Photoelectron and extended-Hueckel study of the double-metal-layered zirconium monochloride, the related zirconium and scandium chloride carbides M/sub 2/Cl/sub 2/C, and their relationship to carbon-centered clusters

Journal Article · Wed May 14 04:00:00 EDT 1986 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00270a017· OSTI ID:5584039

Ziebarth, R P; Hwu, S J; Corbett, J D

The bonding in the double-metal-layered ZrCl(AbcA), the hypothetical reordered ZrCl(AbaB), and the product of insertion of carbon into the latter to give M/sub 2/Cl/sub 2/C (Ab(c)aB), M = Zr, Sc, have been examined by photoelectron spectroscopy (UPS, XPS) and by extended-Hueckel band calculations. The compounds characteristically exhibit well-resolved chlorine 3p and carbon 2p (when present) valence bands and a zirconium conduction band, with the substantial metal-nonmetal covalency in the first two bands. A significant amount of M-M bonding is contained within the carbon-binding states. The calculated density-of-states curves are in good agreement with UPS data for all three compounds in both energy and band shape, with the zirconium phases being metallic by both criteria. Bonding correlations between the known Zr/sub 6/Cl/sub 12/C-type clusters and Zr/sub 2/Cl/sub 2/C condensation product of these are examined. The energies of the chlorine, carbon, and metal MO's (bands) in the two limits show a close correspondence in both experiment and theory. The orbital description of the relatively localized bonding of carbon within the Zr/sub 6/C cluster unit is also preserved on condensation. On the other hand, substantial delocalization leads to marked dispersion of the Zr-Zr bonding HOMO and LUMO cluster orbitals within the conduction band. Theoretical predictions of unknown derivatives of the title phases are also considered.

• Research Organization: Iowa State Univ., Ames
• OSTI ID: 5584039
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 108:10; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
BAND THEORY
CALCULATION METHODS
CARBIDES
CARBON COMPOUNDS
CHEMICAL BONDS
CHLORIDES
CHLORINE COMPOUNDS
DATA
ELECTRON SPECTROSCOPY
EXPERIMENTAL DATA
HALIDES
HALOGEN COMPOUNDS
INFORMATION
MOLECULAR STRUCTURE
NUMERICAL DATA
PHOTOELECTRON SPECTROSCOPY
SCANDIUM CHLORIDES
SCANDIUM COMPOUNDS
SPECTROSCOPY
TRANSITION ELEMENT COMPOUNDS
VALENCE
ZIRCONIUM COMPOUNDS