4th EucheMs chemistry congress

Poster Session 1
s870
chem. Listy 106, s587–s1425 (2012)
Poster session 1 - Physical, theoretical chemistry
P - 0 0 2 2
eLeCtrideS, nonLineAr oPtiCAL ProPertieS
And viBrAtionS
J. M. LuiS 1 , M. GArCiA-BorrAS 1 , M. SoLA 1 ,
B. KirtMAn 2
1 Institut de Química Computacional Universitat de Girona,
Química, Girona, Spain
2 University of California – Santa Barbara, Chemistry and
Biochemistry, Santa Barbara, USA
Electrides are ionic compounds in which electrons behave
as anions. These special electrons are separated from any nuclei,
occupying positions typically populated by anions in ionic
compounds. It is well-known that electrides have very large NLO
electronic properties. [1–4] The main goal of this study has been to
determine and analyze the vibrational, as compared to the
electronic, NLO properties for a representative set of electrides
•+ •- including Li@Calix, Na@Calix, Li@B H , Li TCNQ and
10 14 2
Na 2
•+ TCNQ •- . Our results, obtained by UB3LYP level using
different Pople basis set, vary depending upon the electride and
the NLO process. In general, however, we find that the average
static vibrational first and second hyperpolarizability exceed the
corresponding electronic property values, sometimes in the latter
case by more than an order of magnitude. As far as dynamic
properties are concerned, on average they are roughly the same
as the corresponding static electronic hyperpolarizability, and in
particular cases they may be twice as large or more. The role of
anharmonicity in the (NR) hyperpolarizabilities is variable. It
plays a dominant role for the Li@B H first and second
10 14
•+ •- hyperpolarizability, but is negligible for the Li TCNQ first
2
(though not the second) hyperpolarizability.
references:
1. W. Chen, Z. R. Li, D. Wu, Y. Li, C. C. Sun, F. L. Gu,
J. Am. Chem. Soc., 127, 10977 (2005).
2. Z. J. Li, F. F. Wang, Z. R. Li, H. L. Xu, X. R. Huang,
D. Wu, W. Chen, G. T. Yu, F. L. Gu, Y. Aoki, Phys. Chem.
Chem. Phys., 11, 402 (2009).
3. S. Muhammad, H. L. Xu, Y. Liao, Y. H. Kan, Z. M. Su,
J. Am. Chem. Soc., 131, 11833 (2009).
4. F. Ma, Z. R. Li, H. L. Xu, Z. J. Li, Z. S. Li, Y. Aoki,
F. L. Gu, J. Phys. Chem. A, 112, 11462 (2008).
Keywords: electride; Non linear optical properties;
hyperpolarizabilities; vibrational contributions;
4 th EucheMs chemistry congress
P - 0 0 2 3
SoLvent And ioniC StrenGth effeCtS on the
StABiLity of dioxovAnAdiuM (v) CoMPLexeS
with idA And dtPA
K. MAJLeSi 1 , S. BALALi 1 , z. CetvAti 1
1 Islamic Azad University Science and Research Branch,
Chemistry, Tehran, Iran
Our laboratory has taken up the study of complexation of
+ 2- various aminopolycarboxylic acids with VO and MoO4 ions in
2
order to study the influence of the solvents and ionic medium and
to determine the contribution of Kamlet-Abboud-Taft (KAT)
parameters in recent years. [1–3] Polarity of a liquid is defined as
the sum of all possible specific and non-specific interactions
between the solvent and a potential solute. The goal of this
study is to investigate the H O-CH OH composition and
2 3
the ionic strength influences on the stability of dioxovanadium
(V) + iminodiacetic acid (IDA) and dioxovanadium (V) +
diethylenetriaminepentaacetic acid (DTPA) complexes
respectively. UV data have been gathered at a fixed ionic strength
(I = 0.1 mol.dm-3 of sodium perchlorate) and t = 25°C for the
+ solvent effect study. Complexation of VO ion with DTPA was
2
studied at different ionic strengths of sodium chloride
(0.1 ≤I/mol.dm-3 ≤ 1.0). It was concluded that the increase in
the hydrogen-bond acceptor capability of the solvent favors a
higher thermodynamic stability of the products with respect to the
reactants and consequently, an increase in the corresponding
stability constants. Determination of the activity coefficients of
aqueous electrolyte solutions is a very important area of research.
At higher concentrations short range and non electrostatic
interactions have to be taken into account, and this is usually done
by adding terms to the Debye-Hückel expression. The most
popular models are the Pitzer and specific ion interaction theory
(SIT) equations. The errors and R2 values for the models showed
that the SIT model is the best for this research.
references:
1. K. Majlesi, S. Rezaienejad, J. Chem. Eng. Data 56, 3194
(2011)
2. K. Majlesi, S. Rezaienejad, J. Solution. Chem 40, DOI:
10.1007/s0953-011-9754-7 (2011)
3. K. Majlesi, S. Rezaienejad, A. Rouhzad, J. Chem. Eng.
Data 56, 541 (2011)
Keywords: Thermodynamics; Solvent effects; Hydrogen bonds;
UV/Vis spectroscopy;
AUGUst 26–30, 2012, PrAGUE, cZEcH rEPUbLIc