One approach to calculating the solvent reorganization energy of intramolecular electron transfer

On the basis of the electromagnetic field theory and the spherical cavity approximation, the expressions of Gibbs free energies under equilibrium and non-equilibrium solvation conditions are obtained by solving the electrostatic potential equations with boundary conditions. The surface charges produced by the orientational polarization of equilibrium solvation are taken fixed in the case of non-equilibrium situation, for the slow-response of the orientational polarization to electron transfer of the solvent molecules. A new expression of solvent reorganization energy has been obtained and this method is applied to the electron transfer systems, NO+/NO, NO 2 + /NO2, and NO 2 + /NO. The solvent reorganization energies have been evaluated.