Multiplet Calculations Research Articles

(Digital Presentation) Investigations into the Capacity Degradation Due to an Electronic Structural Change in Homogenous Boron-Substituted Ni-Rich Layered Oxides

Ni-rich layered oxides (LiNixCoyMnzO2, x≥0.8, x+y+z=1) would fulfil the energy density requirements of the automobile industry since they offer outstanding capacities at relatively high mean voltages and sufficient power densities1-3. However, the materials still show significant capacity and voltage fade which requires substantial research. Recently we have shown that the electronic structure is the key to understand the performance but also the failure of the materials1. Thus, we intend to modify the electronic structure using anionic dopants such as Boron. Thus, homogenous B-substituted NCM811s (BNCM811_x%, x% means the x at. % of Boron) are synthesized and the materials reveal a significant change in the electronic structure as evident from x-ray photoelectron spectroscopy (XPS) and near edge x-ray absorption spectroscopy (NEXAFS). Interestingly, a shift of the so called H2-H3 peak4 to higher potentials was observed by Boron substitution and BNCM811s_2% shows relative higher initial discharge capacity (Figure 1A.) at a slightly higher mean voltage, but a lower cycling stability compared to NCM811 (Figure 1B.).The H2-H3 differential capacity peak (Figure 1C) might also include oxygen release5, which is one of the main reasons restricting the cycling stability. Near edge x-ray absorption spectroscopy (NEXAFS) shows that the H2-H3 peak corresponds to a reaction from Ni3+ to Ni2+ (upon charge) and Ni2+ to Ni3+ (upon discharge) which suggest a reaction like NiO2 ⥂ NiO + ½ O2 as the underlying process. At the same time, an Oxygen K peak at 531 eV appears in the NEXAFS spectra, which was assigned to O-O formation in the host structure of Li-rich materials6, 7. Note that the electronic structure of the materials was determined in 5 mAh/g steps over the H2-H3 peak and due to the high resolution, this process became visible for the first time. The findings suggest that dimer formation is not only a phenomenon of Li-rich materials but can also be found in Ni-rich layered oxides at high states of charge.The origin of dimer formation and oxygen release can be traced back to the electronic configuration of Ni. Charge transfer multiplet calculations reveal, that Ni2+ reacts to covalent Ni3+ upon charge (and vice versa upon discharge)1. Ni3+ has a 3d7 electronic state, whose low spin configuration is more preferred than its high spin configuration. Thus, Ni3+ is more prone to Jahn-Teller (JT) distortions and tends to form covalent bonds. Consequently, the electrons are more bound to the individual sites making a further oxidation of the transition metal almost impossible. In conclusion, Boron substitution helps us to understand the function and failure of layered oxides in Li-ion batteries on an atomistic scale and the findings can be used as a design guide for future materials. K. Kleiner, C. A. Murray, C. Grosu, B. Ying, M. Winter, P. Nagel, S. Schuppler and M. Merz, Journal of The Electrochemical Society, 2021.J. Zhao, W. Zhang, A. Huq, S. T. Misture, B. Zhang, S. Guo, L. Wu, Y. Zhu, Z. Chen and K. Amine, Advanced Energy Materials, 2017, 7, 1601266.S.-J. Yoon, K.-J. Park, B.-B. Lim, C. S. Yoon and Y.-K. Sun, Journal of the Electrochemical Society, 2014, 162, A3059.S. Jamil, G. Wang, L. Yang, X. Xie, S. Cao, H. Liu, B. Chang and X. Wang, Journal of Materials Chemistry A, 2020, 8, 21306-21316.K. Märker, P. J. Reeves, C. Xu, K. J. Griffith and C. P. Grey, Chemistry of Materials, 2019, 31, 2545-2554.E. Hu, X. Yu, R. Lin, X. Bi, J. Lu, S. Bak, K.-W. Nam, H. L. Xin, C. Jaye and D. A. Fischer, Nature Energy, 2018, 3, 690-698.K. Kleiner, B. Strehle, A. R. Baker, S. J. Day, C. C. Tang, I. Buchberger, F.-F. Chesneau, H. A. Gasteiger and M. Piana, Chemistry of Materials, 2018, 30, 3656-3667. Figure 1

Excited-state exchange interaction in NiO determined by high-resolution resonant inelastic x-ray scattering at the Ni M2,3 edges

