Eighth Condensed Phase and Interfacial Molecular Science (CPIMS)

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Figure 2: Schematic on the effects of two different solvents on the surface adsorption of hard-sphere ions. Our results indicate that the driving force of ions to interfaces is model dependent [2]. continuum theory to explain the surface tension of the halide salts. Levin and co-workers [Physical Review Letters 103, 257802 (2009)] have used a polarizable ion dielectric continuum theory to also explain the surface tension data of halide salts. Interestingly, the single ion potential of mean force (PMF) for iodide agrees quite well (regarding the depth of the shallow local minimum at the interface) with these two very different approaches. Our Recent DFT calculations that intrinsically include polarization also show good agreement with the aforementioned PMFs for iodide [10]. The question regarding the role of polarization and the connection of molecular simulation to dielectric continuum theory still remains. To this end, we constructed molecular simulations of charged hardspheres (HS) in model solvents (SPC/E and Stockmayer fluid) where the separation of cavitation and dielectric response is clear (see Figure 2). We proposed a dielectric theory that contains the free energy of cavitation (proportional to volume of HS), and charging (proportional to square of the charge) where the dielectric constants and volume scaling was determined by molecular simulation [2]. Our results indicate that the underlying physics of anion adsorption is dependent on the nature of the solvent (e.g. SPC/E or Stockmayer). The symmetric nature of the Stockmayer fluid precludes the existence of a surface potential and it is only cavitation that determines surface activity. SPC/E water has a surface potential due to the broken symmetry of both the cavity and interface. It was shown in our study [2] and a recent independent study [Arslagarin and Beck, Journal of Chemical Physics 136, 104503 (2012)] that this notional “surface potential” provides an additional crucial driving force that allows point-charge models in SPC/E to give rise to surface adsorption. Future directions The role of this notional “surface potential” is currently being explored in the context of DFT and the use of inherently polarizable models for the solute and solvent (with G.K. Schenter). Future research will be extended to elucidation of the solvation and surface properties of more complex anions such as the oxyanions (with G.K. Schenter and J. Fulton) such as ClO3 - and BrO3 - where both exhibit very interesting behavior in the context of the Hofmeister series. We are currently investigating the role of hydrophobic solvation with John D. Weeks. We are using multiple representations of the molecular interaction for water (e.g. TIP5P, SPC/E, flavors of DFT) to understand the structural response to a model hydrophobe and the signatures of volume to area scaling. Acknowledgements. This work was performed with Yan Levin (Brazil) John D. Weeks (U. Maryland), D.J. Tobias (UC-I), Ilja Siepmann (U. Minn.), and I.-F.W. Kuo (LLNL), Greg Schenter (PNNL), Liem Dang (PNNL), Marcel D. Baer (PNNL), Abe Stern (UC-I), Joost VandeVondele (U. Zurich), Greg Kimmel (PNNL), John Fulton (PNNL), Roger Rousseau (PNNL) and Shawn M. Kathmann ( PNNL). 137
Publications from BES support (2010- present) 1. Baer, MD and Mundy, CJ, “An ab initio approach to understanding the specific ion effect,” Faraday Discussions, (accepted) 2. Baer, MD; Stern, AC; Levin, Y; Tobias, DJ; Mundy, CJ, “Electrochemical Surface Potential Due to Classical Point Charge Models Drives Anion Adsorption to the Air-Water Interface,” Journal of Physical Chemistry Letters 3, 1948-7185 (2012) 3. Kimmel, GA; Baer, M; Petrik, NG; VandeVondele, J; Rousseau, R; Mundy, CJ, “Polarization and Azimuth-Resolved Infrared Spectroscopy of Water on TiO2(110): Anisotropy and the Hydrogen-Bonding Network,” Journal of Physical Chemistry Letters 3, 1948-7185 (2012) 4. Lewis, T; Winter, B; Stern, AC; Baer, MD; Mundy, CJ; Tobias, DJ; Hemminger, JC, “Does Nitric Acid Dissociate at the Aqueous Solution Surface?,” Journal of Physical Chemistry C 115, 21183 (2011) 