Application of the Statistical Phase-Space Theory to the Reactions of Rare-Gas Ions with Nitrogen Molecules

Abstract

The statistical phase‐space theory of chemical reactions has been applied to molecular and dissociative charge‐transfer reactions of He⁺, Ne⁺, Ar⁺, and Kr⁺ with neutral N₂ molecules in the 0.05–200‐eV energy range. Comparison between calculated and experimental cross sections for the molecular charge‐transfer channels have indicated an incomplete mixing of statistically available N₂⁺ product ion electronic states. Cross sections computed for endoergic dissociative channels of reaction are in good agreement with experiment. Calculated product ion vibrational distributions have been compared with those inferred from product N₂⁺ kinetic energies and with vibrational distributions obtained from spontaneous radiative transitions of excited N₂⁺ ions produced in the respective ion–molecule reactions.