High-resolution spectroscopy of difference and combination bands of SF6 to elucidate the ν3 + ν1 − ν1 and ν3 + ν2 − ν2 hot band structures in the ν3 region

Abstract

The strong infrared absorption in the ν3 S–F stretching region of sulphur hexafluoride (SF6) near 948 cm−1 makes it a powerful greenhouse gas. Although its present concentration in the atmosphere is very low, it is increasing rapidly, due to industrial pollution. The ground state population of this heavy species is only 32% at room temperature and thus many hot bands are present. Consequently, a reliable remote-sensing spectroscopic detection and monitoring of this species require an accurate modelling of these hot bands. We used two experimental set-ups at the SOLEIL French synchrotron facility to record some difference and combination bands of SF6: (1) a new cryogenic multiple pass cell with 93 m optical path length and regulated at 163 ± 2 K temperature and (2) the Jet-AILES supersonic expansion set-up. With this, we could obtain high-resolution absorption spectra of the ν3 − ν1, ν3 − ν2, ν1 + ν3 and ν2 + ν3 bands at low temperature. These spectra could be assigned and analysed, thanks to the SPVIEW and XTDS computer programs developed in Dijon. We performed two global fits of effective Hamiltonian parameters. The first one is a global fit of the ground state, ν2, ν3, ν3 − ν2, ν2 + ν3, 2ν3 and 2ν3 − ν3 rovibrational parameters, using the present spectra and previous infrared, Raman and two-photon absorption data. This allows a consistent refinement of the effective Hamiltonian parameters for all the implied vibrational levels and a new simulation of the 2ν3 + ν2 − ν2 hot band. The second global fit involves the present ν3 − ν1 and ν1 + ν3 lines, together with previous ν1 Raman data, in order to obtain refined ν1 parameters and also ν1 + ν3 parameters in a consistent way. This allows to simulate the ν3 + ν1 − ν1 hot band.