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

Abstract

Accurate potential energy surfaces (PESs) have been determined for the 3A' and 3A'' states of N2O using electronic structure calculations at the multireference configuration interaction level with Davidson correction (MRCI+Q)...

Rovibrational-Specific QCT and Master Equation Study on $\text{N}_2(\text{X}^1Σ_g^+)$+$\text{O}({}^3\text{P})$ and $\text{NO}(\text{X}^2Π)$+$\text{N}({}^4\text{S})$ Systems in High-Energy Collisions

“…As a downside, CASPT2 method makes the PESs less reliable for studying dissociation reactions. Furthermore, it was found in later studies, [5][6][7] that the 3 A ′ surface has additional transition states and local minima that were not accounted for in the PES by Gamallo et al 3 . Accurate consideration of the stationary points is important since they directly affect the reaction pathways of the system being studied.…”

“…The several PESs have been constructed for the N 2 (X 1 Σ + g )+O( 3 P) and NO(X 2 Π)+N( 4 S) systems 2,3,[5][6][7] . The collisions predominantly occur on the lowest triplet surfaces in the A ′ and A ′′ symmetry and, therefore, the focus has been placed on developing the 3 A ′ and 3 A ′′ PESs.…”

“…In addition to the Zel'dovich mechanism (1), collisional energy transfer and dissociation processes of individual collision pairs in the N 2 O system (i.e., N 2 +O and NO+N) are also relevant in developing a reliable thermochemical non-equilibrium model for high-temperature air. Regarding the N 2 O system, previous theoretical studies [2][3][4][5][6][7][8] have been carried out by means of ab-initio potential energy surface (PES) constructions followed by quasi-classical trajectory (QCT) calculations for particular chemical reaction channels. Each of the PESs developed by Bose and Candler 2 , and Gamallo et al 3 was employed to compute thermal rate coefficients for the Zel'dovich reaction (1).…”

“…Luo et al 4 computed the same quantity along with the thermal dissociation rate coefficient in N 2 +O collisions by relying on the PESs from Gamallo et al 3 . Koner et al 5 improved the accuracy of the PESs of Denis-Alpizar et al 6 by using neural networks. Lin et al 7,8 constructed global PESs that cover a wide range of reactive configurations, and they numerically investigated the reactive trajectories for the Zel'dovich mechanism (1).…”

“…Lin et al 7,8 constructed global PESs that cover a wide range of reactive configurations, and they numerically investigated the reactive trajectories for the Zel'dovich mechanism (1). The aforementioned studies [2][3][4][5][6][7][8] focused on specific portions of the reaction dynamics that can occur on the N 2 O surfaces, instead of the overall energy transfer and dissociation mechanisms. In addition, to the authors' best knowledge, no detailed state-to-state (StS) master equation analysis has been carried out for the N 2 O system.…”