Communications: Chain and double-ring polymeric structures: Observation of AlnH3n+1 − (n=4–8) and Al4H14 −

A pulsed arc discharge source was used to prepare gas-phase, aluminum hydride cluster anions, AlnHm−, exhibiting enhanced hydrogen content. The maximum number of hydrogen atoms in AlnHm− species was m=3n+1 for n=5–8, i.e., AlnH3n+1−, and m=3n+2 for n=4, i.e., Al4H14−, as observed in their mass spectra. These are the most hydrogen-rich aluminum hydrides to be observed thus far, transcending the 3:1 hydrogen-to-aluminum ratio in alane. Even more striking, ion intensities for AlnHm− species with m=3n+1 and m=3n+2 hydrogen atoms were significantly higher than those of nearby AlnHm− mass peaks for which m\u3c3n+1, i.e., the ion intensities for AlnH3n+1− and for Al4H14− deviated from the roughly bell-shaped ion intensity patterns seen for most AlnHm−species, in which m ranges from 1 to 3n. Calculations based on density functional theory showed that AlnH3n+1− clusters have chain and/or double-ring polymericstructures

The viability of aluminum Zintl anion moieties within magnesium-aluminum clusters

Through a synergetic combination of anion photoelectron spectroscopy and density functional theory based calculations, we have investigated the extent to which the aluminum moieties within selected magnesium-aluminum clusters are Zintl anions. Magnesium-aluminum cluster anions were generated in a pulsed arc discharge source. After mass selection, photoelectron spectra of Mg m Al n − (m, n = 1,6; 2,5; 2,12; and 3,11) were measured by a magnetic bottle, electron energy analyzer. Calculations on these four stoichiometries provided geometric structures and full charge analyses for the cluster anions and their neutral cluster counterparts, as well as photodetachment transition energies (stick spectra). Calculations revealed that, unlike the cases of recently reported sodium-aluminum clusters, the formation of aluminum Zintl anion moieties within magnesium-aluminum clusters was limited in most cases by weak charge transfer between the magnesium atoms and their aluminum cluster moieties. Only in cases of high magnesium content, e.g., in Mg 3 Al 11 and Mg 2 Al 12 −, did the aluminum moieties exhibit Zintl anion-like characteristics

Communication: In search of four-atom chiral metal clusters

A combined study utilizing anion photoelectron spectroscopy and density functional theory was conducted to search for four-atom, chiral, metal, and mostly metal clusters. The clusters considered were AuCoMnBi−/0, AlAuMnO−/0, AgMnOAl−/0, and AuAlPtAg−/0, where the superscripts, −/0, refer to anionic and neutral cluster species, respectively. Based on the agreement of experimentally and theoretically determined values of both electron affinities and vertical detachment energies, the calculated cluster geometries were validated and examined for chirality. Among both anionic and neutral clusters, five structures were identified as beingchiral

A Combined Theoretical and Photoelectron Spectroscopy Study of Al3Hn- (n=1-9) clusters

Combined photoelectron spectroscopic experiments and computational studies have been performed on Al3Hn- (n=1-9) clusters. Three modes of hydrogen bonding to the Al-3 moiety have been observed: terminal, bridging, and capping. Among various hydrides, Al3H5- and Al3H8- clusters have highest HOMO-LUMO gap and largest electron affinity, respectively. Our studies indicate that as the number of hydrogen atoms increase the presence of AlH2 groups, representing the tetrahedral coordination of the Al atom, which in turn led to the stoichiometric ring structure

Aluminum Zintl anion moieties within sodium aluminum clusters

Through a synergetic combination of anion photoelectron spectroscopy and density functional theory based calculations, we have established that aluminum moieties within selected sodium-aluminum clusters are Zintl anions. Sodium–aluminum cluster anions, Na m Al n −, were generated in a pulsed arc discharge source. After mass selection, their photoelectron spectrawere measured by a magnetic bottle, electron energy analyzer. Calculations on a select sub-set of stoichiometries provided geometric structures and full charge analyses for both cluster anions and their neutral cluster counterparts, as well as photodetachment transition energies (stickspectra), and fragment molecular orbital based correlation diagrams

Size-selected gold clusters on porous titania as the most “gold-efficient” heterogeneous catalysts

Research on homogeneous and heterogeneous catalysis is indeed convergent and finds subnanometric particles to be at the heart of catalytically active species. Here, monodisperse gold clusters are deposited from the gas phase onto porous titania generating well-defined model systems and the resulting composite materials exhibit a sharp size-dependency on the number of gold atoms per cluster and exceptionally high-turnovers toward the bromination of 1,4-dimethoxybenzene are observed. This indicates that the deliberate generation of active centres is of utmost importance for the creation of the most “gold-efficient” catalysts.ISSN:1463-9084ISSN:1463-907

On the Existence of Designer Magnetic Superatoms

The quantum states in small, compact metal clusters are bunched into electronic shells with electronic orbitals resembling those in atoms, enabling classification of stable clusters as superatoms. The filling of superatomic orbitals, however, does not generally follow Hund’s rule, and it has been proposed that magnetic superatoms can be stabilized by doping simple metal clusters with magnetic atoms. Here, we present evidence of the existence of a magnetic superatom and the determination of its spin moment. Our approach combines first principles studies with negative ion photoelectron experiments and enables a unique identification of the ground state and spin multiplicity. The studies indicate VNa₈ to be a magnetic superatom with a filled d-subshell and a magnetic moment of 5.0 μ_B. Its low electron affinity is consistent with filled subshell and enhanced stability. The synthesis of this species opens the pathway to investigate the spin-dependent electronics of the new magnetic motifs