Steric effects and quantum interference in the inelastic scattering of NO(X) + Ar.

Abstract

Rotationally inelastic collisions of NO(X) with Ar are investigated in unprecedented detail using state-to-state, crossed molecular beam experiments. The NO(X) molecules are selected in the Ω = 0.5, j = 0.5, f state and then oriented such that either the 'N' or 'O' end of the molecule is directed towards the incoming Ar atom. Velocity map ion imaging is then used to probe the scattered NO molecules in well-defined quantum states. We show that the fully quantum state-resolved differential steric asymmetry, which quantifies how the relative efficiency for scattering off the 'O' and the 'N' ends of the molecule varies with scattering angle, is strongly affected by quantum interference. Significant changes in both integral and differential cross sections are found depending on whether collisions occur with the N or O ends of the molecule. The results are well accounted for by rigorous quantum mechanical calculations, in contrast to both classical trajectory calculations and more simplistic models that provide, at best, an incomplete picture of the dynamics.