Quantum dynamical simulation of ultrafast photoinduced electron transfer processes in a mixed-valence compound

Accurate quantum dynamical simulations are performed to study photoinduced electron transfer (ET) reactions in a mixed-valence compound in solution. Applying the self-consistent hybrid method to a model that is based on the analysis of optical line shapes by Barbara and coworkers, we investigate the dynamics of the back ET after photoexcitation. The simulation reveals that both the coupling to intramolecular vibrational modes and solvation dynamics have significant effects on the ET process, resulting in oscillatory features of the population decay and a dynamic solvent effect. Conventional approximate methods based on perturbation theory fail to describe the ET process.