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• W1985556891 abstract "The predicted dependence of the bimolecular rate constant for outer-sphere electron exchange kex upon the longitudinal relaxation time τL for Debye solvents is examined numerically on the basis of a suitably combined rate formulation in order to examine the manner and extent to which the rate-solvent friction dependence, of particular experimental significance, should be sensitive to the degree of donor–acceptor electronic coupling and related factors. The treatment accounts for the contributions to kex from a spatial distribution of reactant pairs as well as for the effects of donor–acceptor interactions upon the unimolecular rate constant, ket (s−1), for each encounter geometry. The latter include the influence of electronic interactions as prescribed by the matrix coupling element H12 upon the effective frequency for adiabatic barrier crossing νn, as well as upon the electronic transmission coefficient κel (i.e., the degree of reaction nonadiabaticity). The anticipated dependence of the free-energy barrier, as well as νn and κel, upon the donor–acceptor separation is accounted for in the kex calculations. The form of the resulting log kex −log τ−1L plots exhibit, as expected, a marked dependence on the value of H12 for reactant contact, H○12. Over the τ−1L range appropriate for common solvents at ambient temperatures, ∼1×1011 to 5×1012 s−1, the log kex −log τ−1L slopes, x, are significantly (or substantially) below unity for H○12≲0.5 kcal mol−1; x decreases markedly with increasing τ−1L and/or for decreasing H○12. The approach to the solvent inertial limit (for large τ−1L) also tends to decrease x further. Numerical comparisons are made with corresponding log kex −log τ−1L plots obtained using the simple ‘‘encounter preequilibrium’’ treatment which presumes that only a fixed narrow range of encounter-pair geometries contribute to kex. While the form of the plots are not greatly different, former more sophisticated treatment generally yields smaller slopes. Some corresponding numerical calculations for electrochemical-exchange reactions are also included." @default.
• W1985556891 created "2016-06-24" @default.
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• W1985556891 date "1989-07-15" @default.
• W1985556891 modified "2023-10-18" @default.
• W1985556891 title "Solvent dynamical effects in electron transfer: Predicted influences of electronic coupling upon the rate-dielectric friction dependence" @default.
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• W1985556891 doi "https://doi.org/10.1063/1.457651" @default.
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