Solvent Effects on Internal Conversions and Intersystem Crossings: The Radiationless De-Excitation of Acrolein in Water
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- 作者：Aurora Muñ ; oz Losa ; Ignacio Fdez. Galvá ; n ; M. Luz Sá ; nchez ; M. Elena Martí ; n ; Manuel A. Aguilar
- 刊名：Journal of Physical Chemistry B
- 出版年：2008
- 出版时间：January 24, 2008
- 年：2008
- 卷：112
- 期：3
- 页码：877 - 884
- 全文大小：130K
- 年卷期：v.112,no.3(January 24, 2008)
- ISSN：1520-5207
文摘
An extended version of the averaged solvent electrostatic potential from molecular dynamics data (ASEP/MD) method oriented to the study of the solvent effects on internal conversion and intersystem crossingprocesses is presented. The method allows for the location of crossing points between free energy surfacesboth in equilibrium and in frozen solvent conditions. The ground and excited states of the solute moleculeare described at the complete active space self-consistent field (CASSCF) level while the solvent structure isobtained from molecular dynamics simulations. As an application, we studied the nonradiative de-excitationof s-trans-acrolein 1(n 
*) in aqueous solution. We found that the solvent modifies the relative stabilityof the different crossing points but not enough as to alter the relative order of stability with respect to the invacuo situation. The relaxation through an equilibrium path involves a strong solvent reorganization. On thecontrary, the nonequilibrium path does not involve solvent motion and the de-excitation could proceed withthe same speed as in vacuo.
*) in aqueous solution. We found that the solvent modifies the relative stabilityof the different crossing points but not enough as to alter the relative order of stability with respect to the invacuo situation. The relaxation through an equilibrium path involves a strong solvent reorganization. On thecontrary, the nonequilibrium path does not involve solvent motion and the de-excitation could proceed withthe same speed as in vacuo.