Formation, Fragmentation, and Structures of YxOy(+) (x = 1, 2, y = 1 - 13) Clusters: Collision-Induced Dissociation Experiments and Density Functional Theory Calculations.

Yttrium oxide cluster cations have been experimentally and theoretically studied. We produced small, oxygen-rich yttrium oxide clusters, YxOy+ (x = 1, 2, y = 1­13), by mixing the laser-produced yttrium plasma with a molecular oxygen jet. Mass spectrometry measurements showed that the most stable clusters are those consisting of one yttrium and an odd number of oxygen atoms of the form YO(+)(2k+1) (k = 0­6). Additionally, we performed collision induced dissociation experiments, which indicated that the loss of pairs of oxygen atoms down to a YO+ core is the preferred fragmentation channel for all clusters investigated. Furthermore, we conduct DFT calculations and we obtained two types of low-energy structures: one containing an yttrium cation core and the other composed of YO+ core and O2 ligands, being in agreement with the observed fragmentation pattern. Finally, from the fragmentation studies, total collision cross sections are obtained and these are compared with geometrical cross sections of the calculated structures.

Collision-induced dissociation studies on Fe(O2)n(+) (n = 1-6) clusters: application of a new technique based on crossed molecular beams.

Gas-phase oxygen-rich iron oxide clusters Fe(O2)n(+) (n = 1-6), are produced in a molecular beam apparatus. Their stability and structure are investigated by measuring the fragmentation cross-sections from collision-induced-dissociation experiments. For this purpose, two different techniques have been employed. The first one relies on the measurement of the fragments resulting after collisional activation and subsequent dissociation of mass selected cluster ions in a molecular beam passing through a cell filled with noble gas atoms. The second one is a new approach that we introduce and is based on crossed molecular beams to measure the fragmentation cross-sections, in a more efficient manner without mass selection of the individual clusters. The cross-sections obtained with the different techniques are compared with each other as well as with theoretical ones resulting from the application of a simple geometrical projection model. Finally, the general trends observed are compared with results for other Fe-molecule clusters available in the literature.

Symmetry-switching molecular Fe(O2)n(+) clusters.

Experimental and theoretical studies based on mass spectrometry, collision-induced dissociation, and ab initio calculations are performed on the formation and stability of FeO(n)(+) clusters, as well as on their structural, electronic, and magnetic properties. In the mass spectra, clusters with an even number of oxygen atoms show increased stability, most prominently for FeO(10)(+). The extra stability of this cluster is confirmed by measurements of fragmentation cross sections through crossed molecular beam experiments. In addition, the calculations indicate a structural phase transition at this size, and most importantly, the FeO(n)(+) clusters show unique magnetic features, exhibiting isoenergetic low-spin (LS) and high-spin (HS) ground states. In the LS state, the magnetic moments of the O atoms adopt an antiferromagnetic alignment with respect to the magnetic moment of Fe(+), whereas in the HS state, the alignment is ferromagnetic. FeO(10)(+) is the largest thermodynamically stable complex, with the highest magnetic moment among the FeO(n)(+) clusters (13 µ(B) in HS).