title: Depolarization of rotational angular momentum in CN(A2Π, v = 4) + Ar collisions.
abstract: Angular momentum depolarization and population transfer in CN(A(2)Π, v = 4, j, F(1)e) + Ar collisions have been investigated both experimentally and theoretically. Ground-state CN(X(2)Σ(+)) molecules were generated by pulsed 266-nm laser photolysis of ICN in a thermal (nominally 298 K) bath of the Ar collision partner at a range of pressures. The translationally thermalized CN(X) radicals were optically pumped to selected unique CN(A(2)Π, v = 4, j = 2.5, 3.5, 6.5, 11.5, 13.5, and 18.5, F(1)e) levels on the A-X (4,0) band by a pulsed tunable dye laser. The prepared level was monitored in a collinear geometry by cw frequency-modulated (FM) spectroscopy in stimulated emission on the CN(A-X) (4,2) band. The FM lineshapes for co- and counter-rotating circular pump and probe polarizations were analyzed to extract the time dependence of the population and (to a good approximation) orientation (tensor rank K = 1 polarization). The corresponding parallel and perpendicular linear polarizations yielded population and alignment (K = 2). The combined population and polarization measurements at each Ar pressure were fitted to a 3-level kinetic model, the minimum complexity necessary to reproduce the qualitative features of the data. Rate constants were extracted for the total loss of population and of elastic depolarization of ranks K = 1 and 2. Elastic depolarization is concluded to be a relatively minor process in this system. Complementary full quantum scattering (QS) calculations were carried out on the best previous and a new set of ab initio potential energy surfaces for CN(A)-Ar. Collision-energy-dependent elastic tensor and depolarization cross sections for ranks K = 1 and 2 were computed for CN(A(2)Π, v = 4, j = 1.5-10.5, F(1)e) rotational/fine-structure levels. In addition, integral cross sections for rotationally inelastic transitions out of these levels were computed and summed to yield total population transfer cross sections. These quantities were integrated over a thermal collision-energy distribution to yield the corresponding rate constants. A complete master-equation simulation using the QS results for the selected initial level j = 6.5 gave close, but not perfect, agreement with the near-exponential experimental population decays, and successfully reproduced the observed multimodal character of the polarization decays. On average, the QS population removal rate constants were consistently 10%-15% higher than those derived from the 3-level fit to the experimental data. The QS and experimental depolarization rate constants agree within the experimental uncertainties at low j, but the QS predictions decline more rapidly with j than the observations. In addition to providing a sensitive test of the achievable level of agreement between state-of-the art experiment and theory, these results highlight the importance of multiple collisions in contributing to phenomenological depolarization using any method sensitive to both polarized and unpolarized molecules in the observed level.
authors.affiliation: School of Engineering and Physical Sciences, Heriot-Watt University, Edinburgh EH14 4AS, United Kingdom.
authors.forename: S J
authors.initials: SJ
authors.lastname: McGurk
authors.forename: K G
authors.initials: KG
authors.lastname: McKendrick
authors.forename: M L
authors.initials: ML
authors.lastname: Costen
authors.forename: D I G
authors.initials: DI
authors.lastname: Bennett
authors.forename: J
authors.initials: J
authors.lastname: Kłos
authors.forename: M H
authors.initials: MH
authors.lastname: Alexander
authors.forename: P J
authors.initials: PJ
authors.lastname: Dagdigian