Electron transfer from the excited electronic singlet state of chemisorbed ruthenium(II) cis-di(isothiocyanato)bis(2,2‘-bipyridyl-4,4‘-dicarboxylate) into empty electronic states in a colloidal anatase TiO2 film was measured as a transient absorption signal of the injected hot electrons with a rise time <25 fs. Optical absorption of the anchored dye molecules led to the excited singlet state of the dye with a small admixture of charge transfer states. The electron transfer reaction reported here did not involve redistribution of vibrational excitation energy and was thus completely different from the well-known Marcus−Levich−Jortner−Gerischer type of electron transfer in the case of weak electronic interaction. It was also not a direct optical charge transfer transition from the donor to the acceptor level but rather an electron transfer reaction with an ultrashort but finite reaction time.

Electronic properties of dye-sensitized semiconductor nanocrystals, consisting of perylene (Pe) chromophores attached to 2 nm TiO2 nanocrystals via different anchor-cum-spacer groups, have been studied theoretically using density functional theory (DFT) cluster calculations. Approximate effective electronic coupling strengths for the heterogeneous electron-transfer interaction have been extracted from the calculated electronic structures and are used to estimate femtosecond electron-transfer times theoretically. Results are presented for perylenes attached to the TiO2 via formic acid (Pe-COOH), propionic acid (Pe-CH2-CH2-COOH), and acrylic acid (Pe-CH [Formula: see text] CH-COOH). The calculated electron transfer times are between 5 and 10 fs with the formic acid and the conjugated acrylic acid bridges and about 35 fs with the saturated propionic acid bridge. The calculated electron injection times are of the same order of magnitude as the corresponding experimental values and qualitatively follow the experimental trend with respect to the influence of the different substitutions on the injection times.

Modified perylene chromophores were adsorbed with virtually constant reaction distance on the surface of a spongelike TiO2 electrode. Interfacial electron transfer was probed with femtosecond resolution in ultrahigh vacuum via transient absorption and fluorescence up-conversion measurements. Identical time constants were measured for the decay of the reactant and rise of the product states. The dominant fast time constant was 190 fs. It remained constant between 300 and 22 K.

The essential role of the dark equilibrium potential is discussed for charge separation and the photovoltaic functioning of the title cell. A quantitative model is presented for the potential distribution in the sponge-type title cell. The unique screening process for the photogenerated electrons is discussed that facilitates their extremely long lifetime since the screening ions cannot function as recombination centers. A general analogy is pointed out for the photovoltaic functioning of the sponge-type electrochemical solar cell and of a conventional single-crystal solid-state solar cell. † Parts of this letter have been presented as an invited talk at the Spring