Quantum cascade laser measurements of CH4 linestrength and temperature-dependent self-broadening and narrowing parameters at 7.16 µm

Abstract

Absorption lineshapes for 10 CH4 transitions in the v2 and v4 band were measured at high-resolution in a thermodynamically-controlled optical cell using a quantum cascade laser near 7.16 µm. Linestrength, self-broadening, -narrowing, pressure-shift coefficients and their temperature dependence were recorded over a temperature and pressure range of 290–1050 K and 3–80 kPa, respectively. Voigt, Rautian, speed-dependent Voigt profiles were least-squares fit to the measured absorption spectra to determine the best-fit lineshape parameters. Significant collisional-narrowing and speed-dependent effects were observed but no line mixing behaviour was found in pure CH4 at the experimental conditions. The self-pressure-shift coefficients were found to change signs from negative to positive with increasing temperature and the Frost's formula fit well their temperature dependence for the studied transitions. The measured spectra provided tests of the CH4 line lists near 1397 cm−1 released in HITEMP 2020 and the recorded spectroscopic parameters compared well with the values in the database. Several weak transitions excluded from the HITEMP database were observed at elevated temperatures with the line positions given here. The analyses of uncertainties in all the measured spectroscopic parameters were also demonstrated in this work.