Modified Marrone-Treanor model: parameterization and benchmarking for five-species air

TL;DR

This paper updates parameters for a five-species air model used in hypersonic flow simulations, demonstrating high accuracy in reproducing nonequilibrium conditions and improving upon previous models in predicting chemical reaction rates.

Contribution

The paper introduces new parameters for the Modified Marrone-Treanor model, validated against molecular simulations, enhancing the accuracy of hypersonic air chemistry modeling.

Findings

Model reproduces benchmark solutions with high accuracy.

Predicts slower N2 dissociation below 10000 K.

Shows more NO production across temperatures.

Abstract

We present updated parameters for five-species air (N2, O2, NO, N and O) reactions to be used with the Modified Marrone-Treanor two-temperature model. The vibrational relaxation and chemical reaction rates are derived from quasiclassical trajectory calculations and direct molecular simulations using ab initio potential energy surfaces. The resulting model enables efficient computational fluid dynamics simulations of nonequilibrium air chemistry in hypersonic flows. We show that the model reproduces direct molecular simulation benchmark solutions with high accuracy in zero-dimensional heat baths representative of strong nonequilibrium post-shock conditions. The model's analytical expressions for dissociation rate coefficient and vibrational energy change per reaction ensure that the correct amount of energy is transferred between the vibrational and trans-rotational modes. Detailed balance is imposed for three-body recombination reactions and our simulations exhibit quasi-steady-state dissociation rates and proper approach to thermochemical equilibrium. In direct comparison with the Park TTv model, the Modified Marrone-Treanor model predicts significantly slower conversion of N2 into N below 10000 K and significantly more NO production at all temperatures. This is likely due to its significantly higher Zeldovich reaction rates compared to Park.