Pressure dependence of the measured line intensity and super-Lorentzian effects in the absorption spectra of pure HCl.

Super-Lorentzian effects in the troughs between lines and the pressure dependence of the line intensities retrieved from fits of absorption spectra of pure HCl have been investigated both experimentally and theoretically. For that, spectra of pure HCl gas in the 2-0 band were recorded with a Fourier Transform spectrometer at room temperature and for pressures ranging from 1 to 10 atm. The line intensities, retrieved from fits of the measurements with the Voigt profile using a single spectrum fitting technique, reveal large decreases with increasing pressure - up to 3% per atm - with a relatively weak rotational dependence. We also show that the absorptions in-between successive P and R transitions are significantly larger than those predicted using Voigt profiles. Requantized classical molecular dynamics simulations were made in order to predict absorption spectra of pure HCl matching the experimental conditions. The pressure dependence of the intensities retrieved from the calculated spectra as well as the predicted super-Lorentzian behavior between lines are in good agreement with the measurements. Our analysis shows that these effects are essentially due to incomplete collisions, which govern the dipole auto-correlation function at very short times.

Non-impact effects in the absorption spectra of HCl diluted in CO2, air, and He: Measurements and predictions.

Non-impact effects in the absorption spectra of HCl in various collision-partners are investigated both experimentally and theoretically. Fourier transform spectra of HCl broadened by CO2, air, and He have been recorded in the 2-0 band region at room temperature and for a wide pressure range, from 1 to up to 11.5 bars. Comparisons between measurements and calculations using Voigt profiles show strong super-Lorentzian absorptions in the troughs between successive lines in the P and R branches for HCl in CO2. A weaker effect is observed for HCl in air, while for HCl in He, Lorentzian wings are in very good agreement with measurements. In addition, the line intensities retrieved by fitting the Voigt profile on the measured spectra decrease with the density of the perturber. This perturber-density dependence decreases with the rotational quantum number. For HCl in CO2, the decrease in the retrieved line intensity can reach 2.5% per amagat for the first rotational quantum numbers. This number is about 0.8% per amagat for HCl in air, while for HCl in He, no density dependence of the retrieved line intensity is observed. Requantized classical molecular dynamics simulations have been performed for HCl-CO2 and HCl-He in order to simulate the absorption spectra for various perturber-density conditions. The density dependence of the intensities retrieved from the simulated spectra and the predicted super-Lorentzian behavior in the troughs between lines are in good agreement with experimental determinations for both HCl-CO2 and HCl-He. Our analysis shows that these effects are due to incomplete or ongoing collisions, which govern the dipole auto-correlation function at very short times. The effects of these ongoing collisions strongly depend on the details of the intermolecular potential: they are negligible for HCl-He but significant for HCl-CO2 for which a line-shape model beyond the impact approximation will be needed to correctly model the absorption spectra from the center to the far wings.