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The N(4S) + O2(X3Sigma) O(3P) + NO(X2Pi) reaction: thermal and vibrational relaxation rates for the 2A', 4A' and 2A'' states

San Vicente Veliz, Juan Carlos and Koner, Debasish and Schwilk, Max and Bemish, Raymond J. and Meuwly, Markus. (2020) The N(4S) + O2(X3Sigma) O(3P) + NO(X2Pi) reaction: thermal and vibrational relaxation rates for the 2A', 4A' and 2A'' states. Physical Chemistry Chemical Physics, 22 (7). pp. 3927-3939.

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Abstract

The kinetics and vibrational relaxation of the N(4S) + O2(X3Sigma-g) O(3P) + NO(X2Pi) reaction is investigated over a wide temperature range based on quasiclassical trajectory simulations on 3-dimensional potential energy surfaces (PESs) for the lowest three electronic states. Reference energies at the multi reference configuration interaction level are represented as a reproducing kernel and the topology of the PESs is rationalized by analyzing the CASSCF wavefunction of the relevant states. The forward rate matches one measurement at 1575 K and is somewhat lower than the high-temperature measurement at 2880 K whereas for the reverse rate the computations are in good agreement for temperatures between 3000 and 4100 K. The temperature-dependent equilibrium rates are consistent with results from JANAF and CEA results. Vibrational relaxation rates for O + NO(nu = 1) O + NO(nu = 0) are consistent with a wide range of experiments. This process is dominated by the dynamics on the 2A' and 4A' surfaces which both contribute similarly up to temperatures T 3000 K, and it is found that vibrationally relaxing and non-relaxing trajectories probe different parts of the potential energy surface. The total cross section depending on the final vibrational state monotonically decreases which is consistent with early experiments and previous simulations but at variance with other recent experiments which reported an oscillatory cross section.
Faculties and Departments:05 Faculty of Science > Departement Chemie > Chemie > Physikalische Chemie (Meuwly)
UniBasel Contributors:San Vicente Veliz, Juan Carlos
Item Type:Article, refereed
Article Subtype:Research Article
Publisher:Royal Society of Chemistry
ISSN:1463-9076
e-ISSN:1463-9084
Note:Publication type according to Uni Basel Research Database: Journal article
Language:English
Identification Number:
Last Modified:25 Feb 2020 14:42
Deposited On:25 Feb 2020 14:42

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