posted on 2007-05-24, 00:00authored byNelly M. Reilly, J. Ulises Reveles, Grant E. Johnson, Shiv N. Khanna, A. W. Castleman
Synergistic studies employing experiments in the gas phase and theoretical first principles calculations have
been carried out to investigate the structure, stability, and reactivity toward CO of iron oxide cluster anions,
FexOy- (x = 1−2, y ≤ 6). Collision-induced dissociation studies of iron oxide species, employing xenon
collision gas, show that FeO3- and FeO2- are the stable building blocks of the larger iron oxide clusters.
Theoretical calculations show that the fragmentation patterns leading to the production of O or FeOn fragments
are governed both by the energetics of the overall process as well as the number of intermediate states and
the changes in spin multiplicity. Mass-selected experiments identified oxygen atom transfer to CO as the
dominant reaction pathway for most anionic iron oxide clusters. A theoretical analysis of the molecular level
pathways has been carried out to highlight the role of energetics as well as the spin states of the intermediates
on the oxidation reaction.