Solvent reorganization and donor/acceptor coupling in electron-transfer processes. Self-consistent reaction field theory and ab initio applications
- Brookhaven National Lab., Upton, NY (United States)
The solvent reorganization energy {lambda}{sub s}, and the donor/acceptor (D/A) coupling element, H{sub DA}, have been evaluated for electron transfer in the radical cations and anions (CH{sub 2}){sub n}{sup +-}, n = 4-13, exploiting the ab initio codes of Friesner et al., adapted so as to permit the evaluation of a nonequilibrium free energy (i.e., {lambda}{sub s}) in terms of equilibrium free energies of suitably defined charge densities placed in realistically shaped dielectric cavities. We obtain, for aqueous solution: (1) {lambda}{sub s} values obeying a nearly linear increase with inverse donor/acceptor separation (r{sub DA}), even though the complex solute structure is quite different from that of the traditional Marcus two-sphere model; (2) {lambda}{sub s} values for cations systematically less than for corresponding anion systems; (3) pronounced sensitivity of {lambda}{sub s} to conformation of terminal D/A groups and carbon framework; (4) exponential decay coefficients, {beta}, for H{sub DA} in polar solution essentially identical to those calculated in vacuum. 47 refs., 4 figs.
- Research Organization:
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- DOE Contract Number:
- AC02-76CH00016
- OSTI ID:
- 102869
- Journal Information:
- Journal of Physical Chemistry, Vol. 99, Issue 33; Other Information: PBD: 17 Aug 1995
- Country of Publication:
- United States
- Language:
- English
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