICS OF PROTEIN HYDRATION WATER NEAR THE GLASS TRANSITION. A
NEUTRON SCATTERING STUDY OF HYDRATED PHYCOCYANIN
W. Doster (1), S. Busch (2), M.S. Appavou (3) and J. Wuttke (3)
(1)Technische Universität München, Physik Department E13, D-85747 Garching, Germany.
(2) Technische Universität München, Forschungsneutronenquelle Heinz Maier-Leibnitz,
D- 85747 Garching bei München, Germany.
(3) Forschungszentrum Jülich GmbH, JCNS, D-85747 Garching bei München, Germany
wdoster@ph.tum.de
The anomalous dynamic and thermodynamic properties of bulk water led to the conjecture of a hidden
critical point deep in the super-cooled region near 220 K [1]. A direct observation of critical
fluctuations at such low temperatures is prevented by crystallization. The attention has thus turned
from bulk water to thin layers, where crystallization is suppressed.
Liquid water near protein surfaces can be super-cooled to TG ~170 K, where an amorphous, glassy
state is formed. The corresponding liquid-to-glass transition is coupled to protein collective motions.
The protein-dynamical transition was defined by the α-relaxation time crossing the experimental
window, which is detected by a decrease of elastic intensity above 220 K with neutron back –
scattering [2]. Recently a “fragile-to-strong” transition in the relaxation times of protein hydration
water at 220 K was deduced with lysozyme similar from neutron experiments. This dynamic result
war interpreted as providing evidence of a structural transition between two phases of amorphous
liquid [3]. Other workers suggest instead a dynamic cross-over of α and β-relaxation due to defect
migration in amorphous ice [4]. We present neutron scattering experiments performed at the new
spectrometer SPHERES (FRM2, Munich) related to water adsorbed on per-deuterated phycocyanin.
The resulting spectra contain an elastic contribution reflecting the nearly rigid protein structure and a
Q-dependent quasi-elastic fraction due water diffusion along the protein surface, reflecting the αrelaxation.
The average relaxation rates display a “fragile” or super-Arrhenius temperature dependence
above 220 K at fixed stretching parameter. The width of the rate distribution increases however
towards lower temperatures, which could be interpreted alternatively as a transition to “strong”
behavior. However, the elastic scattering transition is compatible with a purely dynamic effect of the

α-relaxation crossing the experimental time-window. Measurements of the thermal water-expansion
coefficient suggest a suppression of anomalous fluctuations, since the protein surface acts as a patch
breaker.
[1] P.H. Poole et al. Nature London 320, 324 (1992)
[2] W. Doster et al. Biophys.J. 50, 213(1986), W. Doster et al. Nat. 337, 754 (1989),
W. Doster and M. Settles, Biochim.Biophys.Acta 1749,173 (2005)
[3] S.-H. Chen et al, PNAS, 103, 9012(2006), M. Lagi et al. Phys.Chem.B. Lett.112,1571 (2008)
[4] J. Swenson et al, Phys. Rev. Lett., 96, 247802 (2006), M. Vogel, Phys.Rev. Lett. 101, 225701
(2008)
DNA DRIVEN 2D COLLOIDAL CRYSTALLIZATION
Nienke Geerts (1), Erika Eiser (2)
(1) FOM Institute for Atomic and Molecular Physics [AMOLF], Science Park 113, 1098XG
Amsterdam, The Netherlands.
(2) Cavendish Laboratory, University of Cambridge, J.J. Thomson Avenue, Cambridge CB3 0HE, and
BP Institute, Cambridge CB3 0EZ, United Kingdom.
ee247@cam.ac.uk
Much interest in DNA-coated colloids derives from the fact that such building blocks can be used to
make complex, self-assembling materials [1]. Functionalization of colloids by DNA is interesting for
several reasons: the most obvious one is the high selectivity of hybridization of complementary singlestranded
(ss)DNA sequences making it possible to design structures where colloids with
complementary ssDNA coating tend to be nearest neighbors. This opens the way to design ordered
colloidal structures and is at the basis of applications where such colloids can probe specific gene
fragments. However, even without the functionality due to selective hybridization, DNA plays a
special role in polymer science because very long, monodisperse DNA chains can be made using
bacteria. Here I present recent experiments that show that colloids coated with very long DNA can
assemble into unique ‘floating’ crystalline monolayers. The observed behavior is very different from
that of colloids coated with shorter DNA that cannot form colloidal flying carpets [2].
[1] C. A. Mirkin, R. L. Letsinger, R. C. Mucic, and J. J. Storhoff, Nature, 382, 607, 1996.
[2] N. Geerts and E. Eiser, arXiv:0906.3137v1 [cond-mat.soft].
MOBILE IONS IN NANOCRYSTALLINE AND NANOGLASSY MATERIALS
P. Heitjans, V. Epp, A. Kuhn, B. Ruprecht, E. Tobschall, M. Wilkening
Institut für Physikalische Chemie und Elektrochemie, Leibniz Universität Hannover, Callinstr. 3a,
30167 Hannover, Germany
heitjans@pci.uni-hannover.de
Extending reviews [1,2] on work by our group as well as presenting most recent results, we report on
diffusion studies of nanostructured ion conductors by nuclear magnetic resonance (NMR) and
impedance spectroscopies. Among the NMR techniques, spin-alignment echo (SAE) decay has newly
become an established method for Li ion conductors besides, e.g., spin relaxometry [3]. Both
nanocrystalline cation (Li + ) and anion (F - ) conductors as well as single-phase and composite systems,
such as LiTaO3 and BaF2:CaF2 [4,5], are considered. The nanocrystalline samples were prepared by
high-energy ball milling of microcrystalline starting materials. The largely increased interfacial
regions partly turned out to be amorphous. Whereas nanostructuring of microcrystalline materials by
mechanical treatment led to a substantial increase of the diffusivity, that of glassy samples, resulting in
“nanoglasses”, induced a decrease. Examples for systems, which form both a glass and a crystal and

where a convergence of the respective Li diffusivities with progressive ball milling has been observed,
are LiBO2 and LiAlSi2O6 [6,7].
[1] P. Heitjans, S. Indris, J. Phys.: Condens. Matter 15, R1257, 2003
[2] P. Heitjans, A. Schirmer, S. Indris, in: P. Heitjans, J. Kärger (Eds.), Diffusion in Condensed Matter
– Methods, Materials, Models, Springer, Berlin, 2005, pp. 367 - 415
[3] M. Wilkening, P. Heitjans, Phys. Rev. B 77, 024311, 2008
[4] M. Wilkening, V. Epp, A. Feldhoff, P. Heitjans, J. Phys. Chem. C 112, 9291, 2008
[5] B. Ruprecht, M. Wilkening, A. Feldhoff, S. Steuernagel, P. Heitjans, Phys. Chem. Chem. Phys. 11,
3071, 2009
[6] P. Heitjans, E. Tobschall, M. Wilkening, Eur. Phys. J. Special Topics 161, 97, 2008
[7] A. Kuhn, M. Wilkening, P. Heitjans, Solid State Ion. 180, 302, 2009
THE MIXED NETWORK FORMER EFFECT IN ION-CONDUCTING GLASSES:
STRUCTURE-PROPERTY CORRELATIONS IN PHOSPHATE BASED GLASS SYSTEMS
Hellmut Eckert, Institut für Physikalische Chemie, WWU Münster, Germany
eckerth@uni-muenster.de
Non-linear changes in the physical properties of glasses containing more than one type of network
former species are often exploited for optimizing the technological performance of glasses for optical
and electrical applications. Issues at the structural level concern the identification of the coordination
polyhedra arising from the specific interactions between the network former species involved, their
connectivity distribution, and the competition of both network formers for the network modifier
species. Modern solid state nuclear magnetic resonance (NMR) techniques present a new elementselective,
inherently quantitative approach to this problem, as NMR is not affected by the absence of
periodicity. Specifically, we have developed the site-resolved measurement and quantitative analysis
of internuclear magnetic dipole-dipole interactions, which can be translated into distance information
in a straightforward manner. Using this approach we have studied the mixed network former effect in
a variety of phosphate based glass systems, providing a structural rationale for the compositional
dependence of functional properties.
CALORIMETRY AND THERMODYNAMICS IN MATERALS SCIENCE
Tooru Atake (1)
(1) General Safty Management Center, Tokyo Institute of Technology, 2-12-1 Ookayama, Meguro-ku,
Tokyo, 152-8550 Japan
atake.t.aa@m.titech.ac.jp
Calorimetry and thermodynamics have long been playing a very important role in the research fields
of fundamental science and technology. In the early stages of the 20th century, the verification of the
third law of thermodynamics was one of the great achievements of thermodynamic study realized by
accurate adiabatic calorimetry. After the world war II, electronics and the application have been
extremely developed, and the experiments of calorimetry have been widely automated. Thus high
quality data have been produced extensively, and critical problems in materials science have been
solved [1]. Indeed the history is impressive. In the 21st century, the new frontiers of thermodynamic
studies are spreading into various research fields, such as nano-thermodynamics, bio-thermodynamics,

and environmental/global energy thermodynamics, among others. In the present report, some exciting
topics, examples of precise calorimetry, and fundamental thermodynamics studies are presented and
described on the basis of the present author’s experience, focusing attention on precise measurements
of calorimetry and the application to critical problems in materials science. The studies of phase
transition and polymorphism in some crystals are given, and the studies of glassy states are also given,
such as liquid glass [2], plastic crystal glass, and relaxors [3], etc.
[1] T. Atake, J. Chem. Thermodyn. 99, 1 (2009).
[2] T. Atake, H. Kawaji, T. Tojo, K. Kawasaki, Y. Ootsuka, M. Katou, and Y. Koga, Bull. Chem. Soc.
Jpn. 73, 1987 (2000).
[3] Y. Moriya, H. Kawaji, T. Tojo, and T. Atake, Phys. Rev. Lett. 90, 205901, (2003).
Acoustic excitations and the boson peak in glasses – what can we learn from crystals?
A. Matic (1), G. Monaco (2), C. Masciovecchio (3) and L. Börjesson (1)
(1) Department of Applied Physics, Chalmers University of Technology,
(2) European Synchrotron Radiation Facility, B. P. 220, F-380 43 Grenoble , France
(3) Sincrotrone Trieste, 34012 Basovizza Trieste, Italy
Correspondence author: lars.borjesson@chalmers.se
The origin of the Boson peak, the excess in the low frequency vibrational density of states for
amorphous materials, is not yet understood but there is considerable evidence that it is strongly linked
to the nature of acoustic modes at mesoscopic wave-lengths. In order to directly investigate the
influence of disorder on acoustic excitations we have previouslyperformed inelastic x-ray scattering
experiments (IXS) on both the glass and crystal phases of the same material [1]. In this contribution
we present new results on materials that include covalently bonded (SiO2, lithium borate), hydrogen
bonded (ethanol, glycerol) and van der Waals systems (OTP). From these experiments we can make
the connection between the different spectral contributions from the glass and the acoustic and optical
branches of the crystal and thereby get insight into the origin of the Boson peak for the different
materials.
[1] A. Matic, C. Masciovecchio, D. Engberg, G. Monaco, L. Börjesson, S.C. Santucci, and R. Verbeni,
Phys. Rev. Lett., 93, 145502, 2004.
STATE AND DYNAMICS OF WATER IN MALTOOLIGOMER SOLUTIONS AND
GLASSES: IMPLICATIONS FOR ENCAPSULATION AND BIOSTABILITY
Job Ubbink (1)
(1) Nestlé Research Center, Vers-chez-les-Blanc, CH-1000 Lausanne 26, Switzerland,
johan.ubbink@rdls.nestle.com
Glassy carbohydrates are widely used in foods and as matrix for the encapsulation and stabilization of
bioactive ingredients in foods such as flavors and nutrients. We report on experiments and on
molecular dynamics simulations which we have performed to investigate the properties of
maltooligomer solutions in the approach to the glass transition [1,2]. In particular, we here focus on
the molecular state and dynamics of water in such carbohydrate matrices [3-5]. This includes the
concentration and temperature dependence of the local state of water in maltooligomer matrices,
hydrogen bonding, and the translational and rotational mobility of the water molecule in relation to the
plasticization of amorphous carbohydrates. We find an interesting quantitative relation between the
concentration dependence of the experimental glass transition temperature of the carbohydrate
matrices and the diffusion of water.
[1] S. Townrow, D. Kilburn, A. Alam, J. Ubbink, J. Phys. Chem. 111, 12543, 2007.
[2] H.J. Limbach and J. Ubbink, Soft Matter 4, 1887, 2008.

[3] V. Molinero and W. A. Goddard, Phys. Rev. Lett., 95, 045701, 2005.
[4] C. J. Roberts and P. G. Debenedetti, J. Phys. Chem. B, 103, 7308, 1999.
[5] H.J. Limbach and J. Ubbink, manuscript in preparation, 2009.
SOLID-STATE NMR STUDY OF MOLECULAR DYNAMICS AND DOMAIN SIZES IN
PBT/TCNEO/FULLERENE NANOCOMPOSITE
Aneta Woźniak-Braszak (1) , Kazimierz Jurga (1) , Jan Jurga (2) , Bogusław Brycki (3), Krystyna
Hołderna-Natkaniec (1)
(1) Department of Physics, Adam Mickiewicz University, Umultowska 85, 61-614 Poznan, Poland
(2) Institute of Materials Technology, Poznan University of Technology, Poznan, Poland
(3) Faculty of Chemistry, Adam Mickiewicz University, Poznan, Poland
abraszak@.amu.edu.pl
The work presents the study of molecular dynamics and domain sizes in poly(butylene
terephthalate)/TCNEO/fullerene nanocomposite by solid-state NMR and NMR off-resonance
techniques. The spin–lattice relaxation times in the laboratory frame T 1 , and the spin–lattice relaxation
off
times off-resonance in the rotating frame T1 ρ as well as the second moment M 2 and the slope line
width of the 1 H NMR lines were measured as a function of temperature. To determine the size of
heterogeneities and characterize the morphology of the nanocomposites , the 1 H NMR spin-diffusion
experiment designed by Goldmann-Shen was performed. The measurements were performed using a
home–made pulse spectrometers operating at the frequency of 30.2 MHz. The second moment 1 H
NMR was measured by the continuous wave method. The correlation times of the internal motions
off
were estimated on the basis of the dispersion of the relaxation time T1 ρ below and above the glass
temperature Tg and the temperature dependence of the second moment of 1 H NMR line. The results
indicate that new nanocomposites were obtained by a modification of PBT with nanoparticles
TCNEO-C60. The molecular dynamics and domain sizes of PBT/TCNEO/C60 nanocomposites were
changed relative to those of the virgin PBT.
[1] M. Goldman, L. Shen, Phys. Rev.,144, 321, 1965
[2] J. Brus, J. Dybal, Polymer, 41, 5269, 2000
SMALL SCALE MECHANICAL RESPONSE OF MODEL GLASSES AND ITS
IMPLICATION FOR LOCAL DYNAMICS
Anne Tanguy (1), Michel Tsamados (1), and Jean-Louis Barrat (1)
(1) Université de Lyon, F-69622, Lyon, France ;
Université Lyon 1, Villeurbanne ;
CNRS, UMR 5586, Laboratoire de Physique de la Matière Condensée et Nanostructures
(LPMCN).
Anne.Tanguy@lpmcn.univ-lyon1.fr
Recent calculations of the elasto-plastic response of model amorphous materials (like Lennard-Jones
glasses [1,3] or empirical description of amorphous silicon [2]) show a strongly heterogeneous
response. At small scale (about 5-10 interatomic distances), the glass appears as a composite material
composed of a rigid scaffolding and of soft zones. Only recently calculated in disordered materials, the
local elastic moduli play a crucial role in the dynamical response of the solid material. For a small
macroscopic shear strain, they are related with the spatial structure of the nonaffine reversible
displacement field. For a larger macroscopic strain, the zones of low shear modulus concentrate most
of the plastic deformation. The spatiotemporal evolution of this local elasticity map and its connection

with vibrational modes and long term dynamical heterogeneity is quantified. The possibility to use this
local parameter as a predictor of local plastic activity is also discussed.
[1] M. Tsamados, A. Tanguy, F. Léonforte and J.-L. Barrat, Eur. Phys. J. E, 26, 283, 2008.
[2] M. Talati, T. Albaret and A. Tanguy, Europhysics Letters, 86, 66005, 2009.
[3] M. Tsamados, A; Tanguy, C. Goldenberg and J.-L. Barrat, Phy. Rev. B, 80, 026112, 2009.
A NEUTRON SCATTERING STUDY OF WATER CONFINED IN SEPHADEX G-15
K. Ito (1), K. Yohida (1), T. Yamaguchi (1), E. Moskvin (2) and M-C. Bellissent-Funel (3)
(1) Department of Chemistry, Fukuoka University, Jonan-ku, Fukuoka 8140-180, Japan
(2) Helmholtz-Zentrum Berlin ME, Glienicker Straße 100, 14109 Berlin, Germany
(3) Laboratoire Leon Brillouin, CEA Saclay, bât.563, 91191 Gif-sur-Yvette Cedex, France
ito_kanae@hotmail.com
We describe the low-temperature behaviour of water confined in cross-linked dextran polymer
Sephadex G-15 (average pore size 81 Å), which has flexible walls different from the hard hydroxyl
surface of MCM-41 [1], from quasielastic neutron scattering (QENS) and neutron spin-echo (NSE)
measurements performed over a temperature range of 290 - 245 K and 320 - 200 K and 50 K,
respectively. Within the scattering vector range Q of 0.2-1.4 Å -1 , both NSE and QENS data showed no
Q dependency for the relaxation time of the translational motion of water, suggesting the water motion
in confined space. On the other hand, the NSE data at temperatures above 320 K showed an increase
in inversed relaxation time in the Q range of 1.4-2.4 Å -1 . The self-diffusion coefficient of confined
water obtained at 320 K is smaller by a factor of ~ 30 than that of bulk water. The temperature
dependency of the relaxation time measured by NSE showed a non-Arrhenius behaviour characteristic
for fragile liquid.
[1] P. Smirnov et al, J. Phys. Chem., 104, 5498 (1998).
Molecular Recognition, Fluctuation, and Function of Protein
Studied by a Statistical Mechanics of Liquids
Fumio Hirata
Institute for Molecular Science, Okazaki, Aichi 444-8585, Japan
ABSTRACT
It is a common understanding that the molecular recognition is an essential elementary process for
protein to function. The molecular recognition is a thermodynamic process which is characterized by
the free energy difference between two states of a host-guest system, bound and unbound. On the
other hand, the time to reach the thermodynamic equilibrium depends on the free energy barrier
mainly associated with the conformational fluctuation of protein. Therefore, the molecular recognition
is a thermodynamic process conjugated with the conformational fluctuation of protein.
We have been developing a new theory for the molecular recognition by protein based on the
statistical mechanics of liquids, or the 3D-RISM/RISM theory. The theory has demonstrated its
amazing capability of “predicting” the process from the frist principle. [1] However, what we have
investigated so far is an entirely equilibrium process both in protein conformation and solvation.
Recently, we have started to incorporate the conformational fluctuation of protein into the molecular
recognition process in two ways. The first of those is a “static” one in which we just shake the protein
conformation to find the local minimum of the free energy surface by the combined 3D-RISM/RISM
with conformational sampling algorithms, and to see if one can find the distribution of a guest
molecule in the recognition site. One example of such studies will be presented in the talk. [2] The

other method is to take the “dynamic” fluctuation of protein conformation into account. The process
can be described by hybridized 3D-RISM/RISM with the generalized Langevin dynamics theories.
The methodology is currently under construction, and some prospective view of the theory will be
presented in the lecture.
REFERENCES
[1] T. Imai, et. al., J. Phys. Chem. B(Feature Article), 113, 873 (2009).
[2] Y. Kiyota, et. al., J. Am. Chem. Soc. (Communications), 131, 3852-3853 (2009).
[3] B.S. Kim, et. al., Cond. Matter Phys., 11, 179 (2008).
P-T DEPENDENCE OF RELAXATIONS AND VIBRATIONS IN SOME POLYMERS AND
LOW MOLECULAR GLASS FORMERS AS STUDIED BY INCOHERENT NEUTRON
SCATTERING
B. Frick (1), A. Chauty (2), K. Niss (2,3), J. Dyre (3), C. Dalle-Ferrier (2) and C. Alba-Simionesco
(2,4)
(1) Institute Laue-Langevin, BP 156, F-38042 Grenoble Cedex 9, France
(2) Laboratoire de Chimie Physique, Bâtiment 349, Université Paris-Sud, F-91405 Orsay, France
(3) DNRF centre “Glass and Time, ” IMFUFA, Department of Sciences, Roskilde University, Postbox
260, DK-4000 Roskilde, Denmark
(4) Laboratoire Léon Brillouin, UMR 12, CEA-CNRS, 91191- Gif-sur-Yvette, France
frick@ill.fr
We review pressure and temperature dependent incoherent neutron scattering experiments on
polybutadiene and polyisobutylene and n-diffraction experiments on polybutadiene [1-4]. The
temperature and pressure range extends from 2-400K and from 0.1-500 MPa, respectively. The
independent control of pressure and temperature allowed for examining the structure and dynamics
along isochores, isotherms and isochrones and thus to estimate the relative thermal or density
contributions to the slow and fast relaxations and to the Bosonpeak. On isochores the static structure
factor S(Q) and the Boson peak modes were found to be nearly constant [4], whereas the relaxation
dynamics changed drastically, both on the ns- and ps-time scale. An experimentally determined nsisochrone
[3], (same stretching parameter, thus spectral shape) revealed differences for the psrelaxations,
possibly due to the density dependence of the underlying Boson peak. The Q-dependence
of the KWW-relaxation time along isotherms shows a gradual change with pressure[3]. The
temperature dependence of the mean squared displacement (ns) as deduced from backscattering can be
superimposed for different pressure if a scaling with Tg(P) is applied to the temperature axis [1]. This
latter behaviour is also found for glycerol over a wide temperature range. We discuss the scaling of the
mean squared displacement and its possible relation to the Lindemann criterion including newer data
on low molecular glass forming systems. These molecular glass formers with very different fragility
show also a clear correlation between the temperature dependence of the msd, determined at T/Tg(P),
and the isobaric fragility in close agreement with predictions of elastic models.
[1] B. Frick and Ch. Alba-Simionesco, Physica B 266, 13-19 (1999). [2] B. Frick, C. Alba-Simionesco,
Applied Physics a-Materials Science & Processing 74 (2002) S549. [3] B. Frick, G. Dosseh, A.
Caillaux and C. Alba-Simionesco, Chem. Phys. 292 (2003) 311.[4] B. Frick, C. Alba-Simionesco, K.
H. Andersen, L. Willner, Phys. Rev. E 67(2003). [5] K. Niss, C. Dalle-Ferrier, B. Frick, D. Russo, J.
Dyre and C. Alba-Simionesco,, submitted.

BOSON PEAK AND THE JAMMING TRANSITION
M. Wyart
In repulsive short-range particles, the frequency of the boson peak scales with compression near
the jamming threshold where the particle overlaps vanish.
A variational argument is given, which explicitly unravels the nature and a length scale of the
soft modes at play, to derive the observed scaling. The argument relates the microscopic
structure of a glass to the boson peak, and has broader applications. It is applied to estimate the
density of states of silica and to explain the correspondence between the boson peak of certain
glasses and the Van Hove singularity of the corresponding crystals. This approach enables to
quantify the heterogeneity of stress propagation (force chains), and to derive a microscopic
criterion for the mechanical stability of amorphous structures, which appears to play a key role
in the dynamics near the glass transition in hard spheres.
HIGHER-ORDER TAGGED PARTICLE CORRELATIONS: A FIRST-PRINCIPLES
MODE-COUPLING APPROACH
R. Van Zon, J. Schofield
Higher order correlation of tagged particles involving multiple times and multiple points have
found an interesting application as measures of dynamical hetereogeneities in structural glasses.
We present a theoretical mode-coupling framework for these quantities, using a projection
formalism with a multi-linear basis composed of the slow variables of the system. The formally
exact expressions for multiple point and multiple time correlation functions become tractable by
applying the so-called N ordering method. It will be shown that this theory yields moderatedensity
leading mode coupling expressions for indicators of relaxation type (homogeneous
versus heterogeneous) which use dynamical filters.

Experimental study of out-of-equilibrium fluctuations in a colloidal suspension of
Laponite using optical traps.
Juan Ruben Gomez Solano
(Laboratoire de Physique, Ecole Normale Supérieure de Lyon, CNRS)
We address the issue of the validity of the fluctuation dissipation theorem and the time
evolution of viscoelastic properties during ageing of aqueous suspensions of a clay (Laponite
RD) in a colloidal glass phase. Given the conflicting results reported in the literature for
different experimental techniques, our goal is to check and reconcile them using simultaneously
passive and active microrheology techniques. For this purpose we measure the thermal
fluctuations of microsized Brownian particles immersed in the colloidal glass and trapped by
optical tweezers. We find that several methods based on both microrheology techniques lead to
consistent and complementary results and no violation of the FDT is convincingly observed
either for any frequency as low as 0.25 Hz or as an increase of the effective temperature during
the formation of the viscoelastic glass.
Our results are supported by the study of the probability density functions of heat fluctuations
between the probe particles and the suspension transferred at different timescales. Several
interesting features concerning the statistical properties and the long time correlations of the
particles are observed during the transition.
Beta Peak and Nearly-Constant Loss within Mode-Coupling Theory
Matthias Sperl, (DLR, Cologne, Germany)
Beta peaks, nearly-constant loss, and critical power laws can be
found within the MCT framework as a manifestations of the varying location of a Cole-Cole in
the spectrum. Position and amplitude of the Cole-Cole peak depend on both probe variable and
on the wave vector. It will be shown how simple microscopic models like the hard-sphere
system exhibit the features of the Cole-Cole peak like the difference between incoherent and
coherent scattering functions and their respective wave-vector variation.

Stochastic approach to chaotic stick-slip in granular systems
Alberto Petri, (CNR-ISC)
The sliding of contacting surfaces is a formidable problem with impact in many areas, ranging
from atomic to tectonic in scale. In several cases it can result in steady sliding or periodic stickslip
motion, but often displays an intermittent and erratic nature, for which effective
descriptions are lacking.
In order to investigate this kind of dynamics we have set up an experiment in which a rigid plate
engages in stick-slip shear motion on a granular bed.
We have found that the resulting dynamics can be described in a quantitative way by a simple
stochastic equation, in which the force exerted by the medium on the plate performs a random
walk. systems and comparisons with other phenomena suggest that a large class of driven
instabilities can be described in terms of similar general mechanisms.
Preliminary results on variable height and shaken granular bed are presented.
Diffusion Anomalies and Arrested Dynamics for Hydration Water
Francisco De Los Santos
We present a simple Hamiltonian model that reproduces the basic properties of liquid water and
that, by parameters tuning, reproduces various of the scenarios that have been proposed to
rationalized water anomalies. By means of extensive Monte Carlo simulations, we show results
on the ordering of the hydrogen bonds and the diffusion coefficient over a significant region of
the phase diagram. We discuss the possible relation of the diffusion anomaly to the existence of
a liquid-liquid critical point at low temperatures and some nonequilibrium phenomena at low
temperatures, possibly related to the appearence of a density minimum.

Jamming-like slow dynamics of peptide-induced pore in lipid bilayer membranes
Giulia Fadda (Université Paris 13, UFR SMBH, 93017 Bobigny)
Voltage clamp measurements on lipid bilayer at the onset of peptide attacks and pore formation
are reported. With four di erent peptides (alamethicin,melittin and two peptides of the LK
series), correlations of conductivity fluctuations slowly decay over four decades in time. This
slow dynamics is interpreted as being due to density uctuations at the crowded surface of the
bilayer and found to be compatible with the t −1/2 relaxation of the RSA model.
Fast Crystals: How complex structure drives fast relaxation
David A. Weitz (Harvard University)
Collaborators: E. Sloutskin, P.J. Lu, and T. Kanai
This talk presents new data on the relaxation of dense colloidal suspensions and the disorderorder
transition. The rate of crystallization of hard speheres is measured to be much faster than
predicted by normal theory and simulation. By viewing the structure of the crystals using
confocal microscopy, the crystallites are seen to be highly tenuous when they are small. This
results in a large number of possible morphologies, which provides an additional entropic
contribution to the free energy. When this is incorporated into the free energy, excellent
agreement with the data is obtained.
Soft colloids make strong glasses
David A. Weitz (Harvard University)
Collaborators: J. Mattsson, H. Wyss, A Fernandes-Nieves, K. Miyusaka,
D. Reichman.
Hard sphere colloids exhibit a glass transition as their volume fraction is increased and they
become increasingly crowded. The behavior is invariably 'fragile' within the fragility description
of the approach to the glass transition. We show that soft colloidal particles exhibit a much
richer range of behavior, and become increasingly 'strong' as the colloidal particles become soft.

By comparing the volumes where elastic energy corresponds to thermal energy, the data from
different stiffness particles can be unified.
Interestingly, similar behavior is observed for molecular glasses.
Relaxation of an isolated self-gravitating cloud.
Francesco Sylos Labini
(Enrico Fermi Center and Institute for Complex Systems CNR)
When an open system of classical point particles interacting by Newtonian gravity collapses, it
relaxes violently reaching a quasi-stationary state (QSS) in virial equilibrium. We discuss the
role of the initial density fluctuations and velocity distribution in this relaxation process. For an
initially cold system, it is observed that an arbitrary amount of energy may in principle be
carried away by particles which escape to infinity. We discuss the mechanism of this mass and
energy ejection, showing that it arises from the interplay of the growth of perturbations with the
finite size of the system. In addition we discuss the importance of fluctuations at different scales,
and discreteness (i.e. non-Vlasov) effects in the dynamics. Finally we show that the amount of
energy/particles ejected and the statistical properties of the QSS strongly depends on the initial
velocity dispersion of particles.
References:
M. Joyce, B. Marcos, F. Sylos Labini "Dynamics of finite
and infinite self-gravitating systems with cold quasi-uniform initial
conditions", Journal of Statistical Mechanics, 2009, P04019
M. Joyce, B. Marcos, F. Sylos Labini "Energy ejection in the
collapse of a cold spherical self-gravitating cloud"
Monthly Notices Royal Astronomical Society, in the press (2009)
arXiv:0811.2752
F. Sylos Labini, "Gravitational clustering: an overview", in the
proceedings of the workshop ``Dynamics and Thermodynamics of systems
with long range interactions: theory and experiments'', A. Campa,
A. Giansanti, G. Morigi, F. Sylos Labini Eds., American Institute of

Physics Conference proceedings, 970 (2008) arXiv:0806.2560
GHZ FREQUENCY LONGITUDINAL AND TRANSVERSE ACOUSTIC
SPECTROSCOPY OF GLASS-FORMING LIQUIDS
Christoph Klieber, Kara J. Manke and Keith A. Nelson
(Department of Chemistry, MIT)
We have developed novel picosecond ultrasonics techniques capable of probing the longitudinal
and transverse acoustic responses of glass-forming liquids in the GHz frequency range, which
heretofore has been experimentally inaccessible. Key to this approach is a unique femtosecond
pulse-shaping technique, which is used to generate sequences of optical pulses and
corresponding multiple-cycle acoustic waves at GHz frequencies. This method has been
employed to probe the GHz frequency longitudinal and transverse acoustic response of glycerol
and other liquids over a wide temperature range, and results are used to test the predictions of
mode-coupling theory.
[1] T. Pezeril, C. Klieber, S. Andrieu, and K. A. Nelson, Phys. Rev. Lett., 102 , 107402, 2009
[2] J. D. Choi, T. Feurer, M. Yamaguchi, B. Paxton, and K. A. Nelson, Appl. Phys. Lett., 87,
081907, 2005
Structure of space-time in glass forming liquids
David Chandler
(Department of Chemistry University of California, Berkeley)
Anomolous phenomena associated with super-cooled liquids manifest fluctuation dominance of
correlated dynamics - growing time scales, dynamic heterogeneity and transport de-coupling. A
useful interpretation of these phenomena is obtained by viewing the structure of trajectory space.
Facilitation and excitation lines are found to emerge from the structure of trajectory space for

atomistic models to structural glass formers. At equilibrium, these features are reflected in
mesoscopic segregation of mobile and immobile domains.
These domains become unbounded at non-equilibrium conditions where a first-order transition
appears between ergodic and non-ergodic phases.
Structure of space-time in glass forming liquids
Juan P. Garrahan
(School of Physics & Astronomy University of Nottingham)
Glass forming systems have a much richer dynamical phase structure than their
thermodynamics would suggest. I will show how to explore this by means of large-deviation
methods. In particular, I will describe the dynamical first-order space-time phase transition that
occurs in kinetically constrained models, and other models of glasses, by computing the largedeviation
functions of relevant dynamical observables. I will discuss consequences of this
dynamic phase coexistence, such as dynamic heterogeneity and transport decoupling.

