K- and L-edge X-ray absorption spectroscopy (XAS) and resonant inelastic X-ray scattering (RIXS) determination of differential orbital covalency (DOC) of transition metal sites

Baker, Michael L.; Mara, Michael W.; Yan, James J.; Hodgson, Keith O.; Hedman, Britt; Solomon, Edward I.

doi:10.1016/j.ccr.2017.02.004

Title: K- and L-edge X-ray absorption spectroscopy (XAS) and resonant inelastic X-ray scattering (RIXS) determination of differential orbital covalency (DOC) of transition metal sites

Abstract

Continual advancements in the development of synchrotron radiation sources have resulted in X-ray based spectroscopic techniques capable of probing the electronic and structural properties of numerous systems. This review gives an overview of the application of metal K-edge and L-edge X-ray absorption spectroscopy (XAS), as well as Kα resonant inelastic X-ray scattering (RIXS), to the study of electronic structure in transition metal sites with emphasis on experimentally quantifying 3d orbital covalency. The specific sensitivities of K-edge XAS, L-edge XAS, and RIXS are discussed emphasizing the complementary nature of the methods. L-edge XAS and RIXS are sensitive to mixing between 3d orbitals and ligand valence orbitals, and to the differential orbital covalency (DOC), that is, the difference in the covalencies for different symmetry sets of the d orbitals. Both L-edge XAS and RIXS are highly sensitive to and enable separation of σ and π donor bonding and π back bonding contributions to bonding. Applying ligand field multiplet simulations, including charge transfer via valence bond configuration interactions, DOC can be obtained for direct comparison with density functional theory calculations and to understand chemical trends. Here, the application of RIXS as a probe of frontier molecular orbitals in a heme enzyme demonstrates themore »« less

Authors:

Baker, Michael L. ^[1]; Mara, Michael W. ^[1]; Yan, James J. ^[1]; Hodgson, Keith O. ^[1]; Hedman, Britt ^[2]; Solomon, Edward I. ^[1]

Stanford Univ., Stanford, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
SLAC National Accelerator Lab., Menlo Park, CA (United States)

Publication Date:: 2017-02-09

Research Org.:: SLAC National Accelerator Lab., Menlo Park, CA (United States)

Sponsoring Org.:: USDOE

OSTI Identifier:: 1369247

Alternate Identifier(s):: OSTI ID: 1550617

Grant/Contract Number:: R01GM040392; CHE-1360046; P41GM103393; AC02-76SF00515

Resource Type:: Accepted Manuscript

Journal Name:: Coordination Chemistry Reviews

Additional Journal Information:: Journal Volume: 345; Journal Issue: C; Journal ID: ISSN 0010-8545

Publisher:: Elsevier

Country of Publication:: United States

Language:: English

Subject:: 38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; X-ray absorption spectroscopy; X-ray emission spectroscopy; Transition metal ion active sites; Covalency; Electronic structure; Resonant inelastic X-ray scattering; Bioinorganic chemistry

Citation Formats


                    Baker, Michael L., Mara, Michael W., Yan, James J., Hodgson, Keith O., Hedman, Britt, and Solomon, Edward I. K- and L-edge X-ray absorption spectroscopy (XAS) and resonant inelastic X-ray scattering (RIXS) determination of differential orbital covalency (DOC) of transition metal sites.  United States: N. p., 2017. 
        Web.  doi:10.1016/j.ccr.2017.02.004.

Copy to clipboard


                    Baker, Michael L., Mara, Michael W., Yan, James J., Hodgson, Keith O., Hedman, Britt, & Solomon, Edward I. K- and L-edge X-ray absorption spectroscopy (XAS) and resonant inelastic X-ray scattering (RIXS) determination of differential orbital covalency (DOC) of transition metal sites.  United States.  doi:https://doi.org/10.1016/j.ccr.2017.02.004

Copy to clipboard


                    Baker, Michael L., Mara, Michael W., Yan, James J., Hodgson, Keith O., Hedman, Britt, and Solomon, Edward I. Thu .  
        "K- and L-edge X-ray absorption spectroscopy (XAS) and resonant inelastic X-ray scattering (RIXS) determination of differential orbital covalency (DOC) of transition metal sites".  United States.  doi:https://doi.org/10.1016/j.ccr.2017.02.004.  https://www.osti.gov/servlets/purl/1369247.

