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Selenium Valence-to-Core X-ray Emission Spectroscopy and Kβ HERFD X-ray Absorption Spectroscopy as Complementary Probes of Chemical and Electronic Structure

[Image: see text] Selenium X-ray absorption spectroscopy (XAS) has found widespread use in investigations of Se-containing materials, geochemical processes, and biologically active sites. In contrast to sulfur Kβ X-ray emission spectroscopy (XES), which has been found to contain electronic and struc...

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Autores principales: Henthorn, Justin T., DeBeer, Serena
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2022
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8848279/
https://www.ncbi.nlm.nih.gov/pubmed/35113562
http://dx.doi.org/10.1021/acs.inorgchem.1c02802
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author Henthorn, Justin T.
DeBeer, Serena
author_facet Henthorn, Justin T.
DeBeer, Serena
author_sort Henthorn, Justin T.
collection PubMed
description [Image: see text] Selenium X-ray absorption spectroscopy (XAS) has found widespread use in investigations of Se-containing materials, geochemical processes, and biologically active sites. In contrast to sulfur Kβ X-ray emission spectroscopy (XES), which has been found to contain electronic and structural information complementary to S XAS, Se Kβ XES remains comparatively underexplored. Herein, we present the first Se Valence-to-Core (VtC) XES studies of reduced Se-containing compounds and FeSe dimers. Se VtC XES is found to be sensitive to changes in covalent Se bonding interactions (Se–Se/Se–C/Se–H bonding) while being relatively insensitive to changes in Fe oxidation states as selenide bridges in FeSe dimers ([Fe(2)Se(2)](2+) vs [Fe(2)Se(2)](+)). In contrast, Se Kβ HERFD XAS is demonstrated to be quite sensitive to changes in the Fe oxidation state with Se Kβ HERFD XAS demonstrating experimental resolution equivalent to Kα HERFD XAS. Additionally, computational studies reveal both Se VtC XES and XAS to be sensitive to selenium protonation in FeSe complexes.
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spelling pubmed-88482792022-02-16 Selenium Valence-to-Core X-ray Emission Spectroscopy and Kβ HERFD X-ray Absorption Spectroscopy as Complementary Probes of Chemical and Electronic Structure Henthorn, Justin T. DeBeer, Serena Inorg Chem [Image: see text] Selenium X-ray absorption spectroscopy (XAS) has found widespread use in investigations of Se-containing materials, geochemical processes, and biologically active sites. In contrast to sulfur Kβ X-ray emission spectroscopy (XES), which has been found to contain electronic and structural information complementary to S XAS, Se Kβ XES remains comparatively underexplored. Herein, we present the first Se Valence-to-Core (VtC) XES studies of reduced Se-containing compounds and FeSe dimers. Se VtC XES is found to be sensitive to changes in covalent Se bonding interactions (Se–Se/Se–C/Se–H bonding) while being relatively insensitive to changes in Fe oxidation states as selenide bridges in FeSe dimers ([Fe(2)Se(2)](2+) vs [Fe(2)Se(2)](+)). In contrast, Se Kβ HERFD XAS is demonstrated to be quite sensitive to changes in the Fe oxidation state with Se Kβ HERFD XAS demonstrating experimental resolution equivalent to Kα HERFD XAS. Additionally, computational studies reveal both Se VtC XES and XAS to be sensitive to selenium protonation in FeSe complexes. American Chemical Society 2022-02-03 2022-02-14 /pmc/articles/PMC8848279/ /pubmed/35113562 http://dx.doi.org/10.1021/acs.inorgchem.1c02802 Text en © 2022 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 Henthorn, Justin T.
DeBeer, Serena
Selenium Valence-to-Core X-ray Emission Spectroscopy and Kβ HERFD X-ray Absorption Spectroscopy as Complementary Probes of Chemical and Electronic Structure
title Selenium Valence-to-Core X-ray Emission Spectroscopy and Kβ HERFD X-ray Absorption Spectroscopy as Complementary Probes of Chemical and Electronic Structure
title_full Selenium Valence-to-Core X-ray Emission Spectroscopy and Kβ HERFD X-ray Absorption Spectroscopy as Complementary Probes of Chemical and Electronic Structure
title_fullStr Selenium Valence-to-Core X-ray Emission Spectroscopy and Kβ HERFD X-ray Absorption Spectroscopy as Complementary Probes of Chemical and Electronic Structure
title_full_unstemmed Selenium Valence-to-Core X-ray Emission Spectroscopy and Kβ HERFD X-ray Absorption Spectroscopy as Complementary Probes of Chemical and Electronic Structure
title_short Selenium Valence-to-Core X-ray Emission Spectroscopy and Kβ HERFD X-ray Absorption Spectroscopy as Complementary Probes of Chemical and Electronic Structure
title_sort selenium valence-to-core x-ray emission spectroscopy and kβ herfd x-ray absorption spectroscopy as complementary probes of chemical and electronic structure
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8848279/
https://www.ncbi.nlm.nih.gov/pubmed/35113562
http://dx.doi.org/10.1021/acs.inorgchem.1c02802
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