Retrieval of total ozone in the mesosphere with a new model of electronic-vibrational kinetics of O3 and O2 photolysis products

The paper presents a new model of electronic-vibrational kinetics of the products of ozone and molecular oxygen photodissociation in the terrestrial middle atmosphere. The model includes 45 excited states of the oxygen molecules O₂(b ¹, Σ _g ⁺ ,v= 0?2), O₂ (a ¹Δ _g , v= 0?5), and O₂(X ³Σ _g ^? , v= 1?35) and of the metastable atom O (¹ D) and over 100 aeronomic reactions. The model takes into account the dependence of quantum yields of the production of O₂(a ¹Δ _g , v= 0?5) in a singlet channel of ozone photolysis in the Hartley band on the wavelength of photolytic emission. Taking account of the electronic-vibrational kinetics is important in retrieval of the vertical profiles of ozone concentration from measured intensities of the Atm and IR Atm emissions of the oxygen bands above 65 km and leads to an increase in the ozone concentration retrieved from the 1.27-µm emission, in contrast to the previous model of pure electronic kinetics. Sensitivity analysis of the new model is made for variations in the concentrations of atmospheric constituents ([O₂], [N₂], [O(³P)], [O₃], [CO₂]), the gas temperature, rate constants of the reactions, and quantum yields of the reaction products. A group of reactions that most strongly affect the uncertainty of ozone retrieval from measured intensities of atmospheric emissions of molecular oxygen O₂(b ¹Σ _g ⁺ , v) and O₂(a ¹Δ _g , v) has been determined.