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

Journal Article (Journal Article)

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.

Full Text

Duke Authors

Cited Authors

  • Beratan, DN; Hopfield, JJ

Published Date

  • January 1, 1984

Published In

Volume / Issue

  • 81 / 12

Start / End Page

  • 5753 - 5759

International Standard Serial Number (ISSN)

  • 0021-9606

Digital Object Identifier (DOI)

  • 10.1063/1.447627

Citation Source

  • Scopus