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Author Perng, B. ♦ Newton, M. D. ♦ Raineri, F. O. ♦ Friedman, H. L.
Source United States Department of Energy Office of Scientific and Technical Information
Content type Text
Language English
Subject Keyword CHEMISTRY ♦ SOLUTIONS ♦ INTERACTIONS ♦ WATER ♦ CHARGE EXCHANGE ♦ STATISTICAL MECHANICS ♦ SOLVATION ♦ FREE ENERGY ♦ CORRELATION FUNCTIONS ♦ CARBON TETRACHLORIDE ♦ AQUEOUS SOLUTIONS ♦ SOLVENTS ♦ DIPOLE INTERACTIONS
Abstract We apply the theories developed in the preceding paper (paper I) to calculate various energy quantities of charge transfer (CT) reactions in nine solvents that cover a wide range of polarity, and for which interaction site models (ISM{close_quote}s) may be found in the literature. Besides the two surrogate Hamiltonian theories developed in paper I, the renormalized site-density theory (RST) and the renormalized dielectric theory (RDT), we also investigate a simple harmonic approximation (HXA) for the diabatic free energy profiles, whose characteristic parameters are calculated taking specific advantage of the expression given by the extended reference interaction site method (XRISM) for the free energy of solvation. For each CT process we analyze (a) the solvent reorganization energy {lambda}, (b) the shift of the absorption transition energy due to the solvatochromic effect, and (c) the solvent contribution to the free energy change {Delta}{ital A}. In addition, for a few selected examples, we also report the detailed diabatic free energy profiles. The calculations reported rely on solute{endash}solvent and solvent{endash}solvent pair correlation functions obtained with the XRISM integral equation method applied to nonpolarizable (with fixed mean partial charges) ISM representations of the solute and solvent molecules. To rectify the omission of the solvent electronic degrees of freedom, we correct the dielectric part of the solvent reorganization energy with an additive term designed to compensate for the use of fixed charge ISM models. Contact with theories in which the solvent is represented as a dielectric continuum medium (with or without spatial dispersion) and the solute as a set of charges inside spherical cavities carved out of the dielectric is made straightforwardly within the RDT theory by considering a particularly simple form of the solute{endash}solvent RISM site{endash}site direct correlation functions. (Abstract Truncated)
ISSN 00219606
Educational Use Research
Learning Resource Type Article
Publisher Date 1996-05-01
Publisher Department Brookhaven National Lab. (BNL), Upton, NY (United States)
Publisher Place United States
Journal Journal of Chemical Physics
Volume Number 104
Issue Number 18
Organization Brookhaven National Lab. (BNL), Upton, NY (United States)


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