Special issue: 22nd colloquium on high-resolution molecular spectroscopy HRMS Dijon 2011 (Part 2) Experimental and theoretical studies of room-temperature sub-millimetre CH_3 ~(35)Cl line shapes broadened by H_2

摘要

Hydrogen-broadening coefficients of methyl chloride rotational lines J=6→7, 10→11, 17→18, 22→23 and 31→32 at 296K are measured as functions of the quantum number K using a sensitive frequency-modulation technique. As expected for this light perturber, the observed line shapes are well described by Voigt profile model. A clear dependence of the collisional broadening on K is observed for most transitions. From a detailed study of the K-components of the transition J=6→7 situated at 186GHz no variation of the broadening of the hyperfine components related to 35Cl quadrupole is stated. Given the absence of refined ab initio computed potential energy surfaces and the impracticality of quantum-mechanical calculations for the considered molecular system, theoretical values of these broadening coefficients are estimated by a semi-classical approach with exact trajectories and a model interaction potential including both long-range and short-range (atom-atom) interactions of the active molecule rigorously treated as a symmetric top. It is shown that the short-range forces yield important contributions to the collisional line width for all values of the rotational quantum numbers J and K. Various models are also tested for the isotropic part of the interaction potential which governs the relative translational motion. It is demonstrated that for the very light perturbing molecule H2 the calculated line widths, practically independent from the rotational quantum number J (for K≤J), are particularly sensitive to the position and slope of the repulsive wall. Modifications required in the semi-classical formalism for a correct application of the cumulant expansion are also tested and it is stated that no difference is observed for the CH_3Cl-H_2 system characterised by quite weak interactions.