VARIATIONAL TRANSITION-STATE THEORY FOR ACTIVATED CHEMICAL-REACTIONS IN SOLUTION

An approach is outlined for including solvent effects in variational t ransition state theory calculations of rate constants for activated ch emical reactions in solution. The focus is on methods capable of first -principles predictions of reaction rate constants from interatomic po tential energy surfaces. The approach separates the system into a clus ter model that is treated explicitly and the 'solvent' that is treated approximately, and includes both equilibrium solvation effects on int eraction energies and non-equilibrium effects that enter through a sol vent friction model. We discuss methods used to included quantum-mecha nical effects on bound vibrational motions and quantum-mechanical effe cts on motion along a reaction coordinate (e.g. quantum tunnelling).