Rotational Orientation Effects in NO(X) + Ar Inelastic Collisions.

Abstract

Rotational angular momentum orientation effects in the rotationally inelastic collisions of NO(X) with Ar have been investigated both experimentally and theoretically at a collision energy of 530 cm(-1). The collision-induced orientation has been determined experimentally using a hexapole electric field to select the ϵ = -1 Λ-doublet level of the NO(X) j = 1/2 initial state. Fully quantum state resolved polarization-dependent differential cross sections were recorded experimentally using a crossed molecular beam apparatus coupled with a (1 + 1') resonance-enhanced multiphoton ionization detection scheme and subsequent velocity-map imaging. To determine the NO sense of rotation, the probe radiation was circularly polarized. Experimental orientation polarization-dependent differential cross sections are compared with those obtained from quantum mechanical scattering calculations and are found to be in good agreement. The origin of the collision-induced orientation has been investigated by means of close-coupled quantum mechanical, quantum mechanical hard shell, quasi-classical trajectory (QCT), and classical hard shell calculations at the same collision energy. Although there is evidence for the operation of limiting classical mechanisms, the rotational orientation cannot be accounted for by QCT calculations and is found to be strongly influenced by quantum mechanical effects.