Abstract

The influence of the solvent on the dynamics of reactive processes continues to be of great interest.^1,2 The past decade has seen a substantial increase in our understanding of the effect of solvent friction on activated barrier crossing processes. Less well understood is the role of the solvent in reactions for which there is no potential energy barrier separating reactant from products.³ An example of a barrierless process is the isomerization of stilbene. Isomerization from either the cis or trans side of this molecule involves a twisted intermediate which rapidly internally converts to the ground state. The lack of a barrier along the the torsional coordinate on the cis side leads to extremely rapid cis-trans isomerization rates.

© 1990 Optical Society of America