Gas-phase reactions of the atomic oxygen radical cation with halogenated compounds.

Rate constants and product distributions have been measured for the reactions of O(+)˙((4)S) with the methyl halides (CH(3)F, CH(3)Cl, CH(3)Br, CH(3)I) and three perfluorinated compounds (CF(4), SF(6), SF(5)CF(3)) at 300 K in a flowing afterglow-selected ion flow tube (FA-SIFT). The reactions occur with high efficiency, despite the necessity for spin conversion in some processes. The mechanisms include charge transfer, atom abstraction, and fragmentation reactions. Computational modeling was carried out to provide insight into these processes.