Electron and Ion Reactions with ClN$_{3}$

Since its first synthesis in 1908, there have been relatively few studies addressing chemistry of ClN$_{3}$ and none regarding electron and ion reactions with ClN$_{3}$, probably because of the extremely explosive character of the compound. There are 4 exothermic channels in electron attachment to ClN$_{3}$, but only the Cl$^{-}$ channel was observed to occur at 298 and 400 K in the present work. Electron attachment rates were measured to be 3.5 $\times $ 10$^{-8}$ and 4.5 $\times $ 10$^{-8}$ cm$^{3}$ s$^{-1}$ at 298 K and 400 K, $\pm $35{\%}, using a FALP apparatus. The activation energy for the reaction is 24 $\pm $ 10 meV. The reactivity of ClN$_{3}$ with 17 negative ions and 21 positive ions has been investigated at 300 K using a SIFT apparatus. The electron affinity, (2.48 $\pm $ 0.20 eV), proton affinity (713 $\pm$ 41 kJ mol$^{-1})$, and ionization energy ($>$ 9.6 eV) of ClN$_{3}$ were bracketed. These measurements are in agreement with results from G3 calculations. For negative ion reactions, the major product of the reactions was Cl$^{-}$, while charge transfer, N$_{3}^{-}$ production and O atom incorporation were also observed. Reactions of positive ions often resulted in dissociative charge transfer forming NCl$^{+}$ product.