Ozone destruction due to the recombination of oxygen atoms

Kinetics of ozone destruction due to the recombination of oxygen atoms produced by pulsed 266 nm laser photolysis of O₃/M (M = CO₂ and/or N₂) mixtures was studied using the absorption and emission spectroscopy to follow time evolutions of O₃ and electronically excited molecules O₂* formed in the recombination process 2O(³P) + M → O₂* + M. An unexpected high ozone destruction rate was observed when O₂* was present in the system. The kinetic model developed for the oxygen nightglow on the terrestrial planets was adapted to interpret the detected temporal profiles of the ozone number density and the O₂* emission intensities. It was deduced that the vibrationally excited singlet delta oxygen molecule O₂(a¹Δ, υ) formed in the secondary processes reacts efficiently with ozone in the process O₂(a¹Δ, υ ≥ 3) + O₃ → 2O₂ + O, and the rate constant of this process was estimated to be 3 × 10^-11 cm³ s^-1. Ab initio calculations at the CASPT2(14, 12)/cc-pVTZ/UωB97XD/cc-pVTZ level of theory were applied to find the reaction pathway from the reactants to products on the O₅ potential energy surface. These calculations revealed that the O₂(a¹Δ) + O₃ reaction is likely to proceed via singlet-triplet intersystem crossing exhibiting an energy barrier of 9.6 kcal/mol, which lies between two and three quanta of vibrational excitation of O₂(a¹Δ), and hence, O₂(a¹Δ, υ) with υ ≥ 3 could rapidly react with ozone.