On the role of nuclear motions in electron and excitation transfer rates

Importance of transfer-integral dependence upon nuclear coordinate

Mark A Ratner, Anupam Madhukar

Research output: Contribution to journalArticle

24 Citations (Scopus)

Abstract

The role of nuclear degrees of freedom in modifying the electron or exciton transfer rates between molecules is investigated. In addition to the usual Franck-Condon overlap factors which arise from the overlaps of initial and final vibrational states, we discuss a dependence of the transfer integral upon nuclear motions, a dependence which has been often cited, but nearly always ignored, in the usual dynamical theories of transfer processes. We show, within a Bom-Oppenheimer treatment, that the transfer integral dependence upon librational, rotational and vibrational modes can profoundly change both the rate itself and its functional dependences (upon temperature, upon orientation, etc.). Using a simple cosine form for the dependence of the transfer integral upon the modifying nuclear mode and a simple displaced-oscillator transformation, we obtain a closed-form solution for the transfer rate, which includes a new overlap factor arising from the dependence of the transfer integral upon nuclear coordinates. Some general remarks about the role of this dependence are made, and applications to particular transfer systems are briefly discussed.

Original languageEnglish
Pages (from-to)201-215
Number of pages15
JournalChemical Physics
Volume30
Issue number2
DOIs
Publication statusPublished - May 1 1978

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electron transfer
Molecules
Electrons
excitation
Temperature
LDS 751
vibrational states
vibration mode
degrees of freedom
excitons
oscillators
temperature dependence
molecules

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Spectroscopy
  • Atomic and Molecular Physics, and Optics

Cite this

On the role of nuclear motions in electron and excitation transfer rates : Importance of transfer-integral dependence upon nuclear coordinate. / Ratner, Mark A; Madhukar, Anupam.

In: Chemical Physics, Vol. 30, No. 2, 01.05.1978, p. 201-215.

Research output: Contribution to journalArticle

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