Study of molecular line parameters down to very low temperature

The impact of precise spectroscopic measurements on the P(9) multiplet in the ν3 band of 12CH4, obtained using a newly developed cold Herriott cell coupled with a tunable diode laser spectrometer, is examined in the context of remote sensing of methane in the atmosphere. More specifically, the influence of the air-broadening temperature dependence, of line narrowing and of line-mixing effects is assessed when fitting high resolution atmospheric spectra recorded from a balloon in the solar occultation mode. This is achieved by considering residuals and retrieved methane volume mixing ratio profiles. By combining data from previous studies together with new measurements, the expression for the temperature dependence of the broadening coefficient has been revisited. It is shown that a correcting factor applied to the usual law gives better results, when considering all the available measurements from room temperature down to about 10–20 K, as compared to the usual expression of the width versus temperature. These results clearly demonstrate that collision broadening is more sensitive to long-range attractive forces when the temperature is decreased.