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Raman lineshape study of the A 1 skeletal modes in tert ‐butyl chloride
Author(s) -
Friedman B. Ri.,
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.1250150413
Subject(s) - raman spectroscopy , isotropy , chemistry , chloride , rotational diffusion , normal mode , dipole , relaxation (psychology) , vapor phase , analytical chemistry (journal) , molecular vibration , nuclear magnetic resonance , molecular physics , vibration , thermodynamics , molecule , physics , optics , organic chemistry , psychology , social psychology , quantum mechanics
The polarized and depolarized Raman spectra of the ν 6 (CC 3 stretch), ν 7 (CCl stretch) and ν 8 (CC 3 bend) modes of tert ‐butyl chloride have been studied as a function of temperature in the liquid phase. Isotropic correlation times for the bending mode were found to be 3–4 times longer than values obtained for the two stretching vibrations. An analysis of the isotropic correlation functions using the Kubo lineshape formalism revealed that the less efficient vibrational relaxation of the deformation arises primarily from the lower second monents of this mode. Reorientational times calculated from the two stretching vibrations were almost three times shorter than the earlier reported dipolar relaxation time, indicating that the tumbling motion of tert ‐ butyl chloride is close to the small‐step diffusion limit.