title: Cooperating Dinitrogen and Phenyl Rotations in trans-Azobenzene Photoisomerization.
abstract: Semiempirical OM2/MRCI surface-hopping simulations have been performed to study the trans-to-cis photoisomerization of azobenzene upon excitation to the S1 state. The decay dynamics to the ground state shows an oscillatory pattern that can be attributed to an out-of-plane rotation of the N2 moiety. The reaction is thus initially driven by N2 rotation which triggers phenyl rotations around the C-N bonds. The cis isomer is produced most effectively when the phenyl rings rotate in phase. Mode-specific excitations cause variations in the computed decay times and product yields.
authors.affiliation: Max-Planck-Institut für Kohlenforschung , Kaiser-Wilhelm-Platz 1, 45470 Mülheim an der Ruhr, Germany.
authors.forename: José A
authors.initials: JA
authors.lastname: Gámez
authors.affiliation: Institut für Theoretische Chemie und Computerchemie, Heinrich-Heine-Universität Düsseldorf , Universitätsstrasse 1, 40225 Düsseldorf, Germany.
authors.forename: Oliver
authors.initials: O
authors.lastname: Weingart
authors.affiliation: Max-Planck-Institut für Kohlenforschung , Kaiser-Wilhelm-Platz 1, 45470 Mülheim an der Ruhr, Germany.
authors.forename: Axel
authors.initials: A
authors.lastname: Koslowski
authors.affiliation: Max-Planck-Institut für Kohlenforschung , Kaiser-Wilhelm-Platz 1, 45470 Mülheim an der Ruhr, Germany.
authors.forename: Walter
authors.initials: W
authors.lastname: Thiel