The collisional depolarization of OH(A (2)Sigma(+)) and NO(A (2)Sigma(+)) with Kr

Quantum beat spectroscopy has been used to measure rate coefficients at 300 K for collisional depolarization for NO(A (2)Sigma(+)) and OH(A (2)Sigma(+)) with krypton. Elastic depolarization rate coefficients have also been determined for OH(A) + Kr, and shown to make a much more significant contribution to the total depolarization rate than for NO(A) + Kr. While the experimental data for NO(A) + Kr are in excellent agreement with single surface quasiclassical trajectory (QCT) calculations carried out on the upper 2A' potential energy surface, the equivalent QCT and quantum mechanical calculations cannot account for the experimental results for OH(A) + Kr collisions, particularly at low N. This disagreement is due to the presence of competing electronic quenching at low N, which requires a multi-surface, non-adiabatic treatment. Somewhat improved agreement with experiment is obtained by means of trajectory surface hopping calculations that include non-adiabatic coupling between the ground 1A' and excited 2A' states of OH(X/A) + Kr, although the theoretical depolarization cross sections still significantly overestimate those obtained experimentally. (C) 2014 AIP Publishing LLC.