DOI: 10.1063/1.448623. Stochastic theory of resonance Raman line shapes of polyatomic molecules in condensed phases

Stochastic theory of resonance Raman line shapes of polyatomic molecules in condensed phases

10.1063/1.448623

Crossref journal-article

AIP Publishing

The Journal of Chemical Physics (317)

Abstract

A stochastic model is proposed for the calculation of resonance Raman line shapes of polyatomic molecules in condensed phases. The model assumes that the random force exerted on the molecule by the solvent causes a stochastic modulation of the electronic energy gap. Explicit expressions are derived for the absorption, the excitation spectra, and the dispersed Raman line shapes. The model interpolates all the way from homogeneous broadening (fast modulation) to inhomogeneous broadening (slow modulation). The effects of line broadening cannot be incorporated into the Kramers–Heisenberg formula, commonly used to interpret these spectra, since dephasing-induced terms appear which dominate the line shapes for large dephasing rates. A simple explanation is provided for the nature of the homogenous linewidth and for the broadening of the dispersed Raman line shapes, without having to assume an unrealistically short lifetime.

Bibliography

Mukamel, S. (1985). Stochastic theory of resonance Raman line shapes of polyatomic molecules in condensed phases. The Journal of Chemical Physics, 82(12), 5398â5408.

Authors 1

Shaul Mukamel (first)

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Dates

Type	When
Created	23 years, 1 month ago (July 26, 2002, 9 a.m.)
Deposited	1 year, 6 months ago (Feb. 9, 2024, 10:22 p.m.)
Indexed	2 days, 21 hours ago (Sept. 3, 2025, 6:50 a.m.)
Issued	40 years, 2 months ago (June 15, 1985)
Published	40 years, 2 months ago (June 15, 1985)
Published Print	40 years, 2 months ago (June 15, 1985)

Funders 0

None

BibTeX

@article{Mukamel_1985, title={Stochastic theory of resonance Raman line shapes of polyatomic molecules in condensed phases}, volume={82}, ISSN={1089-7690}, url={http://dx.doi.org/10.1063/1.448623}, DOI={10.1063/1.448623}, number={12}, journal={The Journal of Chemical Physics}, publisher={AIP Publishing}, author={Mukamel, Shaul}, year={1985}, month=jun, pages={5398–5408} }

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