High-temperature non-equilibrium atom–diatom collisional energy transfer

• Published in: The Journal of chemical physics 2024-12, Vol.161 (23)
• Main Authors: Zhao, Xiaorui, Xu, Xuefei, Xu, Haitao
• Format: Article
• Language: English
• Subjects: Energy; Energy distribution; Energy levels; Energy transfer; High temperature; Hypersonic flow; Initial conditions; Internal energy; Plankton; Transition probabilities; Translational motion; Vibrational states
• ISSN: 0021-9606; 1089-7690; 1089-7690
• DOI: 10.1063/5.0241219

The change of the vibrational energy within a molecule after collisions with another molecule plays an essential role in the evolution of molecular internal energy distributions, which is also the limiting process in the relaxation of gases toward equilibrium. Here, we investigate the energy transfer between the translational motion and the vibrational motion of the diatom during the atom–diatom collision, the simplest case involving the transfer between inter-molecular and intra-molecular energies. We are interested in the situation when the translational temperature of the gas is high, in which case, there are significant probabilities for the vibrational energy to change over widely separated energy levels after a collision. Data from quasi-classical trajectory simulations of the N + N2 system with ab initio potential energies suggest that the transition probability dependence on the collisional energy possesses an “activation-saturation” behavior and can be described by a simple model. The model allows for explicit evaluation of the vibrational state-to-state transition rate coefficients, from which the evolution of the vibrational energy distribution from any initial conditions can be solved by using the master equation approach. An example of the vibrational energy relaxation in the N + N2 system mimicking the gas behind strong shocks in a hypersonic flow is shown and the results are in good agreement with the available data.