Non-Boltzmann vibrational energy distributions and coupling to dissociation rate

The Journal of Chemical Physics
Narendra Singh, T E Schwartzentruber

Abstract

In this article, we propose a generalized model for nonequilibrium vibrational energy distribution functions. The model can be used, in place of equilibrium (Boltzmann) distribution functions, when deriving reaction rate constants for high-temperature nonequilibrium flows. The distribution model is derived based on the recent ab initio calculations, carried out using potential energy surfaces developed using accurate computational quantum chemistry techniques for the purpose of studying air chemistry at high temperatures. Immediately behind a strong shock wave, the vibrational energy distribution is non-Boltzmann. Specifically, as the gas internal energy rapidly excites to a high temperature, overpopulation of the high-energy tail (relative to a corresponding Boltzmann distribution) is observed in ab initio simulations. As the gas excites further and begins to dissociate, a depletion of the high-energy tail is observed, during a time-invariant quasi-steady state. Since the probability of dissociation is exponentially related to the vibrational energy of the dissociating molecule, the overall dissociation rate is sensitive to the populations of these high vibrational energy states. The non-Boltzmann effects captured by the new m...Continue Reading

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Dec 20, 2017·Proceedings of the National Academy of Sciences of the United States of America·Narendra Singh, Thomas Schwartzentruber
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Jun 15, 2020·The Journal of Chemical Physics·Narendra Singh, Thomas Schwartzentruber

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Citations

Mar 17, 2021·The Journal of Chemical Physics·Tzu-Jung Pan, Kelly A Stephani
Jul 24, 2020·The Journal of Physical Chemistry. a·Julian ArnoldMarkus Meuwly
Jul 28, 2021··Alessandro MunafòMaitreyee Sharma Priyadarshini

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