Dissociation cross sections and rates in O2 + N collisions: molecular dynamics simulations combined with machine learning

• Published in: Physical chemistry chemical physics : PCCP Vol. 25; no. 43; pp. 29475 - 29485
• Main Authors: Huang, Xia, Kun-Ming Gu, Chang-Min, Guo, Xin-Lu, Cheng
• Format: Journal Article
• Language: English
• Published: Cambridge Royal Society of Chemistry 08.11.2023
• Subjects: Air flow; Cross-sections; Machine learning; Mathematical models; Molecular dynamics; Neural networks; Nitrogen dioxide; Potential energy; Quantum numbers; Reentry; Reentry vehicles; Simulation; Spacecraft reentry
• ISSN: 1463-9076; 1463-9084; 1463-9084
• DOI: 10.1039/d3cp04044e

The collision-induced dissociation reaction of O2 (v, j) + N, a fundamental process in nonequilibrium air flows around reentry vehicles, has been studied systematically by applying molecular dynamics simulations on the 2A′, 4A′ and 6A′ potential energy surfaces of NO2 in a wide temperature range. In particular, we have directly investigated the role of the 6A′ surface in this process and discussed the applicability of the simplified approximate rate models proposed by Esposito et al. and Andrienko et al. based on the lowest two surfaces. The present work indicates that the state-selected dissociation of O2 + N is dominated by the 6A′ surface for all except for the low-lying O2 states. Furthermore, a complete database of rovibrationally detailed cross sections and rate coefficients is a prerequisite for modeling the relevant nonequilibrium air flows in spacecraft reentry. Here, the combination of the quasi-classical trajectory (QCT) and the neural network (NN) has been proposed to predict all state-selected dissociation cross sections and further construct dissociation parameter sets. All NN-based models established in this work accurately reproduce the results calculated from QCT simulations over a wide range of rovibrational quantum numbers with R2 > 0.99. Compared with the explicit QCT simulations, the computational requirement for predicting cross sections and rates based on the NN models significantly reduces. Finally, thermal equilibrium rate coefficients computed from NN models match remarkably well the available theoretical and experimental results in the whole temperature range explored.