Copy to clipboard


                    
@article{osti_1369247,

  title        = {K- and L-edge X-ray absorption spectroscopy (XAS) and resonant inelastic X-ray scattering (RIXS) determination of differential orbital covalency (DOC) of transition metal sites},

  author       = {Baker, Michael L. and Mara, Michael W. and Yan, James J. and Hodgson, Keith O. and Hedman, Britt and Solomon, Edward I.},

  abstractNote = {Continual advancements in the development of synchrotron radiation sources have resulted in X-ray based spectroscopic techniques capable of probing the electronic and structural properties of numerous systems. This review gives an overview of the application of metal K-edge and L-edge X-ray absorption spectroscopy (XAS), as well as Kα resonant inelastic X-ray scattering (RIXS), to the study of electronic structure in transition metal sites with emphasis on experimentally quantifying 3d orbital covalency. The specific sensitivities of K-edge XAS, L-edge XAS, and RIXS are discussed emphasizing the complementary nature of the methods. L-edge XAS and RIXS are sensitive to mixing between 3d orbitals and ligand valence orbitals, and to the differential orbital covalency (DOC), that is, the difference in the covalencies for different symmetry sets of the d orbitals. Both L-edge XAS and RIXS are highly sensitive to and enable separation of σ and π donor bonding and π back bonding contributions to bonding. Applying ligand field multiplet simulations, including charge transfer via valence bond configuration interactions, DOC can be obtained for direct comparison with density functional theory calculations and to understand chemical trends. Here, the application of RIXS as a probe of frontier molecular orbitals in a heme enzyme demonstrates the potential of this method for the study of metal sites in highly covalent coordination sites in bioinorganic chemistry.},

  doi          = {10.1016/j.ccr.2017.02.004},

  journal      = {Coordination Chemistry Reviews},

  number       = C,

  volume       = 345,

  place        = {United States},

  year         = {2017},

  month        = {2}

}

Copy to clipboard

Journal Article:

Free Publicly Available Full Text

Accepted Manuscript (Publisher)

Accepted Manuscript (DOE)

Publisher's Version of Record

DOI: https://doi.org/10.1016/j.ccr.2017.02.004

Other availability

Search WorldCat to find libraries that may hold this journal

Citation Metrics:

Cited by: 8 works

Citation information provided by
Web of Science

Save / Share:

Export Metadata

Save to My Library

Works referencing / citing this record:

Solvent-assisted structural conversion involving bimetallic complexes based on the tris(oxalato)ferrate( iii ) unit with the green → blue → red crystal color sequence
journal, January 2019

Muzioł, Tadeusz M.; Tereba, Natalia; Podgajny, Robert
Dalton Transactions, Vol. 48, Issue 30
DOI: 10.1039/c9dt02216c

Solvent-assisted structural conversion involving bimetallic complexes based on the tris(oxalato)ferrate( iii ) unit with the green → blue → red crystal color sequence
journal, January 2019

Muzioł, Tadeusz M.; Tereba, Natalia; Podgajny, Robert
Dalton Transactions, Vol. 48, Issue 30
DOI: 10.1039/c9dt02216c

In Situ X-ray Absorption Spectroscopy Studies of Nanoscale Electrocatalysts
journal, June 2019

Wang, Maoyu; Árnadóttir, Líney; Xu, Zhichuan J.
Nano-Micro Letters, Vol. 11, Issue 1
DOI: 10.1007/s40820-019-0277-x

Temperature-dependent dynamics of NH ₃ -derived Cu species in the Cu-CHA SCR catalyst
journal, January 2019

Borfecchia, Elisa; Negri, Chiara; Lomachenko, Kirill A.
Reaction Chemistry & Engineering, Vol. 4, Issue 6
DOI: 10.1039/c8re00322j

Glutathione activation of an organometallic half-sandwich anticancer drug candidate by ligand attack
journal, January 2019

Zhang, Xin; Ponte, Fortuna; Borfecchia, Elisa
Chemical Communications, Vol. 55, Issue 97
DOI: 10.1039/c9cc06725f

Attosecond transient absorption spooktroscopy: a ghost imaging approach to ultrafast absorption spectroscopy
journal, January 2020

Driver, Taran; Li, Siqi; Champenois, Elio G.
Physical Chemistry Chemical Physics, Vol. 22, Issue 5
DOI: 10.1039/c9cp03951a

Direct experimental evaluation of ligand-induced backbonding in nickel metallacyclic complexes
journal, January 2019

He, Weiying; Kennepohl, Pierre
Faraday Discussions, Vol. 220
DOI: 10.1039/c9fd00041k

Long-term chemothermal stability of delithiated NCA in polymer solid-state batteries
journal, January 2019

