DOI: 10.1063/1.1732389. Radiationless Transitions: A Semiclassical Model

Radiationless Transitions: A Semiclassical Model

10.1063/1.1732389

Crossref journal-article

AIP Publishing

The Journal of Chemical Physics (317)

Abstract

Radiationless transitions of a solute molecule embedded in a crystalline solvent are treated in close analogy to radiative transitions. A semiclassical interaction Hamiltonian employing empirically determined coupling constants connects solute particles to a force field amplitude set up by the phonons of the solvent. By relating this amplitude to phonon energy density an Einstein B coefficient is derived. Debye's formula for the phonon energy density combined with thermodynamic arguments yield Einstein A coefficients. It is shown that the theory (1) explains the fast rates of radiationless transitions, (2) provides for temperature dependence, (3) has a cutoff frequency for radiationless transition, (4) provides for the Franck—Condon principle, and (5) explains the lack of selection rules. A value is derived for the empirical coupling constants.

Bibliography

Gouterman, M. (1962). Radiationless Transitions: A Semiclassical Model. The Journal of Chemical Physics, 36(11), 2846â2853.

Authors 1

Martin Gouterman (first)

References 10 Referenced 87

{'key': '2024020820444531000_r1'}
10.1016/0022-2852(61)90233-8 / J. Mol. Spectroscopy (1961)
{'key': '2024020820444531000_r3'}
{'key': '2024020820444531000_r4'}
{'key': '2024020820444531000_r5'}
10.1039/df9500900014 / Discussions Faraday Soc. (1950)
{'key': '2024020820444531000_r7'}
10.1063/1.1731636 / J. Chem. Phys. (1961)
10.1063/1.1731795 / J. Chem. Phys. (1961)
10.1103/PhysRev.38.277 / Phys. Rev. (1931)

Dates

Type	When
Created	20 years, 7 months ago (Jan. 5, 2005, 10:19 p.m.)
Deposited	1 year, 6 months ago (Feb. 8, 2024, 3:44 p.m.)
Indexed	1 week ago (Aug. 26, 2025, 2:26 a.m.)
Issued	63 years, 3 months ago (June 1, 1962)
Published	63 years, 3 months ago (June 1, 1962)
Published Print	63 years, 3 months ago (June 1, 1962)

Funders 0

None

BibTeX

@article{Gouterman_1962, title={Radiationless Transitions: A Semiclassical Model}, volume={36}, ISSN={1089-7690}, url={http://dx.doi.org/10.1063/1.1732389}, DOI={10.1063/1.1732389}, number={11}, journal={The Journal of Chemical Physics}, publisher={AIP Publishing}, author={Gouterman, Martin}, year={1962}, month=jun, pages={2846–2853} }

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