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P K-Edge XANES Calculations of Mineral Standards: Exploring the Potential of Theoretical Methods in the Analysis of Phosphorus Speciation
[Image: see text] Phosphorus K-edge X-ray absorption near-edge structure (XANES) spectroscopy is a technique routinely employed in the qualitative and quantitative analysis of phosphorus speciation in many scientific fields. The data analysis is, however, often performed in a qualitative manner, rel...
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical Society
2023
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10354742/ https://www.ncbi.nlm.nih.gov/pubmed/37385975 http://dx.doi.org/10.1021/acs.inorgchem.3c01346 |
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author | Tofoni, Alessandro Tavani, Francesco Persson, Ingmar D’Angelo, Paola |
author_facet | Tofoni, Alessandro Tavani, Francesco Persson, Ingmar D’Angelo, Paola |
author_sort | Tofoni, Alessandro |
collection | PubMed |
description | [Image: see text] Phosphorus K-edge X-ray absorption near-edge structure (XANES) spectroscopy is a technique routinely employed in the qualitative and quantitative analysis of phosphorus speciation in many scientific fields. The data analysis is, however, often performed in a qualitative manner, relying on linear combination fitting protocols or simple comparisons between the experimental data and the spectra of standards, and little quantitative structural and electronic information is thus retrieved. Herein, we report a thorough theoretical investigation of P K-edge XANES spectra of NaH(2)PO(4)·H(2)O, AlPO(4), α-Ti(HPO(4))(2)·H(2)O, and FePO(4)·2H(2)O showing excellent agreement with the experimental data. We find that different coordination shells of phosphorus, up to a distance of 5–6 Å from the photoabsorber, contribute to distinct features in the XANES spectra. This high structural sensitivity enables P K-edge XANES spectroscopy to even distinguish between nearly isostructural crystal phases of the same compound. Additionally, we provide a rationalization of the pre-edge transitions observed in the spectra of α-Ti(HPO(4))(2)·H(2)O and FePO(4)·2H(2)O through density of states calculations. These pre-edge transitions are found to be enabled by the covalent mixing of phosphorus s and p orbitals and titanium or iron d orbitals, which happens even though neither metal ion is directly bound to phosphorus in the two systems. |
format | Online Article Text |
id | pubmed-10354742 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2023 |
publisher | American Chemical Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-103547422023-07-20 P K-Edge XANES Calculations of Mineral Standards: Exploring the Potential of Theoretical Methods in the Analysis of Phosphorus Speciation Tofoni, Alessandro Tavani, Francesco Persson, Ingmar D’Angelo, Paola Inorg Chem [Image: see text] Phosphorus K-edge X-ray absorption near-edge structure (XANES) spectroscopy is a technique routinely employed in the qualitative and quantitative analysis of phosphorus speciation in many scientific fields. The data analysis is, however, often performed in a qualitative manner, relying on linear combination fitting protocols or simple comparisons between the experimental data and the spectra of standards, and little quantitative structural and electronic information is thus retrieved. Herein, we report a thorough theoretical investigation of P K-edge XANES spectra of NaH(2)PO(4)·H(2)O, AlPO(4), α-Ti(HPO(4))(2)·H(2)O, and FePO(4)·2H(2)O showing excellent agreement with the experimental data. We find that different coordination shells of phosphorus, up to a distance of 5–6 Å from the photoabsorber, contribute to distinct features in the XANES spectra. This high structural sensitivity enables P K-edge XANES spectroscopy to even distinguish between nearly isostructural crystal phases of the same compound. Additionally, we provide a rationalization of the pre-edge transitions observed in the spectra of α-Ti(HPO(4))(2)·H(2)O and FePO(4)·2H(2)O through density of states calculations. These pre-edge transitions are found to be enabled by the covalent mixing of phosphorus s and p orbitals and titanium or iron d orbitals, which happens even though neither metal ion is directly bound to phosphorus in the two systems. American Chemical Society 2023-06-29 /pmc/articles/PMC10354742/ /pubmed/37385975 http://dx.doi.org/10.1021/acs.inorgchem.3c01346 Text en © 2023 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/). |
spellingShingle | Tofoni, Alessandro Tavani, Francesco Persson, Ingmar D’Angelo, Paola P K-Edge XANES Calculations of Mineral Standards: Exploring the Potential of Theoretical Methods in the Analysis of Phosphorus Speciation |
title | P K-Edge
XANES Calculations of Mineral Standards:
Exploring the Potential of Theoretical Methods in the Analysis of
Phosphorus Speciation |
title_full | P K-Edge
XANES Calculations of Mineral Standards:
Exploring the Potential of Theoretical Methods in the Analysis of
Phosphorus Speciation |
title_fullStr | P K-Edge
XANES Calculations of Mineral Standards:
Exploring the Potential of Theoretical Methods in the Analysis of
Phosphorus Speciation |
title_full_unstemmed | P K-Edge
XANES Calculations of Mineral Standards:
Exploring the Potential of Theoretical Methods in the Analysis of
Phosphorus Speciation |
title_short | P K-Edge
XANES Calculations of Mineral Standards:
Exploring the Potential of Theoretical Methods in the Analysis of
Phosphorus Speciation |
title_sort | p k-edge
xanes calculations of mineral standards:
exploring the potential of theoretical methods in the analysis of
phosphorus speciation |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10354742/ https://www.ncbi.nlm.nih.gov/pubmed/37385975 http://dx.doi.org/10.1021/acs.inorgchem.3c01346 |
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