Reactions of Kr+, Kr2+, Xe+and Xe2+ions with several molecular gases at 300 K

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Abstract
The reactions of the atomic ions Kr+ and Xe+ and the molecular ions Kr2+ and Xe2+ have been studied with several molecular gases at 300 K using a selected ion flow tube (SIFT). In some of the atomic ion reactions differential reactivity was observed between the spin-orbit states (2P3/2, 2P1/2) of the ions and, when this was so, the lower energy 2P 3/2 state of both ions was observed to react more rapidly than the 2P1/2 state, in accordance with the findings of previous work. Whereas charge transfer was the only reaction mechanism observed for the atomic ions, both charge transfer and inert gas/reactant molecule switching were observed in several reactions of the molecular ions, the latter process producing ions such as KrCH4+ and XeC2H2+. By considering the kinetics of the near-thermoneutral charge transfer reactions of Kr2+ with N2O and Xe2+ with COS, the dissociation energies of the molecular ions have been determined to be 2+ and 2+, both these upper-limit values being in good agreement with previous experimental and theoretical values.