Outer-sphere electron-transfer reactions in polar solvents

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Abstract
A model for outer‐sphere electron‐transfer reactions in polar solutions is suggested. It is based on the idea of dividing the system into two subsystems, a classical solvent and quantum mechanical interacting molecules. The solvent is looked upon as the source of an external field and is coupled parametrically to the reacting species. The model is analytically solved, under some approximations, for the transfer probability. Using a specific macroscopic model of the solvent a usable expression for the rate constant is given. Operational and physical criteria are developed regarding the problems of adiabaticity, nonadiabaticity, and independence on the solvent dynamics.

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