Electronic structure and symmetry in nickel L edge X-ray absorption spectroscopy. Application to a nickel protein

Journal Article · Wed Mar 09 04:00:00 EST 1994 · Journal of the American Chemical Society; (United States)

DOI:https://doi.org/10.1021/ja00084a036· OSTI ID:7162941

Elp, J van ^[1]; Peng, G ^[2]; Searle, B G ^[3]; Mitra-Kirtley, S ^[4]; Huang, Y H; Johnson, M K; Zhou, Z H; Adams, M W.W. ^[5]; Maroney, M J ^[6]; Cramer, S P ^[7]

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1. Lawrence Berkeley Lab., CA (United States)
2. Univ. of California, Davis, CA (United States)
3. SERC Daresbury Lab., Warrington (United Kingdom)
4. Rose-Hulman Inst. of Technology, Terre Haute, IN (United States)
5. Univ. of Georgia, Athens, GA (United States)
6. Univ. of Massachusetts, Amherst, MA (United States)
7. 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), Journal Name: Journal of the American Chemical Society; (United States) Vol. 116:5; ISSN JACSAT; ISSN 0002-7863
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400102 -- Chemical & Spectral Procedures
550200* -- Biochemistry
59 BASIC BIOLOGICAL SCIENCES
ABSORPTION SPECTROSCOPY
COMPLEXES
ELECTRONIC STRUCTURE
LIGANDS
METALLOPROTEINS
NICKEL COMPLEXES
ORGANIC COMPOUNDS
PROTEINS
RUBREDOXIN
SPECTROSCOPY
TRANSITION ELEMENT COMPLEXES
VALENCE
X-RAY SPECTROSCOPY