Test of theoretical models for ultrafast heterogeneous electron transfer with femtosecond two-photon photoemission data

The energy distribution of electrons injected into acceptor states on the surface of TiO2 was measured with femtosecond two-photon photoemission. Shape and relative energetic position of these distribution curves with respect to the corresponding donor states, i.e. of perylene chromophores in the first excited singlet state attached via different bridge-anchor groups to the TiO2 surface, were compared with the predictions of different theoretical models for light-induced ultrafast heterogeneous electron transfer (HET). Gerischer's early scenario for light-induced HET was considered and two recent explicit calculations, i.e. a fully quantum mechanical analytical model and a time-dependent density functional theory model based on molecular dynamics simulations for the vibrational modes were also considered. Based on the known vibrational structure in the photoionization spectrum of perylene in the gas phase and that measured in the linear absorption spectra of the perylene chromophores anchored on the TiO2 surface the energy distribution curves for the injected electrons were fitted assuming the excitation of the dominant 0 center dot 17 eV vibrational mode in the ionized perylene chromophore leading to a corresponding Franck-Condon dictated progression in the energy distribution curves. Each individual peak was fitted with a Voigt profile where the Lorentzian contribution was taken from the time-resolved HET data and the Gaussian contribution attributed to inhomogeneous broadening. The measured room temperature energy distribution curves for the injected electrons are explained with the fully quantum mechanical model for light-induced HET with the high energy, 0 center dot 17 eV, skeletal stretching mode excited in the ionized perylene chromophore. The corresponding energy distribution of the injected electrons is fully accommodated in acceptor states on the TiO2 surface fulfilling the wide band limit.