DOI: 10.1063/1.445712. Temperature effects in the time-correlator theory of resonance Raman scattering

Temperature effects in the time-correlator theory of resonance Raman scattering

10.1063/1.445712

Crossref journal-article

AIP Publishing

The Journal of Chemical Physics (317)

Abstract

Within well-defined ‘‘standard’’ assumptions and the time-correlator theory’s separation of resonance Raman (RR) scattering into orders, previously discussed exact relations allow one to calculate mth-order RR profile line shapes directly from optical absorption data at T≠0 K. At T=0 K, the mth-order profiles are identical with the full m-phonon profiles, which are the experimentally measured quantities, while for T≠0 K, the m-phonon profiles include higher-order corrections due to processes which freeze out at T=0 K and which involve virtual phonon excitation–deexcitation in all Franck–Condon active modes. In this paper we show that for one-phonon scattering from a large class of multimode systems, the correction due to a thermally populated mode is small if (1) the mode’s frequency is small compared with the smallest resolvable width in the optical absorption and/or (2) the mode’s electron–phonon coupling is weak. For the multimode system β-carotene in isopentane at T=123 and 298 K, the sum of corrections due to all thermally populated Franck–Condon active modes is found to be negligible, so that even at room temperature, the first-order and one-phonon profiles are essentially identical. Our first-order profile line shapes calculated from optical absorption data for T=123 and T=298 K account well for the observed thermal broadening and are in good overall agreement with the measured one-phonon profiles. A short-time approximation is developed and is shown to give insight into our numerical results—in particular, in the limit of a large number of thermally populated low-frequency modes of comparable electron–phonon coupling strengths, the sum of these modes’ higher-order corrections to the one-phonon profiles is shown to vanish. The negligibility of the higher-order corrections leads to efficient T≠0 K multimode numerical modeling procedures which allow one to conveniently obtain both the optical absorption and RR profiles from a single one-dimensional fast Fourier transform of the absorption time-correlator. Generalizations to mth-order scattering are briefly discussed.

Bibliography

Chan, C. K., & Page, J. B. (1983). Temperature effects in the time-correlator theory of resonance Raman scattering. The Journal of Chemical Physics, 79(11), 5234â5250.

Authors 2

C. K. Chan (first)
J. B. Page (additional)

References 25 Referenced 109

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{'key': '2024021000144366000_r3'}
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Dates

Type	When
Created	22 years, 5 months ago (Feb. 28, 2003, 12:03 p.m.)
Deposited	1 year, 6 months ago (Feb. 9, 2024, 8:38 p.m.)
Indexed	1 year, 6 months ago (Feb. 10, 2024, 8:38 p.m.)
Issued	41 years, 8 months ago (Dec. 1, 1983)
Published	41 years, 8 months ago (Dec. 1, 1983)
Published Print	41 years, 8 months ago (Dec. 1, 1983)

Funders 0

None

BibTeX

@article{Chan_1983, title={Temperature effects in the time-correlator theory of resonance Raman scattering}, volume={79}, ISSN={1089-7690}, url={http://dx.doi.org/10.1063/1.445712}, DOI={10.1063/1.445712}, number={11}, journal={The Journal of Chemical Physics}, publisher={AIP Publishing}, author={Chan, C. K. and Page, J. B.}, year={1983}, month=dec, pages={5234–5250} }

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