Premium
Conical intersection structure and dynamics for a model protonated schiff base photoisomerization in solution
Author(s) -
Malhado João Pedro,
Spezia Riccardo,
Hynes James T.
Publication year - 2012
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.24095
Subject(s) - photoisomerization , conical intersection , intramolecular force , protonation , chemistry , ground state , solvent , acetonitrile , photochemistry , solvent effects , schiff base , conical surface , chemical physics , molecular physics , computational chemistry , atomic physics , physics , isomerization , geometry , crystallography , mathematics , stereochemistry , organic chemistry , catalysis , ion
Here, we present some highlights of our recent study [Malhado et al. J. Phys. Chem. A 115 , 3729 (2011)] of the photoisomerization involving a conical intersection for a model protonated Schiff base (PSB) in modeled water and acetonitrile solvents, in which the inclusion of energy‐ and momentum‐transfer effects is described via a generalized Langevin equation (GLE) frictional approach and surface‐hopping dynamics. Short‐time GLE frictional effects on the model's three coordinates, the intramolecular bond length alternation, and torsional PSB coordinates and a solvent coordinate, have a number of important features. Among these are the general feature of accelerating nonadiabatic transitions to the ground electronic state and a predicted preferential higher proportion of ground‐state trans isomer, that is, a successful cis to trans photoreaction. This preference is solvent‐dependent and is enhanced in water solvent with its higher friction intensity and short time scales. © 2012 Wiley Periodicals, Inc.