High-Temperature Nonequilibrium Air Chemistry from First Principles

Abstract

We present first-principles calculations for chemically reacting five-species air ([Formula: see text], [Formula: see text], [Formula: see text], [Formula: see text], [Formula: see text]) over a range of gas temperatures ([Formula: see text]), relying exclusively on ab initio potential energy surfaces (PESs) from the University of Minnesota Computational Chemistry group to describe the forces between atoms. We use these PESs within direct molecular simulations (DMSs) and quasi-classical trajectory (QCT) calculations to determine the coupling of internal energy relaxation to chemical reactions. From DMS we extract the internal energy populations of diatomic species during the quasi-steady-state (QSS) dissociation phase and, for all diatomic species, observe depleted high-energy tails relative to corresponding Boltzmann distributions. A comparison of thermochemical equilibrium rate coefficients (from QCT) with those during QSS (from DMS) helps quantify the macroscopic effects of vibrationally depleted distributions on dissociation. In contrast, Zeldovich exchange reactions are almost unaffected by these vibrationally depleted distributions. Unlike dissociation, they do not exhibit significant vibrational bias and take place at near-thermal rates at all temperatures studied. Furthermore, we quantify the amount of vibrational and rotational energy removed and/or gained in exchange and dissociation reactions. Such macroscopic quantities are of interest for enhancing the fidelity of multitemperature nonequilibrium chemistry models used in computational fluid dynamics codes.