Optically Induced Electron Transfer in Mixed-Valence States: A Model Study on Electronic Transitions, Relaxation...

Quantum dynamical model calculations are performed on the optically induced electron transfer in a mixed-valence system interacting with different solvents. The simultaneously occurring processes of population transfer between electronic states and relaxation are studied in detail. Transient absorption traces, as recently recorded in our laboratory, are simulated, and the features of the spectra are related to the dynamics. The agreement with the experiment hints at the fact that the employed one-dimensional models catch the essentials of the photochemistry of the investigated systems and that they can be used for the interpretation of the transient absorption spectra. It is inferred that the ultrafast electron transfer processes take place on a sub-picosecond time scale and afterward relaxation occurs within several picoseconds.