On transition path times for condensed-phase non-adiabatic electron transfer reactions under a two-parabola model

Abstract

Condensed-phase non-adiabatic electron transfer (ET) reactions play an important role in various areas of science. The characteristics of the microscopic transition processes involved in these reactions and their dynamic behavior remain poorly understood. In this study, we performed non-adiabatic simulations based on the Zhu-Nakamura theory, combining the two-parabola model with Kramers-like Langevin dynamics. We numerically analyzed the dependence of the macroscopic reaction time and the timescale of the microscopic transition process on the diabatic coupling between the diabatic states and on the friction parameter in Langevin dynamics. Although the microscopic transfer process is generally regarded as instantaneous in the non-adiabatic regime, we found that the timescale of the microscopic transition process can still be a non-negligible fraction of the macroscopic reaction time.