The dynamics for the NO(X2Π) + 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.
@article{arxiv.2506.06146,
title = {Reaction Dynamics for the [NNO] System from State-Resolved and Coarse-Grained Models},
author = {Juan Carlos San Vicente Veliz and Sung Min Jo and Jingchun Wang and Raymond J. Bemish and Markus Meuwly},
journal= {arXiv preprint arXiv:2506.06146},
year = {2025}
}