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Nonlocal continuum solvation model with oscillating susceptibility kernels: A nonrigid cavity model
Journal article   Open access   Peer reviewed

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

M.V. Basilevsky and D.F. Parsons
The Journal of Chemical Physics, Vol.108(21), pp.9114-9123
1998
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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.

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Citation topics
2 Chemistry
2.89 Ionic, Molecular & Complex Liquids
2.89.677 Liquid Water
Web Of Science research areas
Chemistry, Physical
Physics, Atomic, Molecular & Chemical
ESI research areas
Chemistry
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