N2- and O2-broadening coefficients and profiles for millimeter lines of 14N2O

Abstract

For the purpose of atmospheric applications, we have measured N2- and O2-induced broadenings and shapes of rotational lines of N2O in the 235–350K temperature range, precisely the J=8←7, J=22←21, and J=23←22 lines, located near 201, 552, and 577GHz, respectively. The analysis of experimental lineshapes shows up significant deviations from the Voigt profile, which are characteristic of line narrowing processes. In a first step, the Voigt profile was considered for the determination of pressure broadening parameters and of their temperature dependencies. Results are in good agreement with the dependence from rotational quantum number previously observed for other rotational and rovibrational lines. They are well explained by calculations based on a semiclassical formalism that includes the atom–atom Lennard-Jones potential in addition to electrostatic interactions up to hexadecapolar contributions. In a second step, observed lineshapes were analyzed by using the Galatry profile and a speed-dependent Voigt profile. The nonlinear pressure behavior observed for the diffusion rate β involved in the Galatry profile leads to rule out the possible role of velocity/speed changing collisions, and to infer that discrepancies from the Voigt profile result from the dependence of relaxation rates on molecular speeds. This interpretation is supported by the comparison of optical and kinetic radii and confirmed by theoretical calculations of relaxation rates. Finally, it can be claimed that, for the N2O–N2 and N2O–O2 systems, deviations from the Voigt profile are explained by a speed-dependent Voigt profile.