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

The question of whether mesospheric OH(υ) 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(υ) 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-υ) vibrational relaxation by O atoms. We examine the relationship of the new relaxation pathways with the behavior exhibited by OH(υ) rotational population distributions. Rapid OH(high-υ) + O multi-quantum vibrational relaxation connects high and low vibrational levels and enhances the hot tail of the OH(low-υ) rotational distributions. The effective rotational temperatures of mesospheric OH(υ) are found to deviate from local thermodynamic equilibrium for all observed vibrational levels.

Pressure broadening and fine-structure-dependent predissociation in oxygen B 3sigma(u)-, v = 0.

Both laser-induced fluorescence and cavity ring-down spectral observations were made in the Schumann-Runge band system of oxygen, using a novel-type ultranarrow deep-UV pulsed laser source. From measurements on the very weak (0,0) band pressure broadening, pressure shift, and predissociation line-broadening parameters were determined for the B 3sigma(u)-, v = 0,F(i) fine-structure components for various rotational levels in O2. The information content from these studies was combined with that of entirely independent measurements probing the much stronger (0,10), (0,19), and (0,20) Schumann-Runge bands involving preparation of vibrationally excited O2 molecules via photolysis of ozone. The investigations result in a consistent set of predissociation widths for the B 3sigma(u)-, v = 0 state of oxygen.

Electron energy-dependent product state distributions in the dissociative recombination of O2+.

We present product state distributions and quantum yields from the dissociative recombination reaction of O2+ in its electronic and vibrational ground states as a function of electron collision energy between 0 and 300 meV. The experiments have been performed in the heavy-ion storage ring, CRYRING, and use a cold hollow-cathode discharge source for the production of cold molecular oxygen ions. The branching fractions over the different dissociation limits show distinct oscillations while the resulting product quantum yields are largely independent of electron collision energy above 40 meV. The branching results are well reproduced assuming an isotropic dissociation process, in contrast with recent theoretical predictions.

Vibrationally resolved rate coefficients and branching fractions in the dissociative recombination of O2+.

We have studied the dissociative recombination of the first three vibrational levels of O(2) (+) in its electronic ground X (2)Pi(g) state. Absolute rate coefficients, cross sections, quantum yields and branching fractions have been determined in a merged-beam experiment in the heavy-ion storage ring, CRYRING, employing fragment imaging for the reaction dynamics. We present the absolute total rate coefficients as function of collision energies up to 0.4 eV for five different vibrational populations of the ion beam, as well as the partial (vibrationally resolved) rate coefficients and the branching fractions near 0 eV collision energy for the vibrational levels v=0, 1, and 2. The vibrational populations used were produced in a modified electron impact ion source, which has been calibrated using Cs-O(2)(+) dissociative charge transfer reactions. The measurements indicate that at low collision energies, the total rate coefficient is weakly dependent on the vibrational excitation. The calculated thermal rate coefficient at 300 K decreases upon vibrational excitation. The partial rate coefficients as well as the partial branching fractions are found to be strongly dependent on the vibrational level. The partial rate coefficient is the fastest for v=0 and goes down by a factor of two or more for v=1 and 2. The O((1)S) quantum yield, linked to the green airglow, increases strongly upon increasing vibrational level. The effects of the dissociative recombination reactions and super elastic collisions on the vibrational populations are discussed.