Journal
JOURNAL OF BIOLOGICAL INORGANIC CHEMISTRY
Volume 21, Issue 5-6, Pages 793-805Publisher
SPRINGER
DOI: 10.1007/s00775-016-1358-7
Keywords
Vanadium; X-ray spectroscopy; Density functional theory DFT; XES; XAS
Funding
- Max Planck Society (Institute for Chemical Energy Conversion)
- Max Planck Society
- Deutscher Akademischer Austauschdienst (DAAD)
- Conselho Nacional para o Desenvolvimento Cientifico e Tecnologico-CNPq [311270/2015-8]
- NIH [GM 113389-01]
- National Science Foundation
- National Institutes of Health/National Institute of General Medical Sciences under NSF [DMR-133220]
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A series of vanadium compounds was studied by K-edge X-ray absorption (XAS) and K X-ray emission spectroscopies (XES). Qualitative trends within the datasets, as well as comparisons between the XAS and XES data, illustrate the information content of both methods. The complementary nature of the chemical insight highlights the success of this dual-technique approach in characterizing both the structural and electronic properties of vanadium sites. In particular, and in contrast to XAS or extended X-ray absorption fine structure (EXAFS), we demonstrate that valence-to-core XES is capable of differentiating between ligating atoms with the same identity but different bonding character. Finally, density functional theory (DFT) and time-dependent DFT calculations enable a more detailed, quantitative interpretation of the data. We also establish correction factors for the computational protocols through calibration to experiment. These hard X-ray methods can probe vanadium ions in any oxidation or spin state, and can readily be applied to sample environments ranging from solid-phase catalysts to biological samples in frozen solution. Thus, the combined XAS and XES approach, coupled with DFT calculations, provides a robust tool for the study of vanadium atoms in bioinorganic chemistry.
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