Mutual neutralization of atomic rare-gas cations (Ne{sup +}, Ar{sup +}, Kr{sup +}, Xe{sup +}) with atomic halide anions (Cl{sup −}, Br{sup −}, I{sup −})
We report thermal rate coefficients for 12 reactions of rare gas cations (Ne{sup +}, Ar{sup +}, Kr{sup +}, Xe{sup +}) with halide anions (Cl{sup −}, Br{sup −}, I{sup −}), comprising both mutual neutralization (MN) and transfer ionization. No rate coefficients have been previously reported for these reactions; however, the development of the Variable Electron and Neutral Density Attachment Mass Spectrometry technique makes it possible to measure the difference of the rate coefficients for pairs of parallel reactions in a Flowing Afterglow-Langmuir Probe apparatus. Measurements of 18 such combinations of competing reaction pairs yield an over-determined data set from which a consistent set of rate coefficients of the 12 MN reactions can be deduced. Unlike rate coefficients of MN reactions involving at least one polyatomic ion, which vary by at most a factor of ∼3, those of the atom-atom reactions vary by at least a factor 60 depending on the species. It is found that the rate coefficients involving light rare-gas ions are larger than those for the heavier rare-gas ions, but the opposite trend is observed in the progression from Cl{sup −} to I{sup −}. The largest rate coefficient is 6.5 × 10{sup −8} cm{sup 3} s{sup −1} for Ne{sup +} with I{sup −}. Rate coefficients for Ar{sup +}, Kr{sup +}, and Xe{sup +} reacting with Br{sub 2}{sup −} are also reported.