Vitrification and Polyamorphism of a 2D simple monatomic system
T. Mizuguchi (1), T. Koumyou (1), T. Odagaki (1)
(1) Department of Physics, Kyushu University, Fukuoka, Japan
Correspondence author: t.mizuguchi@cmt.phys.kyushu-u.ac.jp
We present strong evidences of vitrification in a simple monatomic liquid in
two dimensions, where atoms interact isotropically with Lennard-Jones-Gauss
(LJG) potential [1]. It is found that the glass transition temperature Tg is
an increasing function of the cooling rate in the preparation process of the
amorphous state. The glassy state can be formed if the LJG potential has
appropriate parameters favoring the formation of a pentagonal local order. The
effect of frustration with packing of pentagons is the origin of the stability of
the glassy state. One of the features of this system is that the time needed
for crystallization is sufficiently long. It enabled us to determine the Time-
Temperature-Transformation@diagram of a simple system [2]. It has a nose
shape and the transformation time into crystal is the shortest at a temperature
13% below the melting temperature. Above Tg, crystal nuclei rapidly spread
to the whole system. Below Tg, the growth of crystal nuclei becomes slower
as a temperature is decreased. Another characteristic feature of this system
is that polyamorphism is observed. Polyamorphism is that multiple liquid or
amorphous phases exist. Anisotropy of potential has been considered as the
origin of polyamorphism. We call in question about this explanation. It is
found that the glass-glass transition occurs in the LJG system. Since LJG
potential is an isotropic one, we conclude the origin of polyamorphism is not
anisotropy of potential.
[1] M. Engel and H.-R. Trebin, Phys. Rev. Lett. 98, 225505 (2007)
[2] T. Mizuguchi and T. Odagaki, Cent. Eur. J. Phys., in press (2009)

THE LORENTZ MODEL: A PARADIGM FOR TRANSPORT IN
HETEROGENEOUS MEDIA
T. Franosch
Arnold Sommerfeld Center for Theoretical Physics and Center for NanoScience
(CeNS), Department of Physics, Ludwig-Maximilians-Universität München, Theresienstraße
37, D-80333 München, Germany
Correspondence author: franosch@lmu.de
Transport of tagged ions, macromolecules, or nanoparticles in heterogeneous
environments is strongly hindered by the presence of a variety of differently sized
components. Three major transport phenomena are observed: normal diffusion,
immobilization or localization, and anomalous transport. It will be shown that
all aspects may be unified into the concept of transport in a disordered, heterogeneous
medium with a percolation transition [1]. We have investigated
Lorentz models with ballistic and Brownian tracer particles by means of largescale
computer simulations. We have observed the long-time tail in the velocityautocorrelation
function [2] resolving a long-standing debate. It is demonstrated
that in the immediate vicinity of the localization transition, universality holds
at large time scales. The scaling function describing the crossover from anomalous
transport to diffusive motion is found to vary extremely slowly and spans
at least 5 decades in time. To extract the scaling function, one has to allow for
the universal corrections to scaling which are derived by a new cluster-resolved
scaling approach [3].
[1] F. Höfling, T. Franosch, E. Frey, Phys. Rev. Lett. 96, 165901 (2006)
[2] F. Höfling, T. Franosch, Phys. Rev. Lett. 98, 140601 (2007)
[3] A. Kammerer, F. Höfling, T. Franosch, EPL 84 66002 (2008)

Crystallization of polymorphic pharmaceuticals in nanopores
G.P. Rengarajan (1), S. Pankaj (1), D. Enke (1), M. Steinhart (2), M. Beiner (1)
(1) Martin-Luther-Universität Halle-Wittenberg, Fakultät für Naturwissenschaften
II, D-06099 Halle/Saale, Germany
(2) Max-Planck-Institut für Mikrostrukturphysik, D-06120 Halle/Saale, Germany
Correspondence author: beiner@physik.uni-halle.de
The influence of nanoconfinement on the crystallization behavior of the polymorphic
model drug acetaminophen existing in three different crystalline forms
has been studied by conventional DSC as well as complementary wide angle
x-ray scattering measurements. The experiments are performed on two types of
nanoporous host-guest-systems with average pore diameters in the range 4-400
nm. Most of the measurements are done on controlled porous glasses (CPGs)
having a sponge-like topology filled with acetaminophen. Additional measurements
are performed on acetaminophen confined in mesoporous alumina with
isolated and oriented pores. We show that nanoconfinement is a handle to rationally
produce and study (i) polymorphic states which are metastable and
practically inaccessible in case of bulk samples like form III of acetaminophen
[1] and (ii) the amorphous state of strongly crystallizable drugs [2]. The results
are discussed in the light of thermodynamic changes in nanosized systems and
in connection with confinement-induced changes in nucleation behavior as well
as peculiarities in the mobility close to strongly interacting interfaces.
[1] M. Beiner, G.T. Rengarajan, S. Pankaj, D. Enke, M. Steinhart, Nano Letters
7 (2007) 1381-1385.
[2] G.T. Rengarajan, D. Enke, M. Steinhart, M. Beiner, Journal of Materials
Chemistry 18 (2008) 2537-2539

LYAPUNOV SPECTRA AND CONJUGATE-PAIRING RULE
OF CONFINED ATOMIC FLUIDS
Stefano Bernardi (1), Billy D. Todd (2), Debra J. Searles (3),
Jesper S. Hansen (4), Federico Frascoli (5),
(1), (2), (4) Centre for Molecular Simulation, Swinburne University of Technology,
P.O. Box 218, Hawthorn, Victoria 3122, Australia
(3) School of Science, Griffith University, Brisbane, Qld 4111, Australia
(5) Brain Sciences Institute, Swinburne University of Technology, PO Box 218,
Hawthorn, Victoria 3122, Australia
Correspondence author: sbernardi@ict.swin.edu.au
The Lyapunov exponents measure the average rate of expansion and/or contraction
of two initially nearby phase space trajectories of dynamical systems.
They are one of the main tools for the characterization of chaos, providing also
a quantitative measure. They have been used extensively to understand the
chaotic properties of fluids in Molecular Dynamics (MD) and Non-Equilibrium
Molecular Dynamics (NEMD) simulations and have proven to be a particularly
useful tool for the characterization and theoretical analysis of systems far from
equilibrium in thermostatted steady states. Untill now the focus was on homogeneous
systems in which the equations of motion were modified to include
external forces and thermostatting terms and the dissipative character of the
dynamics was distributed among all the degrees of freedom. In this work we try
to characterize Lyapunov spectra for inhomogeneous systems at a nonequilibrium
steady state, thus obtaining an insight into what happens along different
directions in the phase-space characterized by different dynamics with the use
of NEMD. We show detailed results on the effect that real walls have on the
Lyapunov spectra, computing the exponents even for the phase space of wall
atoms. We focus the research on two types of flow, Couette and Poiseuille. The
former describes the motion of a fluid between two surfaces moving in opposite
direction, the latter of a fluid moving inside a channel under the influence of an
external force field (eg. gravity). We show how the spectra reflects the presence
of two different dynamics in the simulation cell: wall and fluid atoms are of the
same species but the selective application of the thermostatting mechanism on
one species only creates two dynamics, one Hamiltonian and one dissipative.
Our study also throws considerable light onto why homogeneously thermostatting
highly confined fluids is an unsound practice.

Nonequilibrium fluctuations of an interface exposed to a shear flow
M. Thiébaud and T. Bickel
CPMOH, Université Bordeaux 1, 33405 Talence, France
Correspondence author: th.bickel@cpmoh.u-bordeaux1.fr
Soft matter systems driven far from equilibrium by a shear flow can manifest
striking properties as a result of their sensitivity to external fields. Here, we
investigate the statistical properties of a fluid interface in a stationary Couette
flow. We first set up a (fluctuating) hydrodynamic theory in order to derive a
mode-coupling equation for the interface. Our study reveals that thermal fluctuations
are driven out of equilibrium by an effective shear rate, different from
the applied one. We then find that the mean square displacement of the interface
is strongly reduced by the flow, in agreement with experiments [1]. We also
show that nonequilibrium fluctuations present a certain degree of universality
in the sense that all features of the fluids can be factorized into a single control
parameter. Finally, the results are discussed in the light of recent experimental
[1] and numerical studies [2,3].
[1] D. Derks, D.G.A.L. Aarts, D. Bonn, H.N.W. Lekkerkerker and A. Imhof,
Phys. Rev. Lett., 97 (2006), 038301.
[2] T.H.R. Smith, O. Vasilyev, D.B. Abraham, A. Maciolek and M. Schmidt,
Phys. Rev. Lett., 101 (2008), 067203.
[3] A.K. Thakre, J.T. Padding, W.K. den Otter and W.J. Briels, J. Chem.
Phys., 129 (2008), 044701.

DYNAMICS OF WATER AND IONS IN CLAYS - EXPERIMENT
AND SIMULATION
N. Malikova (1)
(Presenting author underlined)
(1) Laboratoire Leon Brillouin (CNRS-CEA), CEA Saclay, 91191 Gif-sur-Yvette,
France
Correspondence author: natalie.malikova@cea.fr
Clays are layered alluminosilicates with water retention and ion exchange properties,
which are responsible for many natural phenomena such as retention of
molecules by soil and exploited in the many technological applications of clays,
e.g. in catalysis and radioactive waste disposal. We deal with the microscopic
structure and motion of water and cations (Na + and Cs + ) in clays, as a function
of clay hydration. At low clay hydration, water and ions in clays are found
in a quasi two-dimensional (2D) confinement and very high ionic concentrations
(order of 10 water molecules per ion). Using the examples of a natural
montmorillonite clay and a synthetic hectorite clay we present a comparison of
experimental (quasi-elastic neutron scattering) and simulated (classical Molecular
Dynamics) dynamic data. These agree in the diffusion coefficient of water
confined in clay, predicting its decrease by a factor of 10 and 3 with respect to
bulk water, when a single and a double water layer is confined between clay layers
respectively [1,2]. Simulation points to very different modes of diffusion for
the two ions considered, their diffusion coefficients are however similar. The 2D
nature of water and ion diffusion is clearly seen in simulation, it is obscured in
neutron scattering data due to the use of powder clay samples. can be revealed,
using a novel method based on analyzing the scattered intensity at zero energy
transfers at a wide range of energy resolutions [3].
NM acknowledges E. Dubois, V. Marry, B. Rotenberg, P. Turq, J. Breu,
J.-M. Zanotti and S. Longeville.
[1] N. Malikova, A. Cadène, V. Marry, E. Dubois and P. Turq, J. Phys. Chem
B 110 (2006) 3206-3214.
[2] N. Malikova, A. Cadène, E. Dubois, V. Marry, S. Durand-Vidal, P. Turq, J.
Breu, S. Longeville and J-M. Zanotti, J. Phys. Chem C 111 (2007) 17603-17611.
[3] N. Malikova, S. Longeville, J.-M. Zanotti, E. Dubois, V. Marry, P. Turq and
J. Ollivier, Phys. Rev. Lett. 101 (2008) 265901.

SECONDARY RELAXATIONS IN GLASSES, BINARY SYSTEMS
AND PLASTIC CRYSTALS STUDIED BY 2 H NMR
B. Micko (1), S.A. Lusceac (2), E.A. Rössler (1)
(1) Experimentalphysik II, Universität Bayreuth, Germany
(2) Institut für Festkörperphysik, Technische Universiät Darmstadt, Germany
bjoern.micko@uni-bayreuth.de
We present a deuteron NMR study concerning the Johari-Goldstein β-relaxation.
Bailing the possibilities of 2 H NMR with the aptitude of selective deuteration
we intend to unravel the microscopic properties of the β-process. Therefore we
studied a series of molecular glasses and polymers, many of them previously
investigated by dielectric spectroscopy, by means of one- and two-dimensional
NMR to quantify the reorientation angle a molecule undergoes due to β-process
in a specific temperature range. Furthermore, we investigate binary systems
which yield, via adjusting the concentration of the labeled component, a (controlled)
separation of α− and β-process on the temperature scale and therefore
a wider range in which the β-process can be studied undisturbed by the structural
relaxation. Additionally, we present results from a plastic crystal in which
reduced degrees of freedom may give a more direct insight on the underlying
geometries of motion.

Key experiments in highly viscous liquids
U. Buchenau
Institut für Festkörperforschung, Forschungszentrum Jülich
Postfach 1913, D–52425 Jülich, Germany
Correspondence author: buchenau-juelich@t-online.de
The flow of highly viscous liquids is still a theoretical no-man’s-land, with many
contradictory theories competing for the explanation of the flow process. On
the other hand, a rapid experimental development, in particular in the field
of broadband dielectric spectroscopy, supplies more and more information on
the nature of the highly viscous flow. The flow process itself (the so-called
primary or alpha-process) seems to be intimately related to faster precursor
processes, which appear either as an ”excess wing” of the flow process itself
or as a secondary relaxation peak, the ”Johari-Goldstein”-peak, five orders of
magnitude faster than the primary process. The talk describes some of these
key experiments and their possible theoretical interpretation.

SUBDIFFUSIVE EARLY STAGE POLYMER DIFFUSION IN A
MELT
Jean Farago, Albert Johner, Hendrik Meyer, Joachim Wittmer, Jörg Baschnagel
ICS, Strasbourg, France Correspondence author: farago@ics.u-strasbg.fr
For a decade or so, numerical simulations and experimental works have confirmed
a short-time universal behaviour of the mean square displacement (MSD)
of the center of mass of a polymer in a dense melt: after a microscopic regime,
and before the Rouse time, the MSD generically displays a subdiffusive powerlaw
regime, whose exponent is believed to be around 0.8. We show that simple
arguments combining the traditional theory of polymer dynamics and modecoupling
approaches lead to predictions for the universal prediffusive regime,
which we compare with simulations. Moreover we show that the relaxation of
the Rouse modes is also affected by the same type of “retardation effect” which
introduces some corrections to the expected exponential form, as well as nonanalytical
corrections to the scaling of the relaxation time with respect to the
mode index.

Time-resolved experiments on glass-formers: the water case
A. Taschin, P. Bartolini, R. Eramo and R. Torre
European Lab. for Non-Linear Spectroscopy (LENS) and Dip. di Fisica, Univ.
di Firenze, via N. Carrara 1, I-50019 Sesto Fiorentino, Firenze, Italy
and INFM-CRS-Soft Matter (CNR), Piaz. A. Moro 2, I-00185, Roma c/o Univ.
la Sapienza, Roma, Italy.
Correspondence author: torre@lens.unifi.it
During the last years, time-resolved non-linear spectroscopy has been revealed
one of the best tool for dynamic investigation in complex liquids [1]. These
experimental techniques are complementary to the frequency domain measurements
and are particularly valuable when a complex variety of relaxation channels
are present. In particular, the heterodyne-detected optical Kerr effect (HD-
OKE) experiments have shown to be a unique spectroscopic tool in order to investigate
the glass-former dynamics [2], enabling a deep check of the theoretical
models, especially of the mode-coupling theory (MCT). Recently few HD-OKE
studies have been performed on liquid water and one have been extended to its
supercooled phase [3]. This HD-OKE experiment have been focused on the investigation
of the slower decay, addressing it to a structural/diffusive relaxation
phenomena that is in substantial agreement with the MCT scenario. According
to these results, the water singularity temperature is the signature of an avoided
dynamical arrest.
Using improved experimental set-up [4] and water sample, we have been able
to extend the HD-OKE measurements to a larger time-window and temperature
range. We can thus provide the first unambiguous measurement of the entire
correlation function, inclusive of the fast vibrational dynamics, in supercooled
water up to the nucleation limit.
[1] R. Torre, Time-resolved spectroscopy of complex liquids, an experimental perspective.,
(Springer, New York, 2008)
[2] R. Torre, P. Bartolini, M. Ricci, R.M. Pick. EuroPhys.Lett. 52 (2000) 324
[3] R. Torre, P. Bartolini, R. Righini, Nature 428 (2004) 296
[4] P. Bartolini, A. Taschin, R. Eramo and R. Torre, Phil. Mag. 87 (2007)
731; P. Bartolini, A. Taschin, R. Eramo, R. Righini and R. Torre, J. of Physics:
Conf. Series, in press.

GLASS TRANSITION AND DYNAMICS OF STACKED THIN POLY-
MER FILMS
K. Fukao, Y. Oda, K. Nakamura, D. Tahara
Department of Physics, Ritsumeikan University, Kusatsu, 525-8577, Japan
Correspondence author: fukao.koji@gmail.com
It is well-known that the glass transition temperature Tg of thin polymer films
deviates from that of the corresponding bulk system. However, the origin of the
deviation of Tg is still in debate. In this study, we have investigated the glass
transition temperature and the dynamics of the α-process for stacked ultrathin
films of poly(2-chlorostyrene) using dielectric relaxation spectroscopy. Our measurements
show that Tg of 10 stacked films of 11-nm thickness is lower by about
10 K than that of the single thin film of the same thickness when the sample
is annealed at 120 ◦ C for 2 hours before measurements. The larger reduction
in Tg for the stacked films suggests that there is a stronger confinement effect
or interfacial effect in the stacked films than in the single ultrathin film. On
the other hand, the peak temperature Tα at which the dielectric loss shows a
maximum has almost no difference between the stacked ultrathin films and the
single thin film of the same thickness. The different behavior between Tg and
Tα might be explained if we take into account the frequency dependence of the
confinement effect or interfacial effect. The detailed discussion will be given in
the lecture.

Dynamics and local order in a 2D colloidal
glass former
Florian Ebert, Sylvain Mazoyer, Georg Maret, Peter Keim
University of Konstanz
Email: peter.keim@uni-konstanz.de
Using positional data from video-microscopy we study a bi-disperse colloidal
mixture in two dimensions. Since the colloids are super-paramagnetic a
magnetic field induces a dipolar repulsion between the particles, acting as an
inverse temperature. At low magnetic fields (high temperature) the system is
in a disordered fluid state. Increasing the magnetic field strength (decreasing
the temperature) the system traverses from a fluid to a dynamically arrested
state while staying amorphous on a global scale. The mean square displacement
(MSD) is in good agreement with Mode Coupling Theory for a hard
disc glass former. In the supercooled state dynamic heterogeneities appear
on the timescale of the α-relaxation and the self part of the Van Hove function
shows an exponential tail. Nevertheless small crystallites with distinct
stoichiometries appear on a local scale in the supercooled state. The basic
vectors of the unit cells are used to interpret the position of the peaks in the
pair correlation function of the 2D system. The statistics of the crystalline
unit cells show a continuous increase of local order with decreasing system
temperature. If the system is quenched with huge cooling rates we explore
the relaxation behaviour of the system. The first peak of the partial pair
correlation function evolves nonmonotonically in time.
1

INTERMOLECULAR DYNAMICS OF IONIC LIQUIDS AND THEIR
MIXTURES: THE VIEW OF DIELECTRIC SPECTROSCOPY
R. Buchner (1), J. Hunger (1), A. Stoppa (1)
(Presenting author underlined)
(1) Institut für Physikalische und Theoretische Chemie, Universität Regensburg,
Regensburg, Germany
Correspondence author: richard.buchner@chemie.uni-regensburg.de
Dielectric spectroscopy of room-temperature ionic liquids (RTILs) is challenging
because contributions from electrode polarization and, especially, DC conductivity
largely swamp the spectra up to ∼10 GHz. At the same time, contributions
specific to the intermolecular dynamics (here for simplicity called the dielectric
spectrum, ˆε(ν)), such as dipole reorientation and libration or intermolecular
vibrations, are rather small, overlap strongly and extend over a wide range of
frequencies, ν (∼ 1 MHz to 10 THz [1]). Since most experimental spectra cover
only a fraction of the relevant frequency range their interpretation in terms of
molecular-level processes is problematic.
In this contribution we discuss the dielectric spectra of pure imidazolium
RTILs, covering ∼200 MHz — 10 THz, and 0.2–89 GHz spectra of their mixtures
with acetonitrile and dichloromethane. It appears that the dominant mode for
pure RTILs, at ∼ 1 − 10 GHz depending on RTIL and temperature, can be
assigned to the reorientation of imidazolium cations through large-angle jumps.
Anions with sufficient dipole moment may contribute at ∼5 − 20 GHz. At ν >
200 GHz strongly overlapping intermolecular vibrations and librations dominate.
There is strong evidence for pronounced dipole-dipole correlations. Long-lived
individual ion pairs cannot be detected for pure RTILs but comparison of ˆε(ν)
with optical Kerr-effect spectra suggests the existence of larger aggregates.
The dynamics of the RTIL + polar solvent mixtures remains ionic-liquid
like over a surprisingly large composition region, 0.3 < xRTIL ≤ 1. When
further diluted the mixture behaves like a typical electrolyte solution with ˆε(ν)
dominated by the rotational diffusion of free ions and contact ion pairs.
[1] A. Stoppa, J. Hunger, R. Buchner, G. Hefter, A. Thoman, H. Helm, J. Phys.
Chem. B 112 (2008) 4854.

GLASS TRANSITIONS IN STAR-LINEAR POLYMER MIXTURES
Manuel Camargo (1,2) and Christos N. Likos (1)
(1) Institute for Theoretical Physics, Heinrich Heine University of Düsseldorf,
Universitätsstraße 1, D-40225 Düsseldorf, Germany
(2) Dirección Nacional de Investigaciones, Universidad Antonio Nariño, Kra 3
Este 47a-15 Bogotá, Colombia
Correspondence author: likos@thphy.uni-duesseldorf.de
We apply suitable coarse-graining procedures to investigate the structural and
dynamics behavior of mixtures between multiarm star polymers and linear
copolymer chains [1]. The complex mixture is thereby reduced to a ‘simple’,
two-component fluid in which the central monomers of the stars and the chains
appear as effective coordinates, interacting by means of monomer-mediated effective
potentials. On the basis of these, we examine the influence of the chains
on the structural arrest of concentrated star-polymer solutions and we discover
two distinct scenarios: for high functionality stars, the added chains bring about
a restoration of ergodicity in the mixture [3], whereas for low- and intermediate
star functionalities, a novel glass state shows up, which is not present for the
pure star system. The results are analyzed by means of Mode Coupling Theory
and computer simulations.
[1] C. Mayer and C. N. Likos, Macromolecules 40, 1196 (2007).
[2] G. Foffi, F. Sciortino, P. Tartaglia, E. Zaccarelli, F. Lo Verso, L. Reatto,
K. Dawson, and C. N. Likos, Phys. Rev. Lett. 90, 238301 (2003).
[3] E. Stiakakis, D. Vlassopoulos, C. N. Likos, J. Roovers, and G. Meier, Phys.
Rev. Lett. 89, 208302 (2002).

Molecular dynamics studies of the fragile to strong transition in confined
water: how similar is it to that of the bulk ?
P. Gallo (1)
(1) University Roma Tre, Rome, Italy
Correspondence author: gallop@fis.uniroma3.it
Molecular dynamics simulations of deeply supercooled SPC/E water
confined in a cylindrical pore of MCM-41 silica material are presented
[1] in order to locate the fragile to strong transition recently
measured in experiments on water in MCM-41 [2] and in bulk simulations
[3].
The alpha-relaxation time of the mobile portion of the confined
water is extracted with a layer analysis of the tag-particle density
correlators. From examination of the temperature dependent behavior
of the relaxation time, the dynamic susceptibility and the specific
heat a fragile to strong dynamic transition (FS) at T ∼ 215 K is located.
The maximum found in the specific heat at the FS transition
also shows evidence that this transition is related to the crossing of
the Widom line indicating the presence a low density and high density
liquid-liquid coexistence.
This study points out that experiments on confined water are
extremely relevant for the comprehension of low temperature bulk
properties and gives a strong evidence of a unifying scenario for supercooled
water encompassing dynamics and thermodynamics.
[1] P. Gallo, M. Rovere and S.-H. Chen, in preparation (2009). [2] L.
Liu, S.-H. Chen, A. Faraone, C.-W. Yen and C.-Y. Mou, Phys. Rev.
Lett. 95, 117802 (2005).
[3] L. Xu, P. Kumar, S. V. Buldyrev, S.-H. Chen, P. H. Poole, F.
Sciortino and H. E. Stanley, Proc. Natl. Acad. Sci. U.S.A. 102,
16558 (2005).

Structural cross-over in water confined in MCM-41-S15 (BOLD, LEFT)
R. Mancinelli (1), F. Bruni 1, S. H. Chen 2, K. H. Liu 3, C. Y. Mou 3,M. A. Ricci
(1)
(1)Dipartimento di Fisica ”E. Amaldi”, Universita’ degli Studi ”Roma Tre”,
Via della Vasca Navale 84, 00146 Roma, Italy.
(2) Department of Nuclear Science and Engineering, Massachusetts Institute of
Technology 24-209, 77 Massachusetts Ave. Cambridge, MA 02139.
(3)Department of Chemistry, National Taiwan University, Taipei 106, Taiwan.
Correspondence author: corr_ricci@fis.uniroma3.it
Evidence for the existence of a temperature of minimum density of water has
been found in several computer simulations, while an experimental test is so far
missing, due to ice nucleation in bulk samples below 240 K. Yet it is possible
to supercool water well below this temperature, provided that it is confined in
small enough volumes. Recently Liu and coworkers[1] have reached temperatures
as low as 150K in their small angle neutron scattering (SANS) experiment
on water confined in MCM-41-S15, and observed a minimum of the scattered
intensity, explained as due to a minimum of water density at 210 K. The issue
of structural changes in confined water, associated with the existence of a minimum
of density at this temperature is tackled by neutron diffraction with H/D
isotopic substitution. It is found that water confined in MCM-41-S-15 silica
matrix undergoes a structural cross-over from an inhomogeneous occupancy of
pore volume at ambient temperature to a homogeneous one at low temperature,
where a more open tetrahedral network of hydrogen bonds is recovered.
[1] D. Liu, Y. Zhang, C.-C. Chen, C.-Y. Mou, P. H. Poole, and S. H. Chen,
Proc. Natl. Acad. Sci. USA 104, 9570 (2007).

Thermodynamics and liquid-liquid critical point in the supercooled
sodium chloride aqueous solution
D. Corradini (1), P. Gallo (1) and M. Rovere (1)
(1) Dipartimento di Fisica, Università Roma Tre, Via della Vasca Navale 84,
I-00146, Roma, Italy
Correspondence author: gallop@fis.uniroma3.it
In the past years several theoretical and experimental studies have led to a
picture in which the anomalous properties of water are due to the presence
of a liquid-liquid phase transition in the supercooled region, terminating in a
liquid-liquid critical point. It is thus interesting to investigate the supercooled
region of ionic aqueous solutions in order to study the effect of the ions on
the liquid-liquid critical point phenomenon. We report the results of molecular
dynamics computer simulations on bulk TIP4P water and on the sodium chloride
aqueous solution at three different concentrations (c = 0.67 mol/kg, c =
1.36 mol/kg and c = 2.10 mol/kg), studied upon supercooling. For all systems
the temperatures of maximum density line and the limit of mechanical stability
line are calculated from the analysis of the thermodynamic planes. We found
that although the limit of mechanical stability remains unaltered with respect
to bulk water, the temperatures of maximum density line is shifted to lower
temperatures and pressures and modified in shape. Signatures of the presence
of liquid-liquid coexistence are found for all systems. In order to locate the position
of the liquid-liquid critical point we performed extensive simulations on
bulk water and on the c = 0.67 mol/kg solution in the low temperature region.
The results are presented and discussed.
[1 ]D. Corradini, P. Gallo and M. Rovere, in preparation (2009).
[2] D. Corradini, P. Gallo and M. Rovere, J. Chem. Phys. 130, 154511 (2009).
[3] D. Corradini, P. Gallo and M. Rovere, J. Chem. Phys. 128, 244508 (2008).

Moledular mechanisms of relaxation and deformation in glassy materials
Jörg Rottler (1) and Mya Warren (1)
(1) Department of Physics and Astronomy, University of British Columbia,
6224 Agricultural Rd., Vancouver, BC V6T 1Z1, Canada
Correspondence author: jrottler@phas.ubc.ca
Amorphous solids such as glassy polymers, colloidal glasses, and physical gels
are invariably characterized by slow dynamics. The ensuing nonequilbrium relaxation
or aging process modifies material properties such as creep compliance
and yield stress. The molecular mechanisms of yield and flow in these materials
are much less understood than in crystals, where well defined defects such as
dislocations are the carriers of plastic deformation. We use molecular simulations
and phenomenological models to gain insight into the microscopic origins
of elastoplastic behavior of disordered solids and its interplay with the intrinsic
aging dynamics. We will show how particle mobility controls plastic flow,
and how aging appears to be reduced in solids under load [1]. Analysis of a
trap model, which assumes thermally activated hopping dynamics in a random
energy landscape, provides further insight into the nature of such rejuvenation
and overaging phenomena [2]. By decomposing individual particle trajectories
obtained from molecular dynamics into discrete hopping events, we obtain a
statistical description of the molecular rearrangements in terms of a continuous
time random walk, which provides insight into the scaling of displacement
distributions with material age and the origin of aging at the molecular level [3].
[1] M. Warren and J. Rottler, Phys. Rev. E 76, 031802 (2007)
[2] M. Warren and J. Rottler, Phys. Rev. E 78, 041502 (2008)
[3] M. Warren and J. Rottler, arXiv:0901.0526 (2009)

SCALING LAWS FOR ACTIVE AND NONLINEAR MICRORHE-
OLOGY IN DENSE COLLOIDAL SUSPENSIONS
M. V. Gnann (1), T. Voigtmann (1,2)
(1) Fachbereich Physik, Universität Konstanz, 78457 Konstanz, Germany
(2) Institut für Materialphysik im Weltraum, Deutsches Zentrum für Luft- und
Raumfahrt (DLR), 51170 Köln, Germany
Correspondence author: Manuel.Gnann@uni-konstanz.de
We derive scaling laws of simplified (schematic) models based on a first-principles
theory for the active nonlinear microrheology of a colloidal model system. Recent
developments within the context of the mode-coupling theory (MCT) for
idealized glass transitions have yielded approximations for the friction on a
spherical probe particle embedded in a dense host dispersion, neglecting hydrodynamic
interactions [1]. The friction is connected via a nonlinear, nonequilibrium
generalization of a Green-Kubo relation with the coherent and incoherent
density correlation functions of host and probe particles respectively. The theory
predicts a threshold external force for a (continuous) delocalization transition of
the pulled probe particle in the glass. Based on a simplified version of the model
we derive power laws for the time-dependent density correlation functions and
the friction in the vicinity of the delocalization transition of the probe particle
and the glass transition of the host particles that are related to the known power
laws of mode-coupling theory. The results are compared to simulation data, and
modifications of the model are discussed.
[1] I. Gazuz, A.M. Puertas, T. Voigtmann, M. Fuchs, Phys. Rev. Lett. in print
ArXiv:0810.2627.

MULTIPLE GLASSES IN ASYMMETRIC BINARY MIXTURES
S. Schnyder (1), Th. Voigtmann (1,2)
(1) Fachbereich Physik, Universität Konstanz, 78457 Konstanz, Germany
(2) Institut für Materialphysik im Weltraum, Deutsches Zentrum für Luft- und
Raumfahrt (DLR), 51170 Köln, Germany
Correspondence author: Simon.Schnyder@uni-konstanz.de
We study the glassy dynamics of dense binary mixtures with very disparate
sizes. For a model hard-sphere mixture within mode-coupling theory of the glass
transition (MCT), several different glasses may appear, depending on size ratio,
concentration ratio, and density. We find an idealized discontinuous transition
between large-particle- and small-particle-dominated glasses. The transition
surface is bordered by higher-order singularities implying logarithmic decay of
time-dependent correlation functions. Additionally, for small enough concentrations
and sizes of the small particles, a region appears where the system freezes
only partially, i.e. where small particles stay mobile in a frozen matrix of large
particles. Only at densities inside the big-particle glass, small particles then
become localized at a second, continuous localization transition. The vicinity
of this transition gives rise to anomalous power-law-like diffusion. We discuss
general aspects of the transitions within a schematic model of MCT.

Evolution of Dynamic Heterogeneity in Aging Studied via Micron-PCS: a New Ruote
to The Investigation of Dynamic Correlations in Complex Soft-Matter
Claudio Maggi a
DNRF Centre ’Glass and Time’, IMFUFA,
Department of Sciences, Roskilde University,
Postbox 260, DK-4000 Roskilde, Denmark
(Dated: August 27, 2009)
Non-equilibrium dynamics and dynamic heterogeneity[? ] are distinctive features of complex
disordered systems. We develop a new technique (micro-PCS) that can measure directly the dynamic
heterogeneity for colloidal suspensions of nano-particles. In our experiment we combine heterodyne
and homodyne dynamic light scattering[? ] within micron-sized scattering volumes to reveal a
growing dynamic heterogeneity in an aging solution of Laponite[? ]. The behavior of this dynamical
correlation length is compared with exact prediction for critical coarsening[? ]. These results suggest
a new possibility for the direct measurement of dynamic heterogeneities even in molecular liquids
provided that the radiation is focused to nanometric volumes.
[] M. D. Ediger, Annu. Rev. Phys. Chem. 51 99 (2000).
[] B. Ruzicka, L. Zulian, R. Angelini, et al Physical Review E, 77 (2008).
[] A. Annibale and P. Sollich J. Stat. Mech. 02064 (2009)
[] B. Berne, and R. Pecora. Dynamic Light Scattering. Plenum, New York (1985).
a Electronic address: cmaggi@ruc.dk

Aging to Equilibrium Dynamics of SiO2
K. Vollmayr-Lee (1), J. A. Roman (1), J. Horbach (2)
(1) Bucknell University, PA, US
(2) DLR, Koeln, Germany
Correspondence author: kvollmay@bucknell.edu
We study the aging dynamics of SiO2 (modeled by the BKS model) via molecular
dynamics simulations. Starting from equilibrated configurations at a higher
temperature Ti ∈ {5000 K, 3760 K}, the system is quenched to a lower temperature
Tf ∈ {2500 K, 2750 K , 3000 K, 3250 K} and observed after a waiting
time tw. Since our simulation runs are long enough to reach equilibrium for
Tf = 3000K, 3250 K, we are able to study the transition from out-off equilibrium
to equilibrium dynamics. We present results for the partial structure factors,
and for the generalized intermediate incoherent scattering function Cq(tw, tw+t).
We conclude that there are three different tw regions: (1) At very short waiting
times Cq(tw, tw+t) decays very fast without forming a plateau. (2) With increasing
tw a plateau develops. For intermediate waiting times the plateau height is
independent of tw, time superposition applies, i.e. Cq = Cq(t/τ(tw)), and for
Cq = Cq(h(tw + t)/h(tw)) we find h to be independent of q. (3) At large tw the
system reaches equilibrium (Tf = 3000K, 3250 K) that means Cq(tw, tw + t) is
independent of tw, Ti, and Tf.

A STRUCTURAL MECHAMISM FOR DYNAMICAL ARREST
C. Patrick Royall (1), Stephen Williams (2), Takehiro Ohtsuka (3), Hajime
Tanaka (3)
(Presenting author underlined)
(1) School of Chemistry, University of Bristol, Bristol, BS8 1TS, UK.
(2) Research School of Chemistry, The Australian National University, Canberra,
ACT 0200, Australia.
(3) Institute of Industrial Science, University of Tokyo, 4-6-1 Komaba, Meguroku,
Tokyo 153-8505, Japan.
Corresponding author: paddy.royall@bristol.ac.uk
The mechanism by which a liquid may become arrested, forming a glass or
gel, is a long standing problem of materials science. While possible dynamic
mechanisms have received considerable attention, direct experimental evidence
of structural mechanisms has proved elusive. In particular, long-lived (energetically)
locally favoured structures (LFS), whose geometry may prevent the
system relaxing to its equilibrium state, have long been thought to play a key
role in dynamical arrest. Here we propose a definition of LFS which we identify
with a novel topological method and combine these with experiments on
colloidal liquid-gel, and glass-liquid-glass transitions. The population of LFS is
a strong function of (effective) temperature in the ergodic liquid phase, rising
sharply approaching dynamical arrest, and indeed forms a percolating network
which becomes the ‘arms’ of the gel. Due to the LFS, the gel is unable to reach
equilibrium, crystal-gas coexistence. Our results provide direct experimental
observation of a link between local structure and dynamical arrest, and open a
new perspective on a wide range of metastable materials.
[1] C.P. Royall, S.R. Williams, T. Ohtsuka and H, Tanaka, Nature Materials, 7
(2008) 556.

