title: Ultrafast photoinduced electron transfer at electrodes: the general case of a heterogeneous electron-transfer reaction.
abstract: The general case of a heterogeneous electron-transfer reaction is realized by ultrafast electron transfer from a light-absorbing molecule to a wide continuum of electronic acceptor states, realizing the so-called wide band limit. Experimental data obtained for perylene dye/TiO(2)  systems confirm the predictions of fully quantum mechanical model calculations of the dynamics. The energy distribution of the injected electron shows an energy loss due to excitations of high-energy (quantum) vibrational modes in the ionized perylene moiety. The electron-transfer mechanism is non-adiabatic and the reaction is ultrafast, for example, with a time constant of 9 fs for the COOH anchor-bridge group. The underlying strong coupling of the electronic states to high-energy vibrational modes is a characteristic feature of sensitizer molecules.
authors.affiliation: Department of Chemistry & Biochemistry, University of Delaware, 109 Lammot DuPont Laboratory, Newark, DE 19716, USA. larsg@udel.edu
authors.forename: Lars
authors.initials: L
authors.lastname: Gundlach
authors.forename: Frank
authors.initials: F
authors.lastname: Willig