Analysis of hydroxyl earthlimb airglow emissions: Kinetic model for state‐to‐state dynamics of OH (υ,N)

Detailed spectroscopic analysis of hydroxyl fundamental vibration-rotation and pure rotation emission lines has yielded OH(υ,N) absolute column densities for nighttime earthlimb spectra in the 20 to 110-km tangent height region. High-resolution spectra were obtained in the Cryogenic Infrared Radiance Instrumentation for Shuttle (CIRRIS 1A) experiment. Rotationally thermalized populations in υ = 1–9 have been derived from the fundamental bands between 2000 and 4000 cm−1. Highly rotationally excited populations with N ≤ 33 ( ≤ 2.3 eV rotational energy) have been inferred from the pure rotation spectra between 400 and 1000 cm−1. These emissions originate in the airglow region near 85–90 km altitude. Spectral fits of the pure rotation lines imply equal populations in the spinrotation states F1 and F2 but a ratio Π(A′):Π(A″) = 1.8±0.3 for the Λ-doublet populations. A forward predicting, first-principles kinetic model has been developed for the resultant OH(υ,N) limb column densities. The kinetic model incorporates a necessary and sufficient number of processes known to generate and quench OH(υ,N) in the mesopause region and includes recently calculated vibration-rotation Einstein coefficients for the high-N levels. The model reproduces both the thermal and the highly rotationally excited OH(υ,N) column densities. The tangent height dependence of the rotationally excited OH(υ,N) column densities is consistent with two possible formation mechanisms: (1) transfer of vibrational to rotational energy induced by collisions with O atoms or (2) direct chemical production via H + O3 → OH(υ,N) + O2.