Coherent vibrational dynamics during ultrafast photoinduced electron-transfer reactions: quantum dynamical simulations within multilevel Redfield theory

Multilevel Redfield theory is employed in order to rationalize the origin of vibrational coherences arising during ultrafast photoinduced electron-transfer (ET) reactions in polyatomic systems. After a photoexcitation to a locally-excited state, relaxation to the ground state is supposed to occur via an intermediate charge-transfer state. Stationary and nonstationary initial conditions are considered. It is shown that wave-packet motion in the ground state may be initialized not only by the laser excitation, but also by the reaction itself. (C) 2003 Elsevier B.V. All rights reserved.