Collisional broadening, line shifting, and line mixing in the stimulated Raman 2ν2 Q branch of CH4

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Abstract
Self‐, argon‐, and helium‐broadening coefficients have been measured for 13 lines in the 2ν2 Raman Q branch of CH4 using stimulated inverse Raman spectroscopy. The linewidths clearly show the symmetry‐state dependence characteristic of pressure broadening, and inelastic processes in general, involving spherical‐top molecules. Pressure‐induced line shifts have also been measured for these features in pure methane. The pressure‐shift coefficients do not display the symmetry‐state dependence found for the linewidths. By applying the Rosenkranz perturbation treatment to a pair of collisionally mixed lines, we have been able to obtain an estimate of individual state‐to‐state contributions to the overall linewidth.

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