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An advanced dielectric continuum approach for treating solvation effects: Time correlation functions. I. Local treatment

Basilevsky, M.V., Parsons, D.F.ORCID: 0000-0002-3956-6031 and Vener, M.V. (1998) An advanced dielectric continuum approach for treating solvation effects: Time correlation functions. I. Local treatment. The Journal of Chemical Physics, 108 (3). pp. 1103-1113.

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Abstract

A local continuum solvation theory, exactly treating electrostatic matching conditions on the boundary of a cavity occupied by a solute particle, is extended to cover time-dependent solvation phenomena. The corresponding integral equation is solved with a complex-valued frequency-dependent dielectric function ε(ω), resulting in a complex-valued ω-dependent reaction field. The inverse Fourier transform then produces the real-valued solvation energy, presented in the form of a time correlation function (TCF). We applied this technique to describe the solvation TCF for a benzophenone anion in Debye (acetonitrile) and two-mode Debye (dimethylformamide) solvents. For the Debye solvent the TCF is described by two exponential components, for the two-mode Debye solvent, by three. The overall dynamics in each case is longer than that given by the simple continuum model. We also consider a steady-state kinetic regime and the corresponding rate constant for adiabatic electron-transferreactions. Here the boundary effect introduced within a frequency-dependent theory generates only a small effect in comparison with calculations made within the static continuum model.

Item Type: Journal Article
Publisher: American Institute of Physics
Copyright: © 1998 American Institute of Physics
URI: http://researchrepository.murdoch.edu.au/id/eprint/27709
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