RESUMO
We report the first systematic experimental and theoretical study of the state-to-state transfer of rotational angular momentum orientation in a (2)Π-rare gas system. CN(X(2)Σ(+)) was produced by pulsed 266 nm photolysis of ICN in a thermal bath (296 K) of Ar collider gas. A pulsed circularly polarized tunable dye laser prepared CN(A(2)Π, v = 4) in two fully state-selected initial levels, j = 6.5 F1e and j = 10.5 F2f, with a known laboratory-frame orientation. Both the prepared levels and a range of product levels, j' F1e and j' F2f, were monitored using the circular polarized output of a tunable diode laser via cw frequency-modulated (FM) spectroscopy in stimulated emission on the CN(A-X) (4,2) band. The FM Doppler lineshapes for co-rotating and counter-rotating pump-and-probe geometries reveal the time-dependence of the populations and orientations. Kinetic fitting was used to extract the state-to-state population transfer rate constants and orientation multipole transfer efficiencies (MTEs), which quantify the degree of conservation of initially prepared orientation in the product level. Complementary full quantum scattering (QS) calculations were carried out on recently computed ab initio potential energy surfaces. Collision-energy-dependent tensor cross sections for ranks K = 0 and 1 were computed for transitions from both initial levels to all final levels. These quantities were integrated over the thermal collision energy distribution to yield predictions of the experimentally observed state-to-state population transfer rate constants and MTEs. Excellent agreement between experiment and theory is observed for both measured quantities. Dramatic oscillations in the MTEs are observed, up to and including changes in the sign of the orientation, as a function of even/odd Δj within a particular spin-orbit and e/f manifold. These oscillations, along with those also observed in the state-to-state rate constants, reflect the rotational parity of the final level. In general, parity-conserving collisions conserve rotational orientation, while parity-changing collisions result in large changes in the orientation. The QS calculations show that the dynamics of the collisions leading to these different outcomes are fundamentally different. We propose that the origin of this behavior lies in interferences between collisions that sample the even and odd-λ terms in the angular expansions of the PESs.
RESUMO
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.