title: Experimental and theoretical correlations between vanadium K-edge X-ray absorption and Kβ emission spectra.
abstract: A series of vanadium compounds was studied by K-edge X-ray absorption (XAS) and K[Formula: see text] 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.
authors.affiliation: Max Planck Institute for Chemical Energy Conversion, Stiftstr. 34-36, 45470, Mülheim an der Ruhr, Germany.|Department of Chemistry, University of Washington, Box 351700, Seattle, WA, 98195-1700, USA.
authors.forename: Julian A
authors.initials: JA
authors.lastname: Rees
authors.affiliation: Max Planck Institute for Chemical Energy Conversion, Stiftstr. 34-36, 45470, Mülheim an der Ruhr, Germany.|Faculty of Physics and Applied Computer Science, AGH University of Science and Technology, al. Mickiewicza 30, 30-059, Kraków, Poland.
authors.forename: Aleksandra
authors.initials: A
authors.lastname: Wandzilak
authors.affiliation: Max Planck Institute for Chemical Energy Conversion, Stiftstr. 34-36, 45470, Mülheim an der Ruhr, Germany.
authors.forename: Dimitrios
authors.initials: D
authors.lastname: Maganas
authors.affiliation: Max Planck Institute for Chemical Energy Conversion, Stiftstr. 34-36, 45470, Mülheim an der Ruhr, Germany.
authors.forename: Nicole I C
authors.initials: NI
authors.lastname: Wurster
authors.affiliation: Max Planck Institute for Chemical Energy Conversion, Stiftstr. 34-36, 45470, Mülheim an der Ruhr, Germany.
authors.forename: Stefan
authors.initials: S
authors.lastname: Hugenbruch
authors.affiliation: Max Planck Institute for Chemical Energy Conversion, Stiftstr. 34-36, 45470, Mülheim an der Ruhr, Germany.
authors.forename: Joanna K
authors.initials: JK
authors.lastname: Kowalska
authors.affiliation: Max Planck Institute for Chemical Energy Conversion, Stiftstr. 34-36, 45470, Mülheim an der Ruhr, Germany.|Department of Chemistry, The Pennsylvania State University, University Park, PA, 16802, USA.
authors.forename: Christopher J
authors.initials: CJ
authors.lastname: Pollock
authors.affiliation: Centro Nacional de Pesquisa em Energia e Materiais, Laboratório Nacional de Luz Síncrotron, Rua Giuseppe Máximo Scolfaro 10000, Campinas, SP, 13083-970, Brazil.
authors.forename: Frederico A
authors.initials: FA
authors.lastname: Lima
authors.affiliation: Cornell High Energy Synchrotron Source, Wilson Laboratory, Cornell University, Ithaca, NY, 14853, USA.
authors.forename: Kenneth D
authors.initials: KD
authors.lastname: Finkelstein
authors.affiliation: Max Planck Institute for Chemical Energy Conversion, Stiftstr. 34-36, 45470, Mülheim an der Ruhr, Germany. serena.debeer@cec.mpg.de.|Department of Chemistry and Chemical Biology, Cornell University, Ithaca, NY, 14853, USA. serena.debeer@cec.mpg.de.
authors.forename: Serena
authors.initials: S
authors.lastname: DeBeer
mesh_terms: D011789:Quantum Theory; D013052:Spectrometry, X-Ray Emission; D017968:Vanadium Compounds / Q000737:chemistry*; D056928:X-Ray Absorption Spectroscopy
chemical_list: D017968:Vanadium Compounds
keywords: Density functional theory DFT; Vanadium; X-ray spectroscopy; XAS; XES