INFRARED MULTIPLE-PHOTON DISSOCIATION OF THE NITROBENZENE RADICAL-CATION - A PARADIGM FOR COMPETITIVE REACTIONS

The dissociation of nitrobenzene cation displays a variety of surprising and even apparently nonstatistical reaction behaviors. We have used infrared multiple-photon dissociation experiments to further study the reactions of this system. These experiments along with a previous photoelectron photoion coincidence study indicate that, for some products, the nitrobenzene cation dissociates to form an ion-neutral complex and then reassociates to give the phenyl nitrite cation. A reaction mechanism involving statistical dissociation is shown to account for the experimental data.