Journal
JOURNAL OF CHEMICAL PHYSICS
Volume 129, Issue 19, Pages -Publisher
AIP Publishing
DOI: 10.1063/1.3013456
Keywords
charge exchange; molecular dynamics method; optical constants; polarisation; potential energy surfaces; reaction kinetics theory; solvent effects
Funding
- Alexander von Humboldt Foundation
- EC FP6 [NMP4-CT-2003-505669]
- Volkswagen Foundation [I/78126]
- Fonds der Chemische Industrie
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The solvent contribution lambda(s) to the reorganization energy of electron transfer can be estimated from averages of the potential energy gaps between neutral-pair and ion-pair states over an ensemble of structures generated from molecular dynamics simulations. Invoking a Marcus-type two-sphere model for charge separation and recombination in an aqueous environment, we explored the effect of a polarizable force field and noted a strong reduction of lambda(s) (by similar to 45%) compared to the corresponding value obtained with a standard nonpolarizable force field. Both types of force fields yield lambda(s) values that in agreement with the Marcus theory, vary strictly linearly with the inverse of the donor-acceptor distance; the corresponding slopes translate into appropriate effective optical dielectric constants, epsilon(infinity)approximate to 1.0 +/- 0.2 for a nonpolarizable and epsilon(infinity)approximate to 1.7 +/- 0.4 for a polarizable force field. The reduction in the solvent reorganization energy due to a polarizable force field translates into a scaling factor that is essentially independent of the donor-acceptor distance. The corresponding effective optical dielectric constant, epsilon(infinity)approximate to 1.80, is in excellent agreement with experiment for water.
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