title: Nonadiabatic molecular dynamics study of the cis-trans photoisomerization of azobenzene excited to the S1 state.
abstract: Ab initio nonadiabatic dynamics simulations of cis-to-trans isomerization of azobenzene upon S(1) (n-π*) excitation are carried out employing the fewest-switches surface hopping method. Azobenzene photoisomerization occurs purely as a rotational motion of the central CNNC moiety. Two nonequivalent rotational pathways corresponding to clockwise or counterclockwise rotation are available. The course of the rotational motion is strongly dependent on the initial conditions. The internal conversion occurs via an S(0)/S(1) crossing seam located near the midpoint of both of these rotational pathways. Based on statistical analysis, it is shown that the occurrence of one or other pathway can be completely controlled by selecting adequate initial conditions.
authors.affiliation: J. Heyrovský Institute of Physical Chemistry, Academy of Sciences of the Czech Republic, vvi, Prague, Czech Republic.
authors.forename: Marek
authors.initials: M
authors.lastname: Pederzoli
authors.forename: Jiří
authors.initials: J
authors.lastname: Pittner
authors.forename: Mario
authors.initials: M
authors.lastname: Barbatti
authors.forename: Hans
authors.initials: H
authors.lastname: Lischka
mesh_terms: D001391:Azo Compounds / Q000737:chemistry*; D056004:Molecular Dynamics Simulation; D015394:Molecular Structure; D055668:Photochemical Processes; D011789:Quantum Theory; D012399:Rotation; D013237:Stereoisomerism; D013499:Surface Properties
chemical_list: D001391:Azo Compounds; C009850:azobenzene