Speed dependence of CH3 35Cl–O2 line-broadening parameters probed on rotational transitions: Measurements and semi-classical calculations.

Abstract: Relaxation parameters for K-components (K≤6) of six J→J+1 rotational transitions (J=6, 10, 17, 22, 31 and 33) of CH3 35Cl perturbed by O2 are measured at room temperature with Voigt, speed-dependent Voigt and Galatry profiles in order to probe the speed-dependence effects. With respect to the previous study of CH3 35Cl–N2 system [Guinet et al., J Quant Spectrosc Radiat Transfer 2012;113:1113], higher active-gas pressures are reached, providing better signal-to-noise ratios, and the exact expression of the Beer–Lambert law is introduced in the fitting procedure, leading, among other advantages, to much more realistic low-pressure results. The broadening parameters of the considered lines are also computed by a semi-classical method for various relative velocities of colliders and the powers characterizing the dependence of the collisional cross-sections on relative speeds are deduced as functions of the rotational numbers J and K. Additional calculations performed with the Maxwell–Boltzmann distribution of velocities show no significant difference with the earlier results [Buldyreva et al., Phys Chem Chem Phys 2011;13:20326] obtained within the mean thermal velocity approximation. Weighted sums of the presently measured Voigt-profile O2-broadening parameters and of the previously published N2-broadening ones are calculated to yield experimental air-broadening coefficients for spectroscopic databases. [Copyright &y& Elsevier]