Single Molecule Probes of Glass-Forming Polymers: A Molecular Dynamics
Simulation
R. A. L. Vallée (1), K. Binder (2), W. Paul (2)
(1) Centre de Recherche Paul Pascal, CNRS, 33600 Pessag, France
(2) Institut für Physik, Johannes Gutenberg University, 55099 Mainz, Germany
Correspondence author: Wolfgang.Paul@uni-mainz.de
Molecular Dynamics simulations of a system of short bead-spring chains containing
an additional dumbbell are presented and analyzed. This system represents
a coarse-grained model for a melt of short, flexible polymers containing fluorescent
probe molecules at very dilute concentration. It is shown that such a system
is very well suited to study aspects of the glass transition of the undercooled
polymer melt via single molecule spectroscopy, which are not easily accessed by
other methods [1,2,3,4]. Such aspects include data which can be extracted from
a study of fluctuations along a trajectory of the single molecule, probing the
rugged energy landscape of the glass forming liquid and transitions from one
metabasin of this energy landscape to the next one. Such an information can
be inferred from distance maps constructed from trajectories characterizing the
translational and orientational motion of the probe. At the same time, determining
autocorrelation functions along such trajectories, it is shown for several
types of probes (differing in their size and/or mass within reasonable limits)
and for several choices of the chain length of the glass-forming polymer matrix
that this time-averaged information of the probe is fully compatible with ensemble
averaged information on the relaxation of the matrix, accessible from bulk
measurements. The analyzed quantities include the fluorescence lifetime, linear
dichroism, and also various orientational correlation functions of the probe,
in order to provide guidance to experimental work. Similar to earlier findings
from simulations of bulk molecular fluids, deviations from the Stokes-Einstein
and Stokes-Einstein-Debye relations are observed.
[1] R. A. L. Vallée, M. Van der Auweraer, W. Paul, K. Binder, Phys. Rev. Lett.
97, 217801 (2006)
[2] R. A. L. Vallée, M. Van der Auweraer, W. Paul, K. Binder, Europhys. Lett.
79 46001 (2007)
[3] R. A. L. Vallée, W. Paul, K. Binder, J. Chem. Phys. 127 154903 (2007)

Effective temperature of active matter
D. Loi (1), S. Mossa (2), L. F. Cugliandolo(3)
(1) European Synchrotron Radiation Facility, Boite Postale 220, F-38043 Grenoble,
France
(2) UMR 5819 (UJF, CNRS, CEA) CEA, INAC, SPrAM, 17 Rue des Martyrs,
38054 Grenoble Cedex 9, France
(3) Universitè Pierre et Marie Curie–Paris VI, LPTHE UMR 7589, 4 Place
Jussieu, 75252 Paris Cedex 05, France
Correspondence author: stefano.mossa@cea.fr
Active matter is driven out-of-equilibrium by internal or external energy sources.
Its constituents absorb energy from the environment or from internal fuel reservoirs
and dissipate it by carrying out internal movements that lead to complex
motion.
In this talk we address the question if the concept of effective temperature,
developed in the context of passive glassy systems, can be applied to active
matter. This could help us in rationalizing in a coherent framework extremely
complex dynamical processes. We have studied by means of molecular dynamics
computer simulation two systems: 1) self-propelled particles and 2) motorized
semi-flexible polymers. These systems can be considered as (over-)simplified
models for bacteria colonies or the cytoskeleton, the cellular scaffolding contained
within the cytoplasm. We discuss our findings[1,2] and focus, in particular,
on structure and dynamic behavior as a function of the activity of the
internal stimuli.
[1] D. Loi, S. Mossa, and L. F. Cugliandolo, Phys. Rev. E 77, 051111 (2008)
[2] D. Loi, S. Mossa, and L. F. Cugliandolo, in preparation

Entanglement Dynamics of Stiff Biopolymers
F. Höfling, T. Munk, E. Frey, and T. Franosch
Arnold Sommerfeld Center for Theoretical Physics and Center for NanoScience,
Fakultät für Physik, Ludwig-Maximilians-Universität, Munich, Germany
Correspondence author: felix.hoefling@lmu.de
Entangled networks of stiff biopolymers exhibit complex dynamic response,
emerging from the topological constraints that neighboring filaments impose
upon each other. The relevant dynamic processes cover many decades in time,
posing a tremendous challenge both to experiments and simulations. Pioneered
by Edwards and de Gennes, the many-filament interaction was condensed in the
picture of reptation in a confining tube.
To achieve progress beyond simple scaling arguments, we discuss a minimal
model for entanglement dynamics of stiff biopolymers, where the filament motion
is restricted to a plane, and the constraints appear as obstacles. For the
important limit of an infinitely thin and rigid polymers, i.e., needles, we have
performed large-scale computer simulations. In the highly entangled regime,
our results unambiguously prove the conjectured scaling relations from the fast
transverse equilibration to the slowest process of orientational relaxation [1].
The entanglement constraints lead to a highly anisotropic translational motion,
which is coupled to the reorientation dynamics. We have developed a
mesoscopic description of the anisotropic dynamics [2]. Our theory is based on
the exact solution of the Smoluchowski-Perrin equation; it is in quantitative
agreement with extensive Brownian dynamics simulations in the dense regime.
We show that the emerging sliding motion is characterized by a power law decay
of the intermediate scattering function, F (k, t) ∼ t −1/2 .
[1] F. Höfling, T. Munk, E. Frey, T. Franosch, Phys. Rev. E 77 (2008)
060904(Rapid Comm.).
[2] T. Munk, F. Höfling, E. Frey, T. Franosch, EPL 85 (2009) 30003.

Temperature dependence of the high-frequency dynamics in sorbitol
B. Ruta (1), G. Baldi (2), V. Giordano (1), F. Scarponi (3,4), D. Fioretto (3,4),
G. Monaco (1)
(1) European Synchrotron Radiation Facility, BP220, F-38043 Grenoble,
France
(2) INFM-CNR CRS-SOFT, Operative Group in Grenoble c/o E.S.R.F., BP220,
38043 Grenoble, France
(3) INFM-CNR CRS-SOFT, Univerisità di Roma ”La Sapienza”, P. A. Moro 2,
I-00185 Roma, Italy
(4) Dipartimento di Fisica, Univerisità di Perugia, Via A. Pascoli, I-06100 Perugia,
Italy
ruta@esrf.fr
The relation among low-temperature anomalies, vibrational density of states
and elastic properties of glasses has been recently the subject of a controversial
debate[1]. Examples have been reported of glasses where the boson peak scales
with the Debye frequency when an external perturbation like pressure is applied
[2]. However, this phenomenology seems not to be universal [3]. A possible way
to shed some light on this issue is to study how the dispersion curves of glasses
depend on temperature and/or pressure.
We present here Brillouin light scattering (BLS) and inelastic x-ray scattering
(IXS) measurements of the longitudinal acoustic modes of a glass of sorbitol as
a function of temperature. In fact, the simultaneous presence of both a boson
peak at high energy (∼5 meV) and a high fragility value (m∼ 100) makes sorbitol
an excellent candidate to study the longitudinal acoustic dynamics across
the boson peak energy range. We find that the whole dispersion curve of sorbitol
rigidly scales together with the low-frequency BLS limit when temperature is
changed, in accordance with a quasi-harmonic picture. This in particular applies
in the energy range of the boson peak, where the apparent sound velocity
shows an abrupt decrease which marks the breakdown of the Debye approximation.
These results suggest that the boson peak scales with the Debye frequency
in all those systems where a simple quasi-harmonic approximation holds, while
a more complex scenario characterized by the presence of anharmonic and/or
relaxational effects is likely present in the other cases.
[1] G. Baldi et al., Phys. Rev. Lett. 102, 195502 (2009)
[2] A. Monaco et al., Phys. Rev. Lett. 97, 135501 (2006)
[3] K. Niss et al., Phys. Rev. Lett. 99, 055502 (2007)

Continuous crossover from Kohlrausch to Cole-Davidson susceptibility
R. Kahlau (1), Th. Blochowicz (2), E. A. Roessler (1)
(1) Universität Bayreuth, Germany
(2) Technische Universität Darmstadt, Germany
Correspondence author: robert.kahlau@uni-bayreuth.de
In order to quantify the spectral shape of the α-relaxation peak of supercooled
liquids a new step response function is introduced which includes the Kohlrausch
and Cole-Davidson function as the two limiting cases. The shape of the peak is
described by two parameters whereas one of them controls the exponent of the
high frequency flank (β) while the other one describes the overall width of the
relaxation peak (α). Scaling dielectric datasets of different type-A glass formers
shows that the shape of the α-peak varies slightly with temperature. The interpolation
of those data with the new function shows indeed that it is necessary
to model the α-relaxation peak with two shape parameters. It turns out that
for most type-A systems β can be kept constant for all recorded temperatures
whereas α changes with temperature in a sytematic way, indicating a crossover
of the spectral shape from Kohlrausch characteristics at low T to Cole-Davidson
characteristics at high T .

EXTENDED MODE-COUPLING THEORY AND
DYNAMICAL HETEROGENEITIES
S.-H. Chong
Institute for Molecular Science, Okazaki 444-8585, Japan
chong@ims.ac.jp
The connection of activated hopping processes with dynamical heterogeneities is
explored based on an extended version of the mode-coupling theory (MCT). The
activated hopping processes are taken into account via the dynamical theory,
originally developed to describe diffusion-jump processes in crystals and adapted
here to glass-forming liquids. It is shown that the extended MCT accounts for
the breakdown of the Stokes-Einstein relation observed in a variety of fragile
glass formers. It is also demonstrated that characteristic features of dynamical
heterogeneities revealed by recent computer simulations are reproduced by the
theory. More specifically, a substantial increase of the non-Gaussian parameter,
double-peak structure in the probability distribution of particle displacements,
and the presence of a growing dynamic length scale are predicted by the theory,
which the idealized version of the theory failed to reproduce. These results of
the theory are demonstrated for a model of the Lennard-Jones system, and are
compared with related computer-simulation results and experimental data.
Reference: S.-H. Chong, Phys. Rev. E 78 (2008) 041501

DYNAMICS OF NANOCOMPOSITES BASED ON POLYSTYRENE
AND FULLERENES STUDIED BY DIELECTRIC AND SCATTER-
ING TECHNIQUES
Alejandro Sanz (1), Aurora Nogales (1),Tiberio Ezquerra (1)and João Cabral
(2)
(1) Instituto de Estructura de la Materia (CSIC), C/ Serrano 121, Madrid 28006.
Spain
(2) Department of Chemical Engineering, Imperial College, London SW7 2AZ,
UK
Correspondence author: asanz@iem.cfmac.csic.es
Confined polymers at a nanometre scale exhibit a fascinating structural and dynamic
behaviour which has attracted much attention in recent years. Inelastic
incoherent neutron scattering (INS) provides a direct measurement of local mobility
and has been recently employed to study thin film dynamics, albeit limited
by signal-to-noise ratio and therefore limiting the analysis to the Debye-Waller
factor. Instead of polymer thin film confinement (2D), we study 3D confinement
of polymers in miscible nanocomposites, investigating both structure (SANS
and microscopy) and dynamics (INS, QENS, dielectric spectroscopy, calorimetry
). The model systems chosen are mixtures of polystyerene and Buckminster
fullerenes (C60), which given the size mismatch of particles and polymer Rg,
have been shown to be thermodynamically miscible below a finite (few %) percolation
threshold. In order to study the influence of the nanoparticles on the
local polymer dynamics, measurements of the Debye-Waller factor and QENS
broadening at different time and length scales, were carried out. The model
systems chosen are mixtures of polystyerene and Buckminster fullerenes (C60 ),
which given the size mismatch of particles and polymer Rg, have been shown
to be thermodynamically miscible below a finite (few %) percolation threshold.
In order to study the influence of the nanoparticles on the local polymer
dynamics, measurements of the Debye-Waller factor and QENS broadening at
different time and length scales, were carried out. Based on a simple harmonic
model, the slope of the DW factor is related to the resistance to displacement
of the protons. Top figure shows how the presence of C60 nanoparticles reduces
the stiffness of the PS vitreous matrix [1]. Our experimental results generally
indicate that the addition of C60 to PS leads to enhanced fast dynamics (as measured
by the mean-square amplitude of proton displacements) consistent with
C60 plasticizing PS much like the addition of a typical small molecule solvent to
the polymer melt. QENS measurements show slight differences in the dynamics
as a consequence of the nanoparticles. On the contrary, the elastic incoherent
structure factor seems to me modified by the nanoparticles, suggesting that the
C60 is affecting the geometry of the motion under study. These measurements
open a new opportunity to elucidate the dynamic consequences of 3D confinement.
We have also carried out a deep study of the segmental dynamics of
these nanocomposites by means of DSC and dielectric spectroscopy. Calorimetry
shows that the addition of C60 increases the nanocomposite glass-transition

temperature (Tg) up to a ‘threshold’ C60 concentration (mass fraction 4 %),
whereupon Tg reverts gradually towards its neat value. The corresponding relaxation
map extracted from the dielectric relaxation curves for PS and PS/C60
nanocomposites shows that there is a distinct difference in the relaxation times
between neat PS and the nanocomposites, a result that thus reconcile our previous
results using DSC. From these measurements, we report experimentally
that the fragility of the PS matrix increases with the presence of C60 nanoparticles.
This argument has been recently proposed theoretically indicating that an
enhancement of the polymeric chains frustration induced by the nanoparticles
should increase the fragility of the polymeric matrix [2]. In this communication,
we demonstrate that C60 nanoparticles induce both plasticization (speeded up
dynamics) and antiplasticization (slowed down dynamics) effects depending on
the temperature range studied. This behaviour can be explained assuming that
C60 reduce the efficiency of molecular packing. Fullerenes in PS appear to be
‘fragility enhancing’ additives.
[1] A. Sanz, M. Ruppel,J. F. Douglas and J. T. Cabral, J. Phys.:Condens. Matter,
20, 104209, 2008
[2] T. Psurek, J. Obrzut, C. L. Soles, K. A. Page, M. Cicerone and J. F. Douglas,
Phys. Chem. B, 112, 15980, 2008

Dynamic Arrest in Polymer Melts:
Competition between Packing and Intramolecular Barriers
M. Bernabei (1), A. J. Moreno (2), J. Colmenero (1,2,3)
(1) Donostia <strong>International</strong> Physics Center, San Sebastián, Spain
(2) Centro de Física de Materiales, CSIC-UPV/EHU, San Sebastián, Spain
(3) Departamento de Física de Materiales, UPV/EHU, San Sebastián, Spain
Correspondence author: sckbernm@ehu.es
We present molecular dynamics simulations of a simple model for polymer melts
with intramolecular barriers. We investigate structural relaxation as a function
of the barrier strength. Dynamic correlators can be consistently analyzed within
the framework of the Mode Coupling Theory (MCT) of the glass transition. Unusually
large values of the so-called MCT exponent parameter, obtained from
the data analysis, suggest a competition between general packing effects and
polymer-specific intramolecular barriers as two different mechanisms driving
dynamic arrest in the system [1].Solutions of the MCT equations for the nonergodicity
parameters as a function of the barrier strength are also presented. We
report a quantitative comparison between simulation results and mode coupling
theory calculations. We observe that theory reproduces qualitative trends in the
nonergodicity parameters and critical temperatures. This agreement becomes
worse in the limit of stiff chains. We discuss possible origins of this feature.
[1] M. Bernabei, Angel J. Moreno, Juan Colmenero, Phys. Rev. Lett. 101
(2008) 255701

EFFECT OF POLYMERIZATION ON THE BOSON PEAK, FROM
THE LIQUID TO THE GLASS
S. Caponi (1,2), S. Corezzi (2,3), D. Fioretto (2,3), A. Fontana (1,2), G. Monaco
(4), F. Rossi (1,2)
(1) Dipartimento di Fisica, Università di Trento, Via Sommarive 14, I-38050
Povo (Trento), Italy
(2) CNR-INFM CRS Soft, Università di Roma “La Sapienza”, P. A. Moro 2,
I-00185 Roma, Italy
(3) Dipartimento di Fisica, Università di Perugia, Via A. Pascoli, I-06100 Perugia,
Italy
(4) European Synchrotron Radiation Facility, BP 220, F-38043 Grenoble, France
Correspondence author: caponi@science.unitn.it
Raman scattering measurements are used to follow the modification of the vibrational
density of states in a reactive epoxy–amine mixture during isothermal
polymerization. As the reaction proceeds, in the initially liquid solution
an increasing number of van der Waals bonds are replaced by stiffer covalent
bonds. This process slows down the molecular diffusion and ultimately leads to
a frozen, glassy structure. The gradual transformation from liquid to glass is
accompanied by microscopic structural changes driven by the bonding process.
Meanwhile, the sample density and the sound velocity increase, both contributing
to significantly change the Debye level. Combining Raman with Brillouin
light and inelastic x-ray scattering measurements, we analyze the variations of
the boson peak and of the Debye level while the system changes from liquid to
glass. The shift and intensity variation of the boson peak are fully explained
by the modification of the elastic properties, and a master curve for the boson
peak can therefore be obtained [1]. Surprisingly, bond–induced modifications of
the structure that affect both atomic vibrations and slow cooperative motions
do not modify the relative excess of states over the Debye level. Therefore, the
transformation of the BP -even in the liquid phase- is shown only to be determined
by the change in the elastic moduli of the medium, independently of the
occurrence of modifications of the samples microscopic structure.
[1] S.Caponi et al., Physical Review Letter 102, 027402 (2009).

Dynamics of Water Confined in Partially Hydrophobic Nanosized
Cylindrical Sieves
A. Faraone (1,2), K.-H. Liu (3), C.Y. Mou (3), Y. Zhang (4), S.-H. Chen (4)
(1) NIST Center for Neutron Research, National Institute for Standards and
Technology, Gaithersburg, Maryland 20899-6102, USA
(2) Department of Materials Science and Engineering, University of Maryland,
College Park, Maryland 20742, USA
(3) Department of Chemistry, National Taiwan University, Taipei 106, Taiwan
(4) Department of Nuclear Science and Engineering, Massachusetts Institute of
Technology, Cambridge, Massachusetts 02139, USA
Correspondence author: afaraone@nist.gov
Using three high resolution quasielastic neutron scattering (QENS) spectrometers
we have investigated the single particle dynamics of water confined in
a hydrophobically modified MCM-41-S sample. This latter is a silica matrix
containing cylindrical sieves with diameter < 20 ˚A arranged in a hexagonal geometry.
In the hydrophobically modified sample some of the sylanol groups in
the pores’ wall have been substituted with methanol groups resulting in a partially
hydrophobic confining surface, which could be used as a model system.
In fact, the effect on water dynamics of the hydrophilicity and hydrophobicity
of surfaces, in particular of proteins, has recently attracted increasing attention
and was studied using Molecular Dynamics simulations [1-3]. We have been
able to analyze the QENS data in the temperature range from 300 K to 210 K
using a single consistent model. Because of the heterogenous environment experienced
by the water molecules in the pores, the relaxational dynamics show a
broad distribution of relaxation times. However, the Fickian diffusive behaviour
is retained. The obtained results help clarify the role that the chemical interaction
between the water molecules and the walls of the confining host plays in
determining the characteristics of the water dynamics, as compared to purely
geometric constraints such as the size and shape of the pores.
[1] N. Giovambattista, P.J. Rossky and P.G. Debenedetti, Phys. rev. E, 73,
041604, 2006.
[2] P. Gallo and M. Rovere, Phys. Rev. E, 76, 061202, 2007.
[3] N. Giovambattista, C.F. Lopez, P.J. Rossky and P.G. Debenedetti, Proc.
Natl. Acad. Sci. U.S.A., 105, 2274, 2008.

MODE-COUPLING DESCRIPTION OF THE COLLECTIVE DY-
NAMICS OF SIMPLE LIQUIDS
B. Schmid (1), W. Schirmacher (1,2), H. Sinn (3)
(1) Institut für Physik, Univ. Mainz, Staudinger Weg 7, 55099 Mainz, Germany
(2) Physik-Department E13, TU München, D-85747 Garching, Germany
(3) HASYLAB at DESY, Notkestr. 85 D-22607 Hamburg, Germany
Correspondence author: bernschm@uni-mainz.de
We use the mode-coupling theory (MCT) [1,2] for describing the dynamics of
simple (i.e. monatomic) liquids away from the glass formation regime [3]. We
find that the dynamical structure factor predicted by MCT compares well to
experimental findings in liquid metals and argon as well as results of computer
simulations of these materials [4,5]. The memory function exhibits a two-step
decay as found in the data. The long-time relaxation regime, in which the
relaxation rate depends strongly on density/temperature is identified as the α
relaxation due to the cage effect. The short-time relaxation, which is rather
temperature independent is dominated by the microscopic dynamics.
[1] U. Bengtzelius, W. Götze, A. Sjölander, J. Phys. C, 17, 5915, 1984
[2] W. Götze, Complex Dynamics of Glass-Forming Liquids, Oxford Univ. Press,
Oxford 2009
[3] W. Schirmacher, H. Sinn, Condensed Matter Physics 11, 127, 2008
[4] D. Levesque, L. Verlet and J. Kurkijärvi, Phys. Rev. A 7, 1690, 1973
[5] T. Scopigno, G. Ruocco, F. Sette, Rev. Mod. Phys. 77, 881, 2005

“Isomorphs“ in liquid state diagrams
Nicoletta Gnan, Thomas B. Schrøder, Ulf R. Pedersen,
Nicholas P. Bailey, and Jeppe C. Dyre
DNRF Centre “Glass and Time”, IMFUFA, Department of Sciences,
Roskilde University, Postbox 260, DK-4000, Roskilde, Denmark
A liquid is termed strongly correlating if its virial and potential energy
thermal equilibrium fluctuations in the NVT ensemble are more than 90%
correlated[?][?]. Strongly correlating liquids appear to have simpler physics
than liquids in general, an observation that has particular significance for the
highly viscous phase. Thus it has been shown that strongly correlating viscous
liquids have all eight frequency-dependent thermoviscoelastic response functions
given in terms of just one [?][?][?][?](i.e, are “single-parameter liquids” in the
sense of having dynamic Prigogine-Defay ratio [?]close to unity [?][?][?]). Moreover,
strongly correlating viscous liquids obey density scaling, i.e., their dimensionless
relaxation time ˜τ depends on density ρ = N/V and temperature as
˜τ = F (ργ /T ), where γ is the “slope” of the ellipse appearing in the WU diagram
when the virial is plotted versus the potential energy[?][?][?] and is given
by (NVT averages)
γ =
�
〈(∆W ) 2 〉
〈(∆U) 2 . (1)
〉
What causes strong WU correlations? A hint comes from the fact that
fluctuations of a strongly correlating liquid are well approximated by those of
an inverse power-law intermolecular potential v(r) ∝ r −n (IPL). For IPL liquids
several thermodynamic quantities are invariant along the curves in the phase
diagram given by ρ n/3 /T =Const. Among these quantities we include , e.g,
the Helmholtz free energy over temperature, the excess entropy, the average
potential energy over temperature, the isothermal bulk modulus over density
times temperature, and the virial over temperature. In dimensionless units the
dynamics of IPL liquids is also invariant along ρ n/3 /T =Const. curves. Our
work shows that a number of IPL invariants give rise to general “isomorph
invariants” of strongly correlating liquids. Not all IPL invariants survive this
generalization, though. For instance, the equation of state is generally poorly
represented by the IPL approximation[?]. In fact, most of the above mentioned
thermodynamic IPL invariants are not general isomorph invariants and, e.g.,
the IPL relation W = γU can be completely wrong for liquids that are not
100% correlating.
We demonstrate a number of implications of one single assumption, the
existence of curves in the liquid phase diagram on which there is a one-to-one
correspondence between configurations of different state points with identical
canonical statistical weights. Such curves are referred to as isomorphs.
With the help of molecular dynamic simulations we find for strongly correlating
liquids that:
• A number of thermodynamic, static, and dynamic isomorph invariants can
be identified.
1

• For jumps between isomorphic state points the system is instantaneously
in thermal equilibrium. It is worthy to note that, after the jump, the
relaxation time remains constant and may be very long; what happens
for jumps between isomorphic states is more correctly described as the
system’s relaxation strength vanishing.
• We can develope a general theory of isomorphs of 12-6 Lennard-Jones type
liquids, showing that all such liquids have the same isomorphs; moreover
these may be scaled into a common “master isomorph” for which it is
possible to predict its shape in the WU diagram.
The concept of isomorphs may shed light on the excess-entropy scaling proposed
long ago by Rosenfeld[?], according to which the dimensionless transport
coeffcients (diffusion constant, viscosity, thermal conductivity, etc) of dense fluids
are all functions of the excess entropy. Furthermore, in viscous liquid dynamics,
many predictions and results from experiments can find an explanation
with the introduction of isomorphs [?][?][?][?].
References
[1] U. R. Pedersen et al., Phys. Rev.Lett. 100, 015701 (2008)
[2] N. P. Bailey, U. R. Pedersen, N. Gnan, T. B. Schrøder, and J. C. Dyre, J.
Chem. Phys. 129, 184507 (2008) [paper I].
[3] N. P. Bailey, U. R. Pedersen, N. Gnan, T. B. Schrøder, and J. C. Dyre, J.
Chem. Phys. 129, 184508 (2008) [paper II].
[4] N. L. Ellegaard, T. Christensen, P. V. Christiansen, N. B. Olsen, U. R.
Pedersen, T. B. Schrøder, and J. C. Dyre, J. Chem. Phys. 126, 074502
(2007).
[5] N. P. Bailey, T. Christensen, B. Jakobsen, K. Niss, N. B. Olsen, U. R.
Pedersen, T. B. Schrøder, and J. C. Dyre, J. Phys.: Condens. Matter 20,
244113 (2008).
[6] T. Christensen and J. C. Dyre, Phys. Rev. E 78, 021501 (2008).
[7] U. R. Pedersen, T. Christensen, T. B. Schrøder, and J. C. Dyre, Phys. Rev.
E 77, 011201 (2008).
[8] D. Coslovich and C. M. Roland, J. Phys. Chem. B 112, 1329 (2008).
[9] Y. Rosenfeld, J. Phys.: Condens. Matter 11, 5415 (1999).
[10] C. M. Roland, R. Casalini, and M. Paluch, Chem. Phys. Lett. 367, 259
(2003).
[11] K. L. Ngai, R. Casalini, S. Capaccioli, M. Paluch, and C. M. Roland, J.
Phys. Chem. B 109, 17356 (2005).
[12] J. Mittal, J. R. Errington, and T. M. Truskett, J. Chem. Phys. 125, 076102
(2006).
[13] J. C. Dyre, N. B. Olsen, and T. Christensen, Phys. Rev. B 53, 2171 (1996).
2

GENERALIZED COLLECTIVE MODES IN A BINARY METAL-
LIC GLASS
T. Bryk (1,2), I. Mryglod (1,2)
(1) Institute for Condensed Matter Physics of NASU, 1 Svientsitskii Str., 79011
Lviv, Ukraine
(2) Institute of Applied Mathematics and Fundamental Sciences, Lviv National
Polytechnic University, 79013 Lviv, Ukraine
Correspondence author: bryk@icmp.lviv.ua
An extension of the approach of Generalized Collective Modes (GCM), which is
one of the most advanced methods of analysis of collective dynamics in liquids,
on the case of glass systems is reported. The extension permits to introduce
ultra-slow dynamic variables and treat them on the same footing as the hydrodynamic
ones and more short-time dynamic variables for estimation of dynamical
eigenmodes in glasses.
The developed approach is applied to analysis of collective dynamics in a binary
metallic Mg70Zn30 glass. Time correlation functions, derived in molecular dynamics
simulations, are analyzed in order to estimate the spectra of longitudinal
and transverse collective modes. Special attention is paid to contributions from
concentration fluctuations to the Boson-peak modes.

ROTATIONAL RELAXATION IN STRATIFIED MESOPHASES
G. Cinacchi(1), L. De Gaetani(2)
(1) School of Chemistry, University of Bristol, England
(2) Dipartimento di Chimica, Universita’ di Pisa, Italy
Correspondence author: giorgio.cinacchi@bristol.ac.uk
By using computer simulation on a model colloidal rod–sphere mixture in its
lamellar phase, the mechanism responsible of the rod rotational relaxation has
been identified. It consists of two steps: first, a rod, parallel to the director, has
to escape from the stratum in which is located and go into the intralayer region
mostly populated by spheres, laying perpendicular to the director; then, it has
to insinuate again into one of the adjacent strata, with 50% of probability of
resulting antiparallel to the director. While this mechanism is also operating in
a pure smectic phase of rods, the presence of spheres improves its efficacy, thus
facilitating its observation.

INELASTIC SCATTERING AND ANOMALOUS VIBRATIONAL
EXCITATIONS IN GLASSES
W. Schirmacher (1,2), B. Schmid (2) and C. Tomaras (1,3)
(1) Physik-Department E13, TU München, D-85747 Garching, Germany
(2) Institut für Physik, Univ. Mainz, Staudinger Weg 7, 55099 Mainz, Germany
(3) Arnold-Sommerfeld Center for Theoretical Physics, Theresienstr. 37 Universität
München, 80333 München, Germany
Correspondence author: wschirma@ph.tum.de
A theory of inelastic neutron, X-ray and light scattering from vibrational excitations
in disordered materials (glasses) is presented. The central quantity is the
dynamical susceptibility χ ′′ (q, ω) as a function of wavenumber q and frequency
ω. Whereas inelastic neutron and x-ray scattering probes directly this quantity,
Raman scattering probes this quantity, integrated over the wavenumbers with
a form factor f(q), which is the Fourier transform of the spatial correlation
function of the spatially fluctuating elasto-optic (Pockels) constants. The influence
of the disorder is represented by a complex frequency-dependent sound
velocity, which is the acoustical analogon of the complex index of refraction. Its
real part describes the disorder-induced modification of the sound velocity, its
imaginary part gives the sound attenuation. Explicit results for local-oscillator
[1] and elastic heterogeneity models [2-5] are given. They are compared with
each other and with experiment.
[1] E. Maurer and W. Schirmacher, J. Low-Temperature Physics, 137, 453 (2004)
[2] W. Schirmacher, Europhysics Letters, 73, 892 (2006)
[3] W. Schirmacher, G. Ruocco, T. Scopigno, Phys. Rev. Lett. 98, 025501
(2007)
[4] B. Schmid, W. Schirmacher, Phys. Rev. Lett 100, 137402 (2008)
[5] W. Schirmacher, B. Schmid, C. Tomaras, G. Viliani, G. Baldi, G. Ruocco,
T. Scopigno, phys. stat. sol. (c) 5, 862 (2008)

Critical and Universal Properties of the Mode Coupling Glass Transition
Giulio Biroli
IPhT CEA Saclay, France
Correspondence author: giulio.biroli@cea.fr
The Mode Coupling Equations derived and analyzed by Goetze and collaborators
have been, and still are, very instrumental in studying several aspects of
glassy dynamics. In this talk I will describe several results pointing out that
the Mode Coupling Transition revealed by the analysis of these equations is a
critical phenomenon characterized by diverging length and time scales and by
universal laws. These results allow one to characterize the status of the Mode
Coupling transition, revealing that it turns out to be much more general than
the equations it has been discovered from. Furthermore they provide a framework
to address quantitatively the phenomenon of dynamical heterogeneity that
appears at the glass and jamming transitions of molecular liquids, colloids and
granular media.
[1] A. Andreanov, G. Biroli, J.-P. Bouchaud, arXiv:0903.4619.
[2] Marco Tarzia, Giulio Biroli, Jean-Philippe Bouchaud, Alexandre Lefèvre,
arXiv:0812.3514.
[3] Thomas Sarlat, Alain Billoire, Giulio Biroli, Jean-Philippe Bouchaud, arXiv:0905.3333.
[4] Giulio Biroli, Jean-Philippe Bouchaud, J. Phys. Cond. Matt. 19 205101
(2008).
[5] Ludovic Berthier, Giulio Biroli, Jean-Philippe Bouchaud, Walter Kob, Kunimasa
Miyazaki, David Reichman, J. Chem. Phys. 126, 184504 (2007); 184503
(2007).
[6] Giulio Biroli, Jean-Philippe Bouchaud, Kunimasa Miyazaki, David R. Reichman,
Phys. Rev. Lett. 97 195701 (2006).
[7] G. Biroli, J.-P. Bouchaud, Europhys. Lett. 67 21 (2004).

THE INFLUENCE OF THE ANHARMONIC INTERACTON ON
SOUND ATTENUATION IN GLASSY SYSTEMS
C. Tomaras (1,2), W. Schirmacher (2,3)
(1) Arnold-Sommerfeld Center for Theoretical Physics, Theresienstr. 37 Universität
München, 80333 München, Germany
(2) Physik-Department E13, TU München, D-85747 Garching, Germany
(3) Institut für Physik, Univ. Mainz, Staudinger Weg 7, 55099 Mainz, Germany
Correspondence author: ctomaras@ph.tum.de
We investigate a 3-dimensional continuum model for vibrational excitations in
a disordered environment, based on the anharmonic generalisation of Lame’s
elasticity theory. The disorder is introduced into the theory via a spatially
short-range correlated fluctuating shear modulus µ(r), obeying
〈µ(r)〉 = µ0, 〈δµ(r)δµ(0)〉 = γ exp −|r|/ξ .
It can be shown by a mean-field treatment that the low-frequency Brillouin
linewidth (sound attenuation coefficient) obeys a Rayleigh law Γ(ω) ∝ ω 4 in the
case of zero anharmonicity, the density of vibrational states exhibits the well
known boson peak [1,2,3].
The anharmonic interaction provides an additional scattering mechanism for
the effective disordered phonons, which can be visualized by common quantumfield
theoretical methods. For low frequencies we obtain an Akhiezer-like soundattenuation
law
Γ(ω) ∝ T ω 2
. The same effect leads to a temperature dependent enhancement of the excess
density of states g(ω)/gDebye(ω), which is observed in Neutron and X-ray
scattering experiments at frequencies below the boson peak. The theory is in
qualitative good agreement with the experimental data.
[1] W. Schirmacher, Europhysics Letters, 73, 892 (2006)
[2] W. Schirmacher, G. Ruocco, T. Scopigno, Phys. Rev. Lett. 98, 025501
(2007)
[3]W. Schirmacher, B. Schmid, C. Tomaras, G. Viliani, G. Baldi, G. Ruocco, T.
Scopigno, phys. stat. sol. (c) 5, 862 (2008)

The dynamic crossover in supercooled liquids as observed by light
scattering
N. Petzold, A. Brodin, E. A. Rössler
Universität Bayreuth, Germany
Correspondence author: nikolaus.petzold@uni-bayreuth.de
The existence of a dynamic crossover predicted to appear as a singularity of the
non-ergodicity parameter f(T) has always been highly debated. Attempting to
identify this crossover it appears more or less pronounced depending on technique
applied which has led to the conclusion that the transition may be masked
by further relaxation processes. To resolve this unclear situation regarding the
glass former o-Terphenyl (OTP) and toluene, we revisit spectral analysis carried
out on OTP by depolarized light scattering (DLS) and optical Kerr effect
(OKE) and present new DLS spectra of OTP avoiding spectral artifacts which
spoiled previous studies. Additionally we extend our DLS study of toluene[1]
with recent results from photon correlation spectroscopy (PCS) reaching down
to nanoseconds to shade some more light on the evolution of the dynamic susceptibility
χ ′′ (ω) especially at frequencies around MHz to GHz. Furthermore
we will show that analyzing DLS, PCS as well as OKE[2] data the excess-wing,
the latter well known from dielectric spectroscopy (DS), has to be accounted
for when separating spectral contributions from fast and slow dynamics, for
example to get the rotational non-ergodicity parameter frot(T). In any case, a
pronounced change in frot(T) can be identified in the DLS data which agrees
with recent results from electron paramagnetic resonance studies (EPR)[3] on
OTP.
[1] Wiedersich, J.; Surovtsev, N. V. & Rössler, E.; JCP 2000, 113, 1143-1153
[2] Gottke, S.; Brace, D.; Hinze, G. & Fayer, M.; JPC 2001, 105, 238-245
[3] Bercu, V.; Martinelli, M.; Massa, C. A.; Pardi, L. A.; Rössler, E. A. & Leporini,
D.; JCP 2008, 129

Slow dynamics and glassiness in a lattice model
Z. Rotman , E. Eisenberg
Raymond and Beverly Sackler School of Physics and Astronomy, Tel Aviv
University, Tel Aviv 69978 Israel
Correspondence author: rotmanzi@tau.ac.il
We study the supercooled liquid state of the hard-core N3 lattice gas model
(exclusion up to 3 rd nearest neighbors on the 2D square lattice) . The model
undergoes a first order transition at activity zc ∼ 40 with ρf ∼ 0.80 and ρs ∼
0.95 [1]. Analysis of the Mayer cluster integral expansion predicts[2] critical
termination of the super cooled liquid branch at finite activity zt > zc with
termination density ∼ 0.85, lower than the closest packing density ρcp = 1 and
close to the random closest packing density for this model ρrcp = 0.858.
We conduct a Monte Carlo study of the density-density correlation, looking
for the characteristics of glassy behavior. Both the β regime plateau and
the α regime stretched-exponential decay are observed. The β plateau time increases
with density and seems to diverge at density close to ρrcp. The soft core
(finite-temperature) version of the model is studied as well and shows stretched
exponential decay of the correlation for densities above ρrcp. The differences
between the hard-core and soft-core are discussed.
These results suggest that the N3 model could serve as a simple minimalistic
model to provide insight into glassy phenomena.
[1] E. Eisenberg, A. Baram, Europhys. Lett. 71, 900 (2005).
[2] E. Eisenberg, A. Baram, PNAS 104, 5755 (2007).

