Photoinduced electron transfer processes in dye-semiconductor systems with different spacer groups

Photoinduced electron transfer processes in perylene-titanium dioxide dye-semiconductor systems are studied. In particular, the influence of saturated and unsaturated aliphatic spacer groups inserted between the chromophore and the semiconductor substrate is investigated. The study is based on a recently developed method that combines first-principles electronic structure calculations to characterize the dye-semiconductor systems and accurate multilayer multiconfiguration time-dependent Hartree simulations to reveal the underlying nonadiabatic dynamics. The results show that, in agreement with previous experimental studies, the spacer groups may affect the electron transfer dynamics significantly. Furthermore, the influence of electronic-vibrational coupling on the electron transfer dynamics and absorption spectra is discussed.