Parity-Dependent Rotational Energy Transfer in CN(A2Π, ν = 4, j F1ε) + N2, O2, and CO2 Collisions

We report state-resolved total removal cross sections and state-to-state rotational energy transfer (RET) cross sections for collisions of CN(A(2)Pi, nu = 4, j F-1 epsilon) with N-2, O-2, and CO2. CN(X-2 Sigma(+)) was produced by 266 nm photolysis of ICN in a thermal bath (296 K) of the collider gas. A circularly polarized pulse from a dye laser prepared CN(A(2)Pi, nu = 4) in a range of F(1)e rotational states,) = 2.5, 3.5, 6.5, 11.5, 13.5, and 18.5. These prepared states were monitored using the circularly polarized output of an external cavity diode laser by frequency-modulated (FM) spectroscopy on the CN(A-X)(4,2) band. The FM Doppler profiles were analyzed as a function of pump-probe delay to determine the time dependence of the population of the initially prepared states. Kinetic analysis of the resulting time dependences was used to determine total removal cross sections from the initially prepared levels. In addition, a range of j' F(1)e and F(2)f product states resulting from rotational energy transfer out of the j = 6.5 F(1)e initial state were probed, from which state-to-state RET cross sections were measured. The total removal cross sections lie in the order CO2 > N-2 > O-2, with evidence for substantial cross sections for electronic and/or reactive quenching of CN(A, nu = 4) to unobserved products with CO2 and O-2. This is supported by the magnitude of the state-to-state RET cross sections, where a deficit of transferred population is apparent for CO2 and O-2. A strong propensity for conservation of rotational parity in RET isobserved for all three colliders. Spin-orbit-changing cross sections are approximately half of those of the respective conserving cross sections. These results are in marked disagreement with previous experimental observations with N-2 as a collider but are in good agreement with quantum scattering calculations from the same study (Khachatrian et al. J. Phys. Chem. A 2009, 113, 3922). Our results with CO2 as a collider are similarly in strong disagreement with a related experimental study (Khachatrian et al. J. Phys. Chem. A 2009, 113, 13390). We therefore propose that the previous experiments substantially underestimated the spin-orbit-changing cross sections for collisions with both N-2 and CO2, suggesting that even approximate quantum scattering calculations may be more successful for such molecule-molecule systems than was previously concluded.