Abstract
Analytical expressions for the Born solvation free energy (BSFE) of a pair of ions with arbitrary charges, unequal sizes, and fixed separation are obtained via an interaction-site approach under the mean spherical approximation (MSA). The results for ions in a dipolar dumbbell solvent, in a dipolar hard-sphere solvent, and in an ionic solution in a dielectric continuum solvent are compared. A general equation for the reorganization free energy in a fluid of nonpolarizable molecules indicates that a state-dependent force constant and a non-parabolic free-energy surface will be obtained if a nonlinear theory instead of the MSA is used. It is found that the Marcus cross relation is very accurate within the MSA and the dielectric Green function theory. Results for the Fe +2-Fe +3 electron transfer reaction are qualitatively compared with recent simulation results. An analytical expression (under the MSA) for the average relaxation time that characterizes the response of the solvent to charge transfer between the ions is also obtained.
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