title: State-specific tunneling lifetimes from classical trajectories: H-atom dissociation in electronically excited pyrrole.
abstract: A trajectory method of calculating tunneling probabilities from phase integrals along straight line tunneling paths, originally suggested by Makri and Miller [J. Chem. Phys. 91, 4026 (1989)] and recently implemented by Truhlar and co-workers [Chem. Sci. 5, 2091 (2014)], is tested for one- and two-dimensional ab initio based potentials describing hydrogen dissociation in the (1)B1 excited electronic state of pyrrole. The primary observables are the tunneling rates in a progression of bending vibrational states lying below the dissociation barrier and their isotope dependences. Several initial ensembles of classical trajectories have been considered, corresponding to the quasiclassical and the quantum mechanical samplings of the initial conditions. It is found that the sampling based on the fixed energy Wigner density gives the best agreement with the quantum mechanical dissociation rates.
authors.affiliation: Department of Chemistry, Technical University of Munich, Lichtenbergstr. 4, 85747 Garching, Germany.
authors.forename: Weiwei
authors.initials: W
authors.lastname: Xie
authors.affiliation: Department of Chemistry, Technical University of Munich, Lichtenbergstr. 4, 85747 Garching, Germany.
authors.forename: Wolfgang
authors.initials: W
authors.lastname: Domcke
authors.affiliation: Department of Chemistry, Technical University of Munich, Lichtenbergstr. 4, 85747 Garching, Germany.
authors.forename: Stavros C
authors.initials: SC
authors.lastname: Farantos
authors.affiliation: Department of Chemistry, Technical University of Munich, Lichtenbergstr. 4, 85747 Garching, Germany.
authors.forename: Sergy Yu
authors.initials: SY
authors.lastname: Grebenshchikov