Solution reaction path Hamiltonian for reactions in polar solvents. I. Formulation

Abstract

A solution reaction path Hamiltonian (SRPH) is constructed for heavy particle charge transfer reactions in a nondissipative polar solvent. This formulation includes anharmonicities arising from, e.g., potential anharmonicity and reaction path curvature. The SRPH is used in conjunction with variational transition state theory (VTST) to obtain an expression for the reaction rate constant. This expression generalizes the van der Zwan–Hynes rate theory to include the influence of anharmonic effects as well as nonequilibrium solvation. A discussion of the reaction path in solution and its departure from an equilibrium solvation perspective is given.