Transition state theory for photoisomerization rates of t r a n s-stilbene in the gas and liquid phases

Abstract

Recently measured isomerization rates of t r a n s‐stilbene and diphenylbutadiene over a very large pressure range indicate that a medium can seemingly increase the rate beyond the gas phase high pressure limit. A model based on a generalized Langevin equation is proposed and solved using transition state theory. Rates obtained are in good agreement with experiment. The model incorporates a solvent shift which lowers the barrier to reaction. The model is based on the unification of two different approaches to the description of a dissipative harmonic bath.