The electronic and magnetic excitations of bulk NiO have been determined using the ${}^{3}{A}_{2g}$ to ${}^{3}{T}_{2g}$ crystal-field transition at the Ni ${M}_{2,3}$ edges with resonant inelastic x-ray scattering at 66.3- and 67.9-eV photon energies and 33-meV spectral resolution. Unambiguous assignment of the high-energy side of this state to a spin-flip satellite is achieved. We extract an effective exchange field of $89\ifmmode\pm\else\textpm\fi{}4$ meV in the ${}^{3}{T}_{2g}$ excited final state from empirical two-peak spin-flip model. The experimental data is found consistent with crystal-field model calculations using exchange fields of 60--100 meV. Full agreement with crystal-field multiplet calculations is achieved for the incident photon energy dependence of line shapes. The lower exchange parameter in the excited state as compared to the ground-state value of 120 meV is discussed in terms of the modification of the orbital occupancy (electronic effects) and of the structural dynamics: (A) With pure electronic effects, the lower exchange energy is attributed to the reduction in effective hopping integral. (B) With no electronic effects, we use the $S=1$ Heisenberg model of antiferromagnetism to derive a second-nearest-neighbor exchange constant ${J}_{2}$ = $14.8\ifmmode\pm\else\textpm\fi{}0.6$ meV. Based on the linear correlation between ${J}_{2}$ and the lattice parameter from pressure-dependent experiments, an upper limit of 2% local Ni-O bond elongation during the femtosecond scattering duration is derived.

Anisotropy of 4f states in 3d−4f single-molecule magnets

We have measured angular-dependent fluorescence-yield x-ray magnetic circular dichroism spectra on single crystals of the heterometallic $3d\ensuremath{-}4f$ 12-metallacrown-4 ${\mathrm{TbMn}}_{4}$ and ${\mathrm{DyMn}}_{4}$ complexes. Simulated spectra using crystal-field multiplet calculations reproduce the experimentally observed spectra. The orientation of the molecules causes linear dichroism spectra of the $4f$ absorption spectra. This natural linear dichroism shows the anisotropic charge distribution of the rare-earth $4f$ state in the tetragonal crystal field despite the small $4f$ crystal-field splitting. The magnetic moment of the molecule is dominated by the rare-earth moment revealing a considerably large contribution of orbital moment. From a sum-rule analysis of experimental and simulated x-ray magnetic circular dichroism, we determined corrected spin and orbital Dy moments at low temperature (14 K) within a magnetic field of 7 T. We find a significant angular dependence of the Dy magnetic moments, indicating the presence of fourth-order magnetic anisotropy.

Engineering Periodic Dinuclear Lanthanide-Directed Networks Featuring Tunable Energy Level Alignment and Magnetic Anisotropy by Metal Exchange.

The design of lanthanide multinuclear networks is an emerging field of research due to the potential of such materials for nanomagnetism, spintronics, and quantum information. Therefore, controlling their electronic and magnetic properties is of paramount importance to tailor the envisioned functionalities. In this work, a multidisciplinary study is presented combining scanning tunneling microscopy, scanning tunneling spectroscopy, X-ray absorption spectroscopy, X-ray linear dichroism, X-ray magnetic circular dichroism, density functional theory, and multiplet calculations, about the supramolecular assembly, electronic and magnetic properties of periodic dinuclear 2D networks based on lanthanide-pyridyl interactions on Au(111). Er- and Dy-directed assemblies feature identical structural architectures stabilized by metal-organic coordination. Notably, despite exhibiting the same +3 oxidation state, there is a shift of the energy level alignment of the unoccupied molecular orbitals between Er- and Dy-directed networks. In addition, there is a reorientation of the easy axis of magnetization and an increment of the magnetic anisotropy when the metallic center is changed from Er to Dy. Thus, the results show that it is feasible to tune the energy level alignment and magnetic anisotropy of a lanthanide-based metal-organic architecture by metal exchange, while preserving the network design.

Magnetic anisotropy of the van der Waals ferromagnet Cr2Ge2Te6 studied by angular-dependent x-ray magnetic circular dichroism

The van der Waals ferromagnet ${\mathrm{Cr}}_{2}{\mathrm{Ge}}_{2}{\mathrm{Te}}_{6}$ (CGT) has a two-dimensional crystal structure where each layer is stacked through van der Waals force. We have investigated the nature of the ferromagnetism and the weak perpendicular magnetic anisotropy (PMA) of CGT by means of x-ray absorption spectroscopy and x-ray magnetic circular dichroism (XMCD) studies of CGT single crystals. The XMCD spectra at the Cr ${L}_{2,3}$ edge for different magnetic field directions were analyzed on the basis of the cluster-model multiplet calculation. The Cr valence is confirmed to be $3+$ and the orbital magnetic moment is found to be nearly quenched, as expected for the high-spin ${t}_{2g}^{3}$ configuration of the ${\mathrm{Cr}}^{3+}$ ion. A large ($\ensuremath{\sim}0.2$ eV) trigonal crystal-field splitting of the ${t}_{2g}$ level caused by the distortion of the $\mathrm{Cr}{\mathrm{Te}}_{6}$ octahedron has been revealed, while the single-ion anisotropy (SIA) of the Cr atom is found to have a sign opposite to the observed PMA and too weak compared to the reported anisotropy energy. The present result suggests that anisotropic exchange coupling between the Cr atoms through the ligand Te $5p$ orbitals having strong spin-orbit coupling has to be invoked to explain the weak PMA of CGT, as in the case of the strong PMA of ${\mathrm{CrI}}_{3}$.

