Implication of Barrier Fluctuations on the Rate of Weakly Adiabatic Electron Transfer

TL;DR

This paper investigates how fluctuations in a cusp-shaped barrier affect the escape rate of a Brownian particle, providing insights into electron transfer reactions in fluctuating environments.

Contribution

It introduces a model for escape over a dichotomously fluctuating barrier, linking barrier fluctuations to electron transfer rates in weakly-adiabatic conditions.

Findings

Barrier fluctuations significantly influence escape times.

Medium dynamics alter electron transfer kinetics.

Model applicable to high-temperature condensed media.

Abstract

The problem of escape of a Brownian particle in a cusp-shaped metastable potential is of special importance in nonadiabatic and weakly-adiabatic rate theory for electron transfer (ET) reactions. Especially, for the weakly-adiabatic reactions, the reaction follows an adiabaticity criterion in the presence of a sharp barrier. In contrast to the non-adiabatic case, the ET kinetics can be, however considerably influenced by the medium dynamics. In this paper, the problem of the escape time over a dichotomously fluctuating cusp barrier is discussed with its relevance to the high temperature ET reactions in condensed media.