Metal clusters, transition structure variation

The microscopic imderstanding of the chemical reactivity of surfaces is of fundamental interest in chemical physics and important for heterogeneous catalysis. Cluster science provides a new approach for the study of the microscopic mechanisms of smface chemical reactivity [48]. Smfaces of small clusters possess a very rich variation of chemisorption sites and are ideal models for bulk surfaces. Chemical reactivity of many transition-metal clusters has been investigated [49]. Transition-metal clusters are produced using laser vaporization, and the chemical reactivity studies are carried out typically in a flow tube reactor in which the clusters interact with a reactant gas at a given temperature and pressure for a fixed period of time. Reaction products are measured at various pressures or temperatures and reaction rates are derived. It has been found that the reactivity of small transition-metal clusters with simple molecules such as H2 and NH can vary dramatically with cluster size and structure [48, 49, 50, 51 and 52]. 

The transition-metal clusters often display highly symmetrical metal frameworks, normally with symmetries derived from the platonic or archimedian solids or variations thereof. The post-transition element clusters, on the other hand, are not necessarily aflfected by such confinements. However, as will be explained in Sec. 1.29.4, relationships between the structure and the electron count do exist for the naked clusters, and regular, closed geometries are found for a rather large group of these species. For instance, the trigonal prismatic symmetry of the Rhf, framework in Fig. lA is also found in the naked tellurium cluster... 

Figure 6. The variation in the measured ionization potential of mercury clusters as a function of cluster size. The work function for bulk Hg (4.49 eV) is indicated. The dashed line is a plot of the ionization potential calculated for the classical (liquid drop) electrostatic model for a metalUc sphere of diameter d. Region III contains clusters which are classified as insulating. Region II denotes the size-induced metal-insulator transition, in which overlap of the 6s and 6p states sets in at around Hgn. The larger clusters, located in Region I, have valence electronic structures that closely resemble the band structures of liquid and crystalline mercury. Adapted from Rademann. i...

This structural variation notwithstanding, only a few cationic transition-metal ions react efficiently with molecular oxygen under gas-phase conditions (see below). In contrast, many anionic metal complexes and clusters are readily oxidized by O2 to afford various metal-oxide anions [19]. From a conceptual point of view, however, anionic species appear to be inadequate reagents for the activation of hydrocarbons, because they generally require electrophilic attack. At present, only a few oxidations by transition-metal oxide anions have been reported to occur in the gas phase, and they are mostly limited to relatively polar substrates, such as the CH3OH CH2O conversion [20]. Because of the lower reactivity of hydrocarbons, their C-H bond activation by metal-oxide anions is likely to be limited to radical pathways driven purely thermodynamically, i.e., when Z)(0-H) exceeds Z)(C-H) of the substrate [21]. As radical-type pathways are prone to create selectivity problems, and over-oxidation is particularly difficult to control, the anionic route appears less attractive as far as partial oxidation of alkanes is concerned. 

In the third step, our ZT-TBMD method has been extended by incorporating the Nose-bath (Nose 1984) and the Multiple Histogram approximations (Fanourgakis et al. 1997), so as to be applicable to cluster studies at finite temperatures in an efficient way (Andriotis et al. 2006, 2007 Fthenakis et al. 2003). This generalization allows one to calculate the caloric curve for the cluster and use this to study the effect of temperature on the structural, electronic, and magnetic properties of transition metal clusters and binary systems containing transition metal and semiconductor atoms. The method has been used to study the variation of structural and magnetic properties with temperature as well as to obtain the caloric curves of the Ni-clusters (Andriotis et al. 2006,2007 Fthenakis et al. 2003). 

Polymetallic anions, prepared by dissolution of alloys of the alkali and post-transition metals in amine solvents (often with a complexand for the alkali metal cation), have been characterized in crystalline and solution phases. Clusters TlSng3, Ge92 (with 20 skeletal bonding electrons), Sn93- (21 skeletal e) and Bi95+ (22 skeletal e) possess a tricapped trigonal prismatic structure, symmetry D3A, with variations of dimensional detail which correlate with the electron population.291 292 This structure is a ctoso-deltahedron, and with 20 (2h + 2) skeletal electrons can be construed to be three-dimensionally aromatic.292 The 22e clusters M94 (M = Ge, Sn, Pb) occur as the C4v monocapped square antiprism, a nido polyhedron. 

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