Besli, Münir M.; Usubelli, Camille; Metzger, Michael
Journal of Materials Chemistry A, Vol. 7, Issue 47
DOI: 10.1039/c9ta11103d

L-edge spectroscopy of dilute, radiation-sensitive systems using a transition-edge-sensor array
journal, December 2017

Titus, Charles J.; Baker, Michael L.; Lee, Sang Jun
The Journal of Chemical Physics, Vol. 147, Issue 21
DOI: 10.1063/1.5000755

Resonant inelastic X-ray scattering determination of the electronic structure of oxyhemoglobin and its model complex
journal, February 2019

Yan, James J.; Kroll, Thomas; Baker, Michael L.
Proceedings of the National Academy of Sciences, Vol. 116, Issue 8
DOI: 10.1073/pnas.1815981116

Similar Records in DOE PAGES and OSTI.GOV collections:

L-Edge X-ray Absorption Spectroscopic Investigation of {FeNO}⁶: Delocalization vs Antiferromagnetic Coupling

Journal Article Yan, James J. ; Gonzales, Margarita A. ; Mascharak, Pradip K. ; ... - Journal of the American Chemical Society

NO is a classic non-innocent ligand, and iron nitrosyls can have different electronic structure descriptions depending on their spin state and coordination environment. These highly covalent ligands are found in metalloproteins and are also used as models for Fe–O₂ systems. Here, this study utilizes iron L-edge X-ray absorption spectroscopy (XAS), interpreted using a valence bond configuration interaction multiplet model, to directly experimentally probe the electronic structure of the S = 0 {FeNO}⁶ compound [Fe(PaPy₃)NO]²⁺ (PaPy₃ = N,N-bis(2-pyridylmethyl)amine-N-ethyl-2-pyridine-2-carboxamide) and the S = 0 [Fe(PaPy₃)CO]⁺ reference compound. This method allows separation of the σ-donation and π-acceptor interactions of the ligand through ligand-to-metalmore »« less
Cited by 4
DOI: https://doi.org/10.1021/jacs.6b11260

Full Text Available
Resonant Inelastic X-ray Scattering on Ferrous and Ferric Bis-imidazole Porphyrin and Cytochrome c : Nature and Role of the Axial Methionine–Fe Bond

Journal Article Kroll, Thomas ; Hadt, Ryan G. ; Wilson, Samuel A. ; ... - Journal of the American Chemical Society

Axial Cu–S(Met) bonds in electron transfer (ET) active sites are generally found to lower their reduction potentials. An axial S(Met) bond is also present in cytochrome c (cyt c) and is generally thought to increase the reduction potential. The highly covalent nature of the porphyrin environment in heme proteins precludes using many spectroscopic approaches to directly study the Fe site to experimentally quantify this bond. Alternatively, L-edge X-ray absorption spectroscopy (XAS) enables one to directly focus on the 3d-orbitals in a highly covalent environment and has previously been successfully applied to porphyrin model complexes. However, this technique cannot be extendedmore »« less
Cited by 16
DOI: https://doi.org/10.1021/ja5100367
X-ray spectroscopic characterization of Co(IV) and metal–metal interactions in Co₄O₄: Electronic structure contributions to the formation of high-valent states relevant to the oxygen evolution reaction

Journal Article Hadt, Ryan G. ; Hayes, Dugan ; Brodsky, Casey N. ; ... - Journal of the American Chemical Society

In this paper, the formation of high-valent states is a key factor in making highly active transition metal-based catalysts of the oxygen-evolving reaction (OER). These high oxidation states will be strongly influenced by the local geometric and electronic structures of the metal ion, which is difficult to study due to spectroscopically active and complex backgrounds, short lifetimes, and limited concentrations. Here, we use a wide range of complementary X-ray spectroscopies coupled to DFT calculations to study Co₄O₄ cubanes, which provide insight into the high-valent Co(IV) centers responsible for the activity of molecular and heterogeneous OER catalysts. The combination of X-raymore »« less
Cited by 14
DOI: https://doi.org/10.1021/jacs.6b04663

Full Text Available
Determining Relative f and d Orbital Contributions to M–Cl Covalency in MCl ₆ ^2– (M = Ti, Zr, Hf, U) and UOCl ₅ ^– Using Cl K-Edge X-ray Absorption Spectroscopy and Time-Dependent Density Functional Theory

Journal Article Minasian, Stefan G. ; Keith, Jason M. ; Batista, Enrique R. ; ... - Journal of the American Chemical Society

