skip to main content

Title: The 2ν{sub 3} Raman overtone of sulfur hexafluoride: Absolute spectra, pressure effects, and polarizability properties

Of the six normal vibrations of SF{sub 6}, ν{sub 3} has a key role in the mechanisms of radiative forcing. This vibration, though inactive in Raman, shows up through the transition 2ν{sub 3} allowing for a complementary view on the asymmetric stretch of the molecule. Here, we look back into this topic, which has already caught some interest in the past but with some points been left out. We make a systematic incoherent-light-scattering analysis of the overtone with the use of different gas pressures and polarization orientations for the incident beam. Absolute-scale isotropic and anisotropic spectra are reported along with natural and pressure-induced widths and shifts, and other spectral features such as the peaks corresponding to the (experimentally indistinguishable) interfering channels E{sub g} and F{sub 2g} hitherto seen solely as two-photon IR-absorption features. We make the first-ever prediction of the SF{sub 6} polarizability second derivative with respect to the ν{sub 3}-mode coordinate and we develop a heuristic argument to explain why the superposition of the three degenerate stretching motions that are related to the ν{sub 3} mode cannot but generate a polarized Raman band.
Authors:
; ;  [1]
  1. LUNAM Université, Université d’Angers, CNRS UMR 6200, Laboratoire MOLTECH-Anjou, 2 Bd Lavoisier, 49045 Angers (France)
Publication Date:
OSTI Identifier:
22253401
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 140; Journal Issue: 12; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ABSORPTION; ANISOTROPY; LIGHT SCATTERING; POLARIZABILITY; POLARIZATION; PRESSURE DEPENDENCE; SPECTRA; SULFUR; SULFUR FLUORIDES