Resonant Inelastic X-ray Scattering of Molybdenum Oxides and Sulfides

Thomas, Rowena; Kas, J.J.; Glatzel, Pieter; Samarai, Mustafa Al; Groot, Frank M. F. de; Alonso-Mori, Roberto; Kavčič, M.; Žitnik, M.; Bučar, K.; Rehr, J. J.; Tromp, Moniek

doi:10.1021/jp509376q

Cited by 21 publications

(20 citation statements)

References 26 publications

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“…Figure 2 shows the x-ray absorption [panel (a)] and resonant photoemission spectra [panel (b)] taken across the Mo L 3 edge for the x = 0.25 compound. The absorption spectrum corresponds to the Mo 2p → 4d transitions, in close agreement with previously reported Mo L edge spectra of Mo-based oxide perovskites [30][31][32][33]. The valence band resonant photoemission is obtained by tuning the excitation photon energy at selected energies (marked with dots) across the Mo L 3 absorption edge.…”

Section: Resultssupporting

confidence: 88%

Origin of itinerant carriers in antiferromagnetic LaFe1−xMoxO3 studied by x-ray sp

Phuyal

Mukherjee

Panda

et al. 2020

Phys. Rev. Materials

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We report on the electronic structure of doped LaFeO 3 at the crossover from an insulating-to-metallic phase transition. Comprehensive x-ray spectroscopic methodologies are used to understand core and valence electronic structure as well as crystal structure distortions associated with the electronic transition. Despite the antiferromagnetic (AFM) ordering at room temperature, we show direct evidence of itinerant carriers at the Fermi level revealed by resonant photoemission spectroscopy (RPES) at the Mo L 3 edge. RPES data taken at the Fe L 3 edge show spectral weight near the valence band edge and significant hybridization with O 2p states required for AFM ordering. Resonant inelastic x-ray scattering spectra taken across Fe L 2,3 edges show electron correlation effects (U) driven by Coulomb interactions of d electrons as well as broad charge-transfer excitations for x 0.2 where the compound crosses over to a metallic state. Site substitution of Fe by Mo ions in the Fe-O 6 octahedra enhances the separation of the two Fe-O bonds and Fe-O-Fe bonding angles relative to the orthorhombic LaFeO 3 , but no considerable distortions are present to the overall structure. Mo ions appear to be homogeneously doped, with average valency of both metal sites monotonically decreasing with increasing Mo concentration. This insulator-to-metal phase transition with AFM stability is primarily understood through intermediate interaction strengths between correlation (U) and bandwidth (W) at the Fe site, where an estimation of this ratio is given. These results highlight the important role of extrinsic carriers in stabilizing a unique phase transition that can guide future efforts in antiferromagnetic-metal spintronics.

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Section: Resultssupporting

confidence: 88%

Origin of itinerant carriers in antiferromagnetic LaFe1−xMoxO3 studied by x-ray sp

Phuyal

Mukherjee

Panda

et al. 2020

Phys. Rev. Materials

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“…In the present CCR the focus is on metal-based X-ray absorption methods: metal K- and metal L-edge XAS, and 1s2p resonant inelastic X-ray scattering (Kα-RIXS) which couples these in a 2D experiment with complementary selection rules. While this review primarily covers the studies done in the Hodgson, Hedman, and Solomon group, in addition the interested reader is referred to reviews and studies[10–13] that provide further insight utilizing metal K-edge XAS [14–23], L-edge XAS[24], and RIXS [25–34]. …”

Section: Introductionmentioning

confidence: 99%

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

Mara

Yan

et al. 2017

Coordination Chemistry Reviews

215

183

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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 K 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 and donor bonding and 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. 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.

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“…The spectral broadening can be further reduced by using an x-ray emission spectrometer for recording the fluorescence lines instead of a conventional solid state detector. To date, this approach has been applied in the field of catalysis 14 , Li-S batteries 15 , and actinides chemistry 16,17 .…”

Section: Introductionmentioning

confidence: 99%

TEXS: in-vacuum tender X-ray emission spectrometer with 11 Johansson crystal analyzers

Rovezzi¹,

Harris²,

Detlefs³

et al. 2020

J Synchrotron Rad

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We describe the design and show first results of a large solid angle x-ray emission spectrometer that is optimised for energies between 5.5 keV and 1.5 keV. The spectrometer is based on an array of eleven cylindrically bent Johansson crystal analysers arranged in a point-to-point Rowland circle geometry. The smallest achievable energy bandwidth is smaller than the core hole lifetime broadening of the absorption edges in this energy range. Energy scanning is achieved using an innovative design, maintaining the Rowland circle conditions for all crystals with only four motor motions. The entire spectrometer is encased in a high-vacuum chamber that allows fitting a liquid helium cryostat and provides sufficient space for in situ cells and operando catalysis reactors.

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Resonant Inelastic X-ray Scattering of Molybdenum Oxides and Sulfides

Cited by 21 publications

References 26 publications

Origin of itinerant carriers in antiferromagnetic LaFe1−xMoxO3 studied by x-ray sp

Origin of itinerant carriers in antiferromagnetic LaFe1−xMoxO3 studied by x-ray sp

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

TEXS: in-vacuum tender X-ray emission spectrometer with 11 Johansson crystal analyzers

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