title: Photodynamics of azomethane: a nonadiabatic surface-hopping study.
abstract: The internal conversion and hot ground-state dynamics of trans- and cis-azomethane starting in the S(1) state have been investigated by nonadiabatic ab initio surface hopping dynamics using MCSCF-GVB-CAS and MRCISD methods and by determining energy minima and saddle points, minima on the crossing seam, and minimum energy pathways on the ground and first excited-state surfaces. The lifetimes and photoproducts from the dynamics simulations, geometric properties, excitation energies of selected stationary points and minimum energy pathways between them are reported. Our results favor a statistical model with trans-AZM moving to the ground-state minima before the first CN dissociation takes place. A detailed discussion in comparison to recent experimental and theoretical data is presented.
authors.affiliation: Institute for Theoretical Chemistry, University of Vienna, Waehringerstrasse 17, A 1090 Vienna, Austria.
authors.forename: Bernhard
authors.initials: B
authors.lastname: Sellner
authors.forename: Matthias
authors.initials: M
authors.lastname: Ruckenbauer
authors.forename: Ivan
authors.initials: I
authors.lastname: Stambolić
authors.forename: Mario
authors.initials: M
authors.lastname: Barbatti
authors.forename: Adelia J A
authors.initials: AJ
authors.lastname: Aquino
authors.forename: Hans
authors.initials: H
authors.lastname: Lischka
mesh_terms: D001391:Azo Compounds / Q000737:chemistry*; D056004:Molecular Dynamics Simulation; D010777:Photochemistry; D011789:Quantum Theory; D013237:Stereoisomerism
chemical_list: D001391:Azo Compounds; C001825:azomethane