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Title: Computational study of collisions between O({sup 3}P) and NO({sup 2}Π) at temperatures relevant to the hypersonic flight regime

Abstract

Reactions involving N and O atoms dominate the energetics of the reactive air flow around spacecraft when reentering the atmosphere in the hypersonic flight regime. For this reason, the thermal rate coefficients for reactive processes involving O({sup 3}P) and NO({sup 2}Π) are relevant over a wide range of temperatures. For this purpose, a potential energy surface (PES) for the ground state of the NO{sub 2} molecule is constructed based on high-level ab initio calculations. These ab initio energies are represented using the reproducible kernel Hilbert space method and Legendre polynomials. The global PES of NO{sub 2} in the ground state is constructed by smoothly connecting the surfaces of the grids of various channels around the equilibrium NO{sub 2} geometry by a distance-dependent weighting function. The rate coefficients were calculated using Monte Carlo integration. The results indicate that at high temperatures only the lowest A-symmetry PES is relevant. At the highest temperatures investigated (20 000 K), the rate coefficient for the “O1O2+N” channel becomes comparable (to within a factor of around three) to the rate coefficient of the oxygen exchange reaction. A state resolved analysis shows that the smaller the vibrational quantum number of NO in the reactants, the higher the relativemore » translational energy required to open it and conversely with higher vibrational quantum number, less translational energy is required. This is in accordance with Polanyi's rules. However, the oxygen exchange channel (NO2+O1) is accessible at any collision energy. Finally, this work introduces an efficient computational protocol for the investigation of three-atom collisions in general.« less

Authors:
; ;  [1];  [2]
  1. Department of Chemistry, University of Basel, Klingelbergstrasse 80, CH-4056 Basel (Switzerland)
  2. Air Force Research Laboratory, Space Vehicles Directorate, Kirtland AFB, New Mexico 87117 (United States)
Publication Date:
OSTI Identifier:
22310760
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 141; Journal Issue: 16; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0021-9606
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS; 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ATOM COLLISIONS; ATOMS; GROUND STATES; HILBERT SPACE; LEGENDRE POLYNOMIALS; MOLECULES; MONTE CARLO METHOD; NITRIC OXIDE; NITROGEN DIOXIDE; OXYGEN; POTENTIAL ENERGY

Citation Formats

Castro-Palacio, Juan Carlos, Nagy, Tibor, Meuwly, Markus, and Bemish, Raymond J. Computational study of collisions between O({sup 3}P) and NO({sup 2}Π) at temperatures relevant to the hypersonic flight regime. United States: N. p., 2014. Web. doi:10.1063/1.4897263.
Castro-Palacio, Juan Carlos, Nagy, Tibor, Meuwly, Markus, & Bemish, Raymond J. Computational study of collisions between O({sup 3}P) and NO({sup 2}Π) at temperatures relevant to the hypersonic flight regime. United States. https://doi.org/10.1063/1.4897263
Castro-Palacio, Juan Carlos, Nagy, Tibor, Meuwly, Markus, and Bemish, Raymond J. 2014. "Computational study of collisions between O({sup 3}P) and NO({sup 2}Π) at temperatures relevant to the hypersonic flight regime". United States. https://doi.org/10.1063/1.4897263.
@article{osti_22310760,
title = {Computational study of collisions between O({sup 3}P) and NO({sup 2}Π) at temperatures relevant to the hypersonic flight regime},
author = {Castro-Palacio, Juan Carlos and Nagy, Tibor and Meuwly, Markus and Bemish, Raymond J.},
abstractNote = {Reactions involving N and O atoms dominate the energetics of the reactive air flow around spacecraft when reentering the atmosphere in the hypersonic flight regime. For this reason, the thermal rate coefficients for reactive processes involving O({sup 3}P) and NO({sup 2}Π) are relevant over a wide range of temperatures. For this purpose, a potential energy surface (PES) for the ground state of the NO{sub 2} molecule is constructed based on high-level ab initio calculations. These ab initio energies are represented using the reproducible kernel Hilbert space method and Legendre polynomials. The global PES of NO{sub 2} in the ground state is constructed by smoothly connecting the surfaces of the grids of various channels around the equilibrium NO{sub 2} geometry by a distance-dependent weighting function. The rate coefficients were calculated using Monte Carlo integration. The results indicate that at high temperatures only the lowest A-symmetry PES is relevant. At the highest temperatures investigated (20 000 K), the rate coefficient for the “O1O2+N” channel becomes comparable (to within a factor of around three) to the rate coefficient of the oxygen exchange reaction. A state resolved analysis shows that the smaller the vibrational quantum number of NO in the reactants, the higher the relative translational energy required to open it and conversely with higher vibrational quantum number, less translational energy is required. This is in accordance with Polanyi's rules. However, the oxygen exchange channel (NO2+O1) is accessible at any collision energy. Finally, this work introduces an efficient computational protocol for the investigation of three-atom collisions in general.},
doi = {10.1063/1.4897263},
url = {https://www.osti.gov/biblio/22310760}, journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 16,
volume = 141,
place = {United States},
year = {Tue Oct 28 00:00:00 EDT 2014},
month = {Tue Oct 28 00:00:00 EDT 2014}
}