Probing the oxidation state of transition metal complexes: a case study on how charge and spin densities determine Mn L-edge X-ray absorption energies

Kubin, Markus; Guo, Meiyuan; Kroll, Thomas; Löchel, Heike; Källman, Erik; Baker, Michael L.; Mitzner, Rolf; Gul, Sheraz; Kern, Jan; Föhlisch, Alexander; Erko, Alexei; Bergmann, Uwe; Yachandra, Vittal; Yano, Junko; Lundberg, Marcus; Wernet, Philippe

doi:10.1039/C8SC00550H

Title: Probing the oxidation state of transition metal complexes: a case study on how charge and spin densities determine Mn L-edge X-ray absorption energies

Journal Article · Tue Jul 17 00:00:00 EDT 2018 · Chemical Science

DOI:https://doi.org/10.1039/C8SC00550H· OSTI ID:1461356

^[1];

^[2]; Kroll, Thomas ^[3]; Löchel, Heike ^[4]; Källman, Erik ^[2];

^[5]; Mitzner, Rolf ^[1];

^[6];

^[7];

^[8]; Erko, Alexei ^[4];

^[9]; Yachandra, Vittal ^[6];

^[6];

^[2];

^[1]

Institute for Methods and Instrumentation for Synchrotron Radiation Research; Helmholtz-Zentrum Berlin für Materialien und Energie GmbH; 12489 Berlin; Germany
Department of Chemistry-Ångström Laboratory; Uppsala University; Sweden
SSRL; SLAC National Accelerator Laboratory; Menlo Park; USA
Institute for Nanometre Optics and Technology; Helmholtz-Zentrum Berlin für Materialien und Energie GmbH; 12489 Berlin; Germany
The School of Chemistry; The University of Manchester at Harwell; OX11 OFA; UK
Molecular Biophysics and Integrated Bioimaging Division; Lawrence Berkeley National Laboratory; Berkeley; USA
Molecular Biophysics and Integrated Bioimaging Division; Lawrence Berkeley National Laboratory; Berkeley; USA; LCLS
Institute for Methods and Instrumentation for Synchrotron Radiation Research; Helmholtz-Zentrum Berlin für Materialien und Energie GmbH; 12489 Berlin; Germany; Institut für Physik und Astronomie
Stanford PULSE Institute; SLAC National Accelerator Laboratory; Menlo Park; USA

Transition metals in inorganic systems and metalloproteins can occur in different oxidation states, which makes them ideal redox-active catalysts. To gain a mechanistic understanding of the catalytic reactions, knowledge of the oxidation state of the active metals, ideally in operando, is therefore critical. L-edge X-ray absorption spectroscopy (XAS) is a powerful technique that is frequently used to infer the oxidation state via a distinct blue shift of L-edge absorption energies with increasing oxidation state. A unified description accounting for quantum-chemical notions whereupon oxidation does not occur locally on the metal but on the whole molecule and the basic understanding that L-edge XAS probes the electronic structure locally at the metal has been missing to date. Here we quantify how charge and spin densities change at the metal and throughout the molecule for both redox and core-excitation processes. We explain the origin of the L-edge XAS shift between the high-spin complexes Mn^II(acac)₂ and Mn^III(acac)₃ as representative model systems and use ab initio theory to uncouple effects of oxidation-state changes from geometric effects. The shift reflects an increased electron affinity of Mn^III in the core-excited states compared to the ground state due to a contraction of the Mn 3d shell upon core-excitation with accompanied changes in the classical Coulomb interactions. This new picture quantifies how the metal-centered core hole probes changes in formal oxidation state and encloses and substantiates earlier explanations. The approach is broadly applicable to mechanistic studies of redox-catalytic reactions in molecular systems where charge and spin localization/delocalization determine reaction pathways.

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Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division; Human Frontier Science Program (HFSP), Strasbourg (France); Swedish Research Council (SRC); Knut and Alice Wallenberg Foundation (Sweden); National Institutes of Health (NIH); USDOE Office of Science (SC), Biological and Environmental Research (BER)

Grant/Contract Number:: AC02-76SF00515; AC02-05CH11231; RGP0063/2013; P41GM103393; KAW-2013.0020; GM110501; GM55302

OSTI ID:: 1461356

Alternate ID(s):: OSTI ID: 1476324; OSTI ID: 1506286

Journal Information:: Chemical Science, Journal Name: Chemical Science Vol. 9 Journal Issue: 33; ISSN 2041-6520

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United Kingdom

Language:: English

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Cited by: 49 works

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