Flowing afterglow measurements of the density dependence of gas-phase ion-ion mutual neutralization reactions

We have studied the dependence of several ion-ion mutual neutralization (MN) reactions on helium density in the range from 1.6 × 10(16) to 1.5 × 10(17) cm(-3) at 300 K, using the Variable Electron and Neutral Density Attachment Mass Spectrometry method. The rate coefficients of the reactions Ar(+) + Br2(-), Ar(+) + SF6(-), and Ar(+) + C7F14(-) were found to be independent of gas density over the range studied, in disagreement with earlier observations that similar MN reactions are strongly enhanced at the same gas densities. The cause of the previous enhancement with density is traced to the use of "orbital-motion-limit" theory to infer ion densities from the currents collected by ion-attracting Langmuir probes in a region where it is not applicable.