Parity-dependent oscillations in collisional polarization transfer: CN(A²Π, v = 4) + Ar

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.