High-Energy Reaction Dynamics of N$_{3}$
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arXiv
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| Autores principales: | , , |
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| Formato: | Preprint |
| Publicado: |
2024
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| _version_ | 1866917652822228992 |
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| author | Wang, JingChun Veliz, Juan Carlos San Vicente Meuwly, Markus |
| author_facet | Wang, JingChun Veliz, Juan Carlos San Vicente Meuwly, Markus |
| contents | The atom-exchange and atomization dissociation dynamics for the N($^4$S) + N$_2(^1 Σ_{\rm g}^+)$ reaction is studied using a reproducing kernel Hilbert space (RKHS)-based, global potential energy surface (PES) at the MRCI-F12/aug-cc-pVTZ-F12 level of theory. For the atom exchange reaction $({\rm N_A N_B} + {\rm N_C} \rightarrow {\rm
N_A N_C} + {\rm N_B}$), computed thermal rates and their temperature dependence from quasi-classical trajectory (QCT) simulations agree to within error bars with the available experiments. Companion QCT simulations using a recently published CASPT2-based PES confirm these findings. For the atomization reaction, leading to three N$(^4{\rm
S})$ atoms, the computed rates from the RKHS-PES overestimate the experimentally reported rates by one order of magnitude whereas those from the PIP-PES agree favourably, and the $T$-dependence of both computations is consistent with experiment. These differences can be traced back to the different methods and basis sets used. The lifetime of the metastable N$_3$ molecule is estimated to be $\sim 200$ fs depending on the initial state of the reactants. Finally, neural network-based exhaustive state-to-distribution models are presented using both PESs for the atom exchange reaction. These models will be instrumental for a broader exploration of the reaction dynamics of air. |
| format | Preprint |
| id |
arxiv_https___arxiv_org_abs_2404_18877 |
| institution | arXiv |
| publishDate | 2024 |
| record_format | arxiv |
| spellingShingle | High-Energy Reaction Dynamics of N$_{3}$ Wang, JingChun Veliz, Juan Carlos San Vicente Meuwly, Markus Chemical Physics The atom-exchange and atomization dissociation dynamics for the N($^4$S) + N$_2(^1 Σ_{\rm g}^+)$ reaction is studied using a reproducing kernel Hilbert space (RKHS)-based, global potential energy surface (PES) at the MRCI-F12/aug-cc-pVTZ-F12 level of theory. For the atom exchange reaction $({\rm N_A N_B} + {\rm N_C} \rightarrow {\rm N_A N_C} + {\rm N_B}$), computed thermal rates and their temperature dependence from quasi-classical trajectory (QCT) simulations agree to within error bars with the available experiments. Companion QCT simulations using a recently published CASPT2-based PES confirm these findings. For the atomization reaction, leading to three N$(^4{\rm S})$ atoms, the computed rates from the RKHS-PES overestimate the experimentally reported rates by one order of magnitude whereas those from the PIP-PES agree favourably, and the $T$-dependence of both computations is consistent with experiment. These differences can be traced back to the different methods and basis sets used. The lifetime of the metastable N$_3$ molecule is estimated to be $\sim 200$ fs depending on the initial state of the reactants. Finally, neural network-based exhaustive state-to-distribution models are presented using both PESs for the atom exchange reaction. These models will be instrumental for a broader exploration of the reaction dynamics of air. |
| title | High-Energy Reaction Dynamics of N$_{3}$ |
| topic | Chemical Physics |
| url | https://arxiv.org/abs/2404.18877 |