Core photoelectron shifts in reduced zirconium halides. Relaxation effects and delocalized metal-metal bonding

Journal Article · Wed Sep 14 04:00:00 EDT 1983 · Inorg. Chem.; (United States)

DOI:https://doi.org/10.1021/ic00161a005· OSTI ID:5641582

Corbett, J D

Trends in binding energies of the zirconium (Zr) 3d/sub 5/2/ and chlorine (Cl) 2p/sub 3/2/ levels for Zr, zirconium chloride/sub n/ (ZrCl/sub n/) (n = 1-4), zirconium bromide (ZrBr), zirconium X hydride/sub x/ (ZrXH/sub x) (X = Cl, Br; x = 0.5, 1), and ZrClO/sub 0/ /sub 4/ are considered as a function of oxidation state. The zirconium binding energy exhibits a regular and consistent increase on oxidation for all phases with formal oxidation states between 0 and +2, while those for ZrCl/sub 3/ and ZrCl/sub 4/ are displaced about 1.3 eV to higher binding energy. Structural and property data for the compounds suggest that the break in zirconium binding energy takes place at the point at which metal-metal bonding and the consequent valence-electron delocalization cease. This effect is considered in terms of the metal valence bands and the final-state relaxation processes that occur in response to the core hole. The apparent relaxation is otherwise remarkably insensitive to differences in valence bands and structure. The only change of significance seen in the chlorine data reflects the different Fermi level reference in ZrCl/sub 4/. 2 figures, 1 table.

• Research Organization: Ames Lab., IA
• DOE Contract Number: W-7405-ENG-82
• OSTI ID: 5641582
• Journal Information: Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 22:19; ISSN INOCA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400104 -- Spectral Procedures-- (-1987)
400201* -- Chemical & Physicochemical Properties
400500 -- Photochemistry
BINDING ENERGY
BROMIDES
BROMINE COMPOUNDS
CHLORIDES
CHLORINE COMPOUNDS
COMPARATIVE EVALUATIONS
ELECTRON SPECTROSCOPY
ELECTRONIC STRUCTURE
ELEMENTS
ENERGY
HALIDES
HALOGEN COMPOUNDS
HYDRIDES
HYDROGEN COMPOUNDS
MATERIALS
METALS
MOLECULAR STRUCTURE
OXYCHLORIDES
OXYGEN COMPOUNDS
PHOTOELECTRON SPECTROSCOPY
RELAXATION
SEMICONDUCTOR MATERIALS
SPECTRAL SHIFT
SPECTROSCOPY
TRANSITION ELEMENT COMPOUNDS
TRANSITION ELEMENTS
VALENCE
ZIRCONIUM
ZIRCONIUM BROMIDES
ZIRCONIUM CHLORIDES
ZIRCONIUM COMPOUNDS
ZIRCONIUM HYDRIDES