VARIATIONAL TRANSITION-STATE THEORY FOR MULTIDIMENSIONAL ACTIVATED RATE-PROCESSES IN THE PRESENCE OF ANISOTROPIC FRICTION

Variational transition state theory (VTST) is applied to the study of the activated escape of a particle trapped in a multidimensional potential well and coupled to a heat bath. Special attention is given to the dependence of the rate constant on the friction coefficients in the case of anisotropic friction. It is demonstrated explicitly that both the traditional as well as the nontraditional scenarios for the particle escape are recovered uniformly within the framework of VTST. Effects such as saddle point avoidance and friction dependence of the activation energy are derived from VTST using optimized planar dividing surfaces.