A molecular theory of electron transfer reactions in polar liquids

Abstract

Outer sphere and inner sphere electron transfer reactions in the solvent of hard spheres with permanent dipoles are considered. The solvent reorganization energy has been shown to be the sum of the reorganization energy of reorientation of the permanent dipoles and the reorganization energy of changes in coordinates of solvent molecules. Analytical expressions for both contributions have been obtained. The free energy of activation appears to be temperature dependent, which can result in a negative activation enthalpy.