Outer sphere electron transfer in polar solvents. Activationless and inverted regimes

Abstract

In this paper we apply the stochastic Liouville equation for the study of outer sphere electron transfer (ET) in a polar solvent, which is characterized by a Debye dielectric relaxation. Explicit expressions, which bridge between the nonadiabatic and solvent-controlled adiabatic limits, are derived for the ET rates spanning a broad range of the energetic parameters, which include normal ET, activationless ET, and ET in the inverted region. The many-body result for the ET rate, which is accurate for symmetric ET, constitutes a useful approximate interpolation formula, which accounts well for the ET dynamics over a broad range of the energetic parameters.