Reaction Dynamics for the [NNO] System from State-Resolved and Coarse-Grained Models
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| Format: | Preprint |
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2025
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| _version_ | 1866909641179398144 |
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| author | Veliz, Juan Carlos San Vicente Jo, Sung Min Wang, Jingchun Bemish, Raymond J. Meuwly, Markus |
| author_facet | Veliz, Juan Carlos San Vicente Jo, Sung Min Wang, Jingchun Bemish, Raymond J. Meuwly, Markus |
| contents | The dynamics for the NO($X^2 Π$) + N($^4$S) $\leftrightarrow$ N$_{2}(X^{1}Σ_{g}^{+}$) + O($^{3}$P) reaction was followed in the $^3$A' 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 $\sim 10^{-6}$ s whether or not reverse rates are from assuming microreversibility or explicitly given. Conversion from NO to N$_2$ 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. |
| format | Preprint |
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arxiv_https___arxiv_org_abs_2506_06146 |
| institution | arXiv |
| publishDate | 2025 |
| record_format | arxiv |
| spellingShingle | Reaction Dynamics for the [NNO] System from State-Resolved and Coarse-Grained Models Veliz, Juan Carlos San Vicente Jo, Sung Min Wang, Jingchun Bemish, Raymond J. Meuwly, Markus Chemical Physics The dynamics for the NO($X^2 Π$) + N($^4$S) $\leftrightarrow$ N$_{2}(X^{1}Σ_{g}^{+}$) + O($^{3}$P) reaction was followed in the $^3$A' 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 $\sim 10^{-6}$ s whether or not reverse rates are from assuming microreversibility or explicitly given. Conversion from NO to N$_2$ 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. |
| title | Reaction Dynamics for the [NNO] System from State-Resolved and Coarse-Grained Models |
| topic | Chemical Physics |
| url | https://arxiv.org/abs/2506.06146 |