Continuous medium theory for nonequilibrium solvation: IV. Solvent reorganization energy of electron transfer based on conductor-like screening model.

In this work the authors present some evidences of defects in the popular continuous medium theories for nonequilibrium solvation. Particular attention has been paid to the incorrect reversible work approach. After convincing reasoning, the nonequilibrium free energy has been formulated to an expression different from the traditional ones. In a series of recent works by the authors, new formulations and some analytical application models for ultrafast processes were developed. Here, the authors extend the new theory to the cases of discrete bound charge distributions and present the correct form of the nonequilibrium solvation energy in such cases. A numerical solution method is applied to the evaluation of solvent reorganization energy of electron transfer. The test calculation for biphenyl–cyclohexane–naphthalene anion system achieves excellent agreement with the experimental fitting. The central importance presented in this work is the very simple and a consistent form of nonequilibrium free energy for both continuous and discrete charge distributions, based on which the new models can be established. © 2005 Wiley Periodicals, Inc. J Comput Chem 27: 368–374, 2006 [ABSTRACT FROM AUTHOR]