Kinetic and spectroscopic characterization of the isomers of the allyl bromide molecular ion

The kinetics of the ion/molecule reactions of the molecular ion of allyl bromide (3-bromopropene), C₃H₅Br⁺., with its neutral show that only (82 ± 2)% of these ions are reactive. This percentage is mildly sensitive to ionization energy below 13 eV, but is pressure insensitive. The collisionless infrared multiphoton-induced photofragmentation of these ions at 10.25 μm and at variable power densities is consistent with the presence of two ionic species in the ratio obtained from the kinetic experiments. The most abundant species undergoes much faster photofragmentation at this wavelength, but at 10.59 μm the photofragmentation rates become comparable. Experiments performed by isolating the remaining molecular ions after completion of the ion/molecule reaction confirm that the unreactive species corresponds to the slow photodissociating ion at 10.25 μm. A combination of kinetic experiments and photodissociation is used to establish that the less abundant species behaves unlike the molecular ion obtained from 1-bromopropene, 2-bromopropene, or bromocyclopropane. The two structures for the molecular ion are shown to originate from ionization and not by isomerization through collisions.