Get access

Conical intersection structure and dynamics for a model protonated schiff base photoisomerization in solution

Authors

  • João Pedro Malhado,

    1. Departement de Chimie, CNRS UMR 8640 PASTEUR, École Normale Supérieure, 24 rue Lhomond 75005 Paris, France
    Search for more papers by this author
  • Riccardo Spezia,

    1. Laboratoire Analyse et Modélisation pour la Biologie et l'Environement, CNRS UMR 8587, Université d'Évry Vald'Essonne, Bd. F. Mitterrand, 91025 Évry, France
    Search for more papers by this author
  • James T. Hynes

    Corresponding author
    1. Department of Chemistry and Biochemistry, University of Colorado, Boulder, Colorado 80309-0215
    2. Département de Chimie, CNRS UMR 8640 PASTEUR, École Normale Supérieure, 24 rue Lhomond, 75005 Paris, France
    • Department of Chemistry and Biochemistry, University of Colorado, Boulder, Colorado 80309-0215
    Search for more papers by this author

Abstract

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.

Ancillary