title: Quantum Chemical Calculations of the Influence of Anchor-Cum-Spacer Groups on Femtosecond Electron Transfer Times in Dye-Sensitized Semiconductor Nanocrystals.
abstract: 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.
authors.affiliation: Department of Quantum Chemistry, Uppsala University, Box 518, SE-751 20 Uppsala, Sweden, Materials and Process Simulation Center, Beckman Institute 13974, California Institute of Technology, Pasadena, California 91125, and Hahn-Meitner-Institut, Glienickerstrasse 100, D-14109 Berlin, Germany.
authors.forename: P
authors.initials: P
authors.lastname: Persson
authors.affiliation: Department of Quantum Chemistry, Uppsala University, Box 518, SE-751 20 Uppsala, Sweden, Materials and Process Simulation Center, Beckman Institute 13974, California Institute of Technology, Pasadena, California 91125, and Hahn-Meitner-Institut, Glienickerstrasse 100, D-14109 Berlin, Germany.
authors.forename: M J
authors.initials: MJ
authors.lastname: Lundqvist
authors.affiliation: Department of Quantum Chemistry, Uppsala University, Box 518, SE-751 20 Uppsala, Sweden, Materials and Process Simulation Center, Beckman Institute 13974, California Institute of Technology, Pasadena, California 91125, and Hahn-Meitner-Institut, Glienickerstrasse 100, D-14109 Berlin, Germany.
authors.forename: R
authors.initials: R
authors.lastname: Ernstorfer
authors.affiliation: Department of Quantum Chemistry, Uppsala University, Box 518, SE-751 20 Uppsala, Sweden, Materials and Process Simulation Center, Beckman Institute 13974, California Institute of Technology, Pasadena, California 91125, and Hahn-Meitner-Institut, Glienickerstrasse 100, D-14109 Berlin, Germany.
authors.forename: W A
authors.initials: WA
authors.lastname: Goddard
authors.affiliation: Department of Quantum Chemistry, Uppsala University, Box 518, SE-751 20 Uppsala, Sweden, Materials and Process Simulation Center, Beckman Institute 13974, California Institute of Technology, Pasadena, California 91125, and Hahn-Meitner-Institut, Glienickerstrasse 100, D-14109 Berlin, Germany.
authors.forename: F
authors.initials: F
authors.lastname: Willig