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Experimental and theoretical correlations between vanadium K-edge X-ray absorption and K[Formula: see text] emission spectra
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...
Autores principales: | , , , , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
Springer Berlin Heidelberg
2016
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4989026/ https://www.ncbi.nlm.nih.gov/pubmed/27251139 http://dx.doi.org/10.1007/s00775-016-1358-7 |
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author | Rees, Julian A. Wandzilak, Aleksandra Maganas, Dimitrios Wurster, Nicole I. C. Hugenbruch, Stefan Kowalska, Joanna K. Pollock, Christopher J. Lima, Frederico A. Finkelstein, Kenneth D. DeBeer, Serena |
author_facet | Rees, Julian A. Wandzilak, Aleksandra Maganas, Dimitrios Wurster, Nicole I. C. Hugenbruch, Stefan Kowalska, Joanna K. Pollock, Christopher J. Lima, Frederico A. Finkelstein, Kenneth D. DeBeer, Serena |
author_sort | Rees, Julian A. |
collection | PubMed |
description | 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. ELECTRONIC SUPPLEMENTARY MATERIAL: The online version of this article (doi:10.1007/s00775-016-1358-7) contains supplementary material, which is available to authorized users. |
format | Online Article Text |
id | pubmed-4989026 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2016 |
publisher | Springer Berlin Heidelberg |
record_format | MEDLINE/PubMed |
spelling | pubmed-49890262016-09-01 Experimental and theoretical correlations between vanadium K-edge X-ray absorption and K[Formula: see text] emission spectra Rees, Julian A. Wandzilak, Aleksandra Maganas, Dimitrios Wurster, Nicole I. C. Hugenbruch, Stefan Kowalska, Joanna K. Pollock, Christopher J. Lima, Frederico A. Finkelstein, Kenneth D. DeBeer, Serena J Biol Inorg Chem Original Paper 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. ELECTRONIC SUPPLEMENTARY MATERIAL: The online version of this article (doi:10.1007/s00775-016-1358-7) contains supplementary material, which is available to authorized users. Springer Berlin Heidelberg 2016-06-01 2016 /pmc/articles/PMC4989026/ /pubmed/27251139 http://dx.doi.org/10.1007/s00775-016-1358-7 Text en © The Author(s) 2016 Open AccessThis article is distributed under the terms of the Creative Commons Attribution 4.0 International License (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution, and reproduction in any medium, provided you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. |
spellingShingle | Original Paper Rees, Julian A. Wandzilak, Aleksandra Maganas, Dimitrios Wurster, Nicole I. C. Hugenbruch, Stefan Kowalska, Joanna K. Pollock, Christopher J. Lima, Frederico A. Finkelstein, Kenneth D. DeBeer, Serena Experimental and theoretical correlations between vanadium K-edge X-ray absorption and K[Formula: see text] emission spectra |
title | Experimental and theoretical correlations between vanadium K-edge X-ray absorption and K[Formula: see text] emission spectra |
title_full | Experimental and theoretical correlations between vanadium K-edge X-ray absorption and K[Formula: see text] emission spectra |
title_fullStr | Experimental and theoretical correlations between vanadium K-edge X-ray absorption and K[Formula: see text] emission spectra |
title_full_unstemmed | Experimental and theoretical correlations between vanadium K-edge X-ray absorption and K[Formula: see text] emission spectra |
title_short | Experimental and theoretical correlations between vanadium K-edge X-ray absorption and K[Formula: see text] emission spectra |
title_sort | experimental and theoretical correlations between vanadium k-edge x-ray absorption and k[formula: see text] emission spectra |
topic | Original Paper |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4989026/ https://www.ncbi.nlm.nih.gov/pubmed/27251139 http://dx.doi.org/10.1007/s00775-016-1358-7 |
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