Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Analyzing the Local Electronic Structure of Co₃O₄ Using 2p3d Resonant Inelastic X-ray Scattering.

ABSTRACT: We present the cobalt 2p3d resonant inelastic X-ray scattering (RIXS) spectra of Co₃O₄. Guided by multiplet simulation, the excited states at 0.5 and 1.3 eV can be identified as the ⁴ T ₂ excited state of the tetrahedral Co²⁺ and the ³ T _2g excited state of the octahedral Co³⁺, respectively. The ground states of Co²⁺ and Co³⁺ sites are determined to be high-spin ⁴ A ₂(T _d ) and low-spin ¹ A _1g (O_h ), respectively. It indicates that the high-spin Co²⁺ is the magnetically active site in Co₃O₄. Additionally, the ligand-to-metal charge transfer analysis shows strong orbital hybridization between the cobalt and oxygen ions at the Co³⁺ site, while the hybridization is weak at the Co²⁺ site.

SUBMITTER: Wang RP

PROVIDER: S-EPMC9150098 | biostudies-literature | 2022 May

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Analyzing the Local Electronic Structure of Co3O4 Using 2p3d Resonant Inelastic X-ray Scattering.

Wang Ru-Pan RP Huang Meng-Jie MJ Hariki Atsushi A Okamoto Jun J Huang Hsiao-Yu HY Singh Amol A Huang Di-Jing DJ Nagel Peter P Schuppler Stefan S Haarman Ties T Liu Boyang B de Groot Frank M F FMF

The journal of physical chemistry. C, Nanomaterials and interfaces 20220511 20

We present the cobalt 2p3d resonant inelastic X-ray scattering (RIXS) spectra of Co3O4. Guided by multiplet simulation, the excited states at 0.5 and 1.3 eV can be identified as the 4 T 2 excited state of the tetrahedral Co2+ and the 3 T 2g excited state of the octahedral Co3+, respectively. The ground states of Co2+ and Co3+ sites are determined to be high-spin <sup ...[more]

PMID: 35655938

Similar Datasets

In-Situ 2p3d Resonant Inelastic X-ray Scattering Tracking Cobalt Nanoparticle Reduction.

Project description:In-situ carbon-thermal reduction of cobalt oxide nanoparticles supported on carbon nanotubes was studied by cobalt 2p3d resonant inelastic X-ray scattering (RIXS). The in-situ 2p X-ray absorption spectroscopy (XAS) and RIXS measurements were performed at 500, 600, and 700 °C, where four consistent excitation energies were used for RIXS acquisitions. After 700 °C reduction, the XAS spectrum shows a cobalt metal-like shape, while the RIXS spectra reveal the minority cobalt monoxide phase. The holistic fit on both XAS and RIXS data reveals the respective contributions from metal and monoxide. We show that the relative precision to determine the monoxide content changes from ∼5.6% in XAS results to better than 0.8% in the RIXS analysis, suggesting that RIXS is a useful tool to track the oxidation state of nanoparticles under in situ conditions. We determined a relative radiative ratio (P) factor of approximately 5, where this factor gives the ratio between the relative strengths of the radiative decay channels compared to the nonradiative channels in CoO and Co metal.

| S-EPMC5563841 | biostudies-literature

Charge-Transfer Analysis of 2p3d Resonant Inelastic X-ray Scattering of Cobalt Sulfide and Halides.

Project description:We show that with 2p3d resonant inelastic X-ray scattering (RIXS) we can accurately determine the charge-transfer parameters of CoF2, CoCl2, CoBr2, and CoS. The 160 meV resolution RIXS results are compared with charge-transfer multiplet calculations. The improved resolution and the direct observation of the crystal field and charge-transfer excitations allow the determination of more accurate parameters than could be derived from X-ray absorption and X-ray photoemission, both limited in resolution by their lifetime broadening. We derive the crystal field and charge-transfer parameters of the Co2+ ions, which provides the nature of the ground state of the Co2+ ions with respect to symmetry and hybridization. In addition, the increased spectral resolution allows the more accurate determination of the atomic Slater integrals. The results show that the crystal field energy decreases with increasing ligand covalency. The L2 edge RIXS spectra show that the intensity of the (Coster-Kronig induced) nonresonant X-ray emission is a measure of ligand covalency.

| S-EPMC5694969 | biostudies-literature

Detecting Crystallographic Lattice Chirality using Resonant Inelastic X-ray Scattering.

