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Journal of Physical Chemistry, Vol.98, No.47, 12103-12107, 1994
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.
Keywords:S(N)1 IONIC DISSOCIATION;ORBITAL WAVE-FUNCTIONS;THEORETICAL-MODEL;FREE-ENERGY;ENERGETICS;COMPLEXES;TERMS