Ultrafast heterogeneous electron transfer reactions: comparative theoretical studies on time- and frequency-domain data.

Recent theoretical studies on linear absorption spectra of dye-semiconductor systems [perylene attached to nanostructured TiO2, L. Wang et al., J. Phys. Chem. B 109, 9589 (2005)] are extended here in different respects. Since the systems show ultrafast photoinduced heterogeneous electron transfer the time-dependent formulation used to compute the absorbance is also applied to calculate the temporal evolution of the sub-100 fs charge injection dynamics after a 10 fs laser-pulse excitation. These studies complement our recent absorption spectra fit for two perylene bridge-anchor group TiO2 systems. Moreover, the time-dependent formulation of the absorbance is confronted with a frequency-domain description. The latter underlines the central importance of the self-energy caused by the coupling of the dye levels to the semiconductor band continuum. The used model is further applied to study the effect of different parameters such as (1) the dependence on the reorganization energies of the involved intramolecular transitions, (2) the effect of changing the transfer integral which couples the excited dye state with the band continuum, and (3) the effect of the concrete form of the semiconductor band density of states. Emphasis is also put on the case where the charge injection level of the dye is near or somewhat below the band edge. This nicely demonstrates the change from a structureless absorption to a well-resolved vibrational progression including characteristic shifts of the absorption lines which are a direct measure for the dye-semiconductor coupling.