The N(⁴S) + O₂(X³Σ−g) ↔ O(³P) + NO(X²Π) reaction: thermal and vibrational relaxation rates for the ²A′, ⁴A′ and ²A′′ states

Abstract

Cross sections, rates, equilibrium constants and vibrational relaxation times for the N(4S) + O2(X3Σ−g) ↔ O(3P) + NO(X2Π) reaction from simulations on new, RKHS-based surfaces for the three lowest electronic states.

Accurate reproducing kernel-based potential energy surfaces for the triplet ground states of N2O and dynamics for the N + NO ↔ O + N2and N2+ O → 2N + O reactions

“…These findings underline the point that different observables (here reaction and vibrational relaxation rates) can be sensitive to different parts of the PES in the dynamics. 39 This is also manifest from Fig. S3 (ESI †): PNR and QR trajectories sample and are sensitive to distinctly different regions of the multidimensional PESs.…”

“…This level of theory has been found to describe the electronic structures for the C-, N-, O-containing species quite well for the global PES. 27,37,39 State-averaged complete active space self-consistent field [47][48][49][50] calculations were carried out prior to the MRCI calculations in order to obtain a smooth topology of the MRCI PESs. In the State-averaged CASSCF calculations a total of eight states were included (the two lowest states from each spin (singlet and triplet) and spatial (A 0 and A 00 ) symmetry).…”

“…36 and 52 and has also been used to construct PESs for other triatomic systems. [37][38][39] Fig. 1 Schematic energy diagram for the N 2 O system showing different reactant channels, minima (MIN i) and transition states (TS i).…”

“…On the other hand the reproducing kernel Hilbert space (RKHS) interpolation procedure can capture the correct long range behavior for different types of interactions. [36][37][38][39] Another relevant quantity that balances the energy content of hot gas flow is the exchange and relaxation of vibrational energy which can also be determined from QCT simulations. 40,41 This property has been found to be sensitive to different regions of the PES than reaction rates 39 and provides an additional possibility to validate the quality of the PESs.…”

A Theoretical Study of the N2 + H2 Reactive Collisions for High Vibrational and Translational Energies

“…Both curves experience a very rapid increase until the formation of a high-value plateau after the translational temperature of 15,000 K. Such temperatures, and higher, are obtained in the modeling studies reported in [1][2][3] for the shock wave produced by hypersonic objects in the atmosphere; thus, the formation of abundant atomic hydrogen considering the high chemical rate predicted by Equation ( 17) is a real possibility in the air around hypersonic objects. In a recent paper [30], a QCT study of the reaction (18) for a wide range of temperatures (300 ≤ T/K ≤ 20,000) was presented. The total rate for the reaction (18) was reported, including also the weighted contribution of the…”