TY  - JOUR
AU  - Ruckenbauer, Matthias
AU  - Barbatti, Mario
AU  - Müller, Thomas
AU  - Lischka, Hans
TI  - Nonadiabatic Photodynamics of a Retinal Model in Polar and Nonpolar Environment
JO  - The journal of physical chemistry  / A
VL  - 117
IS  - 13
SN  - 1520-5215
CY  - Washington, DC
PB  - Soc.
M1  - FZJ-2014-02945
SP  - 2790 - 2799
PY  - 2013
AB  - 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.
LB  - PUB:(DE-HGF)16
UR  - <Go to ISI:>//WOS:000317317300014
C6  - pmid:23470211
DO  - DOI:10.1021/jp400401f
UR  - https://juser.fz-juelich.de/record/153302
ER  -