2025/06/06 by Veliz, Juan Carlos San Vicente, Jo, Sung Min, Wang, Jingchun +2 · 2 citations
#Chemical Physics (physics.chem-ph) #FOS: Physical sciences
paper · doi:10.48550/arxiv.2506.06146
The dynamics for the NO(X2 Π) + N(4S) ↔ N2(X1Σg+) + O(3P) reaction was followed in the 3A' electronic state using state-to-state (STS) and Arrhenius-based rates from two different high-level potential energy surfaces represented as a reproducing kernel (RKHS) and permutationally invariant polynomials (PIPs). Despite the different number of bound states supported by the RKHS- and PIP-PESs the ignition points from STS and Arrhenius rates are at ∼ 10-6 s whether or not reverse rates are from assuming microreversibility or explicitly given. Conversion from NO to N2 is incomplete if Arrhenius-rates are used but complete turnover is observed if STS-information is used. This is due to non-equilibrium energy flow and state dynamics which requires a state-based description. Including full dissociation leads asymptotically to the correct 2:1 [N]:[O] concentration with little differences for the species' dynamics depending on the PES used for the STS-information. In conclusion, concentration profiles from coarse-grained simulations are consistent over 14 orders of magnitude in time using STS-information based on two different high-level PESs.