Effect of solvent discreteness on solvation

Journal of Physical Chemistry B

Volumn 102, Issue 27, 1998, Pages 5348-5357

  Papazyan, Arno ^a   Warshel, Arieh ^a  

^a UNIVERSITY OF SOUTHERN CALIFORNIA   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0001397317     PISSN: 15206106     EISSN: None     Source Type: Journal    
DOI: 10.1021/jp981725g     Document Type: Article

References (23)

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15. This does not mean that quadrupole moments are inconsequential in dielectric phenomena. Many factors, including molecular quadrupole moments, affect the relationship between microscopic properties and the macroscopic dielectric constant. For example, the high dielectric constant of water has been explained as the consequence of the relatively small quadrupole moment of water molecules (Goldman, S.; Joslin, C. J. Phys. Chem. 1993, 97, 12349-12355). By introducing interactions that compete with interdipolar interactions, a solvent quadrupole moment can reduce the dielectric constant. However, once we know the dielectric constant, the dielectric behavior relevant to solvation energetics can be fairly well represented by dipoles, without resorting to solvent quadrupoles, in much the same way as macroscopic dielectric phenomena.
16. In a more realistic description, the radius of exclusion would correspond to the sum of van der Waals radii of the solute and solvent particles.
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18. sc and fcc lattices have quite different interdipolar interactions, as evidenced by their opposite dielectric divergence behaviors at high polarity and quite different radial profiles of solvation polarization.
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