title: Photodissociation dynamics of the pyridinyl radical: Time-dependent quantum wave-packet calculations.
abstract: The H-atom photodissociationreaction from the pyridinyl radical (C5H5NH) via the low-lying πσ*excited electronic state is investigated by nonadiabatic time-dependent quantum wave-packet dynamics calculations. A model comprising three electronic states and three nuclear coordinates has been constructed using ab initio multi-configurational self-consistent-field and multi-reference perturbation theory methods. Two conical intersections among the three lowest electronic states have been characterized in the framework of the linear vibronic-coupling model. Time-dependent wave-packet simulations have been performed using the multi-configuration time-dependent Hartree method. The population dynamics of the diabatic and adiabatic electronic states and the time-dependent dissociation behavior are analyzed for various vibrational initial conditions. The results provide detailed mechanistic insight into the photoinduced H-atom dissociation process from a hypervalent aromatic radical and show that an efficient dissociationreaction through two conical intersections is possible.
authors.affiliation: Department of Chemistry, Technical University of Munich, D-85748 Garching, Germany.
authors.forename: Johannes
authors.identifier: 0000000225472640
authors.initials: J
authors.lastname: Ehrmaier
authors.affiliation: Department of Chemistry, Technical University of Munich, D-85748 Garching, Germany.
authors.forename: David
authors.initials: D
authors.lastname: Picconi
authors.affiliation: Department of Chemistry, Technical University of Munich, D-85748 Garching, Germany.
authors.forename: Tolga N V
authors.identifier: 0000000205833824
authors.initials: TN
authors.lastname: Karsili
authors.affiliation: Department of Chemistry, Technical University of Munich, D-85748 Garching, Germany.
authors.forename: Wolfgang
authors.initials: W
authors.lastname: Domcke