A harmonically-coupled-anharmonic-oscillator approach for polyatomic chemistry modeling in DSMC

Simone Lauterbach; Franziska Tuttas; Marcel Pfeiffer

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arXiv · 2606.31548

A harmonically-coupled-anharmonic-oscillator approach for polyatomic chemistry modeling in DSMC

Simone Lauterbach·Franziska Tuttas·Marcel Pfeiffer

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Abstract

Atmospheric entry processes are characterized by high-enthalpy gas flows in strong thermo-chemical non-equilibrium. Accurate simulations of such conditions remain challenging due to the extreme conditions and the complex influence of internal energy modes. In particular, the common assumption of uncoupled harmonic vibrations may break down, and excited internal energy states can directly influence reaction rates. Previously, an anharmonic oscillator model has been developed by Civrais et al. to improve the accuracy of the Direct Simulation Monte Carlo (DSMC) method under such conditions. However, this extension has so far been limited to diatomic molecules. To increase the accuracy of the DSMC method in the open-source code PICLas, the anharmonic oscillator model is extended to include polyatomic species. The proposed model explicitly considers anharmonic effects and intramolecular energy redistribution. Vibrational degrees of freedom are treated in a local mode basis, in which anharmonic stretching modes are harmonically coupled by harmonic bending modes. The coupling allows for the redistribution of localized vibrational excitation. Dissociation can occur by the strong excitation of a stretching mode, and specific modes can be coupled to the reaction coordinate of the transition state in bimolecular exchange reactions. The newly developed model is evaluated by the comparison to high-fidelity calculations for a set of representative processes. Investigated are different dissociation reactions, which exhibit a high degree of energy redistribution, and the hydrogen-exchange reaction between methane and a hydrogen radical, in which only selected modes contribute to the reactive process. In addition, the recombination-dissociation equilibrium system has been investigated for methane.

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Simone Lauterbach, Franziska Tuttas, Marcel Pfeiffer. 2026-06-30. A harmonically-coupled-anharmonic-oscillator approach for polyatomic chemistry modeling in DSMC. https://arxiv.org/abs/2606.31548

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