New studies of the unimolecular reaction NO2O+NO. Part 2. Relation between high pressure rate constants and potential parameters

Abstract

The potential energy surfaces of the X 1²A′- and C 1²A″-states of the dissociation/recombination system NO₂O+NO have been characterized by abinitio methods. Thermal rate constants for the high pressure limit of this reaction have been determined by calculating classical trajectories with simplified representations of the two abinitio potentials. The results well agree with the less accurate experimental data in this temperature range. The treatment is compared with relationships for model valence potentials which were derived earlier. It is demonstrated which parts of the potential are most relevant and to what extent the rate constants could have been predicted without specific abinitio information.