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Bulgarevich, S. B.; Bren, D. V.; Movshovich, D. Ya.; Filippov, S. E.; Olekhnovich, E. P.; Korobka, I. V.

doi:10.1023/a:1021642300013

Cited by 8 publications

(19 citation statements)

References 9 publications

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“…These correlations were observed earlier with X-ray dispersion in liquids [36]. Although the theoretical attempt [34,35] undertaken to account for the nearest-neighbor correlations in liquids reflects correct physics, the practical application of the derived formulas to polar and non-polar liquids resulted in errors exceeding the errors of the simpler models based on the orientation EOKE theory.…”

Section: Introductionsupporting

confidence: 54%

“…The average electro-optical parameters of the system are computed with explicit regard to the intermolecular correlations inside the sphere and interaction with the outside medium. Reference [35] showed that T-shape nearest-neighbor molecular correlations are characteristic of liquid aromatic compounds. These correlations were observed earlier with X-ray dispersion in liquids [36].…”

Section: Introductionmentioning

confidence: 99%

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The Role of Intermolecular Interactions in the Electro-Optical Kerr Effect in Liquid Alkanes

et al. 2005

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The electro-optical Kerr effect of n-alkanes from C 5 to C 16 was investigated in gas phase, liquid phase, and solution. The values of the Kerr constants in gas phase are noticeably distinguishable from those in liquids, where the molecules interact by the London dispersion forces. Both the energy of the dispersion interaction and the difference in the Kerr constants in liquid and gas phase grow with molecular size, indicating the key influence of the interaction on the magnitude of the Kerr effect. Several orientation and molecular-statistical theories of electro-optical Kerr effect were applied to model the change in electro-optical Kerr effect due to the dispersion force. Most theories show significant divergence compared to the experimental data. It is argued that the decisive contribution to electro-optical Kerr effect in liquids and the deviations between the experiment and theory arise due to local liquid structures that collectively orient in the external electric field.

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Section: Introductionsupporting

confidence: 54%

Section: Introductionmentioning

confidence: 99%

The Role of Intermolecular Interactions in the Electro-Optical Kerr Effect in Liquid Alkanes

et al. 2005

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“…It contains three pyridine groups, which exhibit both a large polarization and large structural anisotropy. [29] Furthermore, terpy is a tridentate, meridional capping ligand, which may afford a [Au(CN) 2 ] À -based coordination polymer in which all neighboring terpy molecules are aligned face-toface; [30][31][32] this arrangement is not observed in the free ligand. [33,34] As for Pb II , its use in the design of functional coordination polymers is driven primarily by the many materials dependent on the presence of such a highly polarizable cation.…”

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confidence: 99%

“…While these organic moieties show optical anisotropies that are comparable to the polymers reported herein, their birefringence would theoretically be significantly higher if the molecular polarizabilities were aligned, as occurs in polymers 1-3. [29] Substitution of the Pb II center, with its stereochemically active lone pair, for the isotropic Mn II ion elicited no (14), Mn1-N7 2.247 (14). significant change in the birefringence.…”

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confidence: 99%

Highly Birefringent Materials Designed Using Coordination Polymer Synthetic Methodology

et al. 2007

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“…In this context, our goal was to derive extrapolation formulas for determining the molar volume of a solute at infinite dilution and to reveal correlations of this quantity with the molar polarization and molar Kerr ÄÄÄÄÄÄÄÄÄÄÄÄ 1 For communication XLVII, see [1]. constant of the solute.…”

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confidence: 99%

Molecular Polarizability of Organic Compounds and Their Complexes: XLVIII. Molar Volumes of Benzene Derivatives in Solutions at Infinite Dilution, Their Additivity, and Correlation with the Dipole Moments and Kerr Constants

et al. 2005

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Extrapolation formulas were derived for determination of the molar volume of a solute at infinite dilution. This quantity is stable to solvent replacement and additive with respect to increments of substituents in polysubstituted benzenes. The molar polarization and molar Kerr constant of a solute can be expressed through the molar volumes of the solute at infinite dilution and of the solvent. Replacement of the molar volume in the calculation formulas by the quantity calculated by the additive scheme considerably reduces the experimental time required for determining the dipole moments and Kerr constants of compounds in solution.Partial molar volumes of components are the simplest but important characteristics of liquid solutions, furnishing information on their properties [2]. Of particular interest is the molar volume of a solute extrapolated to infinite dilution, at which the solute molecules do not interact with each other and interact only with the solvent. Division of this quantity by the Avogadro number gives the molecular volume, i.e., the volume of the cavity occupied by a particle in the dynamic structure of the solvent. The molecular volume allows certain conclusions on the features of the solvation shell [2, 3] and, as will be shown in the subsequent papers, on the solute steric structure.The molar volumes of molecules and ions at infinite dilution were determined in numerous papers, but the lack of convenient extrapolation formulas decreasing the random experimental errors apparently complicates the calculations. At the same time, extrapolation formulas have been well developed for determining such partial quantities at infinite dilution as polarization [4] and Kerr constant [5].In this context, our goal was to derive extrapolation formulas for determining the molar volume of a solute at infinite dilution and to reveal correlations of this quantity with the molar polarization and molar Kerr ÄÄÄÄÄÄÄÄÄÄÄÄ 1 For communication XLVII, see [1].constant of the solute. It was also interesting to find whether such molar volume is additive with respect to substituents in molecules, like, e.g., molar refraction, dipole moment, or polarizability tensor. The positive answer we obtained is demonstrated with a wide range of mono-and polysubstituted benzene derivatives.The solution molar volume V 12 is additive with respect to the molar volumes of the solvent V 1 and solute V 2 in accordance with their mole fractions 1 3 x and x:where V 12 = M 12 /r 12 ; M 12 is the mean molar weight of the solution, M 12 = M 1 (1 -x) + M 2 x, M 1 and M 2 are the molar weights of the solvent and solute, respectively; r 12 is the solution density; V 1 = M 1 /r 1 is the solvent molar volume; and r 1 is the solvent density. From formula (1), the molar volume V 2 extrapolated to the infinite dilution, E V 2 , can be expressed by formula (2):Apparently, the limit in formula (2) can be replaced by the derivative in the point x = 0 [formula (3)]:

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Cited by 8 publications

References 9 publications

The Role of Intermolecular Interactions in the Electro-Optical Kerr Effect in Liquid Alkanes

The Role of Intermolecular Interactions in the Electro-Optical Kerr Effect in Liquid Alkanes

Highly Birefringent Materials Designed Using Coordination Polymer Synthetic Methodology

Molecular Polarizability of Organic Compounds and Their Complexes: XLVIII. Molar Volumes of Benzene Derivatives in Solutions at Infinite Dilution, Their Additivity, and Correlation with the Dipole Moments and Kerr Constants

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