Electronic structure and symmetry in nickel L edge X-ray absorption spectroscopy. Application to a nickel protein
- Lawrence Berkeley Lab., CA (United States)
- Univ. of California, Davis, CA (United States)
- SERC Daresbury Lab., Warrington (United Kingdom)
- Rose-Hulman Inst. of Technology, Terre Haute, IN (United States)
- Univ. of Georgia, Athens, GA (United States)
- Univ. of Massachusetts, Amherst, MA (United States)
- Lawrence Berkeley Lab., CA (United States) Univ. of California, Davis, CA (United States)
We have studied the effects of electronic structure and symmetry on Ni L[sub 2.3] edge X-ray absorption spectra by measuring the L[sub 2,3] edges of several nickel compounds with different structural symmetries. Using ligand field atomic multiplet calculations, we find that there is a close relationship between the Ni L[sub 2,3] edge spectral features and the electronic structure at the nickel site. The L[sub 2,3] absorption edge is very sensitive to the spin state and the oxidation state of the nickel site, even for the formally trivalent nickel oxidation state. The Ni L[sub 2,3] edge is also sensitive to different structural nickel site symmetries, but less sensitive to changes in individual ligands. In the protein system investigated, the Ni-substituted Pyrococcus furiosus rubredoxin, we find a strongly distorted T[sub d] symmetry and a large zero field splitting, comparable to that observed in an optical MCD study. Because of the chemical sensitivity and specificity for only the nickel site, Ni L[sub 2,3] edges are a strong spectroscopic tool for investigating the nickel sites in large metalloproteins. The information obtained at the Ni L[sub 2,3] edge complements information from EXAFS measurements at the nickel K edge. 39 refs., 5 figs.
- OSTI ID:
- 7162941
- Journal Information:
- Journal of the American Chemical Society; (United States), Vol. 116:5; ISSN 0002-7863
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
METALLOPROTEINS
ABSORPTION SPECTROSCOPY
ELECTRONIC STRUCTURE
X-RAY SPECTROSCOPY
NICKEL COMPLEXES
LIGANDS
PROTEINS
RUBREDOXIN
VALENCE
COMPLEXES
ORGANIC COMPOUNDS
SPECTROSCOPY
TRANSITION ELEMENT COMPLEXES
550200* - Biochemistry
400102 - Chemical & Spectral Procedures