Stability of supercooled binary liquid mixtures
Søren Toxvaerd, Ulf R. Pedersen, Thomas B. Schrøder, and Jeppe C. Dyre
DNRF centre “Glass and Time,” IMFUFA,
Department of Sciences, Roskilde University,
Postbox 260, DK-4000 Roskilde, Denmark
(Dated: August 27, 2009)
Abstract
Molecular Dynamics simulations of Kob-Andersen (KA) binary Lennard-Jones mixture crystal-
lizes in lengthy simulations by forming pure fcc crystals of the majority component. This motivates
this paper that gives a general thermodynamic and kinetic treatment of the stability of supercooled
binary mixtures, emphasizing the importance of negative mixing enthalpy whenever present. The
theory is used to estimate the crystallization time in a Kob-Andersen mixture from the crystal-
lization time in a series of related systems. At T=0.40 we estimate this time to be 5×10 7 time
units ( ≈ 1.ms). Using high-end graphics cards (CUDA) we recently crystallized two out of seven,
independent KA mixtures after 3.7×10 7 time units, consistent with the estimate.
A new binary Lennard-Jones mixture is proposed that is not prone to crystallization and faster
to simulate than the two standard binary Lennard-Jones mixtures; this is obtained by remov-
ing the like-particle attractions by switching to Weeks-Chandler-Andersen type potentials, while
maintaining the unlike-particle attraction.
1

Effect of dimension and mixing on the glass transition
R. Schilling
Institut für Physik
Johannes Gutenberg-Universität Mainz, Staudinger Weg 7
D-55099 Mainz, Germany
Abstract
The dependence of the mode coupling glass transition on the spatial dimension d is studied for
monodisperse and binary systems. For d → ∞ the critical volume fraction φc decays as d 2 2 −d , for
monodisperse colloids. The mixing effects found for binary hard spheres by Götze and Voigtmann
(Phys. Rev. E67, 021502 (2003)) exist for hard disks in d = 2, as well. However, the stabilization
of the glassy phase for small size disparities in 2d is much more pronounced than in 3d and the
plasticization in 2d sets in only at larger size disparities. The quality of these mode coupling
results in 2d is strongly supported by corresponding results for random close packing. The mixing
effects for binary hard disks will be compared with those for binary, dipolar point particles, studied
experimentally by König et al. (Eur. Phys. J. E18, 287 (2005)) .
1

Measuring the difference between isobaric and longitudianal specific
heat
Jon Josef Papini , Tage Christensen
DNRF Centre “Glass and Time”, IMFUFA, Dept. of Sciences, Roskilde University,
P.O. Box 260, DK-4000, Denmark
Correspondence author: papini@ruc.dk
Recently [1,2] showed that measuring the frequency-dependent isobaric specific
heat of an equlibrium liquid approaching the glass transition poses fundamental
difficulties. Perturbing the system thermally induces stresses that relax slowly
due to a high shear modulus, resulting in broken isobaric conditions. The longitudinal
specific heat notoriously enters as the measured quantity in the highfrequency
limit of effusivity measurements, also in a spherically symmetric case.
As for now, no one has ever measured how, and to what extent the two heat
capacities differ. To appreciate the difference, we have worked out a case, pertaining
to spherically symmetric conditions, where the temperature is measured
at the center after a step up in surface temperature is applied.
At very short times one measures the ratio of the two heat capacities, thus indicating
how much/little off-target isobaric specific measurements are.
Furthermore a new (to our knowledge) phenomena occurs, where the temperature
in the center initially decreases as a result of the strong thermomechanical
coupling close to the glass transition.
[1] T Christensen, N B Olsen and J C Dyre Phys. Rev. E, 75, 041502, 2007
[2] T Christensen and J C Dyre Phys. Rev. E, 78, 021501, 2008

Numerical study for the beta relaxation process of supercooled liquids
in the mode coupling theory
T. Narumi (1), M. Tokuyama (2)
(1) Department of Engineering, Tohoku University, Sendai, Japan
(2) World Premier <strong>International</strong> Research Center, Advanced Institute for Materials
Research, Tohoku University, Sendai, Japan
Correspondence author: takayuki.narumi@wpi-aimr.tohoku.ac.jp
One of the most significant problems in the condensed matter physics is understanding
mechanisms of the glass transitions. It is believed that the glass
transition is not a phase transition but a dynamical crossover from equilibrium
to non-equilibrium state. This is one of main reasons why it is difficult to elucidate
the mechanisms theoretically. Since one can treat supercooled liquids as
equilibrium liquids, our strategy is to construct a statistical-physics theory for
their dynamics with adequate approximations.
The mode-coupling theory (MCT) is one of the most well-known theories
for the supercooled liquids near the glass transition [1]. We solve the MCT
equations numerically and compare the results with those of MD simulation in
Kob-Andersen model. Our standpoint is the mean-field theory by Tokuyama [2],
that is, we employ the long-time self-diffusion coefficient as an universal control
parameter. The numerical results implies that the MCT does not describe real
situation in the β relaxation process.
[1] Götze W, 2009 Complex Dynamics of Glass-Forming Liquids - A Mode-
Coupling Theory (Oxford)
[2] Tokuyama M, Physica A 364, 23-62 (2006).

NON-DEBYE ELECTRODE POLARIZATION IN GLASS: EVIDENCE
FOR DYNAMIC HETEROGENEITIES
Christine Biermann, Klaus Funke
Institute of Physical Chemistry and Sonderforschungsbereich 458, University of
Muenster, Corrensstrasse 30, D-48149 Muenster, Germany
cbier_01@uni-muenster.de
Impedance measurements on glassy electrolytes at very low frequencies (1 Hz
to 10 −4 Hz) display the well-known effect of electrode polarization. This effect
is measurable in a sample cell with completely blocking electrodes. With the
(very high) values of the dielectric function there is, at least in principle, a very
challenging route towards determining the number density of the mobile charge
carriers without any knowledge of their mobility. Here, the simplest view is
to assume that the relaxation process at the electrodes is of the Debye type.
However, inspection of the dielectric function at low frequencies clearly proves
that the relaxation is non-Debye. Rather, it is suitably described in terms of a
modified Cole-Cole-type function, Ψ(ω) = (iωτ) β /[1 + (iωτ) β ] with 0 < β ≤ 1.
Such a function may be interpreted by assuming a superposition of elementary
relaxation processes with different relaxation times; it is thus indicative of dynamic
heterogeneities. The systems under study have been alkali borate and
alkali germanate glasses, both being archetypal glassy electrolytes. In addition
to the well-known dispersion of the complex conductivity, the polarization effect
can be precisely seen at low frequencies. The evaluation of our data shows clear
evidence for the existence of dynamic heterogeneities in glass.

Protein thermal stabilization
Jeong-Ah Seo (1,2), Alain Hedoux (1), Laurent Paccou (1), Yannick Guinet (1),
Frederic Affouard (1), Adrien Lerbret (1), Marc Descamps (1)
(1) Laboratoire de Dynamique et Structure des Matériaux Moléculaires, UMR
CNRS 8024, UFR de Physique, Bâtiment. P5, Université de Lille 1, 59650 Villeneuve
d’Ascq Cédex, France
(2) Department of Nanomaterials Engineering and BK21 Nano Fusion Technology
Division, Pusan National University, Miryang 627-706, Korea
Correspondence author: seojeongah@gmail.com
The denaturation process of several proteins(bovine serum albumin, lysozyme,
chymotrypsin, and β-lactoglobulin) dissolved in H2O and D2O was studied from
the investigation of the Raman spectra in three spectral ranges: the low frequency
Raman spectrum(LFRS) region (10∼400 cm −1 ), the amide band region
(800∼1800 cm −1 ), and the intramolecular O-D stretching vibrations region
(2000∼2800 cm −1 ). The amide band region allowed us to probe the molecular
conformation, i.e. the secondary structure of the protein, while the LFRS and
the intramolecular O-D stretching vibrations region provided information on the
structural organization of the solvent, dynamics of the protein, and the coupling
between the dynamics of the protein and the solvent. Information on the structural
organization and the dynamics of the solvent are crucial to understand
protein denaturation process and the biostabilization mechanism.
This work is supported by Agence Nationale de la Recherche (program Physique
Chimie du Vivant).

RAMAN AND INELASTIC NEUTRON SCATTERING STUDY OF
NIOBIUM-PHOSPHATE GLASS FOR RAMAN GAIN APPLICA-
TIONS
T. Unruh (1,2), W. Schirmacher (2,3), B. Schmid (3) A. Schulte (4), Y. Guo, (4), T.
Cardinal (5)
(1) Forschungsneutronenquelle Heinz Maier-Leibnitz (FRM II), Technische Universität
München, D-85747 Garching, Germany
(2) Physik-Department E13, Technische Universität München, D-85747 Garching, Germany
(3) Institut für Physik, Universität Mainz, Staudinger Weg 7, 55099 Mainz, Germany
(4) Department of Physics and College of Optics & Photonics-CREOL, University of
Central Florida, 4000 Central Boul., Orlando, FL 32816, USA
ICMCB, CNRS, Univ. of Bordeaux, F-33608 Pessac Cedex, France SA
Correspondence author: tobias.unruh@frm2.tum.de
Raman gain for optical applications strongly depends on the cross-section for
spontaneous Raman scattering. We present measurements of the Raman spectrum
of binary niobium-phosphate glasses in the frequency range from 5 - 1300 cm −1 [1].
The pronounced low-frequency spectral enhancement (“boson peak”) observed
in these materials suggests a significant gain profile for applications in Raman
amplifiers as well as providing an additional mechanism for Raman gain. To
separate density-of-states and elasto-optic effects we have investigated the vibrational
properties of the material by inelastic neutron scattering using the
time-of-flight spectrometer TOFTOF at the FRM II in Garching, Germany.
Using a new theory of Raman scattering [2] we are able to separate these effects
on a theoretical basis.
[1] A. Schulte, Y. Guo, W. Schirmacher, T. Unruh, T. Cardinal,
Vibrational Spectroscopy, 48,12,2008
[2] B. Schmid, W. Schirmacher, Phys. Rev. Lett 100,137402,2008

Computer simulation studies of polymer dynamics in confinement
H. Meyer, S. Peter, and J. Baschnagel
CNRS Institut Charles Sadron, 67034 Strasbourg, France Correspondence author:
hmeyer@ics.u-strasbg.fr
We present computer simulation results about polymer dynamics in confinement
which may be viewed as model systems of confining nanoparticles. Close
to interfaces without specific interactions, e.g. free surfaces or smooth and
non-adhesive confining walls, polymers exhibit accelerated dynamics. This is
observed for the segmental dynamics when cooling to the glass transition temperature
[1] as well as for the polymer dynamics in molten films where a reduced
entanglement density is found close to the interface [2]. For the segmental dynamics,
the relaxation time can be obtained as a function of the distance from
the interface showing a continuous crossover from bulk-like behaviour to accelerated
dynamics close to the interface. The difference is strongly enhanced close
to the bulk glass transition temperature leading to an apparent decrease of Tg
when averaging over thin films [1].
[1] [1] S. Peter et al J. Phys. Cond. Mat 19 (2007) 205119; S. Peter et al
Macromolecules (2008)
[2] H. Meyer et al Eur. Phys. J. Sp.Top. 141 (2007) 167.

Time correlations of heterogeneous dynamics in supercooled liquids:
Multi-time correlation analysis
K. Kim (1), S. Saito (1)
(1) Institute for Molecular Science, Okazaki, Japan
Correspondence author: kin@ims.ac.jp
A multi-time probing of density fluctuations is introduced to investigate hidden
time scales of heterogeneous dynamics in glass-forming liquids. Molecular dynamics
simulations for simple glass-forming liquids are performed, and a threetime
correlation function is numerically calculated for general time intervals.
It is demonstrated that the three-time correlation function is sensitive to the
heterogeneous dynamics and that it reveals couplings of correlated motions over
a wide range of time scales. Furthermore, the time scale of the heterogeneous
dynamics τhetero is determined by the change in the second time interval in the
three-time correlation function. The present results show that the time scale of
the heterogeneous dynamics τhetero becomes larger than the α-relaxation time
at low temperatures and large wavelengths. We also find a dynamical scaling
relation between the time scale τhetero and the length scale ξ of dynamical
heterogeneity as τhetero ∼ ξ z with z = 3.
[1] K. Kim and S. Saito, arXiv0906.0054.

Universalities of Long-Time Self-Diffusion on Two- and Three-Dimensional
Systems
Y. Terada (1), M. Tokuyama (2,1)
(1) Institute of Fluid Science, Tohoku University, 980-8577, Japan
(2) World Premier <strong>International</strong> Research Center, Advanced Institute for Materials
Research, Tohoku University, Sendai 980-8577, Japan
Correspondence author: terada@ifs.tohoku.ac.jp
The spatial dimensionality dependence of the long-time self-diffusion process is
examined by performing the extensive simulations on two- and three-dimensional
hard sphere fluids, soft sphere fluids, and quasi two-dimensional colloidal suspensions.
The long-time self-diffusion coefficient is one of significant indexes of the
glass transition phenomenon, because it is dramatically decreased near the glass
transition point. The long-time self-diffusion coefficient on three-dimensional
systems obeys a singular function predicted by Tokuyama [1,2]. It also obeys
the singular functions on two-dimensional systems, but the exponent of the singular
functions is different from that on three-dimensional systems. It is finally
shown that the exponent of the singular function is described by only the spatial
dimension d, while the interactions between the particles are different not
only on the molecular fluids but also on the colloidal suspensions. These simulation
results suggest that the long-time self-diffusion coefficient predicted by
Tokuyama is extended to d-dimensional long-time self-diffusion coefficient [1,2].
[1] M. Tokuyama, Physica A, 378 (2007) 157.
[2] M. Tokuyama, Physica A, 383 (2009) 3083.

Mode Coupling Theory under External Flow
J.M. Brader (1), Th. Voigtmann (1,2), M.E. Cates (3) and M. Fuchs (1)
(1) Fachbereich Physik, Universität Konstanz, D-78457 Konstanz, Germany
(2) Institut für Materialphysik im Weltraum, Deutsches Zentrum für Luft- und
Raumfahrt (DLR), 51170 Köln, Germany
(3) SUPA, School of Physics and Astronomy, University of Edinburgh, Kings
Buildings, Mayfield Road, Edinburgh EH9 3JZ, Scotland
Correspondence author: joseph.brader@uni-konstanz.de
Recent developments in nonequilibrium statistical mechanics (the Integration
Through Transients (ITT) formalism) enable the derivation of exact generalized
Green-Kubo relations describing the full nonlinear response of colloidal
dispersions subject to arbitrary time-dependent incompressible flow [1,2]. Mode
coupling-type approximations specifically tailored to incorporate the effects of
external flow make tractable these formal results and lead to a closed theory for
describing the macroscopic rheology. Of particular interest are the predictions
made by the theory for the yielding of glassy states and the nonlinear response
to time-dependent flow. In this talk we will briefly outline the theory before
presenting applications to various situations of rheological relevance.
[1] J.M. Brader, Th. Voigtmann, M.E. Cates, M. Fuchs, Phys.Rev.Lett. 98
(2007) 058301.
[2] J.M. Brader, M.E. Cates and M. Fuchs, Phys.Rev.Lett. 101 (2008) 138301.

TERAHERTZ SPECTROSCOPY FOR DIELECTRIC MATERIAL
ANALYSIS
K. Fukunaga (1), M. Mizuno (1), N. Fuse (2), Y.Ohki (2)
(Presenting author underlined)
(1) National Institute of Information and Communications Technology, Tokyo,
Japan
(2) Waseda University, Tokyo, Japan
K. Fukunaga: kaori@nict.go.jp
vTerahertz waves can penetrate opaque materials, as radio wave, and make it
possible to obtain spectral features of various materials, as for vibrational spectroscopy.
Since the energy of THz wave low enough to be considered completely
non-invasive. By using time domain spectroscopy, the refractive index of materials
can be calculated directly. Almost all materials show their own particular
spectral features in THz range due to their phonon interactions, molecular rotations,
hydrogen bond behaviours, and various low-energy excitation modes.
It can be recognized that superior dielectric characteristics of polymer nanocomposites
are attributed to the enormously large surface area between a polymer
matrix and a nanofiller. Therefore, much attention is paid to molecular vibration
and interaction in surface regions, which would appear in the terahertz frequency
region. We compared the spectra of various specimens with microfillers
or nanofillers, by drawing at high temeprature. The shift of peak frequency at
around 3 THz appeared only in a specimen with nanofillers [2]. In this paper we
introduce THz spectroscopy and the some results obtained with minerals and
some organic materials. We believe that THz spectroscopy will become a useful
and powerful analysing technique in the near future.
[1] M. Tonouchi, , Nature Photonics, 1, 97, 2007
[2] Y. Ohki, M. Okada, N. Fuse, K. Iwai, M. Mizuno, and K. Fukunaga, Appl.
Phys. Express, 1, 122401, 2008

Glasses, Jamming and Spin Glasses
M. A. Moore
School of Physics and Astronomy, University of Manchester,
Manchester, M13 9PL, UK
Correspondence: m.a.moore@manchester.ac.uk
Using an effective potential method, a formalism is set up for describing supercooled
liquids near their glass transition. The resulting potential is equivalent
to that for an Ising spin glass in a magnetic field. Results taken from the droplet
picture of spin glasses are then used to provide an explanation of the main features
of fragile glasses. Near Tg the correlation length which measures the size
of the co-operatively relaxing regions is only a few particle diameters, which
does not allow a quantitative check of the formalism to be made. However, near
the J-point, the correlation length can be as large as 50 particle diameters and
numerical results obtained for the exponent ν are in good agreement in both
two and three dimensions with the predictions of the mapping to spin glasses.

ERGODICITY BREAKING IN STRONG AND NETWORK-FORMING
GLASSY SYSTEMS
S. Caponi (1,2), M. Zanatta (1), A. Fontana (1,2), L. E. Bove (3), L. Orsingher
(1,2), F. Natali (4), C. Petrillo (2,5), and F. Sacchetti (2,5)
(1) Dipartimento di Fisica, Universit di Trento, I-38050 Povo Trento, Italy
(2) Research Center SOFT-INFM-CNR, Universit di Roma La Sapienza, I-00185
Roma, Italy
(3) Departement Physique des Milieux Denses, CNRS-IMPMC, Universit Paris
6, F-75015 Paris, France
(4) INFM-OGG, c/o ILL, 6 rue Jules Horwitz, F-38042 Grenoble Cedex 9,
France and CRS-SOFT, c/o ILL, 6 rue Jules Horwitz,F-38042 Grenoble Cedex
9, France
(5) Dipartimento di Fisica, Universit di Perugia, I-06100 Perugia, Italy
Correspondence author: zanatta@science.unitn.it
The temperature dependence of the nonergodicity factor of vitreous GeO2,
fq (T ), as deduced from elastic and quasielastic neutron scattering experiments,
is analyzed. The data are collected in a wide range of temperatures from the
glassy phase, up to the glass-transition temperature, and well into the undercooled
liquid state. Notwithstanding the investigated system is classified as
prototype of strong glass, it is found that the temperature and the q behavior
of fq (T ) follow some of the predictions of mode coupling theory. The experimental
data support the hypothesis of the existence of an ergodic to nonergodic
transition also in networkforming glassy systems, [1].
[1] S. Caponi, M. Zanatta, A. Fontana, L. E. Bove, L. Orsingher, F. Natali, C.
Petrillo and F. Sacchetti, Phys. Rev. B 79 (2009) 172201

GLASS TRANSITION OF CLUSTERING LIQUID VIA H-BONDS:
DICYCLOHEXYLMETHANOL
Kazuya SAITO
Department of Chemistry, Graduate School of Pure and Applied Sciences,
University of Tsukuba, Tsukuba, Japan
Correspondence author: kazuya@chem.tsukuba.ac.jp
The title compound (DCHM, Tfus = 337.51 K) exhibits a non-monotonous
temperature dependence in heat capacity and dielectric constant in the liquid
state. A coherent analysis of FT-IR spectra, heat capacity and dielectric
constants shows that the neat liquid at low temperatures consists of closed
(square) tetramers via H-bonds [1]. On the other hand, the FT-IR spectra of
a related compound, tricyclohexylmethanol (TCHM, Tfus = 367.2 K), having
a similar molecular structure indicates that TCHM is monomeric in the liquid
state, which is consistent with previous conclusion from thermodynamic study
on the weak ferroelectricity of the TCHM crystal consisting of the H-bonded
dimers [2]. DCHM and TCHM are easily supercooled, and undergo glass transitions
around 250 K and 265 K, respectively, resulting in the liquid quenched
glasses consisting of H-bonded tetramers in DCHM and of monomers in TCHM.
Thermodynamic properties of their glass transitions and dielectric relaxations
will be compared and discussed.
[1] Y. Suzuki, Y. Yamamura, M. Sumita & K. Saito, submitted.
[2] Y. Yamamura, H. Saitoh, M. Sumita & K. Saito, J. Phys.: Cond. Matter,
19, 176219 (2007).

Dynamics of hydration water in a Polymer system
R.Busselez (1), A. Arbe (2), S. Cerveny (2), S.Capponi (1), J. Colmenero (1,2,3),
B. Frick(4), J.M. Zanotti(5)
(1) Donostia <strong>International</strong> Physics Center, San Sebastian, Spain
(2) Centro de Física de Materiales (CSIC-UPV/EHU), Materials Physics Center(MPC),
San Sebastian, Spain
(3) Departamento de Física de Materiales, San Sebastian, Spain
(4) Institut Laue-Langevin, Grenoble, France
(5) Laboratoire Léon Brillouin, CEA Saclay, France
Correspondence author: remi_busselez@ehu.es
Water is of outmost importance in many systems (porous media, gel, biological
objects). In biology, water has a trigger role in the protein activity, that
arises from the complex interplay between water and proteins. A first approach
to understand the water dynamics in biological systems can be made by using
simpler systems owning similarities with biological ones [1]. In this direction
water-polymer solutions share with biological systems the presence of two types
of water molecules, well-bounded and loosely-bounded molecules [2][3]. The former
type is supposed to be in direct contact with the polymer chain and would
exhibit a more restricted dynamics, being this mechanism the dominant one at
low hydration levels. Contrarily, at high hydration levels many of the water
molecules would be bounded having a much less restricted dynamics.
With this idea we have investigated the dynamics of water in a matrix of
Polyvinylpyrrolidone. In the high hydration domain (40% wt), both well bounded
water and loosely bounded water are present [4]. To follow the dynamics of water
on a large time scale (10 −12 → 10 2 s) we have combined different experimental
techniques as NMR, Dielectric spectroscopy and Quasi elastic neutron scattering.
Of particular interest are our QENS results. Using isotopic substitution
for water, we have been able to disentangle dynamics of each component of the
system and obtain spatial information on the geometry of the motions throughout
the Q-dependance of the scattered intensity.
[1] S.Cerveny,A.Alegria,J.Colmenero, Phys. Rev.E,77,(2008),031803
[2] S.K.Pal, A.H.Zewail, Chem. Rev., 104,(2004),2099
[3] B.Bagchi, Chem. Rev.,105,(2005), 3197
[4] S.Cerveny, A.Alegria and J.Colmenero, J.Chem.Phys,128 ,(2008),044901

CONFORMATION AND DYNAMICS OF A SIMPLE POLYPEP-
TIDE AND ITS WATER SOLUTIONS: THE CASE OF GLUTATHIONE
S.E. Pagnotta (1), S. Cerveny (1), A. Alegría (1,2), J. Colmenero (3)
(1) Centro de Fisica de Materiales (CSIC-UPV/EHU) - Materials Physics Center
MPC, San Sebastian, Spain.
(2) Departamento de Fisica de Materiales, Universidad del Pais Vasco (UPV/EHU),
Facultad de Quimica, San Sebastian, Spain
(3) Donostia <strong>International</strong> Physics Center, San Sebastian, Spain
Correspondence author: sckpagns@ehu.es
Glutathione (L-γ-glutamyl-cysteinyl-glycine) is an ubiquitous tripeptide containing
an unusual peptide linkage between the amine group of cysteine and the
carboxyl group of the glutamate side chain. It plays a number of vital roles
in cell metabolism, mainly related to the repair of oxidative damage [1]. Here
broadband dielectric spectroscopy (BDS) and differential scanning calorimetry
(DSC) measurements were performed on glutathione water solutions, revealing
a quite complex dynamical behaviour for this system. At least four relaxation
processes are present at all hydration levels, with contributions arising both
from solvent and solution dynamics. Two dynamical phenomenon normally
observed in other glass forming water containing systems [2] were detected: a
slower, non-Arrhenius, one, attributed to the collective movements of the system
and a faster, Arrhenius-like, one, due to water molecules. Moreover, two
further relaxation phenomena appear well above the calorimetric glass transition
temperature, at low frequencies. These slow relaxations possess a peculiar
temperature dependence and seem to be connected to the polypeptidic nature
of the solute, being previously observed in a hemoglobin water sample [3].
[1] A. Pompella, A. Visvikis, A. Paolicchi, V. De Tata, A. F. Casini, Biochem.
Pharmacol. 1499-1503 (2003) 66.
[2] S. Cerveny, A. Alegría, J. Colmenero, Phys. Rev. E 0318031-5 (2008) 77.
[3] H. Jansson, R. Bergman, J. Swenson, J. Phys. Chem. B 24134-24141 (2005)
109.

Distributions of flow event properties in model supercooled liquids
Nicholas P. Bailey (1,*), Thomas B. Schrøder (1), Jeppe C. Dyre (1)
(1) DNRF centre “Glass and Time,” IMFUFA, Department of Sciences, Roskilde
University, Postbox 260, DK-4000 Roskilde, Denmark
* Corresponding author: nbailey@ruc.dk
We study the statistics of flow events in the inherent dynamics in supercooled
two- and three-dimensional binary Lennard-Jones liquids. The inherent dynamics
are defined by minimizing the potential energy of configurations in the real
dynamics to find a local minimum, which is the associated inherent state; a
flow event is a change of inherent state. Distributions of changes of the collective
quantities energy, pressure and shear stress become exponential at low
temperatures, as does that of the event “size” S, the sum of squares of the individual
particle displacements. The S-distribution controls the others, in that
the other distributions are Gaussian for fixed S; the exponential distribution of
S then gives rise to the other exponential distributions. The distribution of S
itself can be traced to exponential tails in the distributions of (1) single particle
displacements d, involving a Lindemann-like length dL and (2) the number of
active particles (i.e. those with d > dL). Results of barrier height calculations
will also be presented. These also exhibit an exponential distribution.
[1] N. P. Bailey, T. B. Schrøder, J. C. Dyre, Phys. Rev. Lett. 102 (2009) 055701

Secondary relaxation observed by broadband shear-mechanical spectroscopy
B. Jakobsen (1), K. Niss (1), C. Maggi (1), N. B. Olsen (1), T. Christensen (1)
(1) DNRF centre “Glass and Time”, IMFUFA, Department of Sciences, Roskilde
University, Postbox 260, DK-4000 Roskilde, Denmark
Correspondence author: boj@ruc.dk
The major source for information on secondary relaxations is dielectric spectroscopy.
The connection between dielectric response and the more fundamental
mechanical relaxation is, however, not trivial.
The piezoelectric shear-modulus gauge [1] allows for direct studies of the
frequency dependent shear modulus in a frequency range from 1mHz to 10KHz,
on liquids with moduli in the MPa to GPa range. Hence the method is well
suited for studying the shear-mechanical signature of secondary relaxations.
In this presentation we review our existing shear-mechanical data [2] with
focus on how the phenomenology of the secondary relaxation is seen in the shear
modulus. It is generally observed that when a secondary process is seen by
dielectric relaxation it is also seen in the shear modulus, but phenomenological
differences exist. The loss peak of the process is shifted to higher frequencies
and the strength relative to the alpha relaxation is larger in the shear modulus
compared to the dielectric. The phenomenological differences are furthermore
discussed in terms of the Gemant-DiMarzio-Bishop model [3].
[1] T. Christensen and N. B. Olsen, Rev. Sci. Instrum. 66 (1995) 5019 .
[2] B. Jakobsen, K. Niss, and N. B. Olsen, J. Chem. Phys. 123 (2005) 234511.
C. Maggi et al., J. Phys. Chem. B 112 (2008) 16320. B. Jakobsen et al., J.
Chem. Phys. 129 (2008) 184502.
[3] K. Niss, B. Jakobsen, and N. B. Olsen, J. Chem. Phys. 123 (2005) 234510.

The influence of electrode effects on the dielectric behavior of solid
electrolytes
B. Martin (1), H. Kliem (1)
(1) Institute of Electrical Engineering Physics, Saarland University, D-66123
Saarbruecken, Germany
Correspondence author: b.martin@mx.uni-saarland.de
Thin films of ion conducting polyethylene oxide (PEO) doped with different
salt concentrations are used to investigate electrode effects in solid electrolytes.
Capacitance structures are produced by evaporating Al or Cu electrodes. An
ionic space charge polarization is the origin of the dielectric relaxational behavior
in these systems.
For computer simulations, a three-dimensional discrete hopping model is
developed [1,2]. Negative ions can fluctuate thermally activated over energy
barriers in a multiwell potential. The electrostatic interactions between all ions
and between the ions and a positive background charge providing charge neutrality
are considered. The interactions between the ions and the electrodes are
taken into account using the method of images.
The attractive Coulomb forces between the original charges and the image
charges in the electrodes give rise to a charge accumulation at the electrodes even
without applied field as predicted in the simulations. The ions and their images
build dipoles with electrical fields which cause a depletion of mobile charges
towards the volume. This charge distribution creates an internal potential with
a maximum in the middle of the sample. In the experiment, this potential
distribution can be determined using a scanning Kelvin probe which detects the
surface potential between the electrodes contactless [1].
Furthermore, the electrode effects are responsible for the dynamical behavior
of the systems like the Kohlrausch empirical law of the polarization current
at long times and thus the increase of the dielectric permittivity ɛr at low
frequencies [2]. Due to the long range ionic motion this nominal dielectric
permittivity increases with the sample thickness d. We find ɛr ≈ 100 000 at
0.1 Hz for d = 40µm.
[1] B. Martin and H. Kliem, IEEE Trans. Dielectr. Electr. Insul. 15, 560
(2008)
[2] B. Martin and H. Kliem, J. Appl. Phys. 98, 074102 (2005)

Kovacs effects in the relaxation of the Gaussian trap model
Gregor Diezemann (1), Andreas Heuer (2), Christian Rehwald (2)
(1) Institut für Physikalische Chemie, Universität Mainz, Welderweg 11, 55099
Mainz, FRG
(2) Institut für Physikalische Chemie, Universität Münster, Corrensstr. 28/30,
48149 Münster, FRG
Correspondence author: diezeman@uni-mainz.de
The so-called Kovacs effect is found in a variety of complex systems. The protocol
of the experiment is the following: jump from a high temperature T0 to
T1 < T0 and stay there until the energy (or another one-time quantity) has
reached its equilibrium value at T2 with T1 < T2 < T0 at a time t ∗ and then
jump to T2. The naive expectation would be that nothing changes. It is, however,
found that the observed quantity first increases, then reaches a maximum
and finally decreases towards the equilibrium value again. The existence of
this so-called Kovacs hump has been attributed to the distribution of relevant
relaxation times.
We consider the Kovacs effect in a trap model with a Gaussian density of
states. This model shows relaxation to equilibrium at all finite temperatures
along with a broad distribution of relaxation times. We find that after a quench
from a high temperature to a low temperature T1, the time t ∗ passes through a
minimum if considered as a function of T1. This completely unexpected behavior
can be understood via an analysis of the relaxation behavior of the energy. We
will furthermore discuss the ’inverse Kovacs protocol’, where a temperature
jump from a low initial temperature is considered (now with T1 > T2). It is
found that the qualitative behavior is similar to the situation after a quench.
This shows that the memory of the initial conditions has only a quantitative
effect on the results. In addition, the limit of small temperature changes will
be considered, in which case linear response theory can be used to quantify the
effects observed.

CAN MACROSCOPIC GLASS FORMING SYSTEMS BE DESCRIBED
AS SUPERPOSITION OF COUPLED ELEMENTARY SUBSYS-
TEMS?
C. Rehwald, A. Heuer
Institut für Physikalische Chemie, WWU Münster, Corrensstr. 28/30, 48149
Münster, Germany
Correspondence author: rehwaldc@uni-muenster.de
Many recently discussed models for supercooled liquids assume that the liquid
consists of coupled elementary subsystems (cooperative rearranging regions),
but no specific information about that coupling is available.
Our goal is the identification of subsystems and the precise description of the
coupling itself. For this purpose we investigate a binary mixture Lennard-Jones
liquid for different system sizes. We introduce an algorithm to calculate single
particle waiting times between local exchange events. Different observables (like
the diffusion constant D and the alpha relaxation time τα) can be expressed in
terms of the moments of these local waiting time distributions [1].
In a first step we extract from the finite size effects of these waiting time distributions
important information about the coupling strength. In a second step
we analyze in detail the response of the system to a local relaxation processes.
Thereby we can gain additional information about the nature of this coupling.
[1] A. Heuer, J. Phys.: Cond. Mat. 20, 373101, 2008

A Combined Measurement of Thermal and Mechanical Relaxation.
Tage Christensen, Bo Jakobsen, Niels Boye Olsen.
DNRF Centre “Glass and Time”, IMFUFA, Department of Sciences, Roskilde
University, Postbox 260, DK-4000 Roskilde, Denmark.
Corresponding author: tec@ruc.dk
The recent finding [1] that a class of liquids — the strongly correlating liquids
— may be described by a single “order” parameter makes it urgent to
devise methods that concurrently measure thermal and mechanical relaxation
and their interconnection. The classical Prigogine-Defay test of a one “order”
parameter description has recently been rigorously reformulated for the equilibrium
liquid in terms of (four) Dynamic Prigogine Defay ratios [2]. One of
these, ΛSp = −(T0/cp) ′′ (κS) ′′ /((1/βS) ′′ ) 2 is from an experimental viewpoint
the easiest to access. It contains the complex frequency-dependent specific
heat cp(ω), adiabatic compressibility κS(ω) and adiabatic pressure coefficient
βS(ω) ≡ (δp(ω)/δT (ω))S. We can measure κS(ω) by the so-called piezoelectric
bulk modulus gauge (PBG) [3]. The PBG is a hollow sphere of radius 1 cm
with a thin wall of a piezoelectric ceramic material. Pressure/volume changes
are detectable due to the piezoelectric effect. In the middle of the PBG is a
thermistor by which we can measure the longitudinal heat capacity cl(ω) via
the effusivity [4]. Combining the two sensors makes it, in principle, possible to
get βS. That is, nearly all ingredients of ΛSp can be found for the same sample
in the same device. However cl(ω) may differ from cp(ω) [5], in which case a
supplementary measurement of the shear modulus is needed.
[1] U. R. Pedersen, T. Christensen, T. B. Schrøder and J. C. Dyre, Phys. Rev.
E77 (2008) 011201.
[2] N. L. Ellegaard, T. Christensen, P. V. Christiansen, N. B. Olsen, U. R. Pedersen,
T. B. Schrøder and J. C. Dyre, J. Chem. Phys. 126 (2007) 074502.
[3] T. Christensen and N. B. Olsen, Phys Rev. B49 (1994) 15396.
[4] B. Jakobsen, N. B. Olsen and T. Christensen, arXiv: 0809,4617v1 [condmat.soft]
(2008)
[5] T. Christensen and J. C. Dyre, Phys. Rev. E78 (2008) 021501.

