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

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

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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.

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