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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];  [2];  [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 Laboratories (SNL-NM), Albuquerque, NM (United States)
Sponsoring Organization:
USDOE; USDOE National Nuclear Security Administration (NNSA)
Grant/Contract Number:
AC04-94AL85000
OSTI ID:
1512881
Alternate ID(s):
OSTI ID: 1421171
OSTI ID: 22657960
Report Number(s):
SAND2015--9304J; 664890
Journal Information:
Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 17 Vol. 144; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English

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Cited By (12)

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

Figures / Tables (14)

FIG. 1(p. 4)figure FIG. 1
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