5. Baer, MD; Pham, VT; Fulton, JL; Schenter, GK; Balasubramanian, M; Mundy, CJ, “Is Iodate a Strongly Hydrated Cation?,” Journal of Physical Chemistry Letters 2, 2650-2654 (2011) 6. McGrath, MJ; Kuo, IFW; Ghogomu, JN; Mundy, CJ; Siepmann, JI, “Vapor-Liquid Coexistence Curves for Methanol and Methane Using Dispersion-Corrected Density Functional Theory,” Journal of Physical Chemistry B 115, 11688-11692 (2011) 7. Baer, MD; Mundy, CJ; McGrath, MJ; Kuo, IFW; Siepmann, JI; Tobias, DJ, “Re-examining the properties of the aqueous vapor-liquid interface using dispersion corrected density functional theory,” Journal of Chemical Physics 135, 124712 (2011) 8. Lewis, T; Winter, B; Stern, AC; Baer, MD; Mundy, CJ; Tobias, DJ; Hemminger, JC, “Dissociation of Strong Acid Revisited: X-ray Photoelectron Spectroscopy and Molecular Dynamics Simulations of HNO3 in Water,” Journal of Physical Chemistry B 115, 9445 (2011) 9. Murdachaew, G; Mundy, CJ; Schenter, GK; Laino, T; Hutter, J, “Semiempirical Self-Consistent Polarization Description of Bulk Water, the Liquid-Vapor Interface, and Cubic Ice,” Journal of Physical Chemistry A 115, 6046-6053 (2011) 10. Baer, MD; Mundy, CJ, “Toward an Understanding of the Specific Ion Effect Using Density Functional Theory,” Journal of Physical Chemistry Letters 2, 1088-1093 (2011) 11. Kathmann, SM; Kuo, IFW; Mundy, CJ; Schenter, GK, “Understanding the Surface Potential of Water,” Journal of Physical Chemistry B 115, 4369-4377 (2011) 12. Murdachaew G, Mundy CJ, Schenter GK, “Improving the density functional theory description of water with self-consistent polarization,” Journal of Chemical Physics 132, 164102 (2010) 13. McGrath MJ, Ghogomu JN, Mundy CJ, et al. “First principles Monte Carlo simulations of aggregation in the vapor phase of hydrogen fluoride,” Physical Chemistry Chemical Physics 12, 7678 (2010) 14. Fulton JL, Schenter GK, Baer MD, et al. “Probing the Hydration Structure of Polarizable Halides: A Multiedge XAFS and Molecular Dynamics Study of the Iodide Anion,” Journal of Physical Chemistry B 114, 12926 (2010) 15. Baer M, Mundy CJ, Chang TM, et al, “Interpreting Vibrational Sum-Frequency Spectra of Sulfur Dioxide at the Air/Water Interface: A Comprehensive Molecular Dynamics Study,” Journal of Physical Chemistry B 114, 7245 (2010) 16. Mundy CJ, KA Maerzke, MJ McGrath, IFW Kuo, G. Tabbachi, and JI Siepmann, "Vapor-liquid phase equilibria of water modelled by a Kim-Gordon potential." Chemical Physics Letters 479, 60-64 (2010) 138
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Eighth Condensed Phase and Interfac
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Potential energy landscape of the (
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Agenda
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Session III Chair: Jay A. LaVerne,
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Table of Contents
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Transition Metal-Molecular Interact
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Ultrafast Electron Transport across
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CPIMS Principal Investigator Abstra
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VUV LDPI image of a polymer photore
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Publications based on DOE support (
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entirely quenched, presumably due t
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Future Plans In addition to the TiO
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The relative path indexes of the ur
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We have recently carried out molecu
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have been obtained with γ-rays sug
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Two novel plasma devices have been
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(Figure 2) can be adsorbed exclusiv
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3. Future Plans Our planned work de
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Figure 1: Snap shots from molecular
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6. Varilly, P., A. J. Patel and D.
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hypothesis that delocalized charges
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Efforts will be made to observe ele
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Photochemistry and Solvation Dynami
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complementary to work we have carri
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The Co3O4 films for the optical pum
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chamber will allow us to heat the s
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calculations. Additional PMF calcul
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the gas solute first needs to cross
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laser system, which is an infrared
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Publications (10/1/2009-present) fo
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interest are: (i) What is the diffu
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and anilino groups attached to the
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had been formed. This coincides wit
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Figure 1. (A) Simplified bR photocy
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Figure 4. Photocurrent density of b
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single-file diffusion and cannot ca
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PUBLICATIONS SUPPORTED BY USDOE CHE
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arrangement. However, the hydrogen
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(5) “Water Dynamics in Salt Solut
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from high- energy x-ray diffraction
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concentrated aqueous solutions. The
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molecule’s center of mass, or alt
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Moreover, SHG studies by Saykally
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The effective fragment potential (E
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10. D.D. Kemp, J. Rintelman, M.S. G
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temperature dependent, equilibrium
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mimicking real organic photovoltaic
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100 kHz amplifier, SE-FSRS was succ
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photovoltaics will be explored via
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for laser surface reactions to thes
Page 101 and 102: This is a significant advantage of
Page 103 and 104: the STM, which might underlie the u
Page 105 and 106: Future Plans: Figure 3. One and two
Page 107 and 108: methane molecule and a lattice atom
Page 109 and 110: eactive than the Ni, experiment sug
Page 111 and 112: Fig. 1. PE spectra of M3Oy � (M =
Page 113 and 114: each of the intermediates obtained
Page 115 and 116: a regime where each solvent molecul
Page 117 and 118: observables that arise from subtle
Page 119 and 120: total potentials. One can see from
Page 121 and 122: Our calculations have shown that ch
Page 123 and 124: our understanding of structure and
Page 125 and 126: viscosity, η, are inversely relate
Page 127 and 128: photodissociation of the metal - NO
Page 129 and 130: from a Ru 2p3/2 orbital to an orbit
Page 131 and 132: Integrated O 2 PSD (ML) Integrated
Page 133 and 134: anisotropy in the structure of the
Page 135 and 136: XPS studies have been performed on
Page 137 and 138: Publications with BES support since
Page 139 and 140: MLCT (metal to ligand charge transf
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Page 143 and 144: observe the predicted effects, whic
Page 145 and 146: (4*) Lymar, S. V.; Schwarz, H. A. J
Page 147 and 148: (τ .820 ns), but we have not been
Page 149 and 150: B. Photodissociation spectroscopy o
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Page 157 and 158: Our talk will discussion our initia
Page 159 and 160: Figure 1 shows the band structure o
Page 161 and 162: likely to also occur in low coordin
Page 163 and 164: These results are promising indicat
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Page 167 and 168: method recently developed by Prende
Page 169 and 170: and coordination regions. A differe
Page 171 and 172: two ions I - [3] and IO3 - [7]. One
Page 173 and 174: "Probing the Hydration Structure of
Page 175 and 176: world-wide scientific user base sup
Page 177 and 178: 10) C. Zhang, M.E. Grass, A.H. McDa
Page 179 and 180: produce the nanoparticles needed fo
Page 181 and 182: step as a symmetry-breaking templat
Page 183 and 184: work provides what we believe in th
Page 185 and 186: Selected publications acknowledging
Page 187 and 188: 2. Optical Stark study of PtF (Acce
Page 189 and 190: Figure 4. The Q(3.5) line of the [1
Page 191 and 192: In marked contrast to the selective
Page 193 and 194: y depositing cobalt onto copper sin
Page 195 and 196: Carlo calculations, we have carried
Page 197 and 198: approach on a model phenol-amine pr
Page 199 and 200: We performed pump-probe experiments
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may be initially produced in a non-
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4. Inelastic scattering of hydrogen
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Using QM/MM free energy methods we
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This page is intentionally left bla
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gas phase using electrospray ioniza
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order of Li + > Na + > K + for comp
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2. MM Meyer, XB Wang, CA Reed, LS W
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Technical Approach and Progress to
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Ionic liquid synthesis and characte
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Studies of structure and reaction d
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structure theory that include elect
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9. S. Pandelov, J. C. Werhahn, B. M
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pulse duration is a few times longe
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Figure 1 (Left) The HOMO and LUMO e
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slightly preferable in energy, the
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Participant List Dr. Musahid Ahmed
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Professor Kenneth Eisenthal Columbi
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Dr. Ireneusz Janik Notre Dame Radia
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Professor Eric Potma University of
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Dr. James Wishart Brookhaven Nation
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Eighth Condensed Phase and Interfacial Molecular Science (CPIMS)

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