REFLECTIONS ON THE TWO-STATE ELECTRON TRANSFER MODEL.
There is general agreement that the two most important factors determining electron transfer rates in solution are the degree of electronic interaction between the donor and acceptor sites, and the changes in the nuclear configurations of the donor, acceptor, and surrounding medium that occur upon the gain or loss of an electron Ll-51. The electronic interaction of the sites will be very weak, and the electron transfer slow, when the sites are far apart or their interaction is symmetry or spin forbidden. Since electron motion is much faster than nuclear motion, energy conservation requires that, prior to the actual electron transfer, the nuclear configurations of the reactants and the surrounding medium adjust from their equilibrium values to a configuration (generally) intermediate between that of the reactants and products. In the case of electron transfer between , two metal complexes in a polar solvent, the nuclear configuration changes involve adjustments in the metal-ligand and intraligand bond lengths and angles, and changes in the orientations of the surrounding solvent molecules. In common with ordinary chemical reactions, an electron transfer reaction can then be described in terms of the motion of the system on an energy surface from the reactant equilibrium configuration (initial state) to the product equilibrium configuration (final state) via the activated complex (transition state) configuration.
- Research Organization:
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- Sponsoring Organization:
- USDOE Office of Energy Research (ER) (US)
- DOE Contract Number:
- AC02-98CH10886
- OSTI ID:
- 751122
- Report Number(s):
- BNL-67079; KC030101; R&D Project: CO4; KC030101; TRN: AH200037%%69
- Resource Relation:
- Other Information: ELECTRON TRANSFER IN CHEMISTRY, VOL.12, ED:BALZANI,V.; PBD: 12 Jan 2000
- Country of Publication:
- United States
- Language:
- English
Similar Records
ESR and ENDOR study of the photooxidation of magnesium and zinc tetrakis(4-sulfonatophenyl)porphyrins
Computational Modeling of Uranium Corrosion and the role of Impurities(Fe, Cr, Al, C and Si)