A dynamical theory of unimolecular ionic dissociation reactions in polar solvents

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Abstract
A dynamical theory for the rates of unimolecular dissociations in polar solvents is constructed. Two classes of dissociation reactions, with dipolar and ionic transition states, are considered, and the theory is illustrated for a generalized continuum model water solvent. The rate of charge variation along the reaction coordinate is found to play a central role. Deviations from equilibrium solvation transition state theory predictions are found and discussed. Two nonequilibrium solvation regimes—nonadiabatic solvation and polarization caging—occur, and their appearance is connected to whether the solvated transition state has a reactant-like or product-like charge distribution.

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