Stability and magnetic properties of T2Sin (T=Cr,Mn,1≤n≤8) clusters

First-principles studies on the geometry, electronic structure, and magnetic properties of neutral and anionic Cr2Sin and Mn2Sin (1≤n≤8) have been carried out within a gradient corrected density-functional framework. We find that Cr2Sin clusters containing up to five Si atoms and Mn2Sin clusters containing up to eight Si atoms are all marked by finite local spin moments at the transition-metal site that order ferromagnetically or antiferromagnetically depending on the size and the charged state. Our studies of the variation in the binding energy upon addition of successive Si atoms and the gap between the highest occupied molecular orbital and the lowest unoccupied molecular orbital indicate Mn2Si4 to be a potential motif for generating magnetic cluster-assembled material. While the individual Mn2Si4 motif has a ground state with antiferromagnetically coupled local moments, the studies on the assembly of two basic motifs show that it favors a ferromagnetic state. It is hoped that the present work will motivate examination of such assemblies in the recently developed cluster beam deposition experiments

Studies of ions in a drift field: laser diagnostics of excited states and measurements of thermochemical properties at equilibrium

A major technique for investigating the thermochemical properties of ions and their related clusters is the high pressure drift/mass spectrometer detection technique. A crucial question in this regard is the extent to which ions drifting in an electric field are thermalized. This paper is divided into two parts, one describing some laser techniques which are enabling an investigation of the possible presence of excited ions in a drift field, and secondly, a reporting of some recent findings and trends in the stability of ion clusters of single and mixed constituents

Reactivity and electronic structure of aluminum clusters: The aluminum-nitrogen system

The stability of anionic aluminum–nitrogen clusters has been examined and Al2N−, Al3N−2,Al5N−2, Al6N−3, Al8N−3, and Al9N−2 are found to be particularly stable. Theoreticaldensity functional calculations on neutral and anionic AlnN (n=1–8) clusters were performed and the stability and reaction energetics with oxygen examined. Clusters requiring less than 5.7 eV to remove an electron and an Al atom are shown to be resistant to the reaction with oxygen

Formation and properties of halogenated aluminum clusters

The fast-flow tube reaction apparatus was employed to study the halogenation of aluminum clusters. For reactions with HX (X=Cl, Br, and I), acid-etching pathways are evident, and we present findings for several reactions, whereby AlnX− generation is energetically favorable. Tandem reaction experiments allowed us to establish that for AlnCl−, AlnI−, and AlnI−2, species with n=6, 7, and 15 are particularly resistant to attack by oxygen. Further, trends in reactivity suggest that, in general, iodine incorporation leaves the aluminum clusters’ electronic properties largely unperturbed. Ab initio calculations were performed to better interpret reaction mechanisms and elucidate the characteristics of the products. Lowest energy structures for Al13X− were found to feature icosahedral Al13 units with the halogen atom located at the on-top site. The charge density of the highest occupied molecular orbital in these clusters is heavily dependent on the identity of X. The dependence of reactivity on the clusters’ charge state is also discussed. In addition, we address the enhanced stability of Al13I− and Al13I−2, arguing that the superhalogen behavior of Al13 in these clusters can provide unique opportunities for the synthesis of novel materials with saltlike structures

Crystal field effects on the reactivity of aluminum-copper cluster anions

The limits and useful modifications of the jellium model are of great interest in understanding the properties of metallic clusters, especially involving bimetallic systems. We have measured the relative reactivity of CuAl−n clusters (n=11–34) with O2. An odd-even alternation is observed that is in accordance with spin-dependant etching, and CuAl−22is observed as a “magic peak.” The etching resistance of CuAl−22 is explained by an unusually large splitting of the 2D10 subshell that occurs because of a geometric distortion of the cluster that may also be understood as a crystal field splitting of the superatomic orbitals

Photoelectron imaging and theoretical investigation of bimetallic Bi1–2Ga−0–2 and Pb−1–4 cluster anions

