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Molecular reorientation and vibrational relaxation in dibromomethane
Author(s) -
Chen S. J. H.,
Schwartz M.
Publication year - 1984
Publication title -
journal of raman spectroscopy
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.748
H-Index - 110
eISSN - 1097-4555
pISSN - 0377-0486
DOI - 10.1002/jrs.1250150304
Subject(s) - dephasing , chemistry , intermolecular force , raman spectroscopy , molecular vibration , molecular physics , formalism (music) , molecule , relaxation (psychology) , vibrational energy relaxation , vibration , spectral line , normal mode , molecular dynamics , chemical physics , analytical chemistry (journal) , computational chemistry , condensed matter physics , physics , optics , art , musical , social psychology , psychology , organic chemistry , quantum mechanics , astronomy , visual arts , chromatography
The polarized and depolarized Raman spectra of the ν 2 (CH 2 bend) and ν 3 (CBr stretch) vibrations in dibromomethane have been studied as a function of temperature throughout the liquid range. Reorientational correlation times derived from the two modes were simllar in both magnitude and dependence on temperature. This result, together with other structural data, suggests that the rotational dynamics of this molecule in the liquid phase are quasi symmetric‐top in character. Vibrational dephasing times calculated from the two lineshapes were also of the same magnitude. However, modulation times determined via the Kubo lineshpae formalism varied markedly between the vibrations. This provides evidence that vibrational dephasing of the bending and stretching modes are influenced by different intermolecular forces in the liquid.