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- Title
X-Ray Emission Spectroscopy: A Spectroscopic Measure for the Determination of NO Oxidation States in Fe-NO Complexes.
- Authors
Lu, Tsai ‐ Te; Weng, Tsu ‐ Chien; Liaw, Wen ‐ Feng
- Abstract
Extensive study of the electronic structure of Fe-NO complexes using a variety of spectroscopic methods was attempted to understand how iron controls the binding and release of nitric oxide. The comparable energy levels of NO π* orbitals and Fe3d orbitals complicate the bonding interaction within Fe-NO complexes and puzzle the quantitative assignment of NO oxidation state. Enemark-Feltham notation, {Fe(NO)x}n, was devised to circumvent this puzzle. This 40- year puzzle is revisited using valence-to-core X-ray emission spectroscopy (V2C XES) in combination with computational study. DFT calculation establishes a linear relationship between ΔEσ2s*-σ2p of NO and its oxidation state. V2C Fe XES study of Fe-NO complexes reveals the ΔEσ2s*-σ2p of NO derived from NO σ2s*/σ2p→Fe1s transitions and determines NO oxidation state in Fe-NO complexes. Quantitative assignment of NO oxidation state will correlate the feasible redox process of nitric oxide and Fe-nitrosylation biology.
- Subjects
NITRIC oxide; FERRIC nitrate; X-ray emission spectroscopy; OXIDATION states; OXIDATION-reduction reaction; NITROSYLATION
- Publication
Angewandte Chemie, 2014, Vol 126, Issue 43, p11746
- ISSN
0044-8249
- Publication type
Article
- DOI
10.1002/ange.201407603