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Failure of the Born-Oppenheimer and Franck-Condon approximations for long distance electron transfer rate calculations

Publication ,  Journal Article
Beratan, DN; Hopfield, JJ
Published in: The Journal of Chemical Physics
January 1, 1984

Quantum mechanical and semiclassical formulations of nonadiabatic electron transfer theory are usually implemented within a Born-Oppenheimer regime. Calculations on real weakly interacting systems are so difficult that this approximation is rarely questioned. The Born-Oppenheimer approximation becomes qualitatively wrong for electron transfers at very large distances. A model vibronic problem is exactly solved and compared with the Born-Oppenheimer result. Rate expressions are derived from the wave functions using the "golden rule" approximation. Electron propagation is intimately correlated with nuclear motion so that the vibrational energy left on the donor critically affects the electronic decay length. Several deviations from the usual predictions appear for transfers over very large distances. © 1984 American Institute of Physics.

Duke Scholars

Published In

The Journal of Chemical Physics

DOI

ISSN

0021-9606

Publication Date

January 1, 1984

Volume

81

Issue

12

Start / End Page

5753 / 5759

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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MLA
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Beratan, D. N., & Hopfield, J. J. (1984). Failure of the Born-Oppenheimer and Franck-Condon approximations for long distance electron transfer rate calculations. The Journal of Chemical Physics, 81(12), 5753–5759. https://doi.org/10.1063/1.447627
Beratan, D. N., and J. J. Hopfield. “Failure of the Born-Oppenheimer and Franck-Condon approximations for long distance electron transfer rate calculations.” The Journal of Chemical Physics 81, no. 12 (January 1, 1984): 5753–59. https://doi.org/10.1063/1.447627.
Beratan DN, Hopfield JJ. Failure of the Born-Oppenheimer and Franck-Condon approximations for long distance electron transfer rate calculations. The Journal of Chemical Physics. 1984 Jan 1;81(12):5753–9.
Beratan, D. N., and J. J. Hopfield. “Failure of the Born-Oppenheimer and Franck-Condon approximations for long distance electron transfer rate calculations.” The Journal of Chemical Physics, vol. 81, no. 12, Jan. 1984, pp. 5753–59. Scopus, doi:10.1063/1.447627.
Beratan DN, Hopfield JJ. Failure of the Born-Oppenheimer and Franck-Condon approximations for long distance electron transfer rate calculations. The Journal of Chemical Physics. 1984 Jan 1;81(12):5753–5759.

Published In

The Journal of Chemical Physics

DOI

ISSN

0021-9606

Publication Date

January 1, 1984

Volume

81

Issue

12

Start / End Page

5753 / 5759

Related Subject Headings

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