Rotationally inelastic scattering in CH4+He, Ne, and Ar: State-to-state cross sections via direct infrared laser absorption in crossed supersonic jets

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Abstract
Absolute integral state‐to‐state cross sections are reported for rotationally inelastic scattering in crossed jets of CH4 with the rare gases He, Ne, Ar, at center of mass collision energies of 460±90, 350±70, and 300±60 cm−1, respectively. CH4 seeded in Ar buffer gas is cooled in a pulsed supersonic expansion into the three lowest rotational levels allowed by nuclear spin statistics corresponding to A(J=0), F(J=1), and E(J=2) symmetry. Rotational excitation occurs in single collisions with rare gas atoms from a second pulsed supersonic jet. The column integrated densities of CH4 in both initial and final scattering states are subsequently probed in the jet intersection region via direct absorption of light from a narrow bandwidth (0.0001 cm−1), single mode color center laser. Total inelastic cross sections for collisional loss out of the J=0, 1, and 2 methane states are determined in absolute units from the linear decrease of infrared absorption signals as a function of collider gas concentration. Tuning of the ir laser source also permits probing of the collisionally excited rotational states with quantum state and velocity resolution; column integrated scattering densities are measured for all energetically accessible final states and used to infer absolute inelastic cross sections for state‐to‐state energy transfer. The observed trends are in good qualitative agreement with quantum state resolved pressure broadening studies; however, the dependences of the rotationally inelastic cross sections on nuclear spin modification (i.e., J) and rotational inelasticity (i.e., ΔJ) is not well predicted by conventional angular momentum or energy gap models. More rigorous comparison with the quantum state‐resolved scattering data is obtained from full close coupled scattering calculations on trial potential energy surfaces by Buck and co‐workers [Chem. Phys. Lett. 98, 199 (1983); Mol. Phys. 55, 1233, 1255 (1985)] for each of the three CH4+rare gas systems. Agreement between theory and experiment for He+CH4 is nearly quantitative, but some discrepancies are noted for the heavier rare gases. Finally, the possible influence of sequential collision channels on the measurement of the smallest observable cross sections is investigated via a master equation analysis.