Analysis of electron interactions in dielectric gases

Abstract

We present and discuss results concerning electron interactions processes of dielectric gases and their relationship with the macroscopic behavior of these gases, in particular, with their dielectric strength. Such analysis is based on calculating energies of reactions for molecular ionization, dissociative ionization, parent negative ion formation, and dissociative electron attachment processes. We hypothesize that the estimation of the required energy for a reduced number of processes that take place in electrically stressed gases could be related to the gas’ capability to manage the electron flow during an electrical discharge. All calculations were done with semiempirical quantum chemistry methods, including an initial optimization of molecular geometry and heat of formation of the dielectric gases and all of species that appear during electron interaction reactions. The performance of semiempirical methods Austin model 1 and Parametric model 3 (PM3) was compared for several compounds, PM3 being superior in most cases. Calculations performed for a sample of nine dielectric gases show that electron attachment and detachment processes occur in different energy bands that do not overlap for any value of the dielectric strength. We have also analyzed the relationship between dielectric strength and two physical properties: electron affinity and ionization energy. Calculations performed for 43 dielectric gases show no clear correlation between them, although certain guidelines for the qualitative estimation of dielectric strength can still be assessed.