Modified Marrone–Treanor Dissociation Model: Formulation and Benchmarking for Diatom–Atom Mixtures

We present a modified Marrone–Treanor model for dissociation with rate parameters derived exclusively from quasi-classical trajectory calculations on ab initio potential energy surfaces. Analysis of the trajectory dataset for reactant [Formula: see text] and [Formula: see text] diatoms sampled from Boltzmann internal energy distributions over a wide [Formula: see text] range indicates that a modified version of the classical Marrone–Treanor two-temperature model captures the most relevant physics of shock-heated, dissociating diatomic species very well. We find that simple correction factors account for non-Boltzmann depletion effects observed in direct molecular simulations employing the same potentials. The concentration-dependent functional form proposed for these correction factors ensures that depletion effects vanish at chemical equilibrium. Based on comparisons in isothermal and adiabatic heat baths, we verify that the resulting two-temperature dissociation model accurately reproduces all major features observed in the direct molecular simulations, while remaining computationally inexpensive enough for large-scale computational fluid dynamics simulations.