Journal article
An advanced dielectric continuum approach for treating solvation effects: Time correlation functions. I. Local treatment
The Journal of Chemical Physics, Vol.108(3), pp.1103-1113
1998
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.
Details
- Title
- An advanced dielectric continuum approach for treating solvation effects: Time correlation functions. I. Local treatment
- Authors/Creators
- M.V. Basilevsky (Author/Creator)D.F. Parsons (Author/Creator)M.V. Vener (Author/Creator)
- Publication Details
- The Journal of Chemical Physics, Vol.108(3), pp.1103-1113
- Publisher
- American Institute of Physics
- Identifiers
- 991005545257707891
- Copyright
- © 1998 American Institute of Physics
- Murdoch Affiliation
- Murdoch University
- Language
- English
- Resource Type
- Journal article
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