Journal of Physical Chemistry, Vol.98, No.34, 8396-8405, 1994
Tunneling in the Presence of a Bath - A Generalized Transition-State Theory Approach
In this article we propose a new approximation for incorporating tunneling into variational transition state theory when the critical degrees of freedom are coupled to a bath. The new approximation is based on a canonically averaged mean-shape potential which can be evaluated from the bath contribution to the potential of mean force as a function of temperature. The new approximation is applied to a polyatomic organic reaction in which some low-frequency modes are treated as a bath and to a model reaction in solution.
Keywords:CHEMICAL-REACTION RATES;POTENTIAL-ENERGY SURFACE;MODEL ACTIVATED REACTION;NONEQUILIBRIUM SOLVATION;RATE CONSTANTS;POLYATOMIC-MOLECULES;ELECTRON-TRANSFER;DYNAMICS;APPROXIMATION;CURVATURE