Chlorine K-edge X-ray absorption spectroscopy (XAS) and ground-state and time-dependent hybrid density functional theory (DFT) were used to probe electronic structure for O{sub h}-MCl{sub 6}{sup 2-}(M = Ti, Zr, Hf, U) and C{sub 4v}-UOCl{sub 5}{sup -}, and to determine the relative contributions of valence 3d, 4d, 5d, 6d, and 5f orbitals in M-Cl bonding. Spectral interpretations were guided by time-dependent DFT calculated transition energies and oscillator strengths, which agree well with the experimental XAS spectra. The data provide new spectroscopic evidence for the involvement of both 5f and 6d orbitals in actinide-ligand bonding in UCl{sub 6}{sup 2-}. For the MCl{submore »« less
DOI: https://doi.org/10.1021/ja2105015
Time-Dependent Density Functional Calculations of Ligand K-Edge X-Ray Absorption Spectra

Journal Article DeBeer George, S ; /SLAC, SSRL ; Petrenko, T ; ... - Submitted to Inorg.Chim.Acta

X-ray absorption spectra (XAS) at the Cl and S K edge and Mo L edge have been calculated at the TDDFT level for a series of dioxomolybdenum complexes LMoO{sub 2}X (L = hydrotris(3,5-dimethyl-1-pyrazolyl)borate, X = Cl, SCH{sub 2}Ph, OPh), which play an important role in modeling the catalytic cycle of the sulfite oxidase enzyme. Also, the XAS spectra of model molecules of the Mo complexes have been simulated and interpreted in terms of the Mo 4d orbital splitting, in order to find possible correlations with the spectral pattern of the complexes. Comparison with the available experimental data allows us tomore »« less
DOI: https://doi.org/10.1016/j.ica.2007.05.046

Similar Records

Title: K- and L-edge X-ray absorption spectroscopy (XAS) and resonant inelastic X-ray scattering (RIXS) determination of differential orbital covalency (DOC) of transition metal sites

Abstract

Citation Formats

Solvent-assisted structural conversion involving bimetallic complexes based on the tris(oxalato)ferrate( iii ) unit with the green → blue → red crystal color sequence journal, January 2019

Solvent-assisted structural conversion involving bimetallic complexes based on the tris(oxalato)ferrate( iii ) unit with the green → blue → red crystal color sequence journal, January 2019

In Situ X-ray Absorption Spectroscopy Studies of Nanoscale Electrocatalysts journal, June 2019

Temperature-dependent dynamics of NH 3 -derived Cu species in the Cu-CHA SCR catalyst journal, January 2019

Glutathione activation of an organometallic half-sandwich anticancer drug candidate by ligand attack journal, January 2019

Attosecond transient absorption spooktroscopy: a ghost imaging approach to ultrafast absorption spectroscopy journal, January 2020

Direct experimental evaluation of ligand-induced backbonding in nickel metallacyclic complexes journal, January 2019

Long-term chemothermal stability of delithiated NCA in polymer solid-state batteries journal, January 2019

L-edge spectroscopy of dilute, radiation-sensitive systems using a transition-edge-sensor array journal, December 2017

Resonant inelastic X-ray scattering determination of the electronic structure of oxyhemoglobin and its model complex journal, February 2019

Solvent-assisted structural conversion involving bimetallic complexes based on the tris(oxalato)ferrate( iii ) unit with the green → blue → red crystal color sequence
journal, January 2019

Solvent-assisted structural conversion involving bimetallic complexes based on the tris(oxalato)ferrate( iii ) unit with the green → blue → red crystal color sequence
journal, January 2019

In Situ X-ray Absorption Spectroscopy Studies of Nanoscale Electrocatalysts
journal, June 2019

Temperature-dependent dynamics of NH ₃ -derived Cu species in the Cu-CHA SCR catalyst
journal, January 2019

Glutathione activation of an organometallic half-sandwich anticancer drug candidate by ligand attack
journal, January 2019

Attosecond transient absorption spooktroscopy: a ghost imaging approach to ultrafast absorption spectroscopy
journal, January 2020

Direct experimental evaluation of ligand-induced backbonding in nickel metallacyclic complexes
journal, January 2019

Long-term chemothermal stability of delithiated NCA in polymer solid-state batteries
journal, January 2019

L-edge spectroscopy of dilute, radiation-sensitive systems using a transition-edge-sensor array
journal, December 2017

Resonant inelastic X-ray scattering determination of the electronic structure of oxyhemoglobin and its model complex
journal, February 2019