Atomic spectra, transition metal clusters

At the same time cis Smalley and students at Rice University, Houston Texas, developed the laser vaporization method for production of clusters [84], a similar set-up was built at Exxon s Research Laboratory, New Jersey, USA, by the group of Kaldor and Cox [102,103]. They studied in particular transition metal clusters but also produced clusters of carbon containing up to more than hundreds of atoms as shown in the mass spectrum in Fig. 12. 

Similar experiments on a large number of transition metal carbonyls have shown that this process favors dissociation to and detection of metal clusters or atoms. Since most metal-(CO)n photofragments are themselves subject to efficient dissociation, MPI experiments do not identify the primary photoproducts. This situation contrasts sharply with electron impact ionization where the parent ion is usually formed and daughter ions are seen as a result of parent ion fragmentation. Figure 4 shows the electron impact mass spectrum of Mn2(C0) Q (33). for comparison with the MPI mass spectrum of Figure 3. 

This behavior results from the appearance of a new interband transition corresponding to formation of intradendrimer Cu clusters. The measured onset of this transitions at 590 nm agrees with the reported value [121], and the nearly exponential shape is characteristic of a band-like electronic structure, strongly suggesting that the reduced Cu does not exist as isolated atoms, but rather as clusters [122]. The presence of metal clusters is also supported by loss of signal in the EPR spectrum [123] following reduction of the dendrimer Cu + composite. 

Analysis of the valence-band spectrum of NiO helped to understand the electronic structure of transition-metal compounds. It is to be noted that th.e crystal-field theory cannot explain the features over the entire valence-band region of NiO. It therefore becomes necessary to explicitly take into account the ligand(02p)-metal (Ni3d) hybridization and the intra-atomic Coulomb interaction, 11, in order to satisfactorily explain the spectral features. This has been done by approximating bulk NiO by a cluster (NiOg) ". The ground-state wave function Tg of this cluster is given by,... 

In summary, ionisation potentials, dissociation and cohesive energies for mercury clusters have been determined. The mass spectrum of negatively charged Hg clusters is reported. The influence of the transition from van der Waals (n < 13), to covalent (30 < n < 70) to metallic bonding (n > 100) is discussed. A cluster is defined to be metallic , if the ionisation potential behaves like that calculated for a metal sphere. The difference between the measured ionisation potential and that expected for a metallic cluster vanishes rather suddenly around n 100 Hg atoms per cluster. Two possible interpretations are discussed, a rapid decrease of the nearest-neighbour distance and/or the analogue of a Mott transition in a finite system. Electronic correlation effects are strong they make the experimentally observed transitions van der Waals/covalent and covalent/metallic more pronounced than calculated in an independent electron theory. 

We have utilized the embedded cluster DV scheme to study the electronic structure of the Y(Ni] IMI)B2C superconductors (M=Fe, Co, and Ru), with 71 atom variational clusters centered on the substitutional site [109] as shown in Fig. 13. Bonding within the RC plane is found to be highly ionic, while B-C and Ni-B bonding structures are analyzed as typically covalent. In addition, the strong overlap between atoms in the transition metal plane has typical metallic character. Thus the entire spectrum of chemical bonding including ionic, covalent, and metallic structures is found within this peculiar crystal structure. The Ni-B slab is found to be electron-rich, as the result of charge transfer from the RC planes. 

In Chapter 7 we discuss the unique seven-atom surface-ensemble cluster on the Fe(lll) surface (shown in Fig. 2. IOC) that is optimum for N2 activation. Early suggestions that surface ensembles with a particular number of atoms are necessary for a particular reaction to occur are deduced from alloying studies of reactive transition-metal surfaces, with catalytically inert metals such as Au, Ag, Cu or Sn . For example, the infrared spectrum of CO adsorbed on Pd shows the characteristic signature of CO adsorbed one-fold, twofold or three-fold to surface Pd atoms . Alloying Pd with Ag, to which CO only weakly coordinates, dilutes the surface ensembles. One observes a decrease of the three-fold and the two-fold coordinated CO and the one-fold coordinated CO becomes the dominant species. The effect of alloying a reactive metal with a more inert metal is especially dramatic when one compares hydrocarbon hydrogenation reactions with hydrocarbon hydrogenolysis reactionst . 

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