Advanced dielectric continuum models of solvation, their connection to microscopic solvent models, and application to electron transfer reactions

Some recent advances in dielectric continuum models for static and dynamic aspects of molecular solvation an discussed, and connections with molecular-level solvent models are noted. The traditional Born-Onsager-Kirkwood (BKO) model is compared to a more flexible model (the so-called frequency-resolved cavity model (FRCM)) which assigns distinct inner and outer solute cavities in accommodating, respectively, the inertialess (optical) and inertial solvent response. Sample calculations of solvent reorganization energy (lambda(s)) are presented for various thermal and optical electron transfer (ET) processes, based on self-consistent reaction field models using molecular orbital (MO) or configuration interaction (CI) solvent wave functions.