Measurement and kinetic analysis of complex ion-molecule reactions influenced by multiple electronic surfaces.

Energetically and temporally resolved gas phase studies of ion-molecule reactions, particularly those featuring open-shell transition metal ions, are fundamental to understanding complex chemical reactivity paradigms that can help shed light on the behavior of bulk and extended materials. Kinetic studies are particularly revealing as these elucidate mechanistic and dynamic features that would otherwise be impossible to determine. The unique single photon initiated dissociative rearrangement reactions (SPIDRR) technique measures the time dependence of product formation in ion-molecule reactions and is applied here to elucidate the mechanism of several ion-molecule systems. Moreover, the role of the transition metal /metal oxide ion’s electronic structure toward chemical reactivity is determined.