Monte Carlo Simulation Study of Free Energy Curves for Electron Transfer Reactions in Polar Solutions by considering the Electronic Polarizability

Abstract
We have conducted Monte Carlo simulations of polar solutions with a spherical hard core model by properly taking into account the electronic polarizability of solvent molecules. We have calculated the free energy curve as a function of the reaction coordinate of electron transfer reactions in cases where the reactant is neutral and charged. From the analysis of the free energy curvature ratio between the two cases, we have found that the electronic polarizability contributes to enhance the non-linear response of solvent polarizations and that this enhancement is greatly strengthened if the translational motion of solvent molecules is frozen.

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