title: Enhanced photoswitching of bridged azobenzene studied by nonadiabatic ab initio simulation.
abstract: Photoisomerization of a bridged azobenzene derivative (AB-C(2)) is studied by nonadiabatic ab initio molecular dynamics simulation. The effect of the alkyl bridge linking the two phenyl rings on the Z → E and E → Z photoisomerization pathways and efficiencies is analyzed by detailed comparison to the unbridged parent compound. It is found that the bridge makes E → Z photoisomerization considerably faster and increases its quantum yield, whereas Z → E photoswitching is slightly hindered and has a significantly lower quantum yield although still being ultrafast. The simulations reveal that unsuccessful Z → E photoisomerization attempts can interconvert two pro-enantiomeric forms of Z-AB-C(2) via pseudorotation in the excited electronic state.
authors.affiliation: Lehrstuhl für Theoretische Chemie, Ruhr-Universität Bochum, 44780 Bochum, Germany.
authors.forename: Marcus
authors.initials: M
authors.lastname: Böckmann
authors.forename: Nikos L
authors.initials: NL
authors.lastname: Doltsinis
authors.forename: Dominik
authors.initials: D
authors.lastname: Marx
mesh_terms: D001391:Azo Compounds / Q000737:chemistry*; D008958:Models, Molecular; D008968:Molecular Conformation; D055668:Photochemical Processes; D011789:Quantum Theory; D013237:Stereoisomerism
chemical_list: D001391:Azo Compounds; C009850:azobenzene