Theoretical Kinetics Predictions for Reactions on the NH2O Potential Energy Surface

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Vol. 127; no. 41; pp. 8650 - 8662
• Main Authors: Klippenstein, Stephen J., Mulvihill, Clayton R., Glarborg, Peter
• Format: Journal Article
• Language: English
• Published: American Chemical Society 19-10-2023
• Subjects: A: Combustion and Plasma Chemistry
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/acs.jpca.3c05181

Recent modeling studies of ammonia oxidation, which are motivated by the prospective role of ammonia as a zero-carbon fuel, have indicated significant discrepancies among the existing literature mechanisms. In this study, high-level theoretical kinetics predictions have been obtained for reactions on the NH2O potential energy surface, including the NH2 + O, HNO + H, and NH + OH reactions. These reactions have previously been highlighted as important reactions in NH3 oxidation with high sensitivity and high uncertainty. The potential energy surface is explored with coupled cluster calculations, including large basis sets and high-level corrections to yield high-accuracy (∼0.2 kcal/mol 2σ uncertainty) estimates of the stationary point energies. Variational transition state theory is used to predict the microcanonical rate constants, which are then incorporated in master equation treatments of the temperature- and pressure-dependent kinetics. For radical–radical channels, the microcanonical rates are obtained from variable reaction coordinate transition state theory implementing directly evaluated multireference electronic energies. The analysis yields predictions for the total rate constants as well as the branching ratios. We find that the NO + H2 channel contributes 10% of the total NH2 + O flux at combustion temperatures, although this channel is not included in modern NH3 oxidation mechanisms. Modeling is used to illustrate the ramifications of these rate predictions on the kinetics of NH3 oxidation and NO x formation. The present results for NH2 + O are important for predicting the chain branching and formation of NO in the oxidation of NH3 and thermal DeNO x .