X-ray absorption edge spectroscopy of ligands bound to open-shell metal ions: Chlorine K-edge studies of covalency in CuCl sub 4 sup 2 minus
- Stanford Univ., CA (USA)
Information on electronic structure can be obtained from analysis of x-ray absorption edge spectra. This approach has been used to obtain information from edges of transition metals like Cu, Fe, Ni, and Mo. It is also possible to directly study the absorption edge of ligands such as Cl and S bound to the metal. These edges fall in the 2-3-keV energy region where edge features are very well resolved. We report here the observation of an intense preedge transition associated with ligands bound to open-shell central atoms. We further show that the properties of these preedge features can be used to probe covalency in metal-ligand bonding. We have studied the ligand K edge of chlorine complexes of Cu and Zn: Cs{sub 2}CuCl{sub 4}, bis(creatininium)CuCl{sub 4}, and Cs{sub 2}ZnCl{sub 4}. The Cu site in Cs{sub 2}CuCl{sub 4} is distorted tetrahedral (D{sub 2d}), and the Zn site in Cs{sub 2}ZnCl{sub 4} is isostructural. Bis(creatininium)CuCl{sub 4} has a square-planar (D{sub 4h}) geometry. X-ray absorption spectroscopy (XAS) edge data were measured at the Stanford Synchrotron Radiation Laboratory by using methodology that has been previously described.
- OSTI ID:
- 6725111
- Journal Information:
- Journal of the American Chemical Society; (USA), Vol. 112:4; ISSN 0002-7863
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
COPPER CHLORIDES
ABSORPTION SPECTROSCOPY
LIGANDS
ZINC CHLORIDES
CALCULATION METHODS
CHEMICAL BONDS
DATA ANALYSIS
ELECTRONIC STRUCTURE
MEASURING INSTRUMENTS
MEASURING METHODS
VALENCE
CHLORIDES
CHLORINE COMPOUNDS
COPPER COMPOUNDS
COPPER HALIDES
HALIDES
HALOGEN COMPOUNDS
SPECTROSCOPY
TRANSITION ELEMENT COMPOUNDS
ZINC COMPOUNDS
ZINC HALIDES
360104* - Metals & Alloys- Physical Properties
400201 - Chemical & Physicochemical Properties