Controlling the Outcome of Electron Transfer Reactions in Ionic Liquids
Harsha V. R. Annapureddy (1),Claudio J. Margulis (1)
(1) Department of Chemistry, The University of Iowa, Iowa City, IA 52242
Correspondence author: claudio-margulis@uiowa.edu
We investigate the excited state intra molecular electron transfer(ET) reaction
of crystal violet lactone (CVL) in room temperature ionic liquid (RTIL)
N-propyl-N-methylpyrrolidiniumbis(trifluromethylsulfonyl)imide [Pr + 31 ][Tf2N − ].
This system was chosen in light of recent experimental observations by Maroncelli
and co-workers[1] in which the kinetics of electron transfer between S1 and
S2 emission states and therefore the ratio of emitting populations was shown
to be absorption wavelength dependent. Our computational studies indicate
that the kinetics of the intramolecular ET between S1 and S2 states of CVL
in [Pr + 31 ][Tf2N − ]is local solvent environment dependent. Because emission time
scales are smaller than solvent relaxation time scales, this behavior is characteristic
of RTILs but uncommon in conventional solvents. Therefore RTILs open
a window of opportunity for manipulating the outcome of chemical reactions
simply by tunning the initial excitation wavelength. Our studies show that
when acetonitrile is used as a solvent instead of [Pr + 31 ][Tf2N − ]the ratio of populations
of emission states is independent of excitation wavelength eliminating
the opportunity for influencing the outcome of reactions.
[1] H. Jin, X. Li and M. Maroncelli. J. Phys. Chem. B.111(2007), p. 13473

CAVITATION IN WATER : A NO MAN’S LAND AT NEGATIVE
PRESSURE
K. Davitt, A. Arvengas, F. Caupin
Laboratoire de Physique Statistique, Ecole Normale Supérieure,
UPMC Paris 06, Université Paris Diderot, CNRS, 24 rue Lhomond, 75005 Paris,
France
Correspondence author: frederic.caupin@lps.ens.fr
A liquid under mechanical tension is in a metastable state, eventually destroyed
by nucleation of vapor bubbles. Knowledge of this cavitation limit can give
information about the anomalous behavior of water. We have measured the
density of water at the threshold of acoustic cavitation. Our measurements are
extremely reproducible and indicative of homogeneous nucleation. We compare
our results to the densities found in an experiment using mineral inclusions
[1] to stretch water, the only method to-date which has been able to reach a
higher degree of metastability. The comparison reveals a region of the phase
diagram where water has never been observed. To explain this, we propose a
path-dependent nucleation mechanism, associated with a liquid-liquid transition
at negative pressure, supported by some numerical simulations [2]. This
hypothesis is able to explain why the methods yield different cavitation limits
as well to explain an internal discrepancy in the inclusion work.
[1] Q. Zheng, D. J. Durben, G. H. Wolf, C. A. Angell, Science 254 (1991) 829.
[2] I. Brovchenko, A. Geiger and A. Oleinikova, J. Chem. Phys. 123 (2005)
044515.

Boson peak and acoustic-like excitations in glasses
G. Monaco (1)
(1) European Synchrotron Radiation Facility, BP220, F-38043 Grenoble,
France
gmonaco@esrf.fr
The origin of the boson peak in glasses and its relation to the well-known
low-temperature anomalies in the specific heat and thermal conductivity are
generally considered key questions in the physics of glasses and have been a
topic constantly addressed during the last decades. However, the difficulty
of the problem and the lack of a comprehensive set of experimental and/or
numerical data have posed up to now a formidable obstacle for a clear and
agreed upon understanding of the problem. Taking advantage of recent advances
achieved in numerical [1] and experimental techniques, most notably inelastic
x-ray scattering [2], we will here show that it is today possible to study with a
sufficient level of detail the acoustic-like excitations of glasses in the frequency
range where the boson peak is located. We will show that a number of interesting
anomalies in these excitations can be then detected that can be related to the
boson peak, allowing us then to establish a clear connection between boson peak
and acoustic-like properties.
[1] F. Leonforte, R. Boissiére, A. Tanguy, J.P. Wittmer, and J.-L. Barrat, Phys.
Rev. B 72 (2005) 224206.
[2] G. Monaco and V.M. Giordano, Proc. Natl. Acad. Sci. USA 106 (2009)
3659.

How good is the mode coupling theory for polydisperse hard spheres
F. Weyßer (1), J. Reinhardt (1), A.M. Puertas (2), Th. Voigtmann (1,3)
M. Fuchs (1)
(1) Fachbereich Physik, Universität Konstanz, 78464 Konstanz, Germany
(2) Departmento de Física Aplicada, Universidad de Almería, 04.120 Almería,
Spain
(3) Institut für Materialphysik im Weltraum, Deutsches Zentrum für Luft- und
Raumfahrt (DLR), 51170 Köln, Germany
Correspondence author: matthias.fuchsr@uni-konstanz.de
Polydisperse hard spheres approach a glass transition upon increasing the total
packing fraction. The polydispersity can be chosen such as to suppress nucleation
of crystallites sufficiently to enable detailed investigation of the viscoelastic
fluid and glass states. The idealized mode coupling theory (MCT) of the glass
transition predicts the slowing down of coherent and incoherent density and
of stress fluctuations. The latter determine the linear elastic and viscous shear
moduli. Extensions of the MCT within the integration through transients (ITT)
approach go beyond the linear response framework and address the nonlinear
rheology of dispersions. Data from experiments and computer simulations will
be compared quantitatively to predictions from MCT and MCT-ITT in order
to determine how well the theory captures the glass transition of polydisperse
hard particles.

Strongly correlating liquids and thermodynamic scaling of the dynamics:
Examples and counterexamples from hard and soft matter
D. Coslovich (1), C. M. Roland (2)
(1) Technische Universität Wien, Wien, Austria
(2) Naval Research Laboratory, Washington DC, US
Correspondence author: coslovich@cmt.tuwien.ac.at
The relationship between thermodynamic scaling of the dynamics in glassforming
liquids and strong correlations between pressure and energy fluctuations
have been actively investigated during the last two years [1-4]. Computer
simulations have revealed that the link between these two properties lies in
the approximation of the repulsive part of the interaction potential in terms of
generalized inverse-power laws [3]. We will discuss these findings for different
models of glass-forming liquids, contrasting results for models of fragile and
strong liquids. Further, we will investigate the connection between the softness
of the potential and the fragility, reconciling thereby previous inconsistencies
between numerical and experimental data. Finally, we will address the question
if dynamical scaling laws can be extended to models in which particles interact
with bounded potentials as they are encountered as effective interactions
in polymers or other colloidal dispersions. For such ”soft” systems, thermodynamic
scaling is predicted by mean field approaches, but its nature turns out to
be different than in ”hard”, atomic matter.
[1] D. Coslovich and C. M. Roland, J. Phys. Chem. B 112 (2008) 1329
[2] U. R. Pedersen et al. Phys. Rev. Lett. 100 (2008) 015701
[3] N. P. Bailey et al. J. Chem. Phys. 129 (2008) 184507
[4] D. Coslovich and C. M. Roland, J. Chem. Phys. 130 (2009) 014508

Model membrane dynamics by quasi-elastic neutron scattering
U. Wanderlingh(1), G. D’Angelo (1), A. Trimarchi (1), Valeria Conti Nibali(1)
(1) Dipt. di Fisica, Universitá di Messina, Italy
Correspondence author: uwanderlingh@unime.it
In this contribution we report on investigation of model membrane dynamics
in liquid crystalline phase. Hydrogen dynamics has been probed by means of
Quasi Elastic Neutron Scattering and on the effect of insertion the pore forming
peptides within the membrane was also studied.
Model membrane are realized by highly oriented, hydrated phospholipid bilayer
stacks of DMPC (1,2-dimyristoyl-sn-glycero-3-phoshatidylcholine) hydrated with
D2O in excess of solvent condition.
The bilayer were supported on mica substrates and prepared at different concentrations
of Gramicidin, a 15-residue oligopeptide showing antimicrobial activity
by forming pores on the membrane surfaces which allow water and small ions
to permeate across the membrane.
Incoherent QENS spectra, measured on IN5 spectrometer at ILL, allows to obtaining
information on the local diffusion and on phospholipid chains dynamics.
A comparison among different models, used to fit the experimental data, are
presented.
Moreover, by proper orientations of the membrane plane respect to the scattering
wave vector Q, we were able to derive information on in plane and out of
plane motions of the phospholipids.

GLASSY BEHAVIOR OF TWO-DIMENSIONAL LIQUIDS
David Hajnal (1), Joseph M. Brader (2) and Rolf Schilling (1)
(1) Institut für Physik, Johannes Gutenberg-Universität Mainz, Staudinger Weg
7, D-55099 Mainz, Germany
(2) Fachbereich Physik, Universität Konstanz, D-78457 Konstanz, Germany
Correspondence author: hajnalda@uni-mainz.de
We study the glassy behavior of two-dimensional liquids in the framework of
mode coupling theory (MCT). For binary hard discs, we first discuss the liquidglass
transition diagram for the critical packing fraction and the corresponding
critical nonergodicity parameters as function of composition and size disparity.
Second, by solving the dynamical MCT equations, we discuss the influence of
composition changes on the relaxation behavior of the time-dependent density
correlators. It will be demonstrated that the four mixing effects reported by
Götze and Voigtmann [1] for binary hard spheres in three dimensions also occur
for binary hard discs in two dimensions, however with different strength. Some
of these mixing effects for liquids with pure excluded volume interactions will
be compared with those for a binary 2d liquid of dipolar point particles. By
using the well-known separation parameter we derive a general expression for
the slope of a glass transition line. Using this expression in the low concentration
limits of one particle species, we can already present an estimated glass
transition diagram. From this phase diagram we obtain a qualitative dependence
of the structural relaxation on the composition which is consistent with
the experimental results of König et al. [2].
[1] W. Götze and Th. Voigtmann, Phys. Rev. E 67, 021502 (2003).
[2] König et al., Eur. Phys. J. E 18, 287 (2005).

ACTIVE AND NONLINEAR MICRORHEOLOGY IN DENSE COL-
LOIDAL SUSPENSIONS: NUMERICAL SOLUTION OF THE FULL
MCT EQUATIONS
C. J. Harrer (1), T. Voigtmann (1,2)
(1) Fachbereich Physik, Universität Konstanz, 78457 Konstanz, Germany
(2) Institut für Materialphysik im Weltraum, Deutsches Zentrum für Luft- und
Raumfahrt (DLR), 51170 Köln, Germany
Correspondence author: Christian.Harrer@uni-konstanz.de
Recently a mode-coupling theory (MCT) for the active nonlinear microrheology
of colloidal model systems has been developed [1]. It was shown, that the
friction coefficent for a particle driven by an external force embedded in a host
can be obtained via a nonlinear, nonequilibrium generalization of a Green-Kubo
relation if the transient density correlation functions are known. For the latter
so far only generic features of a schematic version of the MCT model have been
discussed. For glassy hosts a finite threshold force was predicted to be necessary
for a (continuous) delocalization transition of the probe particle.
To investigate the microscopic predictions of the full model and to be able to
quantitatively compare the theory to simulations and experiments we numerically
solve the full wave vector dependent, anisotropic mode-coupling equations
considering both the long time limit and the time dependence of the density
correlation functions. This allows us, e.g., to examine the influence of different
particle to probe size ratios in dense hard-sphere systems.
[1] I. Gazuz, A.M. Puertas, T. Voigtmann, M. Fuchs, Phys. Rev. Lett. in print
ArXiv:0810.2627.

The Glass Transition in Binary Mixtures: Concentration Fluctuations
and Confinement Effects
T. Blochowicz (1), E. Gouirand (1), S. Schramm (1), B. Stühn (1), B. Frick (2)
and Y. Chushkin (3)
(1) TU-Darmstadt, 64289 Darmstadt, Germany
(2) Institut Laue-Langevin, 38043 Grenoble, France
(3) European Synchrotron Radiation Facility, 38043 Grenoble, France
Correspondence author: thomas.blochowicz@physik.tu-darmstadt.de
We investigate the dynamics of the glass former Methyl-THF in a series of binary
mixtures with either oligomeric styrene or PMMA using differential scanning
calorimetry (DSC), dielectric spectroscopy (DS), quasielastic neutron scattering
(QENS) and X-ray photon correlation spectroscopy (XPCS). It turns out
that, although the systems are fully miscible in the whole temperature range,
in many mixtures two glass transition steps can be clearly distinguished in DSC
measurements due to the high Tg contrast of the components. By means of
DS the corresponding relaxation processes are identified and it turns out that
contrary to expectation the small molecule M-THF takes part in both glass
transitions. Moreover, the relaxation connected with the lower glass transition
shows properties typical of dynamics in confinement like an Arrhenius-type temperature
dependence and a broad distribution of relaxation times. On the other
hand, when the system crosses the upper glass transition, the matrix transforms
from a “slow” to an actual “hard” confinement. It is revealed by XPCS that
this is reflected in the behaviour of the concentration fluctuations, which show
a crossover from a diffusive to a so-called ballistic wave vector dependence and
from stretched to compressed out-of-equilibrium relaxation functions around the
upper glass transition. Finally we compare the confinement effects observed for
small molecules as part of a binary mixture with other confinement situations,
in particular with the soft confinement of glass formers within microemulsion
droplets.

Static and dynamic length scales in a frustrated atomic glass-forming
liquid
F. Sausset (1,2), G. Tarjus (2), P. Viot (2)
(1) IPhT, CEA, Saclay, France
(2) LPTMC, Université Pierre et Marie Curie, Paris, France
Correspondence author: sausset@lptmc.jussieu.fr
We have investigated by MD simulation a monatomic frustrated liquid model:
a Lennard-Jones fluid on a hyperbolic plane. We find that the one-component
liquid does not crystallize and forms a glass on the hyperbolic plane. The
“fragility” decreases with increasing frustration, and one can tune fragility by
changing the space curvature [1]. We have studied the (point) topological defects
that are present in the liquid. This provides a means to describe the interplay
between structure and dynamics and to investigate the connection between dynamical
heterogeneities and topological defects. More quantitatively, we have
on one hand investigated the now standard four-point space-time correlation
function, which allows us to measure a growing dynamical correlation length.
On the other hand, we have extracted a static correlation length, characteristic
of hexatic ordering, from a bond-orientational correlation function. The
associated susceptibilities have also been computed. We find two regimes as
temperature decreases: one dominated by collective ordering effects controlled
by the avoided crystallization transition, where the two lengths grow together
and one dominated by the dynamics of the few intrinsic topological defects,
where a decoupling between the two lengths occurs.
[1] F.Sausset, G.Tarjus, and P.Viot. Tuning the fragility of a glass-forming liquid
by curving space. Phys. Rev. Lett., 101, 155701 (2008).

THEORIES FOR THE MIXED GLASS FORMER EFFECT
P. Maass (1), C. R. Müller (2), M. Schuch (2), S. W. Martin (3)
(1) Fachbereich Physik, Universität Osnabrück, 49069 Osnabrück, Germany
(2) Institut für Physik, Technische Universität Ilmenau, 98684 Ilmenau, Germany
(3) Department of Material Science & Engineering, Iowa State University, Ames,
IA 500100, USA
Correspondence author: philipp.maass@uni-osnabrueck.de
Mixing of two types of glass formers in ion conducting glasses can be exploited
to optimize ionic conductivities. Considering a glass of general composition
yM2X + (1 − y)[(1 − x)A + xB] with two network formers A, B, and an alkali
modifier M2X (where X is O, or S), the conductivity activation energy Ea(x)
often passes through a minimum as a function of the mixing ratio x, leading to a
pronounced maximum in the ionic conductivity. This phenomenon is commonly
referred to as the “Mixed Glass Former Effect” (MGFE).
We will present two theoretical approaches to explain the MGFE: The first
is the Mixed Barrier Model (MBM, [1]), which applies to situations, where,
upon varying x, the local geometry of the units of each of the network formers
remains the same (as, e.g., the tetrahedral units in a GeO2-GeS2-system).
The second is the Network Unit Trapping model (NUT model), which applies
to situations, where the coordination number of the elementary units changes
(as, e.g., the ratio of tetrahedral BO4 to trigonal BO3 units in borophosphates).
Fits of the MBM to experimental data allow one to estimate the strength of
the barrier reduction, and they indicate a spatial clustering of the two types of
network formers. Fits of the NUT model to the borophosphate system studied
in [2] yield good agreement with the measured data both for the concentration
variation of the units with x and the associated variation of the conductivity
activation energy.
[1] M. Schuch, C.R. Müller, P. Maass, S.W. Martin, Phys. Rev. Lett. 102 (2009)
145902.
[2] D. Zielniok, C. Cramer, H. Eckert, Chem. Mat. 19 (2007) 3162; D. Zielniok,
H. Eckert, C. Cramer, Phys. Rev. Lett. 100 (2008) 035901.

WORK DISTRIBUTIONS IN THE PRESENCE OF FREEZING
DEGREES OF FREEDOM
Mario Einax (1) and Philipp Maass (2)
(1) Institut für Physik, Technische Universität Ilmenau, Weimarer Straße 25,
98684 Ilmenau, Germany
(2) Fachbereich Physik, Universität Osnabrück, Barbarastraße 7, 49069 Osnabrück,
Germany
Correspondence author: mario.einax@tu-ilmenau.de
A First-Reaction Monte-Carlo algorithm for master equations with time-dependent
rates is presented as an efficient tool to determine distributions of the
microscopic work and heat of interacting systems far from equilibrium. We
first apply the method to an Ising chain with Glauber dynamics driven by a
time-dependent magnetic field. The distributions show pronounced singularities
at fast driving and approach the Gaussian fluctuation regime with decreasing
driving rate. Integral fluctuation theorems are explicitly confirmed. In a second
step, we consider the freezing of single spins and its influence on the work
and heat distributions and discuss associated modifications of the fluctuation
theorems. Our results offer a novel characterization for the onset of glassy
dynamics in terms of non-equilibrium fluctuations.

CONNECTIONS BETWEEN STRUCTURE AND DYNAMICS IN
SUPERCOOLED, HYDRATION AND CONFINED WATER
Appignanesi G A (1), Rodriguez Fris J A (1) and Sciortino F (2)
(1) Área de Fisicoquímica, Departamento de Química and INQUISUR, Universidad
Nacional del Sur, Avenida Alem 1253, 8000-Bahía Blanca, Argentina
(2) Dipartimento di Fisica and INFM-CNR-SOFT, Università di Roma La
Sapienza, Piazzale A. Moro 2, 00185 Roma, Italy
Correspondence author: appignan@criba.edu.ar
The belief that liquid water consists of a mixture of molecules in two kinds of
structural “states” (structured, well tetrahedrally hydrogen bonded, low local
density molecules and unstructured, high density ones) is a very old one. This
feature is also thought to underlie many important anomalies that water presents
and which become more prominent as it is cooled within the normal and into
the (metastable) supercooled liquid states (the supercooled state is attained
below the melting temperature and is a precursor of the glassy state). In this
regard, we shall show that the study of structural indexes is of essence in order
both to better state the above-mentioned picture and also to make explicit the
existence of a causal link between structure and dynamics, a long standing issue
in glassy physics. In turn, we’ll also show that such a knowledge is relevant for
the understanding of the behavior of hydration and (nano)confined water, like
water at hydrophobic surfaces and biological water.

A TWO-STATE PICTURE FOR THE SUPERCOOLED WATER
STRUCTURE AND ITS RELATION WITH GLASSY DYNAMICS
Appignanesi G A (1), Rodriguez Fris J A (1) and Sciortino F (2)
(1) Área de Fisicoquímica, Departamento de Química and INQUISUR, Universidad
Nacional del Sur, Avenida Alem 1253, 8000-Bahía Blanca, Argentina
(2) Dipartimento di Fisica and INFM-CNR-SOFT, Università di Roma La
Sapienza, Piazzale A. Moro 2, 00185 Roma, Italy
Correspondence author: appignan@criba.edu.ar
The description of liquid water as consisting of a mixture of molecules of two
different structural states (structured, low-density molecules and unstructured,
high-density ones) represents a belief that has been around for long time awaiting
for a conclusive validation. While in the last years some indicators have indeed
provided certain evidence for the existence of structurally different “species”,
a more definite bimodality in the distribution function of a reliable structural
quantity would be desired. In this context, our molecular dynamics computer
simulations work combines the use of a structural parameter with a minimisation
technique to yield neat bimodal distributions in a temperature range within
the supercooled regime, thus clearly revealing the presence of two populations
of differently structured water molecules. Furthermore, we elucidate the role of
the inter-conversion between the identified two kinds of states with the dynamics
of the structural relaxation, thus linking structural information to dynamics,
a longstanding issue in glassy physics.
Rodriguez Fris J A, Appignanesi G A, La Nave E and Sciortino F, Phys. Rev.
E 75, 041501 (2007).
Appignanesi G A, Rodriguez Fris J A and Sciortino F, to be published elsewhere
(2009).
Appignanesi G A, Rodriguez Fris J A, Montani R A y Kob W, Phys. Rev. Lett.
96, 057801 (2006).

Simulation Study of Dynamics and Structure in Supercooled Liquid
of CuZr
Y. Kimura (1), M. Tokuyama (2)
(1) Department of Nanomechanics, Graduate School of Tohoku University, Sendai,
Japan
(2) World Premier <strong>International</strong> Research Center, Advanced Institute for Materials
Research, Tohoku University, Sendai, Japan
kimura@athena22.wpi-aimr.tohoku.ac.jp
Contrast to ordinary liquid, supercooled liquid shows a complicated dynamical
behavior. As temperature decreases and the glass transition point approaches,
the viscosity of the system increases rapidly and the motion of the particles
become slow dramatically. Under these changes in dynamics, new time scales
appears that results in the two-step decay of the intermediate scattering functions.
Additionally, it is reported that in supercooled liquid, the dynamics of
the particles are not uniform [1]. These dynamical behavior of the supercooled
liquid is also important in study of bulk metallic glasses since it is related to the
some mechanical properties and their structural formations. In order to study
these dynamical properties, we perform molecular dynamics simulation using a
model of CuZr [2]. We investigated the dynamical behavior and structure of the
system, and considered the relation between them. Details are presented in the
meeting.
[1] E. Weeks et al, Science 287 (2000), 627
[2] X. J. Han and H. Teichler, Phys. Rev. E 75 (2007), 061501

CONSTRAINT NETWORKS, DYNAMIC HETEROGENEITIES AND
RELAXATION IN DISORDERED SOLIDS
Vanessa K. de Souza and Peter Harrowell
School of Chemistry, University of Sydney, Sydney, Australia
Correspondence author: vanessa.k.desouza@gmail.com
We use a simple model system to describe inherent structures on the potential
energy surface for a variety of disordered solids [1]. Characterisation of local soft
modes or unconstrained motions allows us to examine dynamical heterogeneities
in these solids. We can also construct long-term relaxation functions and hence
determine dynamical susceptibilities for an evolving system. Furthermore, we
can consider the effects of temperature or density on relaxation.
A disordered network of bonds with a fixed configuration can relax via a variety
of unconstrained motions. These motions can be directly inferred from the topological
arrangement of constraints without any geometrical information. We use
the Pebble Game algorithm of Jacobs and Thorpe [2] to decompose the system
into separate rigid clusters and identify the remaining degrees of freedom. Unconstrained
motions can then be resolved and assigned a characteristic thermal
velocity. We examine the spatial distribution of relaxation timescales and, when
bonds are allowed to change, construct a long-term relaxation function.
[1] V. K. de Souza and P. Harrowell, Prod Natl Acad Sci, in press (2009).
[2] D. J. Jacobs and M. F. Thorpe, Phys Rev Lett 75 (1995), p. 4051.

Heterogeneous Relaxation at Glass Surfaces: Ultra-Stable Glass Films
and Propagating Annealing Fronts
S. Léonard (1), P. Harrowell (1)
(1) School of Chemistry, University of Sydney, Australia
Correspondence author: sebastien.leonard@chem.usyd.edu.au
Motivated by the recent experimental fabrication by Ediger and coworkers
[1] of ultra stable glass films and their observation of front-like response to the
annealing of these glass films. We report on a theoritical study in which a
facilitated kinetic Ising model is used to model the complex kinetics associated
with stabilization of vapour deposited films of glass forming materials and the
heterogeneous kinetics associated with subsequent temperature response. We
find that the model used to describe the microscopic dynamic heterogeneities in
the bulk glass former reproduces qualitatively all the experimental observations.
[1] S. F. Swallen, M. K. Mapes, Y. S. Kim, R. J. McMahon, M. D. Ediger, and
S. Satija, J. Chem. Phys. 124, 184501 (2006), DOI:10.1063/1.2191492

Appearance of Fractional Stokes-Einstein Relation in Water
and Structural Interpretation of its Onset
Limei Xu, 1 Francesco Mallamace, 2 Zhenyu Yan, 3
Francis W. Starr, 4 Sergey V. Buldyrev 5 and H. Eugene Stanley 3
1 World Premier <strong>International</strong> (WPI) Research Center,
Advanced Institute for Materials Research,
Tohoku University, Sendai 980-8577, Japan
2 Dipartimento di Fisica and CNISM,
Universitá di Messina, I-98122, Messina, Italy
3 Center for Polymer Studies and Department of Physics,
Boston University, Boston, MA 02215 USA
4 Department of Physics, Wesleyan University, Middletown, CT 06459 USA
4 Department of Physics, Yeshiva University,
500 West 185th Street, New York, NY 10033 USA
(Dated: August 27, 2009)
Abstract
The Stokes-Einstein relation has long been regarded as one of the hallmarks of transport in
liquids. It predicts that the self-diffusion constant D is proportional to (τ/T ) −1 , where τ is the
structural relaxation time and T the temperature. We present experimental data on water demon-
strating that, below a crossover temperature T× ≈ 290 K, the Stokes-Einstein relation is replaced
by a “fractional” Stokes-Einstein relation D ∼ (τ/T ) −ζ with ζ ≈ 3/5. We interpret the micro-
scopic origin of this crossover by analyzing the OH stretch region of the FTIR spectrum over a
wide T range from 350 K down to 200 K. Simultaneous with the onset of fractional Stokes-Einstein
behavior, we find that water begins to develop a local structure like that of low-density amorphous
solid H2O. These data lead to an interpretation that the fractional Stokes-Einstein relation in wa-
ter arises from a specific change in local water structure. To further test this interpretation, we
perform computer simulations of two molecular models, and our simulation results support our
experimental observations
1

Aging and effective temperatures near a critical point
Joubaud Sylvain (1),Petrossyan Artyom (2),Ciliberto Sergio(2))
(Presenting author underlined)
(1) Physique of Fluids - University of Twente,
P.O. Box 217, 7522AE Enschede The Netherlands
(2) Ecole Normale Supérieure de Lyon, Laboratoire de Physique,
C.N.R.S. UMR5672, 46, Allée d’Italie, 69364 Lyon Cedex 07, France
Correspondence author: sergio.ciliberto@ens-lyon.fr
The mean orientations of the fluctuations of the director of a nematic liquid
crystal are measured using a sensitive polarization interferometer. When an
electric field is applied perpendicularly to the initial alignment of the molecules,
there is a critical point for which molecules try to align to the field. This is called
the Frédericksz transition which is expected to be second order phase transition.
We report experimental evidence that, because of the critical slowing down, the
LC presents, after a quench near the critical point, several properties of an aging
system, such as power law scaling versus time of correlation and response functions.
During this slow relaxation, a well defined effective temperature, much
larger than the heat bath temperature, can be measured using the fluctuation
dissipation relation. The results are in excellent agreement with the theoretical
prediction for the effective temperature.
[1] S. Joubaud, A. Petrosyan, S. Ciliberto, N. Garnier, Experimental evidence
of non-Gaussian fluctuations near a critical point, Phys. Rev. Lett, 2008, 100,
180601.
[2] S. Joubaud, G. Huillard,A. Petrosyan, S. Ciliberto, Work fluctuations in a
nematic liquid crystal, J. Stat. Mech., 2009, P01033.
[3] S. Joubaud, B. Percier,A.Petrosyan, S. Ciliberto, Aging and effective temperatures
Near a critical point, Phys. Rev. Lett., 2009, 102, 130601.

GLASS AND DELOCALIZATION TRANSITIONS DESCRIBED BY
MCT
Th. Voigtmann (1,2)
(1) Institut für Materialphysik im Weltraum, Deutsches Zentrum für Luft- und
Raumfahrt (DLR), 51170 Köln, Germany
(2) Zukunftskolleg und Fachbereich Physik, Universität Konstanz, 78457 Konstanz,
Germany
Correspondence author: thomas.voigtmann@dlr.de
MCT, while offering a description of slow dynamics in dense liquids based on
microscopic equations of motion, makes a number of general predictions that
are expected to be valid irrespective of the interaction details. Schematic models
allow to explore these aspects of the dynamics within a simplified set of
equations. I will discuss some recent advances in applying MCT and schematic
models to describe the interplay between glassy dynamics and the delocalization
of individual particles inside the otherwise frozen matrix. Apart from binary
mixtures with very asymmetric interactions and/or sizes, the main focus will
be on the delocalization of probe particles pulled by external forces (so-called
active micro-rheology).

DENSITY NONLINEARITIES AND FIELD THEORIES IN A TOY
MODEL FOR FLUCTUATING NONLINEAR HYDRODYNAMICS
OF SUPERCOOLED LIQUIDS
J. Yeo (1)
(Presenting author underlined)
(1) Division of Quantum Phases and Devices, School of Physics, Konkuk University,
Seoul 143-701, Korea
Correspondence author: jhyeo@konkuk.ac.kr
We study a zero-dimensional version of the fluctuating nonlinear hydrodynamics
(FNH) of supercooled liquids originally proposed by Das and Mazenko (DM) [1].
The time-dependent density-like and momentum-like variables are introduced
with no spatial dependence in this toy model. The structure of nonlinearities,
however, takes the similar form to the original FNH, which allows one to study
in a simpler setting the subtle issues raised recently regarding the field theoretical
approaches to glass forming liquids. We study the effects of density
nonlinearities on the time evolution of correlation and response functions by
developing field theoretic formalisms in two different ways: first by following
the original prescription of DM and then by constructing a dynamical action
which possesses a linear time reversal symmetry as proposed recently in [2].
We show explicitly that, at one-loop order, the DM-type field theory does not
support a sharp ergodic-nonergodic transition, while the other admits one. The
simple nature of the toy model allows one to develop numerical solutions to a
complete set of dynamical equations for the correlation and response functions
at the one-loop order.
[1] S. P. Das and G. F. Mazenko, Phys. Rev. A 34 (1986), p. 2265.; Phys. Rev.
E 79 (2009) p. 021504.
[2] A. Andreanov, G. Biroli and A. Lefèvre, J. Stat. Mech. (2006), P07008; T.
H. Nishino and H. Hayakawa, Phys. Rev. E 78 (2008), p. 061502.

NON-LINEAR SUSCEPTIBILITY IN GLASS FORMING LIQUIDS:
A PROBE FOR DYNAMICAL HETEROGENEITIES
G. Biroli (1), J.-P. Bouchaud (2,3), A. Lefvre (1), M. Tarzia (4)
(Presenting author underlined)
(1) Institut de Physique Théorique, CEA, IPhT, F-91191 Gif-sur-Yvette, France
CNRS, URA 2306, F-91191 Gif-sur-Yvette, France
(2) Science & Finance, Capital Fund Management, 6 Bd Haussmann, 75009
Paris, France
(3) Service de Physique de l’ État Condensé, Orme des Merisiers – CEA Saclay,
91191 Gif sur Yvette Cedex, France
(4) LPTMC, Tour 24, Bote 121, 4, Place Jussieu, 75252 Paris Cedex 05, France
Correspondence author: alexandre.lefevre@cea.fr
Strong dynamical heterogeneity (DH) is now widely thought to be central in understanding
the slowing down of supercooled liquids. From a theoretical point
of view, it is natural to describe DH through four point density correlation functions.
On the other hands, such description is not well adapted to experiments
on molecular liquids, and other correlations functions - more adapted - have
been designed in the recent years, in order to probe DH experimentally. In this
talk, we will focus on the non-linear response, χ3, to an oscillating field, which
was argued [1] to be simply related to four point density correlation functions.
We will first recall the correspondance between this response and other probes
of DH. Then we will discuss the general scaling form of this function [2]. In
particular, we will show the consequences of time-superposition and discuss in
details the scaling obtained within mode-coupling theory. In support to these
arguments, it will be shown that a precise calculation can be made using a
schematic model, the so-called p-spin model.
[1] J.-P. Bouchaud and G. Biroli, Phys. Rev. B 72 (2005) p. 064205
[2] M. Tarzia, G. Biroli, J.-P. Bouchaud and A.Lefvre, arXiv:0812.3514, unpublished

A colloidal model for eye lens protein mixtures:
relevance for cataract formation
N. Dorsaz (1), G. Thurston (2), A. Stradner (3), P. Schurtenberger (3) and
G. Foffi (1)
(1) ITP & IRRMA, Ecole Polytechnique Fédérale de Lausanne, Switzerland
(2) Department of Physics, Rochester Institute of Technology, US
(3) Adolphe Merkle Institute and Center for Nanomaterials, University of Fribourg,
Switzerland
nicolas.dorsaz@epfl.ch
Cataract is the leading cause of blindness and effective prevention or nonsurgical
cure are nowadays still lacking. This loss of transparency of the eye
lens originates from the alteration of the spatial distribution of the α−, β− and
γ− crystallin proteins that are contained at high concentration in the lens cells.
Biological studies of the chaperone properties of crystallins have given valuable
information about their aggregation in diluted environment. However it is
crucial to complement these studies with investigations at physiological concentrations
where emergent mixture properties, like phase transitions, are expected.
A colloidal model for binary mixtures of α and γ crystallins is developed combining
MD simulations and neutron scattering data. We demonstrate that transparency
of the eye lens is greatly enhanced by a weak, short-range attraction
between α and γ-crystallin. Provided it is not too strong, such mutual attraction
considerably decreases the critical temperature and corresponding opacity due
to light scattering, and it is consequently essential for eye lens transparency [1].
The phase diagram of the α-γ model mixture is then investigated via thermodynamic
perturbation theory. The instability boundary is found to depend on the
α-γ attraction in a manner that is both extremely sensitive and non-monotonic,
in excellent agreement with the experimental and numerical results [2]. Moreover,
the composition of the coexisting phases depends strongly on the strength
of the α-γ interaction.
[1] N. Dorsaz, G. Thurston, A. Stradner, P. Schurtenberger and G. Foffi,
J. Phys. Chem. B, 113 (2009), 1693
[2] A. Stradner, G. Foffi, N. Dorsaz, G. Thurston and P. Schurtenberger,
Phys. Rev. Lett., 99 (2007), 198103

Structure – Dynamics Relations in Multicomponent Viscous Liquids
A. Meyer (1), J. Horbach (1), Th. Voigtmann (1)
(1) Institut für Materialphysik im Weltraum, Deutsches Zentrum für Luft- und
Raumfahrt (DLR), 51170 Köln, Germany
Correspondence author: andreas.meyer@dlr.de
As compared to one component viscous liquids, multicomponent systems exhibit
a rich interplay between chemical ordering and relaxation dynamics. We determine
partial static and dynamic structure factors as well as coefficients of mass
transport in metallic and silicate melts, using various experimental techniques
and molecular dynamics computer simulations. We show, how the self motion
of the various components, the collective dynamics and the melt structure
are related. Static partial structure factors are used to predict the dynamical
behavior from numerical solutions of the mode coupling theory of the glass
transition. The resulting MCT predictions for the relaxation dynamics capture
all main features of the intriguing dynamical behavior found in experiment and
simulation.

