Photodissociation of vanadium, niobium, and tantalum oxide cluster cations

Abstract

Transition-metal oxide clusters of the form M(n)O(m) (+)(M=V,Nb,Ta) are produced by laser vaporization in a pulsed nozzle cluster source and detected with time-of-flight mass spectrometry. Consistent with earlier work, cluster oxides for each value of n produce only a limited number of stoichiometries, where m>n. The cluster cations are mass selected and photodissociated using the second (532 nm) or third (355 nm) harmonic of a Nd:YAG (yttrium aluminum garnet) laser. All of these clusters require multiphoton conditions for dissociation, consistent with their expected strong bonding. Dissociation occurs by either elimination of oxygen or by fission, repeatedly producing clusters having the same specific stoichiometries. In oxygen elimination, vanadium species tend to lose units of O(2), whereas niobium and tantalum lose O atoms. For each metal increment n, oxygen elimination proceeds until a terminal stoichiometry is reached. Clusters having this stoichiometry do not eliminate more oxygen, but rather undergo fission, producing smaller M(n)O(m) (+) species. The smaller clusters produced as fission products represent the corresponding terminal stoichiometries for those smaller n values. The terminal stoichiometries identified are the same for V, Nb, and Ta oxide cluster cations. This behavior suggests that these clusters have stable bonding networks at their core, but additional excess oxygen at their periphery. These combined results determine that M(2)O(4) (+), M(3)O(7) (+), M(4)O(9) (+), M(5)O(12) (+), M(6)O(14) (+), and M(7)O(17) (+) have the greatest stability for V, Nb, and Ta oxide clusters.