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 language | English |
|---|---|
| Pages (from-to) | 201-215 |
| Number of pages | 15 |
| Journal | Chemical Physics |
| Volume | 30 |
| Issue number | 2 |
| DOIs | |
| Publication status | Published - May 1 1978 |
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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 journal › Article
}
TY - JOUR
T1 - On the role of nuclear motions in electron and excitation transfer rates
T2 - Importance of transfer-integral dependence upon nuclear coordinate
AU - Ratner, Mark A
AU - Madhukar, Anupam
PY - 1978/5/1
Y1 - 1978/5/1
N2 - 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.
AB - 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.
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U2 - 10.1016/0301-0104(78)85120-9
DO - 10.1016/0301-0104(78)85120-9
M3 - Article
VL - 30
SP - 201
EP - 215
JO - Chemical Physics
JF - Chemical Physics
SN - 0301-0104
IS - 2
ER -