Electronic excitations of α−Fe2O3 heteroepitaxial films measured by resonant inelastic x-ray scattering at the Fe L edge

Resonant Inelastic X-Ray Scattering (RIXS) spectra of hematite were measured at the Fe L3-edge for heteroepitaxial thin films which were undoped and doped with 1% Ti, Sn or Zn, in the energy loss range in excess of 1 eV to study electronic transitions. The spectra were measured for several momentum transfers (q), conducted at both low temperature (T=14K) and room temperature. While we can not rule out dispersive features possibly owing to propagating excitations, the coarse envelopes of the general spectra did not appreciably change shape with q, implying that the bulk of the observed L-edge RIXS intensity originates from (mostly) non-dispersive ligand field (LF) excitations. Summing the RIXS spectra over q and comparing the results at T=14 K to those at T=300 K, revealed pronounced temperature effects, including an intensity change and energy shift of the 1.4 eV peak, a broadband intensity increase of the 3-4 eV range, and higher energy features. The q-summed spectra and their temperature dependences are virtually identical for nearly all of the samples with different dopants, save for the temperature dependence of the Ti-doped sample's spectrum, which we attribute to being affected by a large number of free charge carriers. Comparing with magnetization measurements for different temperatures and dopings likewise did not show a clear correlation between the RIXS spectra and the magnetic ordering states. To clarify the excited states, we performed spin multiplet calculations which were in excellent agreement with the RIXS spectra over a wide energy range and provide detailed electronic descriptions of the excited states. The implications of these findings to the photoconversion efficiency of hematite photoanodes is discussed.

Quantifying the Steric Effect on Metal-Ligand Bonding in Fe Carbene Photosensitizers with Fe 2p3d Resonant Inelastic X-ray Scattering.

Understanding the electronic structure and chemical bonding of transition metal complexes is important for improving the function of molecular photosensitizers and catalysts. We have utilized X-ray absorption spectroscopy (XAS) and resonant inelastic X-ray scattering (RIXS) at the Fe L3 edge to investigate the electronic structure of two Fe N-heterocyclic carbene complexes with similar chemical structures but different steric effects and contrasting excited-state dynamics: [Fe(bmip)2]2+ and [Fe(btbip)2]2+, bmip = 2,6-bis(3-methyl-imidazole-1-ylidine)pyridine and btbip = 2,6-bis(3-tert-butyl-imidazole-1-ylidene)pyridine. In combination with charge transfer multiplet and ab initio calculations, we quantified how changes in Fe-carbene bond length due to steric effects modify the metal-ligand bonding, including σ/π donation and π back-donation. We find that σ donation is significantly stronger in [Fe(bmip)2]2+, whereas the π back-donation is similar in both complexes. The resulting stronger ligand field and nephelauxetic effect in [Fe(bmip)2]2+ lead to approximately 1 eV destabilization of the quintet metal-centered 5T2g excited state compared to [Fe(btbip)2]2+, providing an explanation for the absence of a photoinduced 5T2g population and a longer metal-to-ligand charge-transfer excited-state lifetime in [Fe(bmip)2]2+. This work demonstrates how combined modeling of XAS and RIXS spectra can be utilized to understand the electronic structure of transition metal complexes governed by correlated electrons and donation/back-donation interactions.

Cationic Ordering and Its Influence on the Magnetic Properties of Co-Rich Cobalt Ferrite Thin Films Prepared by Reactive Solid Phase Epitaxy on Nb-Doped SrTiO3(001).

Here, we present the (element-specific) magnetic properties and cation ordering for ultrathin Co-rich cobalt ferrite films. Two Co-rich films with different stoichiometry ( and ) have been formed by reactive solid phase epitaxy due to post-deposition annealing from epitaxial CoO/FeO bilayers deposited before on Nb-doped SrTiO(001). The electronic structure, stoichiometry and homogeneity of the cation distribution of the resulting cobalt ferrite films were verified by angle-resolved hard X-ray photoelectron spectroscopy. From X-ray magnetic circular dichroism measurements, the occupancies of the different sublattices were determined using charge-transfer multiplet calculations. For both ferrite films, a partially inverse spinel structure is found with increased amount of cations in the low-spin state on octahedral sites for the film. These findings concur with the results obtained by superconducting quantum interference device measurements. Further, the latter measurements revealed the presence of an additional soft magnetic phase probably due to cobalt ferrite islands emerging from the surface, as suggested by atomic force microscope measurements.

