More light on the 2ν{sub 5} Raman overtone of SF{sub 6}: Can a weak anisotropic spectrum be due to a strong transition anisotropy?

Journal Article · Tue Jan 21 04:00:00 EST 2014 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4861047· OSTI ID:22255266

Kremer, D.; Rachet, F.

Long known as a fully polarized band with a near vanishing depolarization ratio [η{sub s} = 0.05, W. Holzer and R. Ouillon, Chem. Phys. Lett. 24, 589 (1974)], the 2ν{sub 5} Raman overtone of SF{sub 6} has so far been considered as of having a prohibitively weak anisotropic spectrum [D. P. Shelton and L. Ulivi, J. Chem. Phys. 89, 149 (1988)]. Here, we report the first anisotropic spectrum of this overtone, at room temperature and for 13 gas densities ranging between 2 and 27 amagat. This spectrum is 10 times broader and 50 times weaker than the isotropic counterpart of the overtone [D. Kremer, F. Rachet, and M. Chrysos, J. Chem. Phys. 138, 174308 (2013)] and its profile much more sensitive to pressure effects than the profile of the isotropic spectrum. From our measurements an accurate value for the anisotropy matrix-element |〈000020|Δα|000000〉| was derived and this value was found to be comparable to that of the mean-polarizability ((000020), α{sup ¯} (000000)). Among other conclusions our study offers compelling evidence that, in Raman spectroscopy, highly polarized bands or tiny depolarization ratios are not necessarily incompatible with large polarizability anisotropy transition matrix-elements. Our findings and the way to analyze them suggest that new strategies should be developed on the basis of the complementarity inherent in independent incoherent Raman experiments that run with two different incident-beam polarizations, and on concerted efforts to ab initio calculate accurate data for first and second polarizability derivatives. Values for these derivatives are still rarities in the literature of SF{sub 6}.

• OSTI ID: 22255266
• Journal Information: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 3 Vol. 140; ISSN JCPSA6; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
ANISOTROPY
DENSITY
DEPOLARIZATION
MATRIX ELEMENTS
POLARIZABILITY
POLARIZATION
PRESSURE DEPENDENCE
RAMAN SPECTROSCOPY
SPECTRA
SULFUR FLUORIDES