Line mixing study of carbon monoxide near [formula omitted] broadened by nitrogen, helium, and hydrogen

Abstract

We present quantitative, broadband absorbance measurements of the fundamental rovibrational band of carbon monoxide (CO) between 1965 and 2230 cm−1 in bath gases of nitrogen (N2), helium (He), and hydrogen (H2). These measurements are then compared to two constructed models capable of reproducing the effects of line mixing present in our measured results. The static cell measurements were taken using a narrow-linewidth, broad-scan external-cavity quantum-cascade laser at pressures of 15–35 atm and temperatures of 293, 453 (CO/H2) and 802 K (CO/N2, CO/He). Our first line mixing approach, based on the modified exponential gap (MEG) law with a fitted inter-branch factor, shows improved agreement with the measured spectra across different pressures and broadening partners relative to purely Lorentzian models. At the elevated temperatures, similar agreement is observed; however, a mismatch is present between extrapolated HITRAN broadening parameters and those observed in the measured spectra. This is likely due to the known deficiency of the single power law over large temperature ranges, and hence a minor scaling of the line-by-line temperature-dependence exponents is incorporated that is supported by previous studies in the literature. Our second, more empirical line mixing approach involves extracting MEG line mixing parameters through a direct fit to the measured spectra. The Direct Fit method bypasses the need for known line shape parameters and produces even stronger agreement with measured data, with a CO/H2 root-mean-square error of 0.4% at the highest-number-density condition of 293 K and 35 atm. The line mixing models presented and discussed will be useful for interpreting future satellite and telescope observations of CO from deeper, higher-number-density layers of exoplanetary gas-giant atmospheres, consisting of mainly H2 and He.