Rotationally inelastic scattering of CD sub(3) and CH sub(3) with He: comparison of velocity map-imaging data with quantum scattering calculations

Rotationally inelastic scattering of methyl radicals (CD sub(3) and CH sub(3)) in collisions with helium is examined by a combination of velocity map imaging experiments and quantum scattering calculations. In the experiments a beam of methyl radicals seeded in Ar intersects a beam of He atoms at 90 degree at a collision energy of 440 plus or minus 35 cm super(-1) (CD sub(3) + He) or 425 plus or minus 35 cm super(-1) (CH sub(3) + He). The methyl radicals are prepared photolytically in a gas expansion that cools them to 15 K, giving a distribution over a small number of initial (low) rotational angular momentum states. By resonance-enhanced multi-photon ionization detection, we obtain velocity map images which are specific to a single rotational angular momentum quantum number n' of the methyl radicals, but averaged over a small subset of the projection quantum number k'. We extract resolved angular scattering distributions for n' = 2-9 (for CD sub(3)). We compare these to predictions of scattering calculations performed based on a recent potential energy surface [P. J. Dagdigian and M. H. Alexander, J. Chem. Phys.2011, 135, 064306] in which the methyl radical was fixed at its equilibrium geometry. The fully (n, k) arrow right (n', k') resolved differential cross sections obtained from the calculations, when combined in weighted sums over initial (n, k) levels corresponding to the 15 K experimental radical temperature, and final k' levels that are not resolved in the spectroscopic detection scheme, show excellent agreement with the experimental measurements for all final states probed. This agreement gives confidence in the calculated dependence of the scattering on changes in both the nand kquantum numbers.