Multistate continuum theory for multiple charge transfer reactions in solution

Abstract

In this article we present a multistate continuum theory for multiple charge transfer reactions such as proton-coupled electron transfer and multiple proton transfer reactions. The solute is described with a multistate valence bond model, the solvent is represented as a dielectric continuum, and the transferring protons are treated quantum mechanically. This theory provides adiabatic free energy surfaces that depend on a set of scalar solvent variables corresponding to the individual charge transfer reactions. Thus this theory is a multidimensional analog of standard Marcus theory for single charge transfer reactions. For processes involving significant inner-sphere (i.e., solute) reorganization, the effects of solute intramolecular vibrations can be incorporated into the adiabatic free energy surfaces. The input quantities required for this theory are gas phase valence bond matrix elements fit to standard quantum chemistry calculations and solvent reorganization energy matrix elements calculated with standard continuum electrostatic methods. The goal of this theory is to provide insight into the underlying fundamental physical principles dictating the mechanisms and rates of multiple charge transfer reactions.