Rate-Constant Expressions for Nonadiabatic Electron-Transfer Reactions
- 1 December 1987
- journal article
- research article
- Published by Taylor & Francis in Comments on Inorganic Chemistry
- Vol. 6 (4) , 209-235
- https://doi.org/10.1080/02603598708072291
Abstract
Expressions for the rate constants for nonadiabatic electron-transfer reactions are presented. These expressions are valid when the electronic coupling between the two redox sites is small and the energy surfaces for the initial and final states are harmonic with identical force constants. High- and low-temperature limiting forms of the rate equations are presented and closed-form expressions which are good approximations to the Franck-Condon sums appearing in these equations are described. Systems in which the electron transfer causes a displacement in one or more vibrational modes are considered. When several vibrational modes are “active,” the higher frequency modes have different effects on the rate constants in the normal and inverted free-energy regions. In the inverted region nuclear tunneling effects are large when hwf > 2kT. Under these conditions the rate has only a weak dependence on temperature and the rate constants can exhibit “quantum beats.” Nuclear tunneling effects are smaller in the normal region: the rate has a stronger dependence on temperature and quantum beats are not observed.This publication has 19 references indexed in Scilit:
- Electron transfer across polypeptides. 5. Rapid rates of electron transfer between osmium(II) and cobalt(III) in complexes with bridging oligoprolines and other polypeptidesJournal of the American Chemical Society, 1985
- Electron transfers in chemistry and biologyBiochimica et Biophysica Acta (BBA) - Reviews on Bioenergetics, 1985
- Distance dependence of photoinduced electron transfer through non-conjugated bridgesChemical Physics Letters, 1985
- Species specificity of long-range electron transfer within the complex between zinc-substituted cytochrome c peroxidase and cytochrome cJournal of the American Chemical Society, 1985
- Electron-transfer kinetics of pentaammineruthenium(III)(histidine-33)-ferricytochrome c. Measurement of the rate of intramolecular electron transfer between redox centers separated by 15.ANG. in a proteinJournal of the American Chemical Society, 1982
- Long range transfer of positive charge between dopant molecules in a rigid glassy matrixThe Journal of Chemical Physics, 1981
- Quantum mechanical tunnelling in biological systemsQuarterly Reviews of Biophysics, 1980
- A semiclassical treatment of electron-exchange reactions. Application to the hexaaquoiron(II)-hexaaquoiron(III) systemJournal of the American Chemical Society, 1980
- Temperature dependent activation energy for electron transfer between biological moleculesThe Journal of Chemical Physics, 1976
- Thermal electron transfer reactions in polar solventsThe Journal of Physical Chemistry, 1974