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Vibrational dephasing and the Raman non-coincidence effect of CHBr3 in isotopic dilution

✍ Scribed by V. Deckert; B. P. Asthana; W. Kiefer; H.-G. Purucker; A. Laubereau

Publisher: John Wiley and Sons
Year: 2000
Tongue: English
Weight: 114 KB
Volume: 31
Category: Article
ISSN: 0377-0486
DOI: 10.1002/1097-4555(200008/09)31:8/9<805::aid-jrs575>3.0.co;2-x

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✦ Synopsis

The n 1 (C-H) stretching mode of CHBr 3 was investigated in the solvent CDBr 3 at room temperature using three-colour femtosecond CARS and scanning multi-channel Raman difference spectroscopy (SMT-RDS). Small but measurable blue shifts (≤1 cm -1 ) of the isotropic part of the Raman scattering relative to the anisotropic component and upon isotopic dilution are the clear signatures of the Raman non-coincidence effect and isotopic lineshift, respectively. The experimental results are discussed in terms of theoretical models providing insight in the intermolecular coupling mechanisms. The measured shift 1n ID = 0.73 ± 0.02 cm -1 upon isotopic dilution is found to be dominated by the attractive interaction and is to be compared with the non-coincidence effect of 1n NCE = 1.02 ± 0.05 cm -1 for the neat liquid. A 5% decrease in the dephasing rate 1/T 2 and a similar change in the linewidth upon infinite dilution are observed and semi-quantitatively explained via repulsive intermolecular interaction in accordance with an estimate of the corresponding (small) wavenumber shift.

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