Consistent Kinetic-Continuum Dissociation Model I: Kinetic Formulation

TL;DR

This paper introduces a generalized non-equilibrium chemical kinetics model derived from ab initio data, accurately capturing high-temperature air dissociation processes and incorporating key physical effects in a computationally efficient manner.

Contribution

It presents a novel kinetic formulation that integrates ab initio data into a non-equilibrium dissociation model, including effects like overpopulation and depletion of high energy states.

Findings

Model accurately reproduces QCT rates for Boltzmann distributions.

Predicts reduced rates due to high energy state depletion.

Captures enhanced rates from vibrational overpopulation.

Abstract

In this article, we propose a generalized non-equilibrium chemical kinetics model from \textit{ab initio} simulation data obtained using accurate potential energy surfaces developed recently for the purpose of studying high-temperature air chemistry. First, we present a simple cross-section model for dissociation that captures recent \textit{ab initio} data accurately. The cross-section model is analytically integrated over Boltzmann distributions and general non-Boltzmann distributions to derive general non-equilibrium dissociation model. The general non-Boltzmann model systematically incorporates key physics such as dependence on translational energy, rotational energy, vibrational energy, internal energy, centrifugal barrier and non-Boltzmann effects such as overpopulation and depletion of high energy states. The model is shown to reproduce the rates from QCT for Boltzmann distributions of internal energy states. Reduced rates in non-equilibrium steady state due to depletion of high internal energy states are also predicted well by the model. Furthermore, the model predicts the enhanced rates as observed due to significant overpopulation of high vibrational states relative to Boltzmann distributions while the gas is in non-equilibrium in the transient phase. The model provides a computationally inexpensive way of incorporating non-equilibrium chemistry without incurring additional cost in the existing computational tools. Further comparisons of the model are carried out in another article, where simplifications to the model are proposed based on the results.