We present the results of photoelectron velocity-map imaging experiments for the photodetachment of small negatively charged BimGan (m=1–2, n=0–2), and Pbn (n=1–4) clusters at 527 nm. The photoelectron images reveal new features along with their angular distributions in the photoelectron spectra of these clusters. We report the vertical detachment energies of the observed multiple electronic bands and their respective anisotropy parameters for the BimGan and Pbn clusters derived from the photoelectron images. Experiments on the BiGan clusters reveal that the electron affinity increases with the number of Ga atoms from n=0 to 2. The BiGa−2 cluster is found to be stable, both because of its even electron number and the high electron affinity of BiGa2. The measured photoelectron angular distributions of the BimGan and Pbn clusters are dependent on both the orbital symmetry and electron kinetic energies. Density-functional theory calculations employing the generalized gradient approximation for the exchange-correlation potential were performed on these clusters to determine their atomic and electronic structures. From the theoretical calculations, we find that the BiGa−2, Bi2Ga−3 and Bi2Ga−5 (anionic), and BiGa3, BiGa5, Bi2Ga4 and Bi2Ga6(neutral) clusters are unusually stable. The stability of the anionic and neutral Bi2Gan clusters is attributed to an even-odd effect, with clusters having an even number of electrons presenting a larger gain in energy through the addition of a Ga atom to the preceding size compared to odd electron systems. The stability of the neutral BiGa3 cluster is rationalized as being similar to BiAl3, an all-metal aromatic cluster

Closed-shell to split-shell stability of isovalent clusters

Metallic clusters containing 2, 8, 18, and 20 electrons are now known to exhibit enhanced stability that can be reconciled because of filled 1S, 1P, 1D, and 2S electronic shells within a simplified confined nearly free electron (NFE) gas. Here, we present first-principles studies on three isovalent clusters, i.e., ZnMg8, CuMg8−, and AuMg8−, each with 18 valence electrons. All the clusters exhibit local energetic stability but with differing origins. Although the stability of ZnMg8 can be reconciled within the conventional confined NFE picture with filled 1S2, 1P6, and 1D10shells, CuMg8− and AuMg8− are shown to be stable despite the unfilled D-shell. Their stability can be understood as a crystal field–like splitting of the otherwise degenerate D-shell because of internal electric fields of the positive ion cores that lead to a filled 1S2, 1P6, 1D8, 2S2 sequence separated by unfilled D2 states that form a large gap. We also examine the progression toward the metallic character in ZnMgn clusters, because isolated Mg and Zn atoms have filled valence 4s2 and 3s2 atomic states. As Mg atoms are added to a Zn atom, the excited atomic p-states in the Mg atoms hybridize rapidly with Zn and Mg s-states to promote a metallic character that evolves more rapidly than in pure Mgn clusters

Cooperative effects in the oxidation of CO by palladium oxide cations

Cooperative reactivity plays an important role in the oxidation of CO to CO2 by palladium oxide cations and offers insight into factors which influence catalysis. Comprehensive studies including guided-ion-beam mass spectrometry and theoretical investigations reveal the reaction products and profiles of PdO2 + and PdO3 + with CO through oxygen radical centers and dioxygen complexes bound to the Pd atom. O radical centers are more reactive than the dioxygen complexes, and experimental evidence of both direct and cooperative CO oxidation with the adsorption of two CO molecules are observed. The binding of multiple electron withdrawing CO molecules is found to increase the barrier heights for reactivity due to decreased binding of the secondary CO molecule, however, reactivity is enhanced by the increase in kinetic energy available to hurdle the barrier. We examine the effect of oxygen sites, cooperative ligands, and spin including two-state reactivity

The applicability of three-dimensional aromaticity in BiSnn- Zintl analogues

Three-dimensional aromaticity is shown to play a role in the stability of deltahedral Zintl clusters and here we examine the connection between aromaticity and stability. In order to gain further insight, we have studied Zintl analogs comprised of bismuthdopedtin clusters with photoelectron spectroscopy and theoretical methods. To assign aromaticity, we examine the ring currents induced around the cage by using the nucleus independent chemical shift. In the current study, BiSn4− is a stable cluster and fits aromatic criteria, while BiSn5− is found to fit antiaromatic criteria and has reduced stability. The more stable clusters exhibit an aromatic character which originates from weakly interacting s-states and bonding orbitals parallel to the surface of the cluster, while nonbonding lone pairs perpendicular to the surface of the cluster account for antiaromaticity and reduced stability. The effect of three-dimensional aromaticity on the electronic structure does not result in degeneracies, so the resulting variations in stability are smaller than those seen in conventional aromaticity

Appearance of bulk properties in small tungsten oxide clusters

Contrary to the conventional understanding that atomic clusters usually differ in properties and structure from the bulk constituents of which they are comprised, we show that even a dimer of tungsten oxide (WO3)2 possesses bulklike features and the geometry of a small cluster containing only 4 tungsten and 12 oxygen atoms bears the hallmarks of crystalline tungsten oxide, WO3. This observation, based on a synergistic approach involving mass distributions under quasisteady state conditions, photoelectron spectroscopy, and first principles molecular orbital theory, not only illustrates the existence of a class of strongly covalent or ionic materials whose embryonic forms are tiny clusters but also lends the possibility that a fundamental understanding of complex processes such as catalyticreactions on surfaces may be achieved on an atomic scale with clusters as model systems