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Title: Ab initio -informed maximum entropy modeling of rovibrational relaxation and state-specific dissociation with application to the O 2 + O system

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.4947590· OSTI ID:1512881
 [1]; ORCiD logo [2]; ORCiD logo [1]
  1. Purdue Univ., West Lafayette, IN (United States)
  2. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
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Quasi-classical trajectory (QCT) calculations are used to study state-specific ro-vibrational energy exchange and dissociation in the O2 + O system. Atom-diatom collisions with energy between 0.1 and 20 eV are calculated with a double many body expansion potential energy surface by Varandas and Pais [Mol. Phys. 65, 843 (1988)]. Inelastic collisions favor mono-quantum vibrational transitions at translational energies above 1.3 eV although multi-quantum transitions are also important. Post-collision vibrational favoring decreases first exponentially and then linearly as Δv increases. Vibrationally elastic collisions (Δv = 0) favor small ΔJ transitions while vibrationally inelastic collisions have equilibrium post-collision rotational distributions. Dissociation exhibits both vibrational and rotational favoring. New vibrational-translational (VT), vibrational-rotational-translational (VRT) energy exchange, and dissociation models are developed based on QCT observations and maximum entropy considerations. Full set of parameters for state-to-state modeling of oxygen is presented. The VT energy exchange model describes 22 000 state-to-state vibrational cross sections using 11 parameters and reproduces vibrational relaxation rates within 30% in the 2500–20 000 K temperature range. The VRT model captures 80 × 106 state-to-state ro-vibrational cross sections using 19 parameters and reproduces vibrational relaxation rates within 60% in the 5000–15 000 K temperature range. The developed dissociation model reproduces state-specific and equilibrium dissociation rates within 25% using just 48 parameters. The maximum entropy framework makes it feasible to upscale ab initio simulation to full nonequilibrium flow calculations.

Research Organization:
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Sponsoring Organization:
USDOE National Nuclear Security Administration (NNSA)
Grant/Contract Number:
AC04-94AL85000; Graduate Fellowship
OSTI ID:
1512881
Alternate ID(s):
OSTI ID: 1421171
Report Number(s):
SAND2015-9304J; 664890
Journal Information:
Journal of Chemical Physics, Vol. 144, Issue 17; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 51 works
Citation information provided by
Web of Science

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Cited By (10)

Combining particle-in-cell and direct simulation Monte Carlo for the simulation of reactive plasma flows journal July 2019
Ab initio state-specific N 2 + O dissociation and exchange modeling for molecular simulations journal February 2017
Exhaustive state-to-state cross sections for reactive molecular collisions from importance sampling simulation and a neural network representation journal June 2019
Development of an impulsive model of dissociation in direct simulation Monte Carlo journal August 2019
Exhaustive state-to-state cross sections for reactive molecular collisions from importance sampling simulation and a neural network representation text January 2019
Exhaustive state-to-state cross sections for reactive molecular collisions from importance sampling simulation and a neural network representation text January 2019
Vibrational state-specific model for dissociation and recombination of the O2(  3Σg−)+O(  3P) system in DSMC journal February 2019
Dissociation cross sections for N 2 + N → 3N and O 2 + O → 3O using the QCT method journal May 2017
Dynamics on Multiple Potential Energy Surfaces: Quantitative Studies of Elementary Processes Relevant to Hypersonics text January 2020
Classical impulsive model for dissociation of diatomic molecules in direct simulation Monte Carlo journal November 2018

Figures / Tables (14)

FIG. 1(p. 4)figure FIG. 1
TABLE I(p. 4)table TABLE I
FIG. 2(p. 6)figure FIG. 2
FIG. 3(p. 7)figure FIG. 3
TABLE II(p. 7)table TABLE II
FIG. 4(p. 9)figure FIG. 4
FIG. 5(p. 9)figure FIG. 5
FIG. 6(p. 10)figure FIG. 6
TABLE III(p. 11)table TABLE III
FIG. 7(p. 12)figure FIG. 7
FIG. 8(p. 12)figure FIG. 8
FIG. 9(p. 13)figure FIG. 9
TABLE IV(p. 13)table TABLE IV
FIG. 10(p. 14)figure FIG. 10

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72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS