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

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. For the weakly-adiabatic reactions, the reaction follows an adiabaticity criterion in the presence of a sharp barrier. In contrast to the nonadiabatic 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.