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Effect of 3d/4p Mix...
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Kroll, ThomasStanford Univ, Dept Chem, Stanford, CA 94305 USA; SLAC Natl Accelerator Lab, Stanford Synchrotron Radiat Lightsource, Menlo Pk, CA 94025 USA
(author)
Effect of 3d/4p Mixing on 1s2p Resonant Inelastic X-ray Scattering : Electronic Structure of Oxo-Bridged Iron Dimers
- Article/chapterEnglish2021
Publisher, publication year, extent ...
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2021-03-17
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American Chemical Society (ACS),2021
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Numbers
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LIBRIS-ID:oai:DiVA.org:uu-441859
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https://urn.kb.se/resolve?urn=urn:nbn:se:uu:diva-441859URI
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https://doi.org/10.1021/jacs.0c11193DOI
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Language:English
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Summary in:English
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Subject category:ref swepub-contenttype
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Subject category:art swepub-publicationtype
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1s2p resonant inelastic X-ray scattering (1s2p RIXS) has proven successful in the determination of the differential orbital covalency (DOC, the amount of metal vs ligand character in each d molecular orbital) of highly covalent centrosymmetric iron environments including heme models and enzymes. However, many reactive intermediates have non-centrosymmetric environments, e.g., the presence of strong metal-oxo bonds, which results in the mixing of metal 4p character into the 3d orbitals. This leads to significant intensity enhancement in the metal K-pre-edge and as shown here, the associated 1s2p RIXS features, which impact their insight into electronic structure. Binuclear oxo bridged high spin Fe(III) complexes are used to determine the effects of 4p mixing on 1s2p RIXS spectra. In addition to developing the analysis of 4p mixing on K-edge XAS and 1s2p RIXS data, this study explains the selective nature of the 4p mixing that also enhances the analysis of L-edge XAS intensity in terms of DOC. These 1s2p RIXS biferric model studies enable new structural insight from related data on peroxo bridged biferric enzyme intermediates. The dimeric nature of the oxo bridged Fe(III) complexes further results in ligand-to-ligand interactions between the Fe(III) sites and angle dependent features just above the pre-edge that reflect the superexchange pathway of the oxo bridge. Finally, we present a methodology that enables DOC to be obtained when L-edge XAS is inaccessible and only 1s2p RIXS experiments can be performed as in many metalloenzyme intermediates in solution.
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Baker, Michael L.Stanford Univ, Dept Chem, Stanford, CA 94305 USA; Univ Manchester, Dept Chem, Manchester M13 9PL, Lancs, England
(author)
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Wilson, Samuel A.Stanford Univ, Dept Chem, Stanford, CA 94305 USA
(author)
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Lundberg, Marcus,1974-Uppsala universitet,Molekylär biomimetik,Stanford Univ, Dept Chem, Stanford, CA 94305 USA(Swepub:uu)marlu250
(author)
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Juhin, AmelieSorbonne Univ, CNRS, UMR7S90, Inst Mineral Phys Mat & Cosmochim IMPMC, F-75005 Paris, France
(author)
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Arrio, Marie-AnneSorbonne Univ, CNRS, UMR7S90, Inst Mineral Phys Mat & Cosmochim IMPMC, F-75005 Paris, France
(author)
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Yan, James J.Stanford Univ, Dept Chem, Stanford, CA 94305 USA
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Gee, Leland B.Stanford Univ, Dept Chem, Stanford, CA 94305 USA
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Braun, AugustinStanford Univ, Dept Chem, Stanford, CA 94305 USA
(author)
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Weng, Tsu-ChienSLAC Natl Accelerator Lab, Stanford Synchrotron Radiat Lightsource, Menlo Pk, CA 94025 USA
(author)
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Sokaras, DimosthenisSLAC Natl Accelerator Lab, Stanford Synchrotron Radiat Lightsource, Menlo Pk, CA 94025 USA
(author)
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Hedman, BrittSLAC Natl Accelerator Lab, Stanford Synchrotron Radiat Lightsource, Menlo Pk, CA 94025 USA
(author)
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Hodgson, Keith O.Stanford Univ, Dept Chem, Stanford, CA 94305 USA; SLAC Natl Accelerator Lab, Stanford Synchrotron Radiat Lightsource, Menlo Pk, CA 94025 USA
(author)
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Solomon, Edward I.Stanford Univ, Dept Chem, Stanford, CA 94305 USA; SLAC Natl Accelerator Lab, Stanford Synchrotron Radiat Lightsource, Menlo Pk, CA 94025 USA
(author)
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Stanford Univ, Dept Chem, Stanford, CA 94305 USA; SLAC Natl Accelerator Lab, Stanford Synchrotron Radiat Lightsource, Menlo Pk, CA 94025 USAStanford Univ, Dept Chem, Stanford, CA 94305 USA; Univ Manchester, Dept Chem, Manchester M13 9PL, Lancs, England
(creator_code:org_t)
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In:Journal of the American Chemical Society: American Chemical Society (ACS)143:12, s. 4569-45840002-78631520-5126
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Kroll, Thomas
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Baker, Michael L ...
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Wilson, Samuel A ...
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Lundberg, Marcus ...
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Juhin, Amelie
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Arrio, Marie-Ann ...
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Yan, James J.
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Gee, Leland B.
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Braun, Augustin
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Hedman, Britt
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