title: Nonadiabatic photodynamics of a retinal model in polar and nonpolar environment.
abstract: The nonadiabatic photodynamics of the all-trans-2,4-pentadiene-iminium cation (protonated Schiff base 3, PSB3) and the all-trans-3-methyl-2,4-pentadiene-iminium cation (MePSB3) were investigated in the gas phase and in polar (aqueous) and nonpolar (n-hexane) solutions by means of surface hopping using a multireference configuration-interaction (MRCI) quantum mechanical/molecular mechanics (QM/MM) level. Spectra, lifetimes for radiationless deactivation to the ground state, and structural and electronic parameters are compared. A strong influence of the polar solvent on the location of the crossing seam, in particular in the bond length alternation (BLA) coordinate, is found. Additionally, inclusion of the polar solvent changes the orientation of the intersection cone from sloped in the gas phase to peaked, thus enhancing considerably its efficiency for deactivation of the molecular system to the ground state. These factors cause, especially for MePSB3, a substantial decrease in the lifetime of the excited state despite the steric inhibition by the solvent.
authors.affiliation: Institute for Theoretical Chemistry, University of Vienna, Währingerstraße 17, 1090 Vienna, Austria.
authors.forename: Matthias
authors.initials: M
authors.lastname: Ruckenbauer
authors.forename: Mario
authors.initials: M
authors.lastname: Barbatti
authors.forename: Thomas
authors.initials: T
authors.lastname: Müller
authors.forename: Hans
authors.initials: H
authors.lastname: Lischka
mesh_terms: D005740:Gases / Q000737:chemistry; D006586:Hexanes / Q000737:chemistry; D008956:Models, Chemical; D015394:Molecular Structure; D011789:Quantum Theory; D012160:Retina / Q000737:chemistry*; D012545:Schiff Bases / Q000737:chemistry*; D014867:Water / Q000737:chemistry
chemical_list: D005740:Gases; D006586:Hexanes; D012545:Schiff Bases; D014867:Water