HOW SOLVENT DEGREES OF FREEDOM LUBRICATE PRO-
TEIN FOLDING PATHWAYS.
O. Collet
Groupe de Physique Statistique, Institut Jean Lamour, Nancy-Université/CNRS
Faculté des Sciences - F-54506 Vandoeuvre-lès-Nancy, France
Correspondence author: Olivier.Collet@lpm.u-nancy.fr
Recently, theoretical studies [1-4] have shown that the degrees of freedom of
the solvent around proteins must be taken into account to capture fundamental
mechanism such as cold denaturation. Here, we show kinetic results obtained
for a two-dimensional lattice model of solvated proteins. Each chain structure
interacts with a highly degenerated solvent. These hydration micro-states are
grouped together in two macro-states. Starting from an out of equilibrium protein
structure distribution, we iterate two master equations of the system to find
the probability of occurrence of the native structure as a function of time. In one
hand, the solvent degrees of freedom are averaged first and the transition rates
between chain structures are then calculated. In an other hand, the transition
rates between each chain conformations in interaction with each solvent configurations
are calculated first. Then, the transition rates between chain structures
in interaction with a solvent macro-state are determined by grouping together
solvent micro-states rates. The results show dramatic differences between the
two approaches. Using the second - more realistic - description, a very large
ratio (around 25%) of proteins finds quasi-instantaneously the native structure.
We show that this conformation is reached by passing very fast by the excited,
highly degenerated, solvent states which act as strong attractors even if their
equilibrium probabilities is quasi-null.
[1] P. De Los Rios, G. Caldarelli, Phys. Rev. E, 62 (2000) 8449
[2] O. Collet, Europhys. Lett., 53 (2001) 6573
[3] O. Collet, Europhys. Lett., 72 (2005) 301
[4] O. Collet, J. Chem. Phys. 129 (2008) 155101

Cluster phases of patchy micelles
C.M.C. Gambi (1,3), S. Marchetti (1,3), E. Fratini (2), S. Sennato (3)
(1)Department of Physics, University of Florence and CNISM Via G. Sansone 1, 50019,
Sesto Fiorentino (Florence), Italy
(2)Department of Chemistry and Consorzio Interuniversitario per lo Sviluppo dei Sistemi
a Grande Interfase (CSGI), University of Florence, Via della Lastruccia 3, 50019, Sesto
Fiorentino (Florence), Italy
(3)CRS-Soft Matter (CNR-INFM) Universita‘ di Roma La SapienzaP.le A. Moro 2, 00185
Rome, Italy
corresponding author: gambi@fi.infn.it
Aggregation processes are an important subject of current research in the liquid state
physics because understanding the aggregation mechanisms makes it possible to build up
new responsive materials and to solve important challenges in medicine/biology as well as
in several industrial-manufacturing processes. We studied a simple aqueous self-assembled
micellar system (Sodium Dodecyl Sulphate in water) doped with various adhesive sites
(mainly the cryptand Kryptofix 222 or the crown ether 18-Crown-6). As a main result naked
SDS micelles do not aggregate whereas micelles with macrocyclic ligand (patchy micelles)
do aggregate depending on the ligand/surfactant ratio as demonstrated by dynamic light
scattering and small-angle x-ray scattering studies. These phases have been named cluster
phases as they seem to be formed by clusters of micelles. The hydrophobicity degree of the
adhesive sites that is greater for Kryptofix 222 than for 18-Crown-6, drives the formation
of the aggregates. Recently, dielectric spectroscopy has also been done on the samples to
study the dynamics of the system. Previous small-angle neutron scattering was employed
to characterize the microstructure of the micelles [1,2].
1995
[1]P. Baglioni, C.M.C. Gambi, R. Giordano and J. Teixeira, Physica B, 213&214, 597,
[2]L. Scaffei, L. Lanzi, C. M. C. Gambi, R. Giordano, P. Baglioni and J. Teixeira, J. Phys.
Chem. B, 106, 10771, 2002
1

SIMULATION OF COOPERATIVE AND NONEXPONENTIAL PRO-
CESSES IN NON-CRYSTALLINE POLYMERS
C. Torregrosa Cabanilles (1), J. Molina-Mateo (1), J. M. Meseguer Dueñas
(1,2), J. L. Gómez Ribelles (1,2,3)
(1) Center for Biomaterials and Tissue Engineering, Universidad Politécnica de
Valencia, Spain
(2) CIBER en Bioingeniería, Biomateriales y Nanomedicina, Valencia, Spain
(3) Regenerative Medicine Unit, Centro de Investigación Príncipe Felipe, Valencia,
Spain
Correspondence author: ctorregr@fis.upv.es
Bond fluctuation model simulations of amorphous materials behave as a very
complex Markov chain [1]. A first order Markov chain would apply also to a
very small isolated region but, in condensed matter, the interactions with its
neighbour regions have to be taken into account. We include them by using a
second order Markov chain model of a small region [2], and some general characteristics
of the dynamics of amorphous polymers are found as a result. This
simple Markov model allows simulating structural relaxation processes with a
few parameters: the energy levels of a small region and the transition probability
between them. Isothermal relaxations at different temperatures from an equilibrium
state were simulated. The nonexponentiality of the energy relaxations in
a temperature interval appears directly related to the cooperativity parameter
included in the transition probability. And the heigth of the potential barriers
between states is also found to control the changes of the relaxation times with
temperature. We show our simulation results and explain the relations found
between cooperativity, nonexponentiality and the relaxation times.
[1] K. Binder (Ed.), Monte Carlo and Molecular Dynamics Simulations in Polymer
Science, Oxford University Press, New York, 1995.
[2] C. Torregrosa Cabanilles, J.M. Meseguer Dueñas, J.L. Gómez Ribelles, J.
Molina-Mateo, Macromol. Theory Simul. DOI: 10.1002/mats.200900008

THERMODYNAMIC ANOMALIES AND REENTRANT GLASS
TRANSITION IN THE REPULSIVE STEP POTENTIAL SYSTEM
Yu.D. Fomin, V.N. Ryzhov
Institute for High Pressure Physics, Russian Academy of Sciences, 142190,
Troitsk, Moscow region, Russia
Correspondence author: ryzhov@hppi.troitsk.ru
It is well known that some systems can be strongly overcooled without crystallization.
In result the dynamics of the system becomes extremely slow and it
experiences glass transition. Usually one-component systems crystallize quite
easily and it is difficult to observe glassy phase in a one-component system. This
work presents the investigation of a repulsive-step system which demonstrates
amorphous behavior in one-component system with purely repulsive isotropic
interaction. The phase diagram demonstrates a sequence of solid phases separated
by a reentrant glass region with thermodynamic water-like anomalies in
the vicinity of this region [1,2].
The glass-transition line was calculated within the mode coupling theory for
the repulsive step potential system. The random phase approximation was used
for calculating the static structure factor. The glass-transition line demonstrates
maxima and minima which correspond to different kinds of glasses occurring in
the system under investigation. The dependence of the phase behavior and
amorphous region properties on the potential step size is presented. The possibility
of the higher order glass transition singularities is discussed.
This work is supported by the Russian Foundation for Basic Research (Grant
No 08-02-00781).
[1] Yu. D. Fomin, N. V. Gribova, V. N. Ryzhov, S. M. Stishov, and Daan
Frenkel, J. Chem. Phys. 129, (2008) 064512.
[2] N.V. Gribova, Yu.D. Fomin, V.N. Ryzhov, Daan Frenkel, Phys. Rev. E
79,(2009) 051202.

Connecting Density Scaling to the Prigogine-Defay Ratio.
K. Niss (1), D. Gundermann (1), A. Nielsen (1), C. Dalle-Ferrier (2), C. Alba-
Simionesco (3), T. Schrøder (1) J. Dyre (1)
(1) DNRF Center “Glass and Time”, Roskilde, Denmark
(2) LCP, Orsay, France
(3) LLB, Paris, France
Correspondence author: kniss@ruc.dk
Recent theoretical and computer simulation results on “strongly correlating liquids”
connect different questions and relations which where earlier regarded as
independent [1,2]. (a) The temperature density scaling of the relaxation time
[3], (b) the invariance of the spectral shape of the relaxation along a line of constant
relaxation time (an isochrone at different pressures and temperatures) [4]
and (c) the old question of whether one or more “order” parameters is needed
to describe the linear relaxation in viscous liquids (is the Prigogine-Defay Ratio
one or more) [1,5]. We review experimental data on the alpha relaxation at
different pressures and temperatures in the view of these new findings. We also
consider the implications for fast dynamics (boson peak, non-ergodicity factor,
mean square displacement) and the restrictions strong correlations imply on the
possible relations between fast and slow dynamics in line with earlier analysis
based on the temperature density scaling [6].
[1] N. P. Bailey, T. Christensen, B. Jakobsen, K. Niss, N. B. Olsen, U. R.
Pedersen, T. B. Schrøder, J. C. Dyre, J. Phys.: Cond. Matt. 20, (2008) 244113.
[2] T. B. Schrøder, U. R. Pedersen, N. P. Bailey, S. Toxværd, J. C. Dyre condmat
(2008) arXiv:0812.4960 , N. Gnan, T. B. Schrøder, U. R. Pedersen, N. P.
Bailey, J. C. Dyre cond-mat (2009) arXiv:0905.3497
[3] C. Alba-Simionesco, A. Cailliaux, A. Alegria, G. Tarjus, Europhys. Lett.
68, (2004) 58, C. M. Roland, M. Paluch, T. Pakula, R. Casalini Phil. Mag. 84
(2004) 1573
[4] K. L. Ngai, R. Casalini, S. Capaccioli, M. Paluch, C. M. Roland, J. Phys.
Chem. B 109 (2005) 17356 , A.I. Nielsen, S. Pawlus, M. Paluch, J.C. Dyre, Phil.
Mag. 88 (2008) 4101, K. Niss, C. Dalle-Ferrier, G. Tarjus, C. Alba-Simionesco
J. Phys-Cond. Mat. 19 (2007) 076102
[5] N. L. Ellegaard, T. Christensen, P. V. Christiansen, N. B. Olsen, U. R.
Pedersen, T. B. Schrøder, J. C. Dyre, J. Chem. Phys. 126 (2007) 074502
[6] K. Niss, C. Dalle-Ferrier, V. M. Giordano, G. Monaco, B. Frick, C. Alba-
Simionesco, J. Chem. Phys. 129 (2008) 194513, K. Niss, B. Begen, B. Frick,
J. Ollivier, A. Beraud, A. Sokolov, V. Novikov, C. Alba-Simionesco Phys. Rev.
Lett. 99 (2007) 055502, K. Niss, C. Alba-Simionesco, Phys. Rev. B 74 (2006)
024205

Generic properties: Prevalence of approximate √ t relaxation for the
dielectric α process in viscous organic liquids
Albena I. Nielsen(1), Tage Christensen(1), Bo Jakobsen(1), Kristine Niss(1),
Niels Boye Olsen(1), and Jeppe C. Dyre(1),
(Presenting author underlined)
(1) DNRF Centre “Glass and Time”, IMFUFA, Department of Sciences, Roskilde
University, Postbox 260, DK-4000 Roskilde, Denmark
Correspondence author: albenan@ruc.dk
We present a comprehensive study of spectral shape of 53 liquids’ dielectric relaxation.
The shape here is characterized by the mathematically well-defined
“minimum slope” of the α dielectric loss plotted as a function of frequency in
a log-log plot and the half width at half maximum. The 347 spectra show
prevalence of numerical minimum slopes close to 1/2. We investigated possible
correlations between minimum slopes and: 1) Temperature; 2) How well an inverse
power law fits data above the loss peak; 3) Degree of time-temperature
superposition; 4) Loss-peak half width; 5) Deviation from non-Arrhenius behavior;
6) Loss strength.
For the first 3 points are correlations that show a special status of liquids
with numerical minimum slopes close to 1/2. For the last 3 points only fairly
insignificant correlations are found, with the exception of large-loss liquids that
have minimum slopes that are Debye-like and half loss peak widths that are
significantly smaller than those of most other liquids. We conclude that - excluding
large-loss liquids - appears to be a generic property of the α relaxation
of organic glass formers.[1]
Furthuremore we show explicit that the so-called temperature-pressure superposition
at constant relaxation times is obeyed for van der Waals liquids
with exception of DHIQ from a collection of ten glass-forming organic liquids’
dielectric data at high pressure along isotherms, i.e., for these liquids the two
shape parameters (minimum slope and the width) depends on relaxation time
[2]. This gives connection to the class of model system - the strongly correlating
liquids [3,4,5,6].
[1] Reference 1 (Journal of Non-Crystalline Solids style should be used)
[2] Reference 2 (Journal of Non-Crystalline Solids style should be used)
[1]A. I. Nielsen, T. Christensen, B. Jakobsen, K. Niss, N. B. Olsen, R. Richert,
and J. C. Dyre, Journal of Chemical Physics 130,154508 (2009).
[2] A. I. Nielsen, S. Pawlus, M. Paluch and J. C. Dyre, Philosophical Magazine
88, 4101 (2008).
[3] T. B. Schrøder, U. R. Pedersen, N. Bailey, S. Toxvrd and J. C. Dyre,
arXiv:0812.4960v1 [cond-mat.soft](2008).
[4] U. R. Pedersen, N. P. Bailey, T. B. Schrder, and J. C. Dyre, Physical Review
Letters 100, 015701 (2008).
[5] N. P. Bailey, U. R. Pedersen, N. Gnan, T. B. Schrder, and J. C. Dyre, Journal
of Chemical Physics 129, 184507 (2008).
[6] N. P. Bailey, U. R. Pedersen, N. Gnan, T. B. Schrder, and J. C. Dyre, Journal
of Chemical Physics 129,184508 (2008).

Non-equilibrium Fluctuation Dissipation Relation for Brownian particles
under steady shear
M. Krüger (1), M. Fuchs (1)
(1) Fachbereich Physik, Universität Konstanz, 78467 Konstanz, Germany
Correspondence author: matthias.krueger@uni-konstanz.de
We present the theoretical study of the relation between response and correlation
function under steady shear. The Fluctuation Dissipation Theorem (FDT)
connecting these functions in equilibrium is violated in the non-equilibrium system
as was demonstrated by simulations. This violation is often interpreted
in terms of an effective temperature. We treat the exact starting point for
the response function within the recently developed mode coupling approach
for sheared systems (MCT-ITT). For systems at high density, which are glassy
without shear, the ratio of response and correlation function takes half the value
as expected from the equilibrium FDT in the simplest approximation, independent
of observable [1]. We briefly summarize other systems where the same
non-equilibrium ratio was found. The derived non-equilibrium FD Relation is
directly compared to simulation results, e.g., for the mean squared displacement
of a tagged particle and its mobility, with good agreement. The physical origin
of the violation of the equilibrium FDT is discussed.
[1] M. Krüger and M. Fuchs, Phys. Rev. Lett. 102 (2009) 135701.

WATER AND PROTON DYNAMICS IN PROTON-CONDUCTING
ALKALI THIO-HYDROXOGERMANATES
M. Karlsson (1,2), M. M. Koza (3), S. F. Parker (4), A. Matic (2), C. R. Nelson
(5), S. W. Martin (5)
(1) European Spallation Source Scandinavia, Lund University, 221 00 Lund,
Sweden
(2) Department of Applied Physics, Chalmers University of Technology, SE-412
96 Göteborg, Sweden
(3) Institut Laue-Langevin, 38042 Grenoble CEDEX 9, France
(4) ISIS Facility, STFC Rutherford-Appleton Laboratory, Chilton, Didcot, OX11
0QX, United Kingdom
(5) Department of Materials Science and Engineering, 2220 Hoover Hall, Iowa
State University of Science and Technology, Ames, Iowa 50011
Correspondence author: maths.karlsson@ill.eu
We report measurements of the proton dynamics and local structure of a novel
class of proton-conducting alkali thio-hydroxogermanates taken over a large temperature
range with the quasielastic neutron scattering spectrometer IN6 at Institut
Laue-Langevin (France) and the inelastic neutron scattering spectrometer
TOSCA at Rutherford-Appleton Laboratory (UK). The investigated materials,
denoted M 2GeS2(OH)2·yH2O (M = K, Rb and Cs; y∼1.1) are amorphous, and
built up of thio-hydroxogermanate anions, charge compensating alkali ions, and
intercalated water molecules [1-4]. We find an onset of anharmonic proton dynamics
at a temperature of about 200 K, related to local rotational diffusional
motion of the water molecules. Moreover, we find that, on the investigated ps
time-scale, the proton dynamics in the three investigated compounds is very
similar. Therefore, the observed proton dynamics cannot be correlated to the
large difference in proton conductivities amongst materials with different type
of alkali.
[1] S. A. Poling, C. R. Nelson and S. W. Martin, Chem. Mater. 17, 1728, 2005
[2] S. A. Poling, C. R. Nelson and S. W. Martin, Mater. Lett. 60, 23, 2006
[3] M. Karlsson et al., Solid State Ionics 177, 1009, 2006
[4] M. Karlsson et al., Chem. Mater. 20, 6014, 2008

ON THE THERMODYNAMIC ORIGIN OF DYNAMICAL HET-
EROGENEITIES
C. Cammarota (1,2), A. Cavagna (2,3), I. Giardina (2,3), G. Gradenigo (4),
T.S. Grigera (5), G. Parisi (1,2) and P. Verrocchio (4)
(1) Dipartimento di Fisica, ”Sapienza ” Università di Roma , Roma, Italy.
(2) Centre for Statistical Mechanics and Complexity (SMC), CNR-INFM.
(3) Istituto Sistemi Complessi (ISC), CNR, Roma, Italy.
(4) Dipartimento di Fisica, Università di Trento, Trento, Italy.
(5) Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas (INIFTA)
and Departamento de Física, Facultad de Ciencias Exactas, Universidad Nacional
de La Plata, La Plata, Argentina.
Correspondence author: gradenigo@science.unitn.it
In supercooled liquids is possible to define both dynamically and from thermodynamic
a correlation length that increases at low temperature : nevertheless
it’s not clear which is the common physical origin of the dynamical ξd(t)
and the statical ξs correlation lengths. We suggest that the interface cost at
the boundary between the different amorphous states of a supercooled liquid
is the common root of the two differently defined lengthscales. This hypothesis
is supported by data from numerical studies on the constrained dynamic
of a glass-forming liquid, the constrain being that a finite overlap with a given
reference configuration must be preserved. This constrain produces a dynamical
lengthscale ξd(t) ever increasing with time, apart from finite size effects,
at variance with the common unconstrained behaviour where ξd(t) increases to
a maximum value and ultimately relaxes to zero. The constrained dynamical
correlation length grows as ξd(t) ∼ t 1/3 suggesting that correlated amorphous
domains have a dynamics similar to coarsening with conserved order parameter.
We believe that the leading mechanism that rules the increase of ξd(t) is
the minimization of the interface between the regions with a high overlap with
the reference state and regions free to change state. Because surface tension
between amorphous states has been shown to be central even for the increasing
of the static lengthscale a unified scenario emerges.

FDT violations in gels of Patchy particles
J. Russo (1), F. Sciortino (1,2)
(1) Dipartimento di Fisica, Universita’ di Roma ’La Sapienza’, Piazzale A. Moro
2, I-00185, Rome, Italy
(2) CNR-INFM SOFT, Universita’ di Roma ’La Sapienza’, Piazzale A. Moro 2,
I-00185, Rome, Italy
Correspondence author: john.russo@roma1.infn.it
We study the aging bahaviour of gels formed from mixtures of Patchy Particles
and the applicability of the concept of effective temperature. Differently
from glasses the dynamic arrest of gels is due to the long-living bonds between
the particles which form a percolating network. We show that the relation between
correlations and response to an external field is linear for density-related
observables, as the Fluctuation-Dissipation theorem predicts for equilibrium
systems. The out-of-equilibrium properties is instead shown in energy-related
observables reflecting the proper arrest mechanism of gels. We show that the
relation between correlations and response functions does not follow the class of
structural glasses but the one of coarsening systems. The consequences of our
results will be discussed.

Dynamical heterogeneity and collective diffusion in Smectic Liquid
Crystals of Colloidal Hard Rods
Alessandro Patti (1), Djamel EL Masri (1), René van Roij (2), Marjolein Dijkstra
(1)
1 Soft Condensed Matter, Debye Institute for NanoMaterials Science, Utrecht
University, Princetonplein 5, 3584 CC, Utrecht, The Netherlands
2 Institute for Theoretical Physics, Utrecht University, Leuvenlaan 4, 3584 CE,
Utrecht, The Netherlands
Correspondence author: J.H.M.alMasri@uu.nl
Smectic liquid crystals are characterized by long-range orientational ordering
of the rods and a one-dimensional periodic density variation along the nematic
director, which lead to ”permanent” barriers between the smectic layers. Due
to the presence of these barriers, we find interesting non-Gaussian diffusive behavior
and heterogeneous dynamics in simulations, which strongly affect the
structural relaxation of the system. Interestingly, we also find that the layerto-layer
diffusion of the rods is characterized by quasi-discretized jumps and
proceeds collectively, giving rise to string-like diffusing clusters of rods. We find
that most of the string-like clusters consist of two or three rods, although strings
of up to 14 rods have been observed as well at increasing pressure. Additionally,
we show that the orientations of the rods that jump to neighbouring layers
are along the nematic director, but in some cases we observe transverse rods in
between the smectic layers, although the free-energy cost to orient to a transverse
state is very high [1]. In conclusion, we find heterogeneous dynamics and
collective motion in an equilibrium smectic-A phase due to the spatially inhomogeneous
density profile resemblant to that of an out-of-equilibrium quenched
supercooled colloidal liquids [2], in which particles are trapped in transient cages
formed by their neighbours.
[1] J. S. Van Duijneveldt and M. P. Allen, Mol. Phys. 90, 243 (1997).
[2] E. R. Weeks et al., Science, 287, 627 (2000); L. Berthier et al., Science, 310,
1797 (2005).

Homogeneous Pd-Catalysts by Neutron spectroscopy and theory: Reactivity
as a function of microscopic dynamics.
G. A. Chasse (1), F. Kargl (2), S. F. Parker (3), D.-C. Fang (4)
(1) Centre for Advanced Functional Materials and Devices, School of Chemistry,
University of Wales, Bangor, LL57 2UW, UK
(2) Centre for Advanced Functional Materials and Devices, Institute of Mathematics
and Physics, Aberystwyth University, Aberystwyth, SY23 3BZ, UK
(3) ISIS Facility, STFC, Rutherford Appleton Laboratories, Didcot, OX11 0QX,
UK.
(4) College of Chemistry, Beijing Normal University, Beijing, PRC.
Correspondence authors: chs40a@bangor.ac.uk, ffk@aber.ac.uk
Here we present results of computationally steered experiments on novel Pd
N-heterocyclic catalysts (Pd-NHCs) used in homogeneous catalysis. Polycrystalline
powder, solvated pre-catalysts and their corresponding ligands were studied.
The series of catalysts studied and distinguished only by their ligands show
largely different catalytic efficiency. Vibrations, librations, rotations, and translations
have been characterised by means of neutron spectroscopy effectively
underpinning results of post-HF and DFT computations on single molecules,
clusters of molecules, and explicit solvent molecule solvated structures. Here,
we show that fine details in the low energy normal modes, particularly in the
range of 0-500 cm-1, are coupled with catalytic activity. The analysis of the
wavefunctions shows that weakly polar interactions and collective motions at
low energies are key to catalyst turnover. This work aids in the formulation of
a series of design rules in the optimisation of homogeneous catalysts. Moreover,
the findings of wavefunction analysis are considered to be of general importance
for the understanding of the function of “molecular machines”, such as e. g.
enzymes and proteins.

Homogeneous Pd-Catalysts by Neutron spectroscopy and theory: Reactivity
as a function of microscopic dynamics.
G. A. Chasse (1), F. Kargl (2), S. F. Parker (3), D.-C. Fang (4)
(1) Centre for Advanced Functional Materials and Devices, School of Chemistry,
University of Wales, Bangor, LL57 2UW, UK
(2) Centre for Advanced Functional Materials and Devices, Institute of Mathematics
and Physics, Aberystwyth University, Aberystwyth, SY23 3BZ, UK
(3) ISIS Facility, STFC, Rutherford Appleton Laboratories, Didcot, OX11 0QX,
UK.
(4) College of Chemistry, Beijing Normal University, Beijing, PRC.
Correspondence authors: chs40a@bangor.ac.uk, ffk@aber.ac.uk
Here we present results of computationally steered experiments on novel Pd
N-heterocyclic catalysts (Pd-NHCs) used in homogeneous catalysis. Polycrystalline
powder, solvated pre-catalysts and their corresponding ligands were studied.
The series of catalysts studied and distinguished only by their ligands show
largely different catalytic efficiency. Vibrations, librations, rotations, and translations
have been characterised by means of neutron spectroscopy effectively
underpinning results of post-HF and DFT computations on single molecules,
clusters of molecules, and explicit solvent molecule solvated structures. Here,
we show that fine details in the low energy normal modes, particularly in the
range of 0-500 cm-1, are coupled with catalytic activity. The analysis of the
wavefunctions shows that key weakly polar interactions and collective motions
at low energies are key to catalyst turnover. This work aids in the formulation
of a series of design rules in the optimisation of homogeneous catalysts.

GLASS TRANSITION AND GEOMETRIC FRUSTRATION: IN SEARCH
OF A THEORY OF SUPERCOOLED LIQUIDS
G. Tarjus
LPTMC, CNRS/Université Pierre et Marie Curie, Paris, France
tarjus@lptmc.jussieu.fr
It should be cause for general embarrassment in our field that there is still no
consensus on even the most basic aspects of the theory of the glass transition.
Accepting nonetheless as a working hypothesis that a detail-independent ’universal’
theory of glassforming liquids should exist, I review the approach which
is based on the concept of geometric frustration. Frustration in this context
describes an incompatibility between extension of the locally preferred order
in a liquid and tiling of the whole space. I provide a critical assessment of
what has been achieved within this approach and discuss its relation with other
theories of the glass transition. Recent results on a simple monatomic glassforming
liquid in curved geometry allows a direct check of the fundamentals of
the frustration-based theoretical scenario.
[1] G. Tarjus, S.A. Kivelson, Z. Nussinov, and P. Viot, J. Phys.: Condens. Matter
17, R1143 (2005).
[2] F.Sausset, G.Tarjus, and P.Viot., Phys. Rev. Lett., 101, 155701 (2008).

Dynamics of low molecular weight glass formers in soft confinement
E. Gouirand (1), T. Blochowicz (1), B. Stühn (1) and B. Frick (2)
(1) Institut für Festkörperphysik, TU Darmstadt, Hochschulstr. 6, 64289 Darmstadt,
Germany
(2) Institut Laue-Langevin, 38042 Grenoble Cedex, France
Correspondence author: emmanuel.gouirand@physik.tu-darmstadt.de
In search of a characteristic length scale associated with cooperative dynamics
at the glass transition, intensive effort has been devoted to investigating the
effect of confinement on the dynamics of glass forming liquids. Nevertheless,
so far no generally accepted picture exists because of the complex interplay of
surface, pressure and finite size effects affecting the dynamics.
It is the aim of the present contribution to investigate the dynamics in confinements
of different nature in order to be able to disentangle these various effects.
We investigate glass formers confined within microemulsion droplets by means
of photon correlation spectroscopy and quasi elastic neutron scattering. In these
systems a hydrophobic substance forms a droplet phase in a hydrophilic environment
(or vice versa) which is stabilized by a surfactant and remains stable
over the whole temperature range. By carefully choosing the components in
these ternary systems it is possible to change the interfacial conditions: first,
we report on the dynamics of glycerol confined in AOT micelles where the Tg
contrast is chosen such that Tg of the matrix (toluene/xylene) is smaller than
Tg of the core. We find glycerol to relax faster than in bulk with an Arrhenius
temperature dependence. This is compared to the dynamics of toluene in
Cremophor micelles where contrary to the former situation the matrix relaxes
slower than the core and slows down the latter due to interfacial effects. Finally,
below Tg of the matrix actual hard confinement of toluene within the droplets
is realized.

Vibrational and mechanical properties of Lennard-Jones and Silica
glasses
F. Leonforte (1), A. Tanguy (2), J.P. Wittmer (3), J.-L. Barrat (2)
(Presenting author underlined)
(1) Institut für Theoretische Physik, Georg-August Universität, 37077 Göttingen,
Germany
(2) Laboratory of Condensed Matter Physics and Nanostructure, University
Lyon I, CNRS UMR 5586, 69622 Villeurbanne, France
(3) CNRS Institut Charles Sadron, 23 Rue du Loess, 67034 Strasbourg Cedex
2, France
Correspondence author: leonforte@theorie.physik.uni-goettingen.de
Amorphous solids present peculiar mechanical and vibrational properties. Although
not having any long range order, they show an higher plastic threshold
and weaker shear modulus than corresponding crystals. Contrary to the response
in terms of dislocations of crystals, the irreversible response of sheared
amorphous solids is strongly localised (shear bands).
We present recent numerical results using Molecular Dynamics simulations on
simple model amorphous solids, a 2D and 3D Lennard-Jones glass [1,2,3] and a
silica glass [4], and demonstrate that the observed excess of vibrational modes
in the Terahertz region, the so-called ”Boson Peak”, is related to the non-affine
response of amorphous solids under external load, i.e. to the breakdown of classical
elasticity continuum theory at small wavelengths.
The non-affine displacement field is then interpreted as the existence of elastic
heterogeneities in such glasses, from which it’s possible to extract a characteristic
length. Below such a length, the disorder becomes pertinent, and affects
either the mechanical and vibrational properties of these solids. Global mechanical
predictions using classical elasticity continuum theory are then recovered
over lengthscales larger than this characteristic length, as soon as elastic modulus
are numerically computed over regions of size also larger than this length.
The effect of pressure on vibrational properties of both Lennard-Jones and silica
glasses is then evaluated in the same framework.
Finally, a detailed study on vibrational eigenvectors is then presented, in the
simplified case of a 2D Lennard-Jones glass, and in order to investigate the effect
of elastic heterogeneities on elastic plane waves. A route to the ”Boson Peak”
anomaly then emerges, and an extension to the silica glass case is also discussed.
[1] ”Continuum limit of amorphous elastic bodies: a finite size study of low
frequency harmonic vibrations”, Phys. Rev. B 66, 174205 (2002)
[2] ”Continuum limit of amorphous elastic bodies (II): linear response to a point
source force” , Phys. Rev. B 70, 014203 (2004)
[3] ”Continuum limit of amorphous elastic bodies (III): three dimensional systems”,
Phys. Rev. B 72, 224206 (2005)
[4] ”Inhomogeneous elastic response of silica glass”, Phys. Rev. Lett. 97,
055501 (2006)

SINGLE-PARTICLE AND COLLECTIVE SLOW DYNAMICS OF
COLLOIDS IN POROUS CONFINEMENT
J. Kurzidim (1), D. Coslovich (1), G. Kahl (1)
(1) Institute for Theoretical Physics and Center for Computational Materials
Science, Vienna University of Technology, Vienna, Austria
Correspondence author: kurzidim@cmt.tuwien.ac.at
Using event-driven molecular dynamics simulations we study the slow dynamics
of a hard-sphere fluid confined in a matrix frozen from an equilibrated hardsphere
fluid [1]. The presence of both discontinuous and continuous glass transitions
as well as the complex interplay between single-particle and collective
dynamics are well captured by a recent extension of mode-coupling theory for
fluids in porous media [2,3]. In order to illustrate the dynamic features of the
system we present the kinetic diagram spanned by the fluid and matrix packing
fractions, as well as the single-particle and collective intermediate scattering
function and the mean-square displacement for selected state points. The degree
of universality of the mode-coupling theory predictions is assessed by numerically
solving the mode-coupling equations upon introducing either size-disparity
between fluid and matrix particles, or softness of the interactions.
[1] J. Kurzidim, D. Coslovich, and G. Kahl, arXiv:0906.0929v1 (2009)
[2] V. Krakoviack, arXiv:0901.3649v2 (2009)
[3] V. Krakoviack, Phys. Rev. E 75 (2007) 031503

The entropy of the Lattice-Hard-Core Model
A. Winkler, O. Rubner, A. Heuer
Institute of Physical Chemistry, University of Münster, Corrensstr. 30, D-48149
Münster, Germany.
Correspondence author: andheuer@uni-muenster.de
A very simple model for disordered systems is the Lattice-Hard-Core Model
in 2 dimensions. Here one considers m particles on a two-dimensional square-cell
lattice with N sites subject to the condition that the particles cannot occupy
neighbouring sites. Though many aspects of this model are well known, the
total number of states for a given N and density ρ = m
N cannot be computed
directly. In this work, firstly, we calculate the entropy S of this model with a
combinatorial method according to [1] and compare the results to those of a
modified Widom’s particle insertion method for small particle numbers. From
ln c(ρ)N
that we can deduce a scaling relation S(ρ) = a(ρ) + b(ρ) N for large N.
Secondly, a method is discussed which uses the idea of path coupling of
Markov chains for the evalutation of the mixing time which determines the time
the system needs to reach equilibrium.
[1] R.B.McQuistan, J.L.Hock, J.Math.Phys 33, August 1992

Dynamic Crossovers and Quantum Effects in Protein Hydration Water
F. Bruni (1), S. E. Pagnotta (2), (Presenting author underlined)
(1) Dipartimento di Fisica, Università degli Studi di Roma Tre, Rome, Italy
(2) Centro de Fisica de Materiales (CSIC-UPV/EHU) - Materials Physics Center
MPC, Donostia-San Sebastian, Spain
Correspondence author: bruni@fis.uniroma3.it
Recent work has focused on dielectric relaxation experiments on hydrated proteins,
aimed at the study of water and protein dynamics [1- 4]. At variance
with these experiments, we will report on the dielectric relaxation of water protons.
In particular, we discuss the temperature dependence of proton dynamics
along chains of hydrogen bonded water molecules at the interface with a globular
protein. The rationale behind this approach is that measurements of the
proton mobility are closely linked to the dynamics and connectivity of the water
molecules in the protein hydration shell.
Quantum effects on the water proton dynamics over the surface of a hydrated
protein are measured by means of broadband dielectric spectroscopy and deep
inelastic neutron scattering [5]
[1] S. Pawlus, S. Khodadadi, and A. P. Sokolov, Phys. Rev. Lett. 100, 108103
(2008).
[2] S. Khodadadi, S. Pawlus, J. H. Roh, V. Garcia-Sakai, E. Mamontov, and A.
P. Sokolov, J. Chem. Phys. 128, 195106 (2008).
[3] S. Khodadadi, S. Pawlus, and A. P. Sokolov, J. Phys. Chem. B. 112, 14273
(2008).
[4] H. Frauenfelder, G. Chen, J. Berendzen, P. W. Fenimore, H. Janssonb, B.
H. McMahon, I. R. Stroe, J. Swenson and Robert D. Young, Proc. Nat. Acad.
Sci. 106, 5129 (2009).
[5] S. E. Pagnotta, F. Bruni. R. Senesi, and A. Pietropaolo, Biophys. J. 96,
1939 (2009)

LINKING STRUCTURE TO DYNAMICS IN SUPERCOOLED WA-
TER
Malaspina D C (1), Rodriguez Fris J A (1), Appignanesi G A (1) and Sciortino
F (2)
(1) Área de Fisicoquímica, Departamento de Química and INQUISUR, Universidad
Nacional del Sur, Avenida Alem 1253, 8000-Bahía Blanca, Argentina
(2) Dipartimento di Fisica and INFM-CNR-SOFT, Università di Roma La
Sapienza, Piazzale A. Moro 2, 00185 Roma, Italy
Correspondence author: rodriguezfris@plapiqui.edu.ar
Finding a causal link between structure and dynamics represents a long standing
issue within the realm of supercooled liquids and glasses, since this task
has proven elusive despite considerable efforts. The introduction by Harowell’s
group of the dynamic propensity concept [1] (the tendency of the molecules
to move in the given configuration) showed that such a correlation should indeed
exist. However, even when dynamic propensity correlated with certain
(dynamically originated) quantities like the Debye-Waller factors (as estimated
from short-time particle motions) and with the soft modes of the system, such
a correlation could not be found for inherently structural parameters (like free
volume or potential energy, for example). In this work, however, we show that
structural indexes (like the Shiratani-Sasai LSI index [2] and tetrahedrality indexes)
clearly correlate with propensity in supercooled water. Moreover, we
show that both the highly structured and the highly unstructured molecules
tend to cluster in space and to be spatially correlated with the low and high
propensity clusters, respectively.
[1] Widmer-Cooper A, Harrowell P and Fynewever H, Phys. Rev. Lett. 93,
135701 (2004).
[2] Shiratani E and Sasai M, J. Chem. Phys. 104, 7671 (1996).

