Past and present aspects of Italian plasma chemistry

The linking between the initial activities of the Rome–Bari group to their present activities is discussed in different fields of plasma chemical-physics. Several topics are presented including (1) plasma catalysis, (2) the interaction of alumina particles with thermal plasmas and its linking with the thermodynamics and transport properties of plasmas, and (3) non-equilibrium vibrational kinetics coupled with the Boltzmann equation for the electron energy distribution functions (eedf) in aerospace and cold plasma applications. The old activities in plasma catalysis pointed out the importance of atomic species affecting catalytic reactions opening also to the possibility of non-equilibrium vibrational distributions on the chemisorbed ad-atoms. This last aspect is discussed also taking into account recent developments. The study of the interaction of alumina particles with thermal plasmas was rationalized assuming that the step controlling the reaction could be the heat transfer plasma-particle. The model used a simplified fluid dynamic approach with the insertion of accurate values of thermodynamic and transport properties of thermal plasmas. This kind of activity can be considered precursor on the intense work in the field with particular attention on the importance of electronic excited states in affecting thermodynamics and transport of plasmas. Moreover, the plasma-particle interactions can be recovered to a given extent in the modern aspects of hypersonics in the boundary layer of re-entering vehicles as well as in the nozzle flow expansion. In both cases, we underline the existence of vibrational distributions (vdf) far from the Boltzmann behaviour and rates presenting an anti-Arrhenius trend as a function of the inverse of gas temperature. Concerning the non-equilibrium vibrational kinetics, we discuss two case studies. The first one deals with the behaviour of cold nitrogen plasmas pointing out the role of superelastic vibrational and electronic collisions on vdf and eedf. In this case, we discuss also the same case study comparing the results obtained by a complete set of electron molecule cross-sections acting on the whole vibrational ladder with the corresponding ones which consider transitions starting and arriving to the vibrational ground state of the molecule. The last case study concerns the dissociation kinetics of CO2 in cold plasmas, a topic largely studied in the past to emphasize the role of vibrational excitation in CO2 destruction. Recent results obtained using a sophisticated model based on the coupling of Boltzmann equation for the eedf and a state-to-state vibrational kinetics of the asymmetric ladder of CO2 are reported. The interplay between dissociation process by direct electron impact collision and by heavy particle collisions with vibrationally excited CO2 molecules is discussed.