A rovibrational collisional model is developed to study energy transfer and dissociation of N(2)((1)Σ(g)(+)) molecules interacting with N((4)S(u)) atoms in an ideal isochoric and isothermal chemical reactor. The system examined is a mixture of molecular nitrogen and a small amount of atomic nitrogen. This mixture, initially at room temperature, is heated by several thousands of degrees Kelvin, driving the system toward a strong non-equilibrium condition. The evolution of the population densities of each individual rovibrational level is explicitly determined via the numerical solution of the master equation for temperatures ranging from 5000 to 50,000 K. The reaction rate coefficients are taken from an ab initio database developed at NASA Ames Research Center. The macroscopic relaxation times, energy transfer rates, and dissociation rate coefficients are extracted from the solution of the master equation. The computed rotational-translational (RT) and vibrational-translational (VT) relaxation times are different at low heat bath temperatures (e.g., RT is about two orders of magnitude faster than VT at T = 5000 K), but they converge to a common limiting value at high temperature. This is contrary to the conventional interpretation of thermal relaxation in which translational and rotational relaxation timescales are assumed comparable with vibrational relaxation being considerable slower. Thus, this assumption is questionable under high temperature non-equilibrium conditions. The exchange reaction plays a very significant role in determining the dynamics of the population densities. The macroscopic energy transfer and dissociation rates are found to be slower when exchange processes are neglected. A macroscopic dissociation rate coefficient based on the quasi-stationary distribution, exhibits excellent agreement with experimental data of Appleton et al. [J. Chem. Phys. 48, 599-608 (1968)]. However, at higher temperatures, only about 50% of dissociation is found to take place under quasi-stationary state conditions. This suggest the necessity of explicitly including some rovibrational levels, when solving a global kinetic rate equation.

The 2022 Roadmap is the next update in the series of Plasma Roadmaps published by Journal of Physics D with the intent to identify important outstanding challenges in the field of low-temperature plasma (LTP) physics and technology. The format of the Roadmap is the same as the previous Roadmaps representing the visions of 41 leading experts representing 21 countries and five continents in the various sub-fields of LTP science and technology. In recognition of the evolution in the field, several new topics have been introduced or given more prominence. These new topics and emphasis highlight increased interests in plasma-enabled additive manufacturing, soft materials, electrification of chemical conversions, plasma propulsion, extreme plasma regimes, plasmas in hypersonics, data-driven plasma science and technology and the contribution of LTP to combat COVID-19. In the last few decades, LTP science and technology has made a tremendously positive impact on our society. It is our hope that this roadmap will help continue this excellent track record over the next 5–10 years.

Abstract. In the present contribution, we derive from kinetic theory a unified fluid model for multicomponent plasmas by accounting for the electromagnetic field influence. We deal with a possible thermal nonequilibrium of the translational energy of the particles, neglecting their internal energy and the reactive collisions. Given the strong disparity of mass between the electrons and heavy particles, such as molecules, atoms, and ions, we conduct a dimensional analysis of the Boltzmann equation and introduce a scaling based on the square root of the ratio of the electron mass to a characteristic heavy-particle mass. We then generalize the Chapman-Enskog method, emphasizing the role of a multiscale perturbation parameter on the collisional operator, the streaming operator, and the collisional invariants of the Boltzmann equation. The system is examined at successive orders of approximation, each of which corresponding to a physical time scale. The multicomponent Navier-Stokes regime is reached for the heavy particles, which follow a hyperbolic scaling, and is coupled to first order drift-diffusion equations for the electrons, which follow a parabolic scaling. The transport coefficients are then calculated in terms of bracket operators whose mathematical structure allows for positivity properties to be determined. They exhibit an anisotropic behavior when the magnetic field is strong enough. We also give a complete description of the Kolesnikov effect, i.e., the crossed contributions to the mass and energy transport fluxes coupling the electrons and heavy particles. Finally, the first and second principles of thermodynamics are proved to be satisfied by deriving a total energy equation and an entropy equation. Moreover, the system of equations is shown to be conservative and the purely convective system hyperbolic, thus leading to a well defined structure.

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A rovibrational collisional model is developed to study the internal energy excitation and dissociation processes behind a strong shock wave in a nitrogen flow. The reaction rate coefficients are obtained from the ab initio database of the NASA Ames Research Center. The master equation is coupled with a one-dimensional flow solver to study the nonequilibrium phenomena encountered in the gas during a hyperbolic reentry into Earth's atmosphere. The analysis of the populations of the rovibrational levels demonstrates how rotational and vibrational relaxation proceed at the same rate. This contrasts with the common misconception that translational and rotational relaxation occur concurrently. A significant part of the relaxation process occurs in non-quasi-steady-state conditions. Exchange processes are found to have a significant impact on the relaxation of the gas, while predissociation has a negligible effect. The results obtained by means of the full rovibrational collisional model are used to assess the validity of reduced order models (vibrational collisional and multitemperature) which are based on the same kinetic database. It is found that thermalization and dissociation are drastically overestimated by the reduced order models. The reasons of the failure differ in the two cases. In the vibrational collisional model the overestimation of the dissociation is a consequence of the assumption of equilibrium between the rotational energy and the translational energy. The multitemperature model fails to predict the correct thermochemical relaxation due to the failure of the quasi-steady-state assumption, used to derive the phenomenological rate coefficient for dissociation.

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[1] An electronic collisional-radiative model is proposed to predict the nonequilibrium populations and the radiation of the excited electronic states CN(A, B) and N 2 (A, B, C) during the entry of the Huygens probe into the atmosphere of Titan. The model is loosely coupled with flow solvers using a Lagrangian method. First, the model was tested against measurements obtained with the shock-tube of NASA Ames Research Center. Then, the model was applied to the simulation of Huygen's entry. Our simulations predict that the population of the CN(B) state is lower than the Boltzmann population by a factor 40 at trajectory time t = 165 s and by a factor 2 at t = 187 s and that the population of the CN(A) state remains close to the Boltzmann population for both trajectory points. The radiative heat fluxes, driven by the CN(A, B) states, are lower than predictions based on the Boltzmann populations by a factor 15 at t = 165 s and a factor 2 at t = 187 s.