LOCAL STRUCTURAL INDEXES IN WATER: A MEASURE OF
RELEVANCE IN HYDRATION AND BIOLOGICAL WATER
Frechero M A, Alarcón L M, Schulz E P, Malaspina D C and Appignanesi G A
Área de Fisicoquímica, Departamento de Química and INQUISUR, Universidad
Nacional del Sur, Avenida Alem 1253, 8000-Bahía Blanca, Argentina
Correspondence author: appignan@criba.edu.ar
The fact that liquid water represents a mixture of two “species” (low density,
structured molecules and high density unstructured ones, with the fraction of
structured molecules increasing as temperature is decreased within the liquid
and continuing in the supercooled regime) represents a notion with far-reaching
consequences. A very interesting application of local structural indexes can be
performed for the study of water at interfaces and biological hydration water.
Here we show that the first water layers (for example, the surfaces of water
clusters, water in contact with a graphite layer and the hydration shells of
proteins) are more structured than subsequent layers and significantly more
structured than the bulk (as determined by the distribution of the structural
indexes of the corresponding molecules). Also, these water molecules exhibit a
dynamics that is considerably slower. This information could be of essence in
biology, since it is expected that the structure and the dynamical behavior of
the surface water layers around proteins also combined with the (de)-hydrating
propensities of certain particular protein local structural motifs are related to
aspects like protein binding and protein reactivity, and could help in areas like
drug design.

CONFINEMENT OF ELECTROLYTE SOLUTIONS IN NANOPORES
P. -A. Cazade (1), J. Dweik (2), B. Coasne (1), F. Henn (1), J. Palmeri (3)
(1) Institut Charles Gerhardt Montpellier, CNRS UMR 5253, Université Montpellier II, ENSCM, Montpellier,
France
(2) Institut Européen des Membranes, CNRS UMR5635, Université Montpellier II, ENSCM, Montpellier,
France
(3) Laboratoire de Physique Théorique, Université Paul Sabatier, Toulouse, France
pacazade@lpmc.univ-montp2.fr
Organic and inorganic nanoporous membranes, which are known to enhance the diffusion of certain
species and to have a strong selectivity, are very attractive for nanofiltration. Nevertheless, despite an
increasing number of fundamental studies [1, 2, 3, 4, 5], the physical mechanisms responsible for these
properties remain to be clarified.
In this work, we report on a molecular simulation study of electrolytes confined in an inorganic membrane:
sodium halides in water (electrolytes) in a carbon nanotube. Two diameters (1 and 3 nm) are considered
for the carbon nanotube in order to address the effect of confinement. We also address the effect of
the size of the ions by considering the series of the sodium halides: NaX with X = F, Cl, Br, and
I, at about 1.85 M. Special attention will be paid to the effect of polarizability as recent works have
shown the crucial role played by this parameter [2, 3]. Finally, we will also consider the effect of the
surface charge of the nanotube by considering host materials that are either neutral or charged. Grand
Canonical Monte Carlo simulations (GCMC) are first employed to investigate the thermodynamical and
structural properties of the confined electrolytes. Then, Molecular Dynamics simulations are used to
determine the dynamical properties of the confined system such as the self-diffusivity. We also discuss
the transport properties of the confined system, which is crucial for most of the practical applications
involving nanoporous membranes.
[1] G. Hummer, J. Rasaiah and J. Noworyta, Nature, 414, 188-190, 2001.
[2] L. Dang, J. Phys. Chem. B, 106, 10388-10394, 2002.
[3] T. Chang and L. Dang, Chem. Rev., 106, 1305-1322, 2006.
[4] A. Alexiadis and S. Kassinos, Chem. Rev., 108, 5014-5034, 2008.
[5] B. Corry, J. Phys. Chem. B, 112, 1427-1434, 2008.

FRAGILITY AND COLD CRYSTALLIZATION IN POLYMERS
Alejandro Sanz, Aurora Nogales and Tiberio A. Ezquerra
Instituto de Estructura de la Materia (CSIC), Serrano 121, Madrid 28006. Spain
Correspondence author: asanz@iem.cfmac.csic.es
In general, upon cooling liquids either crystallize or vitrify. Below the equilibrium
melting temperature, Tm, but above the glass transition temperature,
Tg , a liquid is in a supercooled state. When dealing with crystallizable materials,
the supercooled liquid becomes unstable under these conditions due its
higher free energy as compared with that of the crystal. Consequently, there
exists a probability that the supercooled liquid tends to reduce its free energy
undergoing a first order phase transition by which molecules self-assemble forming
crystals. Supercooled crystallizable polymers can develop a characteristic
folded chain crystalline lamellar morphology at the nanometer level by thermal
treatment within the temperature range defined between Tg and Tm.
According to the thermodynamics, crystallization would be possible as soon
as the energy difference, ∆Gbulk, between the free energy of the crystal, Gcryst,
and that of the melt, Gmelt , is negative. This process should start as soon as
the system is below Tm. Supercooling arises due to the fact that any crystal
must start by a much smaller crystal with a certain specific surface area. In this
case, the free enthalpy of crystallization ∆G (Gibbs free energy) becomes: ∆G
= ∆Gbulk + Gs, where Gs is the surface energy. The surface term is in general
always positive leading to a free enthalpy barrier to crystallization. Therefore
for temperatures below Tm, where ∆Gbulk is negative, ∆G exhibits a maximum
which corresponds to the critical size nucleus. In classical nucleation, ∆G corresponds
to the difference between a crystal and a quiescent melt. Experiments
and theory in some polymer melts indicate that a coupling between density and
chain conformation may induce the appearance of a spinodal texture previous to
the nucleation step. In this case ∆G would correspond to the difference between
a crystal and a pre-ordered melt and one speaks about spinodal-assisted nucleation
[1]. In both cases, the free enthalpy barrier to crystallization is overcome
by thermal random local fluctuations of order in the melt.
Considering that cold crystallization phenomena in polymers are essentially
governed by short distance diffusion, then one may expect fragility to play an
important role. As far as mass transport is concerned, fragility is manifested by
different levels of departure from Arrhenius kinetics.
Based on the analysis of our own results and on literature data we suggest
a relation between fragility [2] and kinetics of cold crystallization in polymers.
In summary, we find that the rate of nucleation increases with fragility.
[1] P.D. Olmsted, W.C. K. Poon, T.C.B. McLeish, N.J. Terrill and A.J. Ryan,
Phys. Rev. Letters, 81, 373, 1998
[2] C.A. Angell, J. Phys. Chem B,103, 3991, 1999

THE ORIGINS OF THE POWER-LAW DIELECTRIC RESPONSE
OF COMPLEX MATERIALS
N. J. McCullen (1), C. J. Budd (1), D. P. Almond (2)
(Presenting author underlined)
(1) Bath Institute for Complex Systems, Dept. Math. Sci., University of Bath,
Bath, UK
(2) Materials Research Centre, Dept. Mech. Eng., University of Bath, Bath,
UK
Correspondence author: n.mccullen@bath.ac.uk
The electrical response characteristics of large networks of randomly positioned
resistors and capacitors are found [1] to closely resemble the well known anomalous
power-law frequency dependencies of permittivity or AC conductivity (the
so called ”Universal Dielectric Response”). It has been suggested [2] that real
materials contain complex microstructural networks of conducting and insulating
material that may be modelled by the large random R-C networks. Furthermore,
the power-law frequency dependencies have been shown [3] to be emergent
properties of these networks.
The bulk response of these resistor-capacitor networks to varying the AC driving
frequency (effecting the conductivity contrast ratio of the two materials)
is found to be dependent not only on the proportion of the two components
but also on the size of the network. This is particularly the case when close
to 50% capacitors, which is the critical value for a 2D square lattice to have a
finite chance of a percolating path of either component from one terminal of the
network to the other. However, in the emergent power-law region the response
is found to be robust to the precise details of the microstructural disorder [4].
This presentation will focus on an approach to describing the bulk response of
complex systems using ideas from linear circuit theory and results derived from
random matrices. Looking at the statistics of the generalised eigenvalues of the
Kirchhoff matrix of random R-C networks, which are closely related to the poles
and zeroes in their transfer function, we show that it is possible to derive asymptotic
formulae describing the expected value for the response characteristics of
such networks. These formulae are found to agree remarkably well to numerical
simulations of these electrical networks, which in turn match the results from
physical experiments.
[1] D.P. Almond and B Vainas, J Phys. C.M. 11 (1999) 9081
[2] D.P. Almond and C.R. Bowen, Phys. Rev. Lett. 92 (2004) 157601
[3] R. Bouamrane and D.P. Almond, J. Phys. C.M. (2003) 4089
[4] N. J. McCullen, D. P. Almond, C. J. Budd and G. W. Hunt, J. Phys. D:
Appl. Phys. 42 (2008) 064001

Numerical Methods of Quantifying Mixing in Polymer Processing
Yasuya Nakayama (1), Toshihisa Kajiwara (1)
(1) Department of Chemical Engineering, Kyushu University, Fukuoka, Japan
Correspondence author: nakayama@chem-eng.kyushu-u.ac.jp
Mixing a polymer matrix with other polymers or low-molecular weight additives
is a key technology in polymer industries. Quantifying the mixing process in a
certain device is a necessary step to design and optimize the process.@ From a
physical point of view, since polymeric liquids are highly viscous non-Newtonian
fluids, the melt mixing is conducted under laminar flow. Therefore, mixing
kinetics should basically be discussed via dynamical system theory. From a
practical point of view, since channels in which polymer melt mixed have rather
narrow and complex structure with moving parts, it makes numerical tasks difficult
to track each trajectory and simultaneously the time development of mixing
state in whole space. We discuss a theoretical framework of characterizing polymer
melt mixing and develop a numerical method to trace and characterize
dynamical evolution of mixing state in a give numerical resolution.

Ionic liquids for electrochemical applications: LiTFSI doping and interactions
in a neutralized Nafion membrane
A. Martinelli (1), Jagath Pitawala (2), Y. Getman (1), N. Sergent (1), Christina
Iojoiu (1), P. Johansson (2), A. Matic (2), P. Jacobsson (2), J.-Y. Sanchez (1)
(1) LEPMI, GIT-CNRS-UJF, 1130 rue de la piscine, BP75, F-38402 Saint Martin
d’Hères, France
(2) Department of Applied Physics, Chalmers University of Technology, S-41296
Göteborg, Sweden
Correspondence to: annamart@chalmers.se
Ionic Liquids (ILs) are materials of huge interest for use in electrochemical
devices such as Li-ion batteries and fuel cells.
In this contribution we present results on the characterization of aprotic ILs
upon addition of the salt LiTFSI. We find that the doping affects both the
phase behavior and the ionic conductivity in the LiTFSI/IL mixtures. Plastic
crystal phases are found with ionic conductivities that increase with the Li +
content, whereas the opposite trend is observed in the liquid phase. Here,
conductivity is mainly governed by viscosity as proved by a Tg-scaled Arrhenius
plot [1]. With Raman spectroscopy we have investigated the nature of the Liion
coordination in ILs, finding that the coordination number in Li + :(TFSI − )n
drastically increases at low LiTFSI concentrations.
To further understand the functionality of ILs we have investigated, by Raman
spectroscopy, the ionic interactions within a Nafion membrane neutralized
with triethylamine (TEA) and swelled with the protic IL TEATF [2-4]. This
polymer electrolyte shows promising conductivities (>10 −3 Scm −1 ) even at low
IL contents (30%) and has been considered for an in-situ confocal Raman experiment.
We aim to probe the electrochemical reactions at the electrode/electrolyte
interface of a working fuel cell and to investigate the concentration profile of
molecular species along an anode-to-cathode line.
[1] A. Martinelli, et al. submitted to the Journal of Phys. Chem. B
[2] C. Iojoiu, M. Martinez, M. Hanna, Y. Molmeret, L. Cointeaux, J.-C. Lepretre,
N. El-Kissi, J. Guinet, P. Judeinstein, J.-Y. Sanchez, Polymers for advanced
Technologies (2008), 19 (10), 1406-1414
[3] C. Iojoiu, P. Judeinstein, J.-Y. Sanchez, Electrochimica Acta (2007), 53 (4),
1395-1403
[4] P. Judeinstein, C. Iojoiu, J.-Y. Sanchez, B. Ancian, Journal of Phys. Chem.
B (2008), 112 (12), 3680-3683

Soft Modes in Glasses: Tunneling, Vibrations and Diffusion
H. R. Schober
(Presenting author underlined)
Institut für Festkörperforschung, Forschungszentrum Jülich, D-52425 Jülich,
Germany
Correspondence author: h.schober@fz-juelich.de
Two low energy features distinguish glasses from typical crystalline matter: the
two level systems (TLS) observed in the Kelvin range and the excess in the low
energy inelastic scattering amplitude, the boson peak (BP), seen at all temperatures
up to the melting. The TLS’s have been explained by tunneling of local
entities whereas the BP is due to vibrational excitations. Assuming a common
origin for both and postulating that both effects are caused by a common distribution
of soft modes which exist in addition to the sound waves the description
in terms of the “soft potential model” (SPM) provides a number of “universal”
relations, e.g. the ω 4 -dependence of the excess spectrum for ω → 0, provided
the underlying distributions are regular.
The additional originally soft vibrations hybridize with the sound waves, leading
to quasi-localized vibrations, also known as resonant vibrations. This means
they are practically not observable in the exact harmonic eigenvectors but only
in additive quantities such as local spectra, i.e. the vibrational spectra of single
atoms or molecules. In the soft potential model the description of the vibrations
by exact, necessarily extended, eigenmodes is replaced by a description in
terms of extended sound waves and “local” modes with a bilinear interaction.
This bilinear interaction between sound waves and local modes in turn leads to
an interaction between the “local” modes. Taking this into account a general
shape of the BP and the experimentally observed density of TLS is derived [1].
The original sound waves are resonantly scattered by the soft modes. We will
discuss the effect on the observed phonon intensities.
In computer simulations it was found that the local modes of the SPM extent
over ten or more atoms. In simple, metallic, glasses they are formed by chains
of atoms. These chains are not only observed in vibration but jumps of them
are also the elementary process in diffusion which thus different to the crystal
is a collective process. This collectivity explains anomalies of glassy diffusion:
vanishing isotope effect, small activation volume and heterogeneity.
[1] D.A. Parshin, H.R. Schober, V.L. Gurevich, Phys. Rev. B 76 (2007) 064206.

HIDDEN SCALE INVARIANCE IN STRONGLY CORRELATING
LIQUIDS
T. B. Schrøder (1), N. Gnan (1), U. R. Pedersen (1), N. Bailey (1), S. Toxværd
(1), and J. C. Dyre (1)
(1) DNRF Centre “Glass and Time,” IMFUFA, Department of Sciences, Roskilde
University, Postbox 260, DK-4000 Roskilde, Denmark
Correspondence author: tbs@ruc.dk
A liquid is termed strongly correlating if its virial and potential energy thermal
equilibrium fluctuations in the NVT ensemble are more than 90% correlated
[1-4]. Results from computer simulations indicate that this class of liquids includes
van der Waals liquids, but not hydrogen bonded liquids or ionic liquids.
We demonstrate that the strong correlation reflects an underlying ”hidden“ approximate
scale invariance of the potential energy surface - this holds even for
molecular liquids [5]. As a consequence, strongly correlating liquids ”inherit“ a
number of scaling properties from inverse power low (IPL) systems, including:
i) In scaled units the structure is a function of ρ γ /T only, where ρ is the density
and the scaling exponent γ is predicted by the equilibrium fluctuations. ii)
Relaxation time and diffusion coefficient are functions of ρ γ /T only. iii) State
points with the same ρ γ /T have the same relaxation spectra. iv) virial and
potential energy are strongly correlated even under non-equilibrium conditions,
provided volume is kept fixed. This includes glasses and inherent structures.
Not all IPL scaling properties are obeyed by strongly correlating liquids. In
particular, the equation of state is predicted not to obey IPL scaling. Finally,
we introduce the theoretical concept ”isomorphs“ [6], which from a single assumption
predicts all the properties found for strongly correlating liquids.
[1] U. R. Pedersen et al., Phys. Rev. Lett. 100 (2008) 015701.
[2] U. R. Pedersen et al., Phys. Rev. E 77 (2008) 011201.
[3] N. P. Bailey et al., J. Chem. Phys. 129 (2008) 184507; 129 (2008) 184508.
[4] N. P. Bailey et al., J. Phys.: Condens. Matter 20 (2008) 244113.
[5] T. B. Schrøder et al., arXiv:0812.4960 (2008); arXiv:0906.0025 (2009).
[6] N. Gnan et al., arXiv:0905.3497 (2009).

Simple atomistic models for glassforming ion conductors: Computer
simulations of binary soft-sphere systems
J. Horbach, Th. Voigtmann
Institute of Materials Physics in Space, German Aerospace Center (DLR), Köln,
Germany
Correspondence author: juergen.horbach@dlr.de
In glassforming alkali silicates, there is a decoupling between the fast self-motion
of the alkali ions and the collective dynamics, the latter reflecting the slow relaxation
of the Si-O network [1,2]. Using molecular dynamics (MD) computer
simulation we show that a similar relaxation behavior as in silicate melts is
found in binary soft-sphere mixtures of small and big particles [3]. Here, the
dynamics can be understood in terms of a double-transition scenario. While
the big particles undergo an “ordinary” glass transition, the self-dynamics of
the small particles exhibits a localization transition. By approaching the latter
transition, anomalous diffusion of the small particles is seen, characterized by a
sublinear increase of the small particle’s mean-squared displacement. Surprisingly,
when the interactions between the small particles are switched off, their
mobility is reduced rather than enhanced. All these findings are related to the
relaxation patterns seen in MD simulations of sodium silicates and discussed in
the framework of mode coupling theory.
[1] J. Horbach, W. Kob, and K. Binder, Phys. Rev. Lett. 88 (2002) 125502
[2] A. Meyer, J. Horbach, W. Kob, F. Kargl, and H. Schober, Phys. Rev. Lett.
93 (2004) 027801
[3] Th. Voigtmann and J. Horbach, preprint arXiv:0812.3599

Nonadditive hard spheres mixtures in random pores: demixing transition
and critical bahaviour
P.G. De Sanctis Lucentini (1,2)
(1) Dipartimento di Fisica, Università degli studi di Roma ’La Sapienza’, Piazzale
A. Moro 5, I-00185, Rome, Italy
(2) INFM-CNR Center for Statistical Mechanics and Complexity, Dipartimento
di Fisica, Università di Roma ’La Sapienza’, Piazzale A. Moro 5, I-00185, Rome,
Italy
Correspondence author: pier.giorgio.desanctislucentini@roma1.infn.it
We investigate the influence of quenched disorder (matrix) on the critical behaviour
of a non-additive hard spheres symmetrical mixture.
Finite size scaling analysis leads to the determination of the critical density for
the system. We detect a behaviour that differs respect to the pure Ising one.
Neither hyperscaling violation nor significant deviations of critical parameters
emerge to support the belonging of the system to the Random Field Ising Model
universality class. The present work results refine the evidences reported in
[Phys. Rev. Lett. 101, 246101 (2008)]. The outcomes relative to an higher
matrix density confirm the above evidences and exclude the hypothesis of being
in a crossover region between Ising Model and Random Field Ising Model. The
scaling plots of the susceptibility and the related determination of the critical
amplitudes ratio, Γ± , suggest that the critical behaviour of our model is compatible
with the Quenched Diluted Ising Model universality class.

Ready to measure relaxation:
New neutron spectrometers at Garching and Oak Ridge
N. Ahrend (1), O. Holderer (2), E. Mamontov (3), M. Ohl (1), G. J. Schneider
(2), G. G. Simeoni (4), N. de Souza (2), T. Unruh (4), J. Wuttke (2), M. Zamponi
(1)
(1) Forschungszentrum Jülich, JCNS at SNS, Oak Ridge, TN, U.S.A.
(2) Forschungszentrum Jülich, JCNS at FRM II, Garching, Germany
(3) Oak Ridge National Laboratory, Oak Ridge, TN, U.S.A.
(4) Technische Universität München, FRM II, Garching, Germany
Correspondence author: j.wuttke@fz-juelich.de
In the past few years, a new generation of high-flux, high-resolution spectrometers
have been put into service at two powerful neutron sources, the reactor
FRM II in Germany, and the Spallation Neutron Source (SNS) in the U.S.A.
Several of these instruments are built and operated by the newly founded Jülich
Centre for Neutron Science (JCNS), carrying on a strong research tradition after
the shut down of Jülich’s own reactor in 2006.
In this poster, we present the instrumental capabilities, the access modes,
and first scientific highlights for the following instruments:
TOFTOF at FRM II, a pure time-of-flight spectrometer, very versatile with
resolution between 5 µeV and 5 meV; especially suited for measurements of
phonon densities of states and fast relaxation.
J-NSE of JCNS at FRM II, a spin-echo spectrometer, relocated from the old
Jülich reactor and refurbished, to measure the intermediate scattering function
S(Q, t) for t between 2 ps and 350 ns, mostly used for studying polymer and
protein dynamics.
SPHERES of JCNS at FRM II, a pure backscattering spectrometer, with a
resolution of 0.65 µeV and a dynamic range of ±31 µeV, for the measurement
of rotational tunneling, diffusion, and slow relaxation.
BASIS at SNS, with JCNS participation, hybrid spectrometer with nearbackscattering
analyzers, resolution of 2.2. . . 2.6 µeV, combined with the wide
dynamic range of a time-of-flight instrument.
NSE of JCNS at SNS, in commissioning, with innovative technology, expected
to become the world-leading spin-echo spectrometer with Fourier times
reaching 1 µs.

RELAXATION MAP ANALYSIS STUDIES OF THE GLASS TRAN-
SITION IN HIGHLY CRYSTALLIZED PET BY TSDC.
J. Sellarès, J.A. Diego, J. Belana
(Presenting author underlined)
Dpt. de Física i E.N. UPC, ETSEIAT, C/ Colon 11, 08228 Terrassa, Spain
Correspondence author: jose.antonio.diego@upc.edu
It is commonly accepted that the glass transition in polymers is a distributed
process. In such processes, a distribution of relaxation times is necessary to adequately
describe its behavior. Calorimetric and dilatometric techniques have
been widely employed to study the glass transition, although interpretation of
the results is complex because of the distributed nature of the relaxation. Thermally
Stimulated Depolarization Currents (TSDC) have shown greater sensitivity
in studying the glass transition and the ability to resolve a complex relaxation
into its elementary components [1]. In this work we perform a relaxation map
analysis (RMA) of the glass transition in PET, fitting calculated depolarization
currents to experimental TSDC spectra.
For amorphous PET, the Tool–Narayanaswami–Moynihan model was used to fit
the TSDC spectra. The most important contributions to the relaxation comes
from modes with non–linearity (x) around 0.7. Activation energies yield by this
model are located around 1 eV for polarization temperature (Tp) below 50 ◦ C
and they raise up to values higher than 8 eV as Tp increases (up to 80 ◦ C).
Highly crystalline PET samples were prepared annealing the material between
140 ◦ C anb 180 ◦ C. The Arrhenius model has been used in this case to fit the
TSDC spectra, as much less cooperative relaxation result. The evolution of the
modes on crystallization reveals that large scale movements of the main chain
are progressively replaced by more localized ones with higher frequency. As a
consequence, the glass transition temperature of the amorphous interlamellar
phase tends to lower values for higher annealing temperatures. An acceptable
correlation is obtained with DSC data.
[1] J. A. Diego, J. Sellarès, A. Aragoneses, M. Mudarra, J. C. Cañadas and J.
Belana, J. Phys. D: Appl. Phys., 40, 1138, 2007

Dynamics of Supercooled Water: Effects of Pressure (BOLD, LEFT)
Giancarlo Franzese
(Presenting author underlined)
(1) Universitat de Barcelona, Barcelona, Spain
Correspondence author: gfranzese@ub.edu
Recent experiments on supercooled water show a complex dynamics whose temperature
dependence and nature are under debate. Here we discuss this dynamics
in terms of the Hydrogen bonds relaxations. In particular, we analyze the
pressure effects in a model that we study by simulations and theoretical calculations,
finding new exciting results at low temperature that compare well with
new experiments.

FREQUENCY DEPENDENT BULK MODULUS OF A NUMBER
OF MOLECULAR LIQUIDS MEASURED USING THE PIEZO-
ELECTRIC BULK MODULUS GAUGE
D. Gundermann (1), T. Hecksher (1), K. Niss (1), T. Christensen (1)
(1) DNRF Center “Glass and Time”, Roskilde, Denmark
Correspondence author: ditteg@ruc.dk
We present data on the frequency dependent bulk modulus for a number of
molecular liquids at frequencies from 100 mHz to 10 kHz. The data are obtained
using the piezoelectric bulk modulus gauge method developed in our laboratory
[1], which utilizes the coupling between the capacitance of a spherical piezoceramic
shell and the stiffness of a contained liquid. The data are characterized
with respect to loss peak frequencies, shape and temperature dependence and
an extended Maxwell model expression is fitted to the data. Furthermore, the
data are analyzed for TTS and secondary processes, and the high frequency
decay of the loss is characterized following the procedure of [2] checking the
suggested correlation between approximate high frequency exponent -1/2 and
degree of TTS. The results are compared to previously published [3] data on
shear modulus for the same liquids obtained in our laboratory. The relation
between bulk and shear modulus has been shown to be of importance when
the frequency dependent specific heat in the highly viscous regime is found via
effusivity measurements. Under these circumstances it was shown that the ordinary
heat diffusion equation fails due to the presence of nonisotropic mechanical
stresses caused by thermal expansion [4].
[1] T. Christensen, N. B. Olsen, Phys. Rev. B 49 (1994) 15396
[2] A. I. Nielsen, T. Christensen, B. Jakobsen, K. Niss, N. B. Olsen, R. Richert,
J. C. Dyre, J. Chem. Phys. 130 (2009) 154508
[3] C. Maggi, B. Jakobsen, T. Christensen, N. B. Olsen, J. Dyre, J. Phys. Chem.
B 112 (2008) 16320
[4] T. Christensen, N. B. Olsen, J. C. Dyre, Phys. Rev. E 75 (2007) 041502

Divergent four-point dynamic density correlation function of a glassy
suspension
G. Szamel (1), E. Flenner (1)
(1) Department of Chemistry, Colorado State University, Fort Collins, CO
80523, USA
Correspondence author: szamel@lamar.colostate.edu
We use a diagrammatic formulation of the dynamics of interacting Brownian
particles [1] to study a four-point dynamic density correlation function of a
glassy colloidal suspension. We re-sum a class of diagrams which separate into
two disconnected components upon cutting a single propagator. The resulting
formula for the four-point correlation function can be expressed in terms of
three-point functions closely related to the three-point susceptibility introduced
by Biroli et al. [2] and the standard two-point correlation function. We numerically
evaluate the four-point function and the associated dynamic correlation
length. Both the amplitude of the four-point function and the correlation length
diverge at the mode-coupling transition.
[1] G. Szamel, J. Chem. Phys. 127, 084515 (2007).
[2] G. Biroli et al., Phys. Rev. Lett. 97, 195701 (2006).

Network-forming and close-packed glasses: Two distinct universality
classes?
D. Coslovich (1), G. Pastore (2,3)
(1) Institut für Theoretische Physik, Technische Universität Wien, Austria
(2) Dipartimento di Fisica Teorica, Università di Trieste, Italy
(3) CNR-INFM Democritos National Simulation Centre, Trieste, Italy
Correspondence author: pastore@ts.infn.it
We report Molecular Dynamics simulations for a new model of tetrahedral network
glass-former, based on short-range, spherical potentials [1]. Despite the
simplicity of the forcefield employed, our model reproduces some essential physical
properties of silica, an archetypal network-forming material. We study in
particular the slow dynamics of the system, including dynamic heterogeneities
and local rearrangements, and perform a direct comparison with models of closepacked,
fragile glass-formers [2]. The outcome of this comparison is rationalized
in terms of the properties of the Potential Energy Surface, focusing on the unstable
modes of the stationary points. Our results indicate that the weak degree
of dynamic heterogeneity observed in network glass-formers may be attributed
to an excess of localized unstable modes, associated to elementary dynamical
events such as bond breaking and reformation. On the contrary, the more fragile
Lennard-Jones mixtures are characterized by a larger fraction of extended
unstable modes, which make the dynamics inherently more cooperative and
heterogeneous.
[1] D. Coslovich and G. Pastore, submitted to J. Phys.: Condens. Matter (2009)
[2] D. Coslovich and G. Pastore, J. Chem. Phys. 127 (2007) 124504

Brownian dynamics simulation of extensional shear flow in dense colloidal
hard-sphere systems
O. Herbst (1), Th. Voigtmann (1,2)
(Presenting author underlined)
(1) Institute of Material Physics in Space, DLR Köln-Porz, Linder Höhe, 51147
Köln, Germany
(2) Fachbereich Physik, Universität Konstanz, 78457 Konstanz, Germany
Correspondence author: olaf.herbst@dlr.de
We describe a novel algorithm based on event-driven MD simulations adapted
for Brownian dynamics. We study the effect of extensional flow on the slow
dynamics of dense hard-sphere systems when shear rates are high enough to
interfere with the slow (alpha) relaxation time. We discuss mean-squared displacements
as a function of time.

DIVERGENCE OR NOT?
Tina Hecksher, Albena I. Nielsen, Niels Boye Olsen, Jeppe C. Dyre
(1) DNRF Centre Glass and Time, Roskilde University, Denmark
Correspondence author: tihe@ruc.dk
The Vogel-Fulcher-Tammann (VFT) prediction that the relaxation time (or viscosity)
diverges at a finite temperature in ultra-viscous liquids is impossible to
test experimentally in a direct way. In [1] we proposed an indirect procedure to
test this, simply comparing the ’goodness’ of fits to relaxation-time data of functions
without divergence to those of the VFT equation. Our analysis of dielectric
data on 42 different ultra-viscous molecular liquids showed no compelling evidence
for a dynamic divergence. In the analysis we kept the pre-factor, τ0, fixed
at a physically meaningful value (10 −14 s). Here we present further analysis, relaxing
this constraint on the pre-factor. The results are in agreement with our
previous findings and also show that the distributions of fitted pre-factors are
very different for the different fitting functions. Interestingly, the distribution
is peaked around 10 −14 s for fits to data of the VFT equation.
[1] T. Heckhser, A.I. Nielsen, N.B. Olsen, J.C. Dyre, Nature Phys. 4 (2008) 737

STRONGLY CORRELATING LIQUIDS AND THEIR “ISOMORPHS”
N. P. Bailey , N. Gnan, U. R. Pedersen, T. B. Schrøder, S. Toxvaerd, J. C. Dyre,
DNRF Center “Glass and Time”, IMFUFA, Dept. of Sciences, Roskilde University,
P.O. Box 260, DK-4000 Roskilde, Denmark
Correspondence author: dyre@ruc.dk
A liquid is termed strongly correlating if its virial and potential energy thermal
equilibrium fluctuations in the NVT ensemble are more than 90% correlated
[1]. This paper reviews the properties of strongly correlating liquids, a class of
liquids that includes van der Waals and metallic liquids, but neither hydrogenbonding
nor ionic or covalently bonded liquids.
Strongly correlating liquids are simpler than liquids in general, stemming
from their hidden scale invariance [2]: For strongly correlating liquids the potential’s
r-dependence may be fitted by a power law plus a constant plus a linear
term. When summed over all nearest neighbor pairs, the linear term is almost
constant (NVT). The hidden scale invariance implies that strongly correlating
liquids, to a good approximation, may be described as single-parameter liquids,
and that these liquids have curves – “isomorphs” – in their state diagrams along
which several properties are invariant [3].
For strongly correlating liquids the relaxation time is an isomorph invariant
which rules out some models for the non-Arrhenius temperature dependence,
including the Adam-Gibbs model and the free volume model(s), but not, e.g.,
the shoving model or models where the excess entropy controls the relaxation
time [5]. For strongly correlating liquids the recently identified “isochronal
temperature-pressure superpositioning” [4] is a consequence of the isomorph
invariance of both relaxation time and relaxation function. Finally, isomorphs
act as wormholes in the state diagram: Any jump between isomorphic state
points brings the system instantaneously to a state of equilibrium, no matter
how long the relaxation time is at the state points involved.
References
[1] U. R. Pedersen, N. P. Bailey, T. B. Schrøder, and J. C. Dyre, Phys.
Rev. Lett. 100, 015701 (2008); U. R. Pedersen, T. Christensen, T. B.
Schrøder, and J. C. Dyre, Phys. Rev. E 77, 011201 (2008); N. P. Bailey,
T. Christensen, B. Jakobsen, K. Niss, N. B. Olsen, U. R. Pedersen,
T. B. Schrøder, and J. C. Dyre, J. Phys.: Condens. Matter 20, 244113
(2008); T. B. Schrøder, U. R. Pedersen, N. P. Bailey, S. Toxvaerd, and J.
C. Dyre, arXiv:0812.4960 (2008); arXiv:0803.2199 (2008); T. B. Schrøder,
U. R. Pedersen, N. Gnan, and J. C. Dyre, arXiv:0903.0516 (2009).
[2] N. P. Bailey, U. R. Pedersen, N. Gnan, T. B. Schrøder, and J. C. Dyre,
J. Chem. Phys. 129, 184507 (2008); J. Chem. Phys. 129, 184508 (2008);

T. B. Schrøder, N. P. Bailey, U. R. Pedersen, N. Gnan, and J. C. Dyre,
arXiv:0609.0025 (2009).
[3] N. Gnan, T. B. Schrøder, U. R. Pedersen, N. P. Bailey, and J. C. Dyre,
arXiv:0605.3497 (2009).
[4] K. L. Ngai, R. Casalini, S. Capaccioli, M. Paluch, and C. M. Roland, J.
Phys. Chem. B 109, 17356 (2005); C. M. Roland, Soft Matter 4, 2316
(2008).
[5] J. Mittal, J. R. Errington, and T. M. Truskett, J. Chem. Phys. 125, 076102
(2006).

