Mechanism of intermolecular dephasings on time-resolved anti-Stokes Raman scattering from a molecular ensemble

M. Hayashi, Michihiko Sugawara, Y. Fujimura

Research output: Contribution to journalArticle

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Abstract

Mechanisms of intermolecular dephasings revealed in the time-resolved coherent anti-Stokes Raman scattering (CARS) spectra of a molecular ensemble are theoretically studied by deriving the microscopical expression for the scattered photon intensity averaged over the heat-bath variables. The intermolecular dephasing means the decay of the intermolecular coherence created by the pumping process, i.e., a linear combination of the vibrational Raman transitions of the molecules at different sites. The intensity of the time-resolved CARS is expressed in terms of time-development matrix elements of the intermolecular coherence. An equation of motion for the intermolecular coherence is derived by using the projection operator method. The structure of the intermolecular-dephasing constant is clarified. The intermolecular-dephasing constant consists of the sum of population decay constants and the intermolecular pure dephasing constant that originates from an elastic interaction between the relevant molecules and a common heat-bath mode. The intermolecular pure dephasing constant is expressed in terms of the intramolecular pure dephasing constants and destructive interference of the intramolecular pure dephasings between the relevant two molecules. The intermolecular-dephasing constant is expressed as the sum of the intramolecular-dephasing constants of the relevant molecules when there is no common heat-bath mode. Inhomogeneous effects on the time-resolved CARS spectra are also investigated. A degree of the structural order is introduced to qualitatively express the inhomogeneity of local structures in the molecular ensemble. The microscopic expression derived in this paper has taken into account both incoherent and coherent optical processes in the thermally distributed molecular ensemble.

Original languageEnglish
Pages (from-to)2416-2429
Number of pages14
JournalPhysical Review A
Volume43
Issue number5
DOIs
Publication statusPublished - 1991
Externally publishedYes

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Raman spectra
baths
heat
molecules
decay
equations of motion
pumping
inhomogeneity
projection
interference
operators
photons
matrices
interactions

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Atomic and Molecular Physics, and Optics

Cite this

Mechanism of intermolecular dephasings on time-resolved anti-Stokes Raman scattering from a molecular ensemble. / Hayashi, M.; Sugawara, Michihiko; Fujimura, Y.

In: Physical Review A, Vol. 43, No. 5, 1991, p. 2416-2429.

Research output: Contribution to journalArticle

Hayashi, M. ; Sugawara, Michihiko ; Fujimura, Y. / Mechanism of intermolecular dephasings on time-resolved anti-Stokes Raman scattering from a molecular ensemble. In: Physical Review A. 1991 ; Vol. 43, No. 5. pp. 2416-2429.
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