Theory of Electron-Transfer Reaction Rates of Solvated Electrons

Abstract

A theory of electron‐transfer reactions of solvated electrons is described. Using an electron‐transfer theory formulated elsewhere and using polaron theory the rate constant is related to the standard reduction potentials of the two reactants, spectral and other data for the solvated electron, and rate data on ordinary chemical or electrochemical electron‐transfer reactions of the second reactant. This calculated rate constant appears in a boundary condition in a diffusion‐reaction differential equation. When that constant is high the reaction becomes diffusion controlled, but when the constant is low it becomes the observed rate constant itself. Some comparison is made with existing data. Conditions for possible but as yet unobserved chemiluminescence are also considered. Solvent‐electron polarization in the vicinity of a solvated electron is also examined, by application of polaron theory for a high lattice frequency continuum.