Viscosity dependence and solvent effects in the photoisomerization of cis-stilbene:: Insight from a molecular dynamics study with an ab initio potential-energy function

Molecular-dynamics simulations of the photoisomerization of cis-stilbene in supercritical argon were performed. The stilbene molecule is represented by ab initio quantum chemistry, while the solvent, the interaction with solvent, and the time evolution were described by classical mechanics. Reaction rate constants are estimated and their dependence on temperature, pressure, and viscosity are investigated. Agreement with available experimental data was obtained. Our simulations strongly suggest a minimum on the excited-state potential-energy surface at a gauche conformation which is very rapidly reached after excitation, which leads to nonequilibrium barrier transitions. Specific solvent effects were identified. Implications on the current opinion on stilbene photoisomerization are discussed. (C) 1999 American Institute of Physics. [S0021-9606(99)50243-2].