Photoisomerization for a model protonated Schiff base in solution: Sloped/peaked conical intersection perspective
- Instituto de Fisica, Universidade de Sao Paulo, CP 66318, 05314-970 Sao Paulo, SP (Brazil)
- Department of Chemistry and Biochemistry, University of Colorado, Boulder, Colorado 80309-0215 (United States)
The topographical character of conical intersections (CIs)-either sloped or peaked-has played a fundamental and important role in the discussion of the efficiency of CIs as photochemical 'funnels.' Here this perspective is employed in connection with a recent study of a model protonated Schiff base (PSB) cis to trans photoisomerization in solution [Malhado et al., J. Phys. Chem. A 115, 3720 (2011)]. In that study, the calculated reduced photochemical quantum yield for the successful production of trans product versus cis reactant in acetonitrile solvent compared to water was interpreted in terms of a dynamical solvent effect related to the dominance, for the acetonitrile case, of S{sub 1} to S{sub 0} nonadiabatic transitions prior to the reaching the seam of CIs. The solvent influence on the quantum yield is here re-examined in the sloped/peaked CI topographical perspective via conversion of the model's two PSB internal coordinates and a nonequilibrium solvent coordinate into an effective branching space description, which is then used to re-analyze the generalized Langevin equation/surface hopping results. The present study supports the original interpretation and enriches it in terms of topographical detail.
- OSTI ID:
- 22099136
- Journal Information:
- Journal of Chemical Physics, Vol. 137, Issue 22; Other Information: (c) 2012 American Institute of Physics; Country of input: International Atomic Energy Agency (IAEA); ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
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