Outer sphere electron transfer in polar solvents. Activationless and inverted regimes

In this paper we apply the stochastic Liouville equation for the study of outer sphere electron transfer (ET) in a polar solvent, which is characterized by a Debye dielectric relaxation. Explicit expressions, which bridge between the nonadiabatic and solvent‐controlled adiabatic limits, are derived for the ET rates spanning a broad range of the energetic parameters, which include normal ET, activationless ET, and ET in the inverted region. The many‐body result for the ET rate, which is accurate for symmetric ET, constitutes a useful approximate interpolation formula, which accounts well for the ET dynamics over a broad range of the energetic parameters.

[1]  J. Jortner,et al.  Dynamic solvent effects on outer‐sphere electron transfer , 1987 .

[2]  R. Marcus,et al.  Dynamical effects in electron transfer reactions. II. Numerical solution , 1987 .

[3]  C. Che,et al.  Electron transfer between cytochrome c and metalloporphyrins at high exothermicities , 1986 .

[4]  N. J. Green,et al.  Distance, stereoelectronic effects, and the Marcus inverted region in intramolecular electron transfer in organic radical anions , 1986 .

[5]  J. Hynes.  Outer-sphere electron-transfer reactions and frequency-dependent friction , 1986 .

[6]  J. Onuchic,et al.  Effect of friction on electron transfer in biomolecules , 1985 .

[7]  D. Huppert,et al.  Correlation of the corrected solvent dielectric relaxation time with the rate of conformational isomerization in excited states of syn-9,10-dioxabimanes , 1985 .

[8]  M. Newton,et al.  Electron Transfer Reactions in Condensed Phases , 1985 .

[9]  Peter G. Wolynes,et al.  Classical solvent dynamics and electron transfer. 1. Continuum theory , 1983 .

[10]  Graham R. Fleming,et al.  Theory of electronic relaxation in solution in the absence of an activation barrier , 1983 .

[11]  J. Hynes,et al.  Dynamical polar solvent effects on solution reactions: A simple continuum model , 1982 .

[12]  I. Alexandrov.  Physical aspects of charge transfer theory , 1980 .

[13]  L. D. Zusman.  Outer-sphere electron transfer in polar solvents , 1980 .

[14]  J. Ulstrup.  Charge Transfer Processes in Condensed Media , 1979 .

[15]  Rudolph A. Marcus,et al.  On the Theory of Oxidation‐Reduction Reactions Involving Electron Transfer. I , 1956 .

[16]  Ryogo Kubo,et al.  Application of the Method of Generating Function to Radiative and Non-Radiative Transitions of a Trapped Electron in a Crystal , 1955 .

[17]  M. Lax.  The Franck‐Condon Principle and Its Application to Crystals , 1952 .

[18]  J. Simon,et al.  Solvent dynamics and twisted intramolecular charge transfer in bis(4-aminophenyl) sulfone , 1986 .

[19]  H. Friedman,et al.  Theory of Fe2+–Fe3+ electron exchange in water , 1982 .