DYNAMICS OF MOLECULAR LIQUIDS CONFINED IN MCM-41 MESOPORES
T. Yamaguchi (1), K. Yoshida (1), S. Kittaka (2), S. Takahara (2), M.-C. Bellissent-Funel (3), and P. Fouquet (4)
(1) Department of Chemistry, Fukuoka University, Fukuoka 814-0180, Japan
(2) Department of Chemistry, Okayama University of Science, Okayama 700-0005, Japan
(3) Laboratoire Léon Brillouin, Saclay, 91191 Gif-sur-Yvette Cedex, France
(4) Institute Laue-Langevin, BP 156, 38042 Grenoble Cedex, France
yamaguch@fukuoka-u.ac.jp
The dynamics of water [1], methanol, ethanol [2], and acetonitrile [3] confined in mesoporous silica glass MCM-41 with pore
diameters 2.1~3.7 nm has been investigated in surface-adsorbed and capillary-condensed states at ambient to undercooled
temperatures by quasi-elastic neutron scattering, neutron spin-echo, and dielectric measurements. It was found that the
dynamics of confined liquids is regulated by a balance between the interaction with surface hydroxyls and the effect of
confinement and the intermolecular interaction with temperature; the higher the cooperativity of molecules together with the
surface hydroxyls, the slower the molecular motions, in such an order of bulk, capillary-condensed, and surfaced-adsorbed
molecule. The relaxation times of nonfreezing confined water for both surface-adsorbed and capillary-condensed states show
a dynamical crossover at 220~230 K from non-Arrhenius to Arrhenius type behavior, which corresponds to structural
transformation from high-density to low-density structures confirmed by X-ray and neutron diffraction.
[1] K. Yoshida, et al. J. Chem. Phys. 129, 054702, 2008
[2] S. Takahara, et al. J. Phys. Chem. C, 112, 14385, 2008
[3] S. Kittaka, et al. J. Phys. Chem. B, 109, 23162, 2005

STRUCTURE, DYNAMICS AND INTERACTIONS IN IONIC LIQ-
UIDS
Tatiana A. Fadeeva(1), Benjamin J. Lee(1), Heather Y. Lee(1), Brenna M.
Krieger(1), Cherry Santos(1), Edward W. Castner, Jr.(1), and James F. Wishart(2)
(1) RUTGERS, The State University of New Jersey, Dept. of Chemistry and
Chemical Biology, 610 Taylor Road, Piscataway, NJ 08854, USA
(2) BROOKHAVEN National Laboratory, Dept. of Chemistry, Bldg. 555A,
Upton, NY 11973-5000, USA
Correspondence author: ed.castner@rutgers.edu
We will present recent research results on ionic liquids, with a focus on both
structural and spectroscopic experiments. Temperature-dependent structural
studies are done using combined small-/wide-angle X-ray scattering (SAXS/
WAXS). Spectroscopic investigations use both ultrafast optical spectroscopy[1]
and NMR studies of ion self-diffusion.[2]
Structural and dynamical results of studies on common ionic liquids having
tetraalkylammonium and dialkylpyrrolidinium cations paired with the bis(trifluoromethylsulfonyl)amide
anion will be discussed.[1] In addition, we will discuss
results on novel ionic liquids created in our labs, including cations with
alkylsilyl and alkylsiloxy groups,[1,2] and other ionic liquids having paramagnetic
Fe(III) complexes as anions.
[1] E. W. Castner, Jr., J. F. Wishart and H. Shirota, Acc. Chem. Res. 40,
(2007), p. 1217.
[2] S. H. Chung, R. Lopato, S. G. Greenbaum, H. Shirota, E. W. Castner, Jr.,
and J. F. Wishart, J. Phys. Chem. B, 111, (2007), p. 4885.

The Pico- to Nanosecond Dynamics of Phospholipids
S. Busch (1), C. Smuda (2), M. Schmiele (1), L.C. Pardo Soto (2), T. Unruh
(1)
(1) Forschungsneutronenquelle Heinz Maier-Leibnitz (FRM II), Technische Universität
München, Lichtenbergstr. 1, D-85747 Garching bei München; and Physik
Department E13, Technische Universität München, James-Franck-Str. 1, D-
85747 Garching bei München.
(2) Center for Radiopharmaceutical Science, ETH Zürich, Wolfgang-Pauli-Str.
10, CH-8093 Zürich
(3) Grup de Caracterització de Materials, ETSEIB, Universitat Politècnica de
Catalunya, Diagonal 647 (planta 11), E-08028 Barcelona
Correspondence author: tobias.unruh@frm2.tum.de
Phospholipids are not only interesting because of their ubiquity and importance
for every living being, but also because they can be used in a variety of technological
applications, e.g. as stabilizers of lipid nanoparticles for drug delivery. It
has been shown that not only the drug release rate but also the storage stability
of these systems highly depends on the properties of the stabilizer [1].
We aim to understand the diffusional dynamics of phospholipids such as
dimyristoylphosphatidylcholine (DMPC) on a molecular scale, the difference in
dynamics of monolayers compared to bilayers, the influence of coemulsifiers, and
the correlation of these microscopic parameters to macroscopic physicochemical
quantities.
On a long timescale, the free volume theory [2] can describe the longrange
diffusive motions of phospholipids satisfactorily. Molecular dynamics simulations
have observed that on a short time scale, collective, flow-like motions
become important [3]. We studied liquid crystals, vesicles, and emulsions with
DMPC using quasielastic neutron scattering at the time-of-flight spectrometer
TOFTOF at FRM II. Experimental evidence was found that the longrange
motion in the pico- to nanosecond time range indeed has a flow-like character.
[1] K. Westesen, B. Siekmann, Int. J. Pharm., 151, 35, 1997
[2] W.L.C. Vaz, P.F. Almeida, Biophys. J., 60, 1553, 1991
[3] E. Falck, T. Róg, M. Karttunen, I. Vattulainen, JACS, 44, 130, 2008

CONNECTING IRREVERSIBLE TO REVERSIBLE AGGREGA-
TION: A MOLECULAR DYNAMICS STUDY OF A PATCHY PAR-
TICLE MODEL
S. Corezzi (1,2), C. De Michele (2,3), E. Zaccarelli (2,3), J. Russo (3), D.
Fioretto (1,2), P. Tartaglia (3,4), F. Sciortino (2,3)
(Presenting author underlined)
(1) Dipartimento di Fisica, Università di Perugia, Perugia, Italy
(2) CNR-INFM-SOFT, Università di Roma ‘La Sapienza’, Roma, Italy
(3) Dipartimento di Fisica, Università di Roma ‘La Sapienza’, Roma, Italy
(4) INFM-CNR-SMC, Università di Roma ‘La Sapienza’, Roma, Italy
Correspondence author: silvia.corezzi@fisica.unipg.it
Several natural and synthetic materials, as well as biological structures, result
from the self-assembly of elementary units into branched aggregates and networks.
The process of aggregation may be reversible or irreversible, depending
on the ratio between the bond energy u0 and the thermal energy kBT . During
irreversible aggregation (u0/kBT ≫ 1), bonds – once formed – never break,
and the final structure of the aggregates results from a delicate balance between
the cluster-size dependence of the diffusion process and the probability of irreversible
sticking. In reversible aggregation (u0/kBT �

Collective Dynamics and Amorphous Character of Protein Hydration Water
A. Orecchini 1,2 , A. Paciaroni 1 , A. De Francesco 3 , C. Petrillo 1 , and F. Sacchetti 1
1 Dipartimento di Fisica, Università di Perugia, and INFM-CNR CRS Soft, Roma, Italy
2 Institut Laue-Langevin, Grenoble, France
3 INFM-CNR CRS Soft, c/o Institut Laue-Langevin, Grenoble, France
E-mail: andrea.orecchini@pg.infn.it
By a detailed experimental study of THz dynamics in the ribonuclease protein, we could detect the
propagation of coherent collective density fluctuations within the protein hydration shell. The
emerging picture indicates the presence of both a dispersing mode, traveling with a speed greater than
3000 m/s, and a nondispersing one, characterized by an almost constant energy of 6-7 meV. In
agreement with molecular dynamics simulations 1 , the features of the dispersion curves closely
resemble those observed in pure liquid water 2 . On the contrary, the observed damping factors are
much larger than in bulk water, with the dispersing mode becoming overdamped at Q = 0.6 Å -1
already. Such novel experimental findings are discussed as a dynamic signature of the disordering
effect induced by the protein surface on the local structure of water.
References:
1 M. Tarek, and D. Tobias, Phys. Rev. Lett. 89, 275501 (2002)
2 F. Sacchetti, J.-B. Suck, C. Petrillo and B. Dorner, Phys. Rev. E 69, 061203 (2004)

Dielectric signatures of hydrogen-bonding, ion-pairing and
micro-phase segregation in ionic liquids
M. G. Del Pópolo
Atomistic Simulation Centre
Queen’s University Belfast
Abstract
The wealth of experimental information on room temperature ionic liquids (ILs) accumulated
over the past years shows that the competition between short- and long-range forces can lead
to a rather varied phenomenology. Two remarkable manifestations of such competition are the
segregation of ionic and neutral domains in molten salts with long aliphatic tails, and the formation
of hydrogen-bond networks in protic ionic liquids (PIL). I will discuss some dynamical aspects of
these phenomena in terms of dielectric spectra and dynamic structure factors. In the first case the
analysis will be based on computer simulations of a primitive model for ILs in which cations are
represented by a charged polymer chain and anions are modeled by single charged spheres. Results
show that as the cation size increases the segregation of tails from ionic bodies leads to a clear peak
in the structure factor at low wave numbers. At the same time the conductivity spectrum and
the time evolution of spatial correlations depict an increase in ionic association and a concomitant
decoupling between mass and charge transport. Hydrogen-bond and ion exchange dynamics in PIL
will be discussed in terms of molecular dynamics simulations of Ethylammonium Nitrate based on
an empirical potential model.
1

The highly fragile glass former Decalin
S. Eibl (1,2), H. Schober (1), M. Johnson (1), M. Plazanet (3), C. Dalle-Ferrier
(2), C. Alba-Simionesco (2)
(1) Institut Laue Langevin, Grenoble, France
(2) Laboratoire Léon Brillouin, Saclay, France
(3) Université Joseph Fourier, Grenoble, France
eibl@ill.eu
Decalin is the saturated analog of naphthalene. It is used as a multi purpose
solvent in research and industry. Applications range from shoe shine to jet
fighter fuel. There are two isomers to Decalin, which are distinct in flexibility
due to the geometry of the respective isomer. Cis Decalin can interchange
between several conformations, where trans Decalin is rigid, confined to only
one conformation. The effect of the geometrical restrictions is big. Among many
differences in micro and macroscopic properties two are remarkable. Firstly the
crystallisation behaviour of the two isomers is very different. Secondly their
fragility was found variable as a function of isomer ratio [1] and attains one of
the highest measured values for molecular liquids at an isomeric mixing ratio of
1:1 [2].
Intensive studies using wide angle neutron diffraction and molecular dynamics
simulations have been dedicated to the structure of Decalin. Indications are
pointing to a possible relation of the fragility to the short range order in the
supercooled liquid and crystalline state.
Equally numerous relaxation experiments using the neutron spin echo technique
and the optical Kerr effect have been carried out. The relaxation behaviour was
studied in the supercooled liquid where data could be collected in the dynamical
crossover regime. Our data does equally suggest high fragility and combining
the optical with the spin echo technique allows us to separate translational from
rotational contributions to the relaxation.
[1] Angell C. A., J Non-Cryst. Sol. 73, 1-17 (1985)
[2] Duvvuri K. et al., J. Chem. Phys. 117, 9 (2002)

Identifying diffusive motions in liquids of short chain molecules on
different time scales
T. Unruh (1), C. Smuda (2), M. Schmiele (1), S. Busch (1)
(1) Forschungsneutronenquelle Heinz Maier-Leibnitz (FRM II), Technische Universität
München, Lichtenbergstr. 1, D-85747 Garching bei München; and Physik
Department E13, Technische Universität München, James-Franck-Str. 1, D-
85747 Garching bei München.
(2) Center for Radiopharmaceutical Science, ETH Zürich, Wolfgang-Pauli-Str.
10, CH-8093 Zürich
Correspondence author: tobias.unruh@frm2.tum.de
The determination of transport mechanisms in molecular liquids is a challenging
task due to the complex correlation of internal and center of mass motions
of the closely packed molecules in the liquid phase. The Rouse theory can
successfully be applied for liquids of short polymers but for the description of
still shorter chain molecules more elaborated theories are needed to reproduce
results from MD simulations and NSE experiments by taking chain stiffness and
intermolecular interactions into account[1].
In this contribution we demonstrate that a general understanding of the diffusive
motions in liquids of short chain molecules can also be obtained by using a simple
model free approach for the evaluation of quasielastic neutron scattering data
collected with different instrumental resolutions when combining it with results
from MD-simulations[2].
[1] M. Guenza, J. Phys.: Condens. Matter, 20, 033101, 2008
[2] C. Smuda, S. Busch, G. Gemmecker, T. Unruh, J. Chem. Phys., 129, 014513,
2008; T. Unruh, C. Smuda, S. Busch, J. Neuhaus, W. Petry, J. Chem. Phys.,
129, 121106, 2008

Liquid Water, the “Most Complex” Liquid:
New Results in Bulk, Nanoconfined, and Biological Environments
H. Eugene Stanley, 1 S. V. Buldyrev, 2 G. Franzese, 1 P. Kumar, 1 M. Mazza, 1 L. Xu, 1
Z. Yan, 1 F. Mallamace, 3 and S.-H. Chen 4
1 Departments of Physics and Chemistry, Boston Univ., Boston, MA 02215 USA
2 Department of Physics, Yeshiva Univ., 500 West 185th Street, New York, NY 10033 USA
3 Dipartimento di Fisica and CNISM, Univ. di Messina, I-98122, Messina, Italy
4 Nuclear Science and Engineering Department, MIT, Cambridge, MA 02139 USA
This talk will introduce some of the 63 anomalies of the most complex of liquids, water.
We will demonstrate some recent progress in understanding these anomalies by combining
information provided by recent experiments and simulations on water in bulk, nanoconfined,
and biological environments. We will interpret evidence from recent experiments
designed to test the hypothesis that liquid water may display “polymorphism” in that it
can exist in two different phases—and discuss recent work on water’s transport anomalies
[1] as well as the unusual behavior of water in biological environments [2]. Finally, we
will discuss how the general concept of liquid polymorphism [3] is proving useful in understanding
anomalies in other liquids, such as silicon, silica, and carbon, as well as metallic
glasses, which have in common that they are characterized by two characteristic length
scales in their interactions.
[1] P. Kumar, S. V. Buldyrev, S. L. Becker, P. H. Poole, F. W. Starr, and H. E. Stanley,
”Relation between the Widom line and the Breakdown of the Stokes-Einstein Relation
in Supercooled Water,” Proc. Natl. Acad. Sci. USA 104, 9575–9579 (2007).
[2] P. Kumar, Z. Yan, L. Xu, M. G. Mazza, S. V. Buldyrev, S.-H. Chen. S. Sastry, and
H. E. Stanley, ”Glass Transition in Biomolecules and the Liquid-Liquid Critical Point
of Water,” Phys. Rev. Lett. 97, 177802 (2006).
[3] H. E. Stanley, ed., Liquid Polymorphism [Advances in Chemical Physics], series edited
by S. A. Rice (Wiley, New York, 2010).
1

Intrinsic nanoscale elastic inhomogeneity governing physical and mechanical
properties of metallic glasses
T. Ichitsubo, E. Matsubara
Department of Materials Science and Engineering, Kyoto University, Kyoto 606-
8501, Japan
Correspondence author: tichi@mtl.kyoto-u.ac.jp
Disordered materials, liquids and glasses, exhibit various physical and mechanical
properties, and complex relaxation processes. Considerable progress has
been made understanding the atomic/molecular configurations in frozen glassforming
liquids, including metallic glasses composed mainly of metallic bonds. It
has been reported that Poisson’s ratio is strongly correlated with the fragility[1],
and ductility[2] of glasses, and structural inhomogeneity (mesoscale) leads to
their excellent plasticity[3]. However, comprehensive understanding of origin
of these physical and mechanical properties is still one of main issues in glass
science. In this work, to seek the fundamental origin of the correlations, we
begin by concentrating on the mysterious “positive dispersion” phenomenon in
the dynamic response of rigid metallic glasses: this is the tendency of the acoustic
mode to disperse faster than expected from measurements of the ultrasonic
sound velocity. This is generally known as positive dispersion, which is frequently
observed in many disordered systems[4]. For liquids, positive dispersion
may be explained within the framework of the mode coupling theory (MCT),
in which a fast rattling process, distinct from α or β (Johari-Goldstein) relaxation,
is supposed to be present. However, positive dispersion is also observed
in rigid glasses, and the phenomenon has been attributed to the residual fast
process in the glass. As was shown previously, elastic moduli of glasses are
frequency-dependent at sufficiently high temperatures where α or β relaxation
can take place. The fast process is one candidate for causing positive dispersion
in relatively low-density glassy materials, but it seems difficult to use this to
explain the positive dispersion in very dense metallic glasses. Here we suggest
that the positive dispersion in glasses fundamentally originates from an intrinsic
elastic inhomogeneity. The intrinsic presence of “elastic inhomogeneity” in the
glass substances is first substantiated by cmbining results from inelastic X-ray
scattering (IXS) and ultrasonic (US) techniques, and elastic wave scattering
theory. We then go on to consider the relationship between this inhomogeneity
and fragility. We show that elastic inhomogeneity can determine physical and
mechanical properties of metallic glasses such as fragility or Poission’s ratio.
[1] V. N. Novikov, A. P. Sokolov, Nature 431 (2004) 961.
[2] J. J. Lewandowski, W. H. Wang, A. L. Greer, Philos. Mag. Lett. 85 (2005)
77.
[3] Y. H. Liu, G. Wang, R. J. Wang, D. Q. Zhao, M. X. Pan, W. H. Wang,
Science 315 (2007) 1385.
[4] T. Scopigno, G. Ruocco, F. Sette, Rev. Mod. Phys. 77 (2005) 881

Gel-forming patchy colloids
Francesco Sciortino
Universita’ di Roma La Sapienza, Italy
I will discuss thermodynamic and dynamic properties of simple models of
particles with patchy interactions. I will show that possibility of controlling
the number of bonded nearest neighbors has interesting consequences on the
thermodynamic of the system:
(i) It reduces the region of the phase diagram where liquid-gas coexistence
is observed
(ii) it offers the possibility of generating liquid states (i.e. states with temperature
lower than the liquid-gas critical temperature) with a vanishing occupied
packing fraction, a case cannot be realized with spherically interacting particles;
(iii) it opens up the region of stability of the liquid phase, favoring the
establishment of homogeneous disordered materials at small packing fraction,
which can be named accordingly stable equilibrium gels or network glasses.
I will show also how the process of self-assembly of the network can be
described theoretically in a rather precise and I will discuss the connections
between physical and chemical gels.
Recent literature related to this presentation includes:
[1] E. Bianchi, J. Largo, P. Tartaglia, E. Zaccarelli, F. Sciortino; Phase
diagram of patchy colloids: towards empty liquids, Phys. Rev. Lett. 97,
168301, 2006
[2] Emanuela Bianchi, Piero Tartaglia, Emilia La Nave and Francesco Sciortino;
Fully Solvable Equilibrium Self-Assembly Process: Fine-Tuning the Clusters
Size and the Connectivity in Patchy Particle Systems, J. Phys. Chem. B 111,
11765 (2007).
[3] F. Sciortino, E. Bianchi, J. Douglas and P. Tartaglia; Self-assembly of
patchy particles into polymer chains: A parameter-free comparison between
Wertheim theory and Monte Carlo simulation, J. Chem. Phys.126, 194903,
2007
4] S. Corezzi, C. De Michele, E. Zaccarelli, P. Tartaglia and F. Sciortino;
Connecting Irreversible to Reversible Aggregation: Time and Temperature, J.
Phys. Chem. B (Letter) January 13 (2009) and Softmatter in press.

Liquid-liquid Transition in Supercooled Silicon determined by First-
Principles Simulation (BOLD, LEFT)
P. Ganesh (1), M. Widom (1,2), P. Ganesh (3), Fo. U. Author (3)
(Presenting author underlined)
(1) Geophysical Lab., Carnegie Institution of Washington,Washington DC , USA
(2) Department of Physics, Carnegie Mellon University, Pittsburgh PA, USA
Correspondence author: pganesh@ciw.edu
First principles molecular dynamics simulations reveal a liquid-liquid phase transition
in supercooled elemental silicon. Two phases coexist below Tc ∼ 1232K.
The low density phase is nearly tetra-coordinated, with a pseudogap at the
Fermi surface, while the high density phase is more highly coordinated and
metallic in nature. The transition is observed through the formation of van der
Waals loops in pressure-volume isotherms below Tc.

Structural relaxation and correlation length scales in glass forming
liquids
Srikanth Sastry (1), Smarajit Karmakar (2), Shiladitya Sengupta (1), Chandan
Dasgupta (2)
(1) Jawaharlal Nehru Centre for Advanced Scientific Research, Bangalore
560064, India. (2) Centre for Condensed Matter Theory, Department of Physics,
Indian Institute of Science, Bangalore - 560012, India
Correspondence author: sastry@jncasr.ac.in
The role of growing static and dynamical length scales in determining relaxation
times in glass forming liquids has received considered attention in recent times.
Spatially heterogeneous dynamics, via the analysis of spatial correlations of the
mobility of particles allows estimation of a dynamical length. We evaluate the
lengthscale associated with spatial heterogeneity of dynamics from finite size
scaling, as well as from the evaluation of the four point density correlation
function. We evaluate quantities related to dynamical heterogeneity, structural
relaxation and configurational entropy in different ensembles and for systems of
different spatial dimensionality. Results from our our analysis of the relationship
between such a dynamical length scale and the relaxation dynamics of the liquid
in different regimes, along with a detailed comparison with various theoretical
predictions, are presented.

Liquid-liquid critical point in supercooled silicon
Srikanth Sastry, Vishwas V. Vasisht, Shibu Saw
Jawaharlal Nehru Centre for Advanced Scientific Research, Bangalore 560064,
India.
Correspondence author: sastry@jncasr.ac.in
Liquid silicon has previously been shown to exhibit a liquid-liquid transition
in the supercooled state at zero pressure, using computer simulations employing
the Stillinger-Weber (SW) potential. The associated liquid-liquid (LL) critical
point lies at negative pressures. Computer simulation evidence of such a negative
pressure critical point is presented. Compressibilities evaluated from the
equation of state and fluctuations in constant pressure-temperature simulations
exhibit a growing maximum upon lowering temperature below 1500 K, a signature
of approach towards a critical temperature. Isotherms below 1120 K exhibit
non-monotonic van der Walls-like behaviour signalling a first order transition.
We identify Tc ∼ 1120 ± 12K, Pc ∼ −0.6 ± 0.15GP a. The structure of the
liquid changes dramatically in going from high temperatures and pressures to
low temperatures and pressures. Diffusivities vary over four order of magniture
and exhibit anomalous pressure dependence near the critical point. A strong
relationship between local geometry quantified by the coordination number and
diffusivity is seen.

Diffusion-limited reactions in crowded environments
Nicolas Dorsaz (1,2), Cristiano De Michele (3), Francesco Piazza (1), Paolo
De Los Rios (1) and Giuseppe Foffi (1,2)
(1) Institute of Theoretical Physics, Ecole Polytechnique Fédérale de Lausanne
(EPFL), CH-1015 Lausanne, Switzerland
(2) Institut Romand de Recherche Numérique en Physique des Matériaux IR-
RMA, PPH-Ecublens, CH-105 Lausanne, Suisse
(3) Dipartimento di Fisica and INFM, Università di Roma “La Sapienza”, P.le
A. Moro 2, 00185 Roma, Italy
Correspondence author: giuseppe.foffi@epfl.ch
Crowding is crucial for reactions occurring in vivo [1-4]. As it is commonly
taken, at low concentrations rates grow with density, as the free energy of the
encounter is reduced by the growing number of reactants. Increasing the density
further, reaction rates are expected to vanish together with the diffusivity.
However, such a radical slowing down occurs at extremely high packing fractions,
unrealistic in living cells [5].
The simplest model of diffusion-limited encounter has been introduced in 1916
by Smoluchowski under the hypothesis of infinite dilution and chemically isotropic
spherical reactants [6]. This framework has been widely used to describe reactions
occurring in vivo. However, biological environments are crowded: cells
cytoplasm, for instance, contains a large number of proteins, nucleic acids, and
other smaller molecules that can occupy up to 30 - 40% of the available volume.
Here we generalize the classical Smoluchowski problem to arbitrary densities.
Borrowing concepts from the physics of colloidal systems, we show and rationalize
the emergence of an optimal packing fraction where the encounter rate
reaches a maximum with respect to infinite dilutions. Remarkably, optimality
is attained far below the dynamical arrest, at a concentration typical of cellular
environment.
[1] R. J. Ellis. Trends. Biochem. Sci., 26(10):597604 (2001)
[2] S. B. Zimmerman and A. P. Minton. Annu. Rev. Biophys. Biomol. Struct.,
22:2765 (1993)
[3] C. Ebel and G. Zaccai. J. Mol. Recognit., 17(5):382389 (2004)
[4] R.J. Ellis and A.P. Minton Nature, 425(6953):2728 (2003)
[5] P. N. Pusey and W. van Megen Nature, 320:340342 (1986)
[6] M. V. Smoluchowski. Phys. Z., 17:557, 1916 and Z. Phys. Chem., 92:129,
1916.

Relaxation of Local Order in Water and Tetrahedral Entropy
Pradeep Kumar (1), S. V. Buldyrev (2), H. E. Stanley (3)
(Presenting author underlined)
(1) Center for Studies in Physics and Biology, The Rockefeller University, 1230
York Avenue, New York, NY 10021 USA
(2) Department of Physics, Yeshiva University, 500 West 185th Street, New
York, NY 10033 USA
(3) Center for Polymer Studies and Department of Physics, Boston University,
Boston, MA 02215 USA
Correspondence author: pradeep.kumar@rockefeller.edu
The local structure around a water molecule arising from the vertices formed
by four nearest neighbors is approximately tetrahedral. The degree of tetrahedrality
can be quantified by a local tetrahedral order parameter Q [1]. We
introduce the spatial correlation function CQ(r) and temporal autocorrelation
function CQ(t) of the local tetrahedral order parameter Q ≡ Q(r, t). Using computer
simulations of the TIP5P model of water, we investigate CQ(r) in a broad
region of the phase diagram. We find that at low temperatures CQ(t) exhibits
a two-step temporal decay similar to the self intermediate scattering function,
and that the corresponding correlation time τQ displays a dynamic crossover
upon crossing the Widom line TW (P ) (line of response function maxima arising
due to the presence of hypothesized liquid-liquid phase transition[4] at low
temperatures [2,3]). Specifically we find that the relaxation changes from non-
Arrhenius behavior for T > TW to Arrhenius behavior for T < TW . We define
a tetrahedral entropy SQ associated with the local tetrahedral order of water
molecules and find that it produces a major contribution to the total specific
heat maximum at the Widom line. Finally we show that τQ can be extracted
from SQ using an analog of the Adam-Gibbs relation.
[1] Chau P-L, Hardwick AJ (1998) A new order parameter for tetrahedral configurations.
Mol Phys 93:511-518; Errington JR, Debenedetti PG (2001) Relationship
between structural order and the anomalies of liquid water. Nature
409:318-321.
[2] L. Xu, P. Kumar, S. V. Buldyrev, S.-H. Chen, P. Poole, F. Sciortino, and
H. E. Stanley, Relation between the Widom line and the dynamic crossover in
systems with a liquid-liquid critical point. Proc Natl Acad Sci USA 102:16558-
16562 (2005).
[3] P. Kumar, S. V. Buldyrev, S. Becker, P. H. Poole, F. W. Starr, H. E. Stanley,
Relation between the Widom line and the breakdown of the Stokes-Einstein
relation in supercooled water. Proc Natl Acad Sci USA 104:95 75–9579 (2007)
[4] P. H. Poole, F. Sciortino, U. Essmann, and H. E. Stanley, Phase behavior of
metastable water.Nature 360:324-328 (1992)

A molecular view of model membranes: The stabilizing effect of disaccacharides
and the dependence of mechanical properties on lipid
composition
Manolis Doxastakis (1), Victoria García Sakai (3), Satoshi Ohtake (2), Shen
Lin-Gibson (4), Robert A. Riggleman (2), Marcus T. Cicerone (4), Janna K.
Maranas (5), and Juan J. de Pablo (2)
(1) Department of Chemical and Biomolecular Engineering, University of Houston,
Texas, 77204-4004
(2) Department of Chemical and Biological Engineering, University of Wisconsin,
Madison, Wisconsin 53706-1691
(3) NIST Center for Neutron Research, Gaithersburg, Maryland 20899 and Department
of Materials Science and Engineering, University of Maryland, College
Park, Maryland 20742
(4) NIST Polymers Division, Gaithersburg, Maryland 20899
(5) Departments of Chemical Engineering and Materials Science & Engineering,
The Pennsylvania State University, University Park, Pennsylvania 16802
Correspondence author: depablo@engr.wisc.edu
Trehalose, a disaccharide of glucose, is often used in the preservation of biological
systems through lyophilization and cryopreservation procedures. The detailed
mechanism responsible for the protecting ability of this sugar remains unknown
with different theories proposed. In this work, atomistic molecular simulations
on model hydrated bilayers predict that the sugar displays important stabilizing
properties by direct interactions with phospholipid headgroups. In anhydrous
conditions, quasielastic neutron scattering experiments probe selectively the dynamics
of the hydrophilic and hydrophobic part of the membranes. Elastic scans
focusing on lipid tail dynamics display clear evidence of a main melting transition
that is significantly lowered in the presence of trehalose, an effect associated
to cell preservation. The lipid headgroup mobility is considerably restricted at
high temperatures and is controlled by the dynamics of the sugar in the mixture.
Molecular simulations are employed to fully explore the nature of the
motions present in the samples with low water content, prior to and after the
main transition.
The lipid lateral organization and the mechanical properties of multicomponent
lipid membranes require a study of the systems on a considerably larger
length scale. Accurate simulation predictions will be shown by concurrent use
of appropriate coarse grained models and Monte Carlo simulations.
[1] M. Doxastakis, V. García-Sakai, S. Ohtake, J. K. Maranas and J. J. de Pablo,
Biophys. J., 92, 147, 2007

COMPLEX DEPLETION FORCES
R. Piazza(1), S. Buzzaccaro (1)
(1) Politecnico di Milano, Italy
Correspondence author: roberto.piazza@polimi.it
Most of experimental studies of the effects brought in a colloidal suspensions by
the presence of depletion forces have so far been performed on systems where
the depletion agent can be regarded as ideal or weakly interacting. Here, we
shall conversely deal with situations where interactions or long-range spatial
correlations are of primary importance in setting the phase behavior of the
colloidal fluid. After reviewing our recent work [1,2], where we have exploited
sedimentation measurements to extract accurate equations of state, unraveling
fine details of the phase diagram, we shall mainly discuss two “paradigmatic”
situations:
• Depletants self-interacting via strong electrostatic forces, where, in spite of
the structural correlations induced by the repulsion, much stronger depletion
effects are observed, together with subtle changes in the competition
between crystallization and kinetic arrest.
• “Critical” depletion, i.e. depletants that, although being almost ideal at
room temperature, show a liquid-liquid phase separation with the solvent
at higher T . Here we show that depletion forces can be amplified by order
of magnitudes by the presence of long-range spatial correlation due the
proximity of the critical demixing point. In particular, we prove that depletion
effects merge continuously into critical Casimir effects, displaying
at the same time interesting scaling properties. Our results suggests an
unified view of these two apparently unrelated phenomena.
[1] S. Buzzaccaro, R. Rusconi, and R. Piazza, Phys. Rev. Lett. 99(2007), p.
098301
[2] S. Buzzaccaro, A.Tripodi, R. Rusconi, D, Vigolo, and R. Piazza, J. Phys.:
Cond. Matt. 20 (2208) p. 494219

Evidence of growing amorphous order in deeply supercooled liquids through
point-to-set correlation functions (A. Cavagna)
The idea that relaxation time in deeply supercooled liquids grows because of the re-
arrangement of larger and larger correlated regions has been probed by many analytical,
numerical and experimental efforts in the last fifteen years. A first breakthrough was the
discovery of a dynamical length-scale ξd, related to dynamically heterogeneous mobility cor-
relations. The conspicuous lack of a static counterpart of ξd fostered for some years the
belief that deeply supercooled liquids had in fact a completely trivial thermodynamics.
Recently, however, a purely static correlation length ξs has been discovered by using a
nonstandard point-to-set correlation function that measures how deeply amorphous bound-
ary conditions penetrate within a system. Not only ξs increases significantly entering the
deeply supercooled phase, but the very correlation function develops a nonexponential decay,
evidence of a thermodynamic anomaly of low temperature glass-forming liquids.
Hence, both dynamics and thermodynamics are nontrivial in supercooled liquids and a
unified description is badly needed.
1

SURFACE TENSION AND SPINODAL LIMIT IN SUPERCOOLED
LIQUIDS
T. S. Grigera (1), C. Cammarota (2), A. Cavagna (3), G. Gradenigo (4), P.
Verrocchio (4)
(1) Universidad Nacional de La Plata (Argentina)
(2) Universitá di Roma “Sapienza”
(3) Istituto Sistemi Complessi (CNR), Roma (Italy)
(4) Universitá di Trento (Italy)
Corresponding author: tgrigera@inifta.unlp.edu.ar
Common physical sense suggests that the sharp slowdown observed in glassforming
supercooled liquids should be accompanied by a growing correlation
length, but finding this length has been nontrivial. In random first-order theory,
this length is given by the size of amorphous excitations, which depends
on a balance between their mutual interfacial energy and their configurational
entropy. But how these excitations disappear when crossing over to the normal
high temperature liquids is unclear, chiefly due to lack of data about the surface
tension. We have measured the energy cost to create amorphous excitations in
a model glassformer, finding that the surface tension vanishes at a well-defined
spinodal energy, above which amorphous excitations cannot be sustained. This
spinodal therefore marks the true onset of glassiness. Furthermore, different
pairs of excitations have different values of the surface energy, giving rise to a
rather broad, temperature-dependent distribution of surface tension.

Liquid-Liquid Phase Transition in Modified Two-Scale Spherically
Symmetric Jagla Potential
Jiayuan Luo 1 , Limei Xu 2 , Sergey V. Buldyrev 3,1 , H. Eugene Stanley 1
1 Center for Polymer Studies and Department of Physics,
Boston University,
Boston, MA 02215 USA
2 World Premier <strong>International</strong> (WPI) Research Center,
Advanced Institute for Materials Research,
Tohoku University,
Sendai 980-8577, Japan
3 Department of Physics,
Yeshiva University,
500 West 185th Street,
New York, NY 10033 USA
(Dated: August 27, 2009)
1

Abstract
Jagla model of liquids which consists of particles interacting via a spherically symmetric two-
scale potential with both repulsive and attractive ramps, is widely studied in simulations of liquids.
In recent study by Xu. et al, the Jagla model of liquids displays anomalies similar to liquid water,
which has the Liquid-Liquid phase transition and dynamics crossover, and leads to locate the second
critical point. However, in their study, the coexistence line of the Jagla model shows a positive
slope, which is the opposite to what has been found in the water experiments. Recent work by
Wilding. et al, uses Morte Carlo simulations to study a series of modified Jagla model with diverse
parameters. Their study indicates the possibility of obtaining negative slope of the coexistence line
by modifying the Jagla potential. So we use the Discrete Molecular Dynamics (DMD) to study the
Liquid-Liquid transition and dynamics of the modified Jagla potential models. We find the negative
slope of the coexistence line in certain models, with exact same phase diagram of real water, and
negative slope of the Widom line above the critical point, based on both the KT and CP maximum
loci. We further find out that the KT maximum line passes through the nose of the Temperature
Maximum Density (TMD) line, while the CP maximum line ends in the glass transition region.
Besides, these models show all the anomalies of water and dynamics crossover. In summery, we
establish to use a simple spherically symmetric two-scale potential model to represent the exactly
liquid water phase transition phenomena, which matches experiment data, hugely implements the
previous Jagla model.
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