Rovibrational internal energy transfer and dissociation of high-temperature oxygen mixture

• Published in: The Journal of chemical physics 2023-02, Vol.158 (6), p.064305-064305
• Main Authors: Jo, Sung Min, Venturi, Simone, Kim, Jae Gang, Panesi, Marco
• Format: Article
• Language: English
• Subjects: Boltzmann distribution; Energy; Energy distribution; Energy of dissociation; Energy transfer; High temperature; Internal energy; Oxygen; Population distribution; Potential energy; Reduced order models; Temperature
• ISSN: 0021-9606; 1089-7690
• DOI: 10.1063/5.0133463

This work constructs a rovibrational state-to-state model for the O2 + O2 system leveraging high-fidelity potential energy surfaces and quasi-classical trajectory calculations. The model is used to investigate internal energy transfer and nonequilibrium reactive processes in a dissociating environment using a master equation approach, whereby the kinetics of each internal rovibrational state is explicitly computed. To cope with the exponentially large number of elementary processes that characterize reactive bimolecular collisions, the internal states of the collision partner are assumed to follow a Boltzmann distribution at a prescribed internal temperature. This procedure makes the problem tractable, reducing the computational cost to a comparable scale with the O2 + O system. The constructed rovibrational-specific kinetic database covers the temperature range of 7500–20 000 K. The reaction rate coefficients included in the database are parameterized in the function of kinetic and internal temperatures. Analysis of the energy transfer and dissociation process in isochoric and isothermal conditions reveals that significant departure from the equilibrium Boltzmann distribution occurs during the energy transfer and dissociation phase. Comparing the population distribution of the O2 molecules against the O2 + O case demonstrates a more significant extent of nonequilibrium characterized by a more diffuse distribution whereby the vibrational strands are more clearly identifiable. This is partly due to less efficient mixing of the rovibrational states, which results in more diffuse rovibrational distributions in the quasi-steady-state distribution of O2 + O2. A master equation analysis for the combined O2 + O and O2 + O2 system reveals that the O2 + O2 system governs the early stage of energy transfer, whereas the O2 + O system takes control of the dissociation dynamics. The findings of the present work will provide a strong physical foundation that can be exploited to construct an improved reduced-order model for oxygen chemistry.