Murdoch University Research Repository

Welcome to the Murdoch University Research Repository

The Murdoch University Research Repository is an open access digital collection of research
created by Murdoch University staff, researchers and postgraduate students.

Learn more

Nonlocal continuum solvation model with oscillating susceptibility kernels: A nonrigid cavity model

Basilevsky, M.V. and Parsons, D.F.ORCID: 0000-0002-3956-6031 (1998) Nonlocal continuum solvation model with oscillating susceptibility kernels: A nonrigid cavity model. The Journal of Chemical Physics, 108 (21). pp. 9114-9123.

[img]
Preview
PDF - Published Version
Download (164kB)
Link to Published Version: http://dx.doi.org/10.1063/1.476358
*Subscription may be required

Abstract

A nonlocal continuum theory of solvation is applied using an oscillatingdielectric function with spatial dispersion. It is found that a convergent solution cannot be calculated using a model of a fixed solute cavity inside the solvent continuum. This is attributed to the fact that the dielectricoscillations appear as a result of coupling between polarization and density fluctuations, contradicting the concept of a fixed cavity. The theory is corrected by allowing the cavity size to vary. A cavitation energy and an interaction between the medium reaction field and the cavity size are added to the solvation free energy, and a new theory obtained by a variational treatment. The interaction term enables convergent solutions to become attainable, resulting in an oscillatingelectrostatic solvation energy as a function of cavity radius, the cavitation term enables these oscillations to be smoothed out, resulting in a regular, monotonic solvation free energy.

Item Type: Journal Article
Publisher: American Institute of Physics
Copyright: © 1998 American Institute of Physics
URI: http://researchrepository.murdoch.edu.au/id/eprint/27707
Item Control Page Item Control Page

Downloads

Downloads per month over past year