Reversibility conditions in radiative single-photon molecular and solid-state electronic transitions
✍ Scribed by T.A. Marsagishvili; M.G. Zakaraya; J. Ulstrup
- Publisher
- Elsevier Science
- Year
- 1988
- Tongue
- English
- Weight
- 569 KB
- Volume
- 149
- Category
- Article
- ISSN
- 0009-2614
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✦ Synopsis
We have evaluated the conditions for the adequacy of first-order perturbation theory and irreversible time evolution in optical electronic transitions between two potential surfaces spanned by a set of classical low-frequency nuclear modes, Perturbation expansion coefficients are large near resonance and the golden rule expression only applies in certain limits of time and values of the nuclear coordinates. The latter can be simply recast in terms of three coordinate intervals which characterize the extension of the intersection region ofthe potential surfaces AqL, the distance the system would move during the uncertainty time for electronic transitions Ago, and the decay of the statistical Boltzmann factor. Irreversibility and golden rule behaviour only emerge when AqLa Aqo, which emphasizes the crucial role of the classical nuclear system in irreversible time evolution.