Project description:The control and detection of crystallographic chirality is an important and challenging scientific problem. Chirality has wide ranging implications from medical physics to cosmology including an intimate but subtle connection in magnetic systems, for example Mn1-xFexSi. X-ray diffraction techniques with resonant or polarized variations of the experimental setup are currently utilized to characterize lattice chirality. We demonstrate using theoretical calculations the feasibility of indirect K -edge bimagnon resonant inelastic X-ray scattering (RIXS) spectrum as a viable experimental technique to distinguish crystallographic handedness. We apply spin wave theory to the recently discovered √5 × √5 vacancy ordered chalcogenide Rb0.89Fe1.58Se2 for realistic X-ray experimental set up parameters (incoming energy, polarization, Bragg angle, and experimental resolution) to show that the computed RIXS spectrum is sensitive to the underlying handedness (right or left) of the lattice. A Flack parameter definition that incorporates the right- and left- chiral lattice RIXS response is introduced. It is shown that the RIXS response of the multiband magnon system RbFeSe arises both from inter- and intra- band scattering processes. The extinction or survival of these RIXS peaks are sensitive to the underlying chiral lattice orientation. This in turn allows for the identification of the two chiral lattice orientations.

| S-EPMC6726621 | biostudies-literature

Kondo quasiparticle dynamics observed by resonant inelastic x-ray scattering.

Project description:Effective models focused on pertinent low-energy degrees of freedom have substantially contributed to our qualitative understanding of quantum materials. An iconic example, the Kondo model, was key to demonstrating that the rich phase diagrams of correlated metals originate from the interplay of localized and itinerant electrons. Modern electronic structure calculations suggest that to achieve quantitative material-specific models, accurate consideration of the crystal field and spin-orbit interactions is imperative. This poses the question of how local high-energy degrees of freedom become incorporated into a collective electronic state. Here, we use resonant inelastic x-ray scattering (RIXS) on CePd3 to clarify the fate of all relevant energy scales. We find that even spin-orbit excited states acquire pronounced momentum-dependence at low temperature-the telltale sign of hybridization with the underlying metallic state. Our results demonstrate how localized electronic degrees of freedom endow correlated metals with new properties, which is critical for a microscopic understanding of superconducting, electronic nematic, and topological states.

| S-EPMC9576770 | biostudies-literature

Resonant inelastic X-ray scattering determination of the electronic structure of oxyhemoglobin and its model complex.

Project description:Hemoglobin and myoglobin are oxygen-binding proteins with S = 0 heme {FeO2}8 active sites. The electronic structure of these sites has been the subject of much debate. This study utilizes Fe K-edge X-ray absorption spectroscopy (XAS) and 1s2p resonant inelastic X-ray scattering (RIXS) to study oxyhemoglobin and a related heme {FeO2}8 model compound, [(pfp)Fe(1-MeIm)(O2)] (pfp = meso-tetra(α,α,α,α-o-pivalamido-phenyl)porphyrin, or TpivPP, 1-MeIm = 1-methylimidazole) (pfpO2), which was previously analyzed using L-edge XAS. The K-edge XAS and RIXS data of pfpO2 and oxyhemoglobin are compared with the data for low-spin FeII and FeIII [Fe(tpp)(Im)2]0/+ (tpp = tetra-phenyl porphyrin) compounds, which serve as heme references. The X-ray data show that pfpO2 is similar to FeII, while oxyhemoglobin is qualitatively similar to FeIII, but with significant quantitative differences. Density-functional theory (DFT) calculations show that the difference between pfpO2 and oxyhemoglobin is due to a distal histidine H bond to O2 and the less hydrophobic environment in the protein, which lead to more backbonding into the O2 A valence bond configuration interaction multiplet model is used to analyze the RIXS data and show that pfpO2 is dominantly FeII with 6-8% FeIII character, while oxyhemoglobin has a very mixed wave function that has 50-77% FeIII character and a partially polarized Fe-O2 π-bond.

| S-EPMC6386657 | biostudies-literature

Targeting Individual Tautomers in Equilibrium by Resonant Inelastic X-ray Scattering.

