EQUILIBRIUM AND NONEQUILIBRIUM SOLVATION AND SOLUTE ELECTRONIC-STRUCTURE .4. QUANTUM-THEORY IN A MULTIDIABATIC STATE FORMULATION

A theory of the solute electronic structure for chemical reaction systems in solution [Kim H. J., Hynes, J. T. J. Chem. Phys. 1992, 96, 5088], in terms of a solute description via two chemically relevant valence bond (VB) states and a dielectric continuum solvent model, is generalized to account for more than two solute VB states. This extension is required for a number of important solution reaction systems. The electronic polarization of the solvent is quantized via a coherent states treatment, and its orientational polarization spans both nonequilibrium and equilibrium solvation regimes. The nonlinear Schrodinger equation and system free energy are obtained in a solvent coordinates framework.