Stochastic-Liouville approach to optically induced electron transfer: electronic coherence in the reaction dynamics

Abstract

Electron transfer (ET) dynamics in the excited state were investigated theoretically by means of the stochastic-Liouville equation. Time dependences of both the diagonal and off-diagonal elements of the density matrix of the three electronic states, the ground state, locally excited (LE) state and the charge-transfer (CT) state, were evaluated by solving the equation numerically. The formalism includes three major effects in the ET dynamics simultaneously: optical transition, electronic interaction between the LE and CT states and solvation dynamics. From results of the numerical calculation, roles of the electronic coupling and solvation dynamics in ET and effects of the electronic coherence created by the optical excitation on ET are discussed. Application of the present method to non-linear optical spectroscopy in briefly considered. Copyright © 2000 John Wiley & Sons, Ltd.