Effect of 3d/4p Mixing on 1s2p Resonant Inelastic X-ray Scattering: Electronic Structure of Oxo-Bridged Iron Dimers

Kroll, Thomas; Baker, Michael L.; Wilson, Samuel A.; Lundberg, Marcus; Juhin, Amélie; Arrio, Marie-Anne; Yan, James J.; Gee, Leland B.; Braun, Augustin; Weng, Tsu-Chien; Sokaras, Dimosthenis; Hedman, Britt; Hodgson, Keith O.; Solomon, Edward I.

doi:10.1021/jacs.0c11193

Title: Effect of 3d/4p Mixing on 1s2p Resonant Inelastic X-ray Scattering: Electronic Structure of Oxo-Bridged Iron Dimers

Journal Article · Wed Mar 17 00:00:00 EDT 2021 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.0c11193· OSTI ID:1781699

Kroll, Thomas ^[1];

^[2]; Wilson, Samuel A. ^[3];

^[4];

^[5];

^[3];

^[3]; Weng, Tsu-Chien ^[6]; Sokaras, Dimosthenis ^[7]; Hedman, Britt ^[7]; Hodgson, Keith O. ^[1];

^[1]

Stanford Univ., CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
Stanford Univ., CA (United States); Univ. of Manchester (United Kingdom)
Stanford Univ., CA (United States)
Stanford Univ., CA (United States); Uppsala Univ. (Sweden)
Sorbonne Univ., Paris (France)
SLAC National Accelerator Lab., Menlo Park, CA (United States); ShanghaiTech Univ. (China)
Stanford Univ., Menlo Park, CA (United States)

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 noncentrosymmetric 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. Lastly, 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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Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Institutes of Health, National Institute of General Medical Sciences; German Research Foundation (DFG)

Grant/Contract Number:: AC02-76SF00515; KR3611/2-1; RM1802-4019; P41GM103393; GM-40392

OSTI ID:: 1781699

Journal Information:: Journal of the American Chemical Society, Vol. 143, Issue 12; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Title: Effect of 3d/4p Mixing on 1s2p Resonant Inelastic X-ray Scattering: Electronic Structure of Oxo-Bridged Iron Dimers

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