Nonequilibrium solvation theory: Comparison, modification and application

Abstract

Faults existing in the current theories of nonequilibrium solvation have been clarified in this report. Based on a novel expression of solvation free energy for nonequilibrium, generalized formulations of solvent reorganization energy for electron transfer and of solvation shift for spectrum have been established. Furthermore, a new form of solvent reorganization energy for electron transfer in two-sphere case, which greatly differs from the one by Marcus, has been deduced. A single-sphere model for solvation shift of spectrum has been put forward both by deducing the generalized formulations and by showing the correct forms of self-energy of reaction field. It has been concluded that the current theories overestimate the solvent reorganization energy and the solvation shift by a factor of about 2. By applying the models established, the discrepancies between the theory and experiments before have been perfectly explained.