Project description:Tautomerism is one of the most important forms of isomerism, owing to the facile interconversion between species and the large differences in chemical properties introduced by the proton transfer connecting the tautomers. Spectroscopic techniques are often used for the characterization of tautomers. In this context, separating the overlapping spectral response of coexisting tautomers is a long-standing challenge in chemistry. Here, we demonstrate that by using resonant inelastic X-ray scattering tuned to the core excited states at the site of proton exchange between tautomers one is able to experimentally disentangle the manifold of valence excited states of each tautomer in a mixture. The technique is applied to the prototypical keto-enol equilibrium of 3-hydroxypyridine in aqueous solution. We detect transitions from the occupied orbitals into the LUMO for each tautomer in solution, which report on intrinsic and hydrogen-bond-induced orbital polarization within the π and σ manifolds at the proton-transfer site.

| S-EPMC8935368 | biostudies-literature

Quartz-based flat-crystal resonant inelastic x-ray scattering spectrometer with sub-10 meV energy resolution.

Project description:Continued improvement of the energy resolution of resonant inelastic x-ray scattering (RIXS) spectrometers is crucial for fulfilling the potential of this technique in the study of electron dynamics in materials of fundamental and technological importance. In particular, RIXS is the only alternative tool to inelastic neutron scattering capable of providing fully momentum resolved information on dynamic spin structures of magnetic materials, but is limited to systems whose magnetic excitation energy scales are comparable to the energy resolution. The state-of-the-art spherical diced crystal analyzer optics provides energy resolution as good as 25 meV but has already reached its theoretical limit. Here, we demonstrate a novel sub-10 meV RIXS spectrometer based on flat-crystal optics at the Ir-L3 absorption edge (11.215 keV) that achieves an analyzer energy resolution of 3.9 meV, very close to the theoretical value of 3.7 meV. In addition, the new spectrometer allows efficient polarization analysis without loss of energy resolution. The performance of the instrument is demonstrated using longitudinal acoustical and optical phonons in diamond, and magnon in Sr3Ir2O7. The novel sub-10 meV RIXS spectrometer thus provides a window into magnetic materials with small energy scales.

| S-EPMC5792644 | biostudies-literature

Resonant inelastic X-ray scattering using a miniature dispersive Rowland refocusing spectrometer.

Project description:X-ray absorption spectroscopy (XAS) beamlines worldwide are steadily increasing their emphasis on full photon-in/photon-out spectroscopies, such as resonant inelastic X-ray scattering (RIXS), resonant X-ray emission spectroscopy (RXES) and high energy resolution fluorescence detection XAS (HERFD-XAS). In such cases, each beamline must match the choice of emission spectrometer to the scientific mission of its users. Previous work has recently reported a miniature tender X-ray spectrometer using a dispersive Rowland refocusing (DRR) geometry that functions with high energy resolution even with a large X-ray spot size on the sample [Holden et al. (2017). Rev. Sci. Instrum. 88, 073904]. This instrument has been used in the laboratory in multiple studies of non-resonant X-ray emission spectroscopy using a conventional X-ray tube, though only for preliminary measurements at a low-intensity microfocus synchrotron beamline. This paper reports an extensive study of the performance of a miniature DRR spectrometer at an unfocused wiggler beamline, where the incident monochromatic flux allows for resonant studies which are impossible in the laboratory. The results support the broader use of the present design and also suggest that the DRR method with an unfocused beam could have important applications for materials with low radiation damage thresholds and that would not survive analysis on focused beamlines.

| S-EPMC7064111 | biostudies-literature

Fingerprints of electronic, spin and structural dynamics from resonant inelastic soft X-ray scattering in transient photo-chemical species.

Project description:We describe how inversion symmetry separation of electronic state manifolds in resonant inelastic soft X-ray scattering (RIXS) can be applied to probe excited-state dynamics with compelling selectivity. In a case study of Fe L3-edge RIXS in the ferricyanide complex Fe(CN)63-, we demonstrate with multi-configurational restricted active space spectrum simulations how the information content of RIXS spectral fingerprints can be used to unambiguously separate species of different electronic configurations, spin multiplicities, and structures, with possible involvement in the decay dynamics of photo-excited ligand-to-metal charge-transfer. Specifically, we propose that this could be applied to confirm or reject the presence of a hitherto elusive transient Quartet species. Thus, RIXS offers a particular possibility to settle a recent controversy regarding the decay pathway, and we expect the technique to be similarly applicable in other model systems of photo-induced dynamics.

| S-EPMC5885270 | biostudies-literature

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

Project description: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. 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.

| S-EPMC8018712 | biostudies-literature