New insights for mesospheric OH: multi-quantum vibrational relaxation as a driver for non-local thermodynamic equilibrium.

The question of whether mesospheric OH(v) rotational population distributions are in equilibrium with the local kinetic temperature has been debated over several decades. Despite several indications for the existence of non-equilibrium effects, the general consensus has been that emissions originating from low rotational levels are thermalized. Sky spectra simultaneously observing several vibrational levels demonstrated reproducible trends in the extracted OH(v) rotational temperatures as a function of vibrational excitation. Laboratory experiments provided information on rotational energy transfer and direct evidence for fast multi-quantum OH(high-v) vibrational relaxation by O atoms. We examine the relationship of the new relaxation pathways with the behavior exhibited by OH(v) rotational population distributions. Rapid OH(high-v) + O multi-quantum vibrational relaxation connects high and low vibrational levels and enhances the hot tail of the OH(low-v) rotational distributions. The effective rotational temperatures of mesospheric OH(v) are found to deviate from local thermodynamic equilibrium for all observed vibrational levels. Dedicated to Tom G. Slanger in celebration of his 5 decades of research in aeronomy.