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Adiabaticlty and nonadiabaticity in bimolecular outer-sphere charge transfer reactions

Publication ,  Journal Article
Beratan, DN; Onuchic, JN
Published in: The Journal of Chemical Physics
January 1, 1988

A model for outer-sphere bimolecular electron transfer reactions is presented which is based on a rate expression correct in the adiabatic, nonadiabatic, and intermediate dynamical regimes for an overdamped solvent coordinate. A complete discussion of the time-scale separations needed to define a bimolecular rate for these electron transfer reactions is given. Bimolecular reaction rates are predicted to display distinct solvent and electronic coupling dependencies, defined by a few experimentally variable parameters, which we now identify. Also, a significant intermediate dynamical regime is predicted to exist in which the rate is sensitive to both electronic coupling and nuclear relaxation. Evidence that both extreme dynamical regimes have been accessed experimentally is recalled, and strategies are presented for fully mapping out the dependence of rate on the electronic coupling and relaxation times. © 1988 American Institute of Physics.

Duke Scholars

Published In

The Journal of Chemical Physics

DOI

ISSN

0021-9606

Publication Date

January 1, 1988

Volume

89

Issue

10

Start / End Page

6195 / 6203

Related Subject Headings

  • Chemical Physics
  • 51 Physical sciences
  • 40 Engineering
  • 34 Chemical sciences
  • 09 Engineering
  • 03 Chemical Sciences
  • 02 Physical Sciences
 

Citation

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ICMJE
MLA
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Beratan, D. N., & Onuchic, J. N. (1988). Adiabaticlty and nonadiabaticity in bimolecular outer-sphere charge transfer reactions. The Journal of Chemical Physics, 89(10), 6195–6203. https://doi.org/10.1063/1.455436
Beratan, D. N., and J. N. Onuchic. “Adiabaticlty and nonadiabaticity in bimolecular outer-sphere charge transfer reactions.” The Journal of Chemical Physics 89, no. 10 (January 1, 1988): 6195–6203. https://doi.org/10.1063/1.455436.
Beratan DN, Onuchic JN. Adiabaticlty and nonadiabaticity in bimolecular outer-sphere charge transfer reactions. The Journal of Chemical Physics. 1988 Jan 1;89(10):6195–203.
Beratan, D. N., and J. N. Onuchic. “Adiabaticlty and nonadiabaticity in bimolecular outer-sphere charge transfer reactions.” The Journal of Chemical Physics, vol. 89, no. 10, Jan. 1988, pp. 6195–203. Scopus, doi:10.1063/1.455436.
Beratan DN, Onuchic JN. Adiabaticlty and nonadiabaticity in bimolecular outer-sphere charge transfer reactions. The Journal of Chemical Physics. 1988 Jan 1;89(10):6195–6203.

Published In

The Journal of Chemical Physics

DOI

ISSN

0021-9606

Publication Date

January 1, 1988

Volume

89

Issue

10

Start / End Page

6195 / 6203

Related Subject Headings

  • Chemical Physics
  • 51 Physical sciences
  • 40 Engineering
  • 34 Chemical sciences
  • 09 Engineering
  • 03 Chemical Sciences
  • 02 Physical Sciences