Solution reaction path Hamiltonian for reactions in polar solvents. II. Applications

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Abstract
The solution reaction path Hamiltonian (SRPH) developed in the previous paper is applied to model SN2 and ionic dissociation reactions in water solvent. The solution reaction paths are determined and show marked deviations from a standard equilibrium solvation picture. The impact of potential anharmonicities, reaction path curvature, and varying solvent mass on the rate constant is calculated via the variational transition state theory approach of I, and the deviations from harmonic van der Zwan–Hynes (ZH) theory are calculated. Typically only minor deviations from ZH theory are found. The reasons for this are discussed.