Clusters metallic properties

Small metal clusters are also of interest because of their importance in catalysis. Despite the fact that small clusters should consist of mostly surface atoms, measurement of the photon ionization threshold for Hg clusters suggest that a transition from van der Waals to metallic properties occurs in the range of 20-70 atoms per cluster [88] and near-bulk magnetic properties are expected for Ni, Pd, and Pt clusters of only 13 atoms [89] Theoretical calculations on Sin and other semiconductors predict that the stmcture reflects the bulk lattice for 1000 atoms but the bulk electronic wave functions are not obtained [90]. Bartell and co-workers [91] study beams of molecular clusters with electron dirfraction and molecular dynamics simulations and find new phases not observed in the bulk. Bulk models appear to be valid for their clusters of several thousand atoms (see Section IX-3). 

Extended X-ray absorption fine structure (EXAFS) and photoemission measurements carried out on the clusters ranging from isolated atoms to aggregates large enough to acquire bulk metal properties, is also could be a measure for the electronic properties [40]. Copper shows a... 

The cluster condensation can be carried on the chains of octahedra sharing edges can be joined to double-strands and finally to layers of octahedra (Fig. 13.18). Every layer consists of metal atoms in two planes arranged in the same way as two adjacent layers of atoms in a closest-packing of spheres. This is simply a section from a metal structure. The X atoms occupy positions between the metal layers and act as insulating layers. Substances like ZrCl that have this structure have metallic properties in two dimensions. 

Although there are a lot of publications on the chemistry of technetium [2-4] and transition-metal clusters [1,5-8], the chemistry of technetium clusters was insufficiently studied until the early eighties [1,2]. Nevertheless, the available scanty data on the compounds with Tc-Tc bonds inspired hope that interesting results would be obtained in the chemistry of technetium in general, in radiochemistry, and in the chemistry of transition-metal cluster compounds. The anticipated results were actually obtained [9-15] and the conclusion was drawn that technetium had a number of anomalous cluster-forming properties [9]. This review looks at the detailed studies of these properties and their interpretation in terms of electronic structure theory. 

When it comes to metal-rich compounds of the alkaline earth and alkali metals with their pronounced valence electron deficiencies it is no surprise that both principles play a dominant role. In addition, there is no capability for bonding of a ligand shell around the cluster cores. The discrete and condensed clusters of group 1 and 2 metals therefore are bare, a fact which leads to extended inter-cluster bonding and results in electronic delocalization and metallic properties for all known compounds. 

In recent publications [120, 121, 122,123] it has been shown that both the ionization potentials and the optical properties of bare and uncharged mercury clusters in a molecular beam experiment demonstrate a gradual size dependent evolution of metallic properties, starting at about 13 atoms and already bulklike at about 70 atoms. It has been predicted theoretically [124] that plasmons should begin to develop for such mercury clusters at about Hgi5. We should keep this in mind in the discussion of the electronic properties of AU55. 

In general terms, building a defined nano-architecture in oxide-type materials further extends the concept of nanocatalysis, e.g. when the electrons are confined, and physical and chemical properties are not scalable from the bulk properties. Studies have been made mainly on clusters/metal particles in the... 

The political justification for transition metal cluster chemistry is the assumption that clusters are models in which metallic properties may be more easily studied than in the metals themselves. These properties include electronic phenomena such as color and conductivities as well as surface phenomena, such as atom arrangements and catalytic activities. Thus, there are two main lines of cluster research. The more academic line leads to the search for new types of clusters and their structure and bonding, whereas the more practical line leads to the investigation of reactivities with the hope that clusters may open catalytic pathways that neither plain metals nor mononuclear catalysts can provide. The interdependence of both lines is obvious. 

Clusters and alloys are molecular species that may show different catalytic activity, selectivity and stability than bulk metals and alloys. Small metal clusters and alloy clusters have been studied reeendy for potential use as catalysts, ceramic precursors, and as thin films. Several fundamental questions regarding such clusters are apparent. How many atoms are needed before metallic properties are observed How are steric and electronic properties related to the number, type and structure of such clusters Do mixed metal clusters behave like bulk alloy phases ... 

Huttner, G. Knoll, K. RP-bridged metal carbonyl clusters Synthesis, properties, and reactions, Angew. Chem., Int. Ed. Engl 1987, 26, 743 Angew. Chem. 1987, 99, 765. 

Lithium clusters have been a popular model for the calculation of metal properties because of their low atomic number. Lasarov and Markov (49) used a Hiickel procedure to determine the properties of a 48-atom Li crystal. They found a transition to metal properties with the binding energy per atom approaching 1.8 eV at 30 atoms. The ionization potential approached the bulk value since some electrons occupy antibonding molecular orbitals, as observed for Ag clusters. The calculated properties of the largest cluster were not those of a bulk metal. 

Clusters of Ag atoms have metal-like properties at 55 atoms, but they are not metals. The gap between HOMO and LUMO being 0.2 eV is still 10 times larger than kT expected for a bulk metal. The work function is calculated to be 1 eV larger than that of the bulk, and the cohesive energy is only about one-third that expected for bulk. The electrons behave like free electrons. The trend in each of these quantities with size is in the direction from single atom properties toward bulk metal properties. Ousters of Pd have characteristics that differ from bulk metal properties in much the same way as do Ag clusters. One exception is the calculated number of unoccupied d states per atom of small clusters, which is very close to bulk values of 0.6. 

It is a well-known fact that, as the size of a metal particle is decreased, the overlap of the bands of valence electrons, with which we are mainly concerned, diminishes, and finally they are replaced by discrete energy levels characteristic of the isolated atom. This results in the loss of electrical conductivity and in the Mie plasmon resonance, an effect that has been noted with the AU55 and smaller clusters, on the basis of which they were described above as being molecular . The extent of band overlap is temperature-sensitive because of thermal excitation, i.e. bands tend to convert to levels as temperature falls thus metallic properties may be seen at high temperature and insulator properties at low temperature. As an approximate guide we may take the relation... 

Supported bimetallic catalysts can be made by adsorption of a bimetallic precursor such as molecular cluster compounds, colloidal particles or dendrimer-stabilised particles. In several cases, homogeneous bimetallic particles have been found where the compositions lie within the miscibility gap of the bulk alloy (e.g. with PtAu particles). This suggests that when the particles are small enough and do not possess metallic properties, the normal rules do not apply. 

The first six-atom cluster, Rh6(CO)i6, was structurally elucidated by Corey, Dahl, and Beck in 1963 today there is an enormous number of them and we can sketch only a few of the main facts. In addition to their intrinsic interest, large clusters, especially the very largest ones, are of importance because they may be expected to show properties verging on those of bulk metals. They provide one approach to answering the question How large does a particle of metal have to be before bulk metal properties begin to appear ... 

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