Dynamics of electron transfer reactions in the presence of mode mixing: Comparison of a generalized master equation approach with the numerically exact simulation

Abstract

A generalized master equation approach is developed to describe electron transfer (ET) dynamics in the presence of mode mixing. Results from this approximate approach are compared to the numerically exact simulations using the multilayer multiconfiguration time-dependent Hartree theory. The generalized master equation approach is found to work well for nonadiabatic resonant ET. Depending on the specific situation, it is found that the introduction of mode mixing may either increase or decrease the ET time scale. The master equation fails in the adiabatic ET regime, where the introduction of mode mixing may lead to electron trapping. From both the approximate theory and the numerically exact simulation it is shown how neglecting mode mixing in practical calculations may lead to inaccurate predictions of the ET dynamics.