State-to-state spin–orbit and rotational energy transfer of very highly vibrationally excited nitric oxide

PUMP–DUMP–PROBE experiments were performed on nitric oxide (NO) in order to study the rotational and spin–orbit energy transfer in a highly vibrationally excited diatomic. Total depopulation as well as state-to-state rotational and spin–orbit energy transfer rate constants were measured for v=8 and 19 of the ground electronic state. By comparing this new set of results with previously measured results for v=2 [Aa. Sudbo and M. M. T. Loy, J. Chem. Phys. 76, 3646 (1982)] the vibrational influence on the rotational and spin–orbit energy transfer dynamics could be evaluated. Total depopulation rate constants for individual rovibrational states were found to be very similar for v=2, 8, and 19. State-to-state rotational energy transfer rate constants could be compared for v=8 and 19, and again only small differences were found. It appears that vibrational energy does not have a significant impact on the rotational and spin–orbit energy transfer dynamics for NO–NO collisions.