Orbital and spin character of doped carriers in infinite-layer nickelates

The discovery of superconductivity in infinite-layer nickelate thin films has produced fervent theoretical research about the doping evolution of their electronic structure. Here, by means of x-ray spectroscopy and atomic multiplet calculations, the authors show that doped holes are mainly introduced in Ni sites in a spin-singlet configuration. The dominant role of the Ni 3${d}_{{x}^{2}\ensuremath{-}{y}^{2}}$ band implies that infinite-layer nickelates are likely a strongly correlated electronic system, reminiscent of their cuprate siblings.

Sub-picometer sensitivity and effect of anisotropic atomic vibrations on Ti L2,3-edge spectrum of SrTiO3

The effect of temperature on the electron energy-loss Ti L2,3-edge spectrum of SrTiO3 was ascertained using monochromated scanning transmission electron microscopy. The results demonstrate that the spectrum is sensitive to structural changes involving volume expansion on the sub-picometer level, and the sensitivity is superior to that obtainable using conventional electron microscopy. Experimental spectra could be accurately reproduced by multiplet calculations that incorporated anisotropic atomic vibrations of oxygen atoms. This spectral technique could represent a powerful tool for investigating infinitesimal structural changes and atomic vibrations at local regions, such as interfaces.

On the Origin of Reversible and Irreversible Reactions in LiNixCo(1−x)/2Mn(1−x)/2O2

Bond formation and breakage is crucial upon energy storage in lithium transition metal oxides (LiMeO2, Me = Ni, Co, Mn), i.e., the conventional cathode materials in Li ion batteries. Near-edge X-ray absorption finestructure spectroscopy (NEXAFS) of the Me L and O K edge performed upon the first discharge of LiNixCo(1−x)/2Mn(1−x)/2O2 (x = 0.33: NCM111, x = 0.6: NCM622, x = 0.8: NCM811) in combination with charge transfer multiplet (CTM) calculations provide unambiguous evidence that redox reactions in NCMs proceed via a reversible oxidation of Ni associated with the formation of covalent bonds to O neighbors, and not, as widely assumed, via pure cationic or more recently discussed, pure anionic redox processes. Correlating these electronic changes with crystallographic data using operando synchrotron X-ray powder diffraction (SXPD) shows that the amount of ionic Ni limits the reversible capacity— at states of charge where all ionic Ni is oxidized (above 155 mAh g−1), the lattice parameters collapse, and irreversible reactions are observed. Yet the covalence of the Ni–O bonds also triggers the electronic structure and thus the operation potential of the cathodes.

Magnetic Hysteresis in a Monolayer of Oriented 6 nm CsNiCr Prussian Blue Analogue Nanocrystals.

Prussian blue analogue nanocrystals of the CsINiII[CrIII(CN)6] cubic network with 6 nm size were assembled as a single monolayer on highly organized pyrolytic graphite (HOPG). X-ray magnetic circular dichroism (XMCD) studies, at the Ni and Cr L2,3 edges, reveal the presence of an easy plane of magnetization evidenced by an opening of the magnetic hysteresis loop (coercive field of ≈200 Oe) when the magnetic field, B, is at 60° relative to the normal to the substrate. The angular dependence of the X-ray natural linear dichroism (XNLD) reveals both an orientation of the nanocrystals on the substrate and an anisotropy of the electronic cloud of the NiII and CrIII coordination sphere species belonging to the nanocrystals' surface. Ligand field multiplet (LFM) calculations that reproduce the experimental data are consistent with an elongated tetragonal distortion of surface NiII coordination sphere responsible for the magnetic behavior of monolayer.

Correlation between Electronic Configuration and Magnetic Stability in Dysprosium Single Atom Magnets.

Single atom magnets offer the possibility of magnetic information storage in the most fundamental unit of matter. Identifying the parameters that control the stability of their magnetic states is crucial to design novel quantum magnets with tailored properties. Here, we use X-ray absorption spectroscopy to show that the electronic configuration of dysprosium atoms on MgO(100) thin films can be tuned by the proximity of the metal Ag(100) substrate onto which the MgO films are grown. Increasing the MgO thickness from 2.5 to 9 monolayers induces a change in the dysprosium electronic configuration from 4f9 to 4f10. Hysteresis loops indicate long magnetic lifetimes for both configurations, however, with a different field-dependent magnetic stability. Combining these measurements with scanning tunneling microscopy, density functional theory, and multiplet calculations unveils the role of the adsorption site and charge transfer to the substrate in determining the stability of quantum states in dysprosium single atom magnets.

Mapping Orbital-Resolved Magnetism in Single Lanthanide Atoms.

Single lanthanide atoms and molecules are promising candidates for atomic data storage and quantum logic due to the long lifetime of their magnetic quantum states. Accessing and controlling these states through electrical transport requires precise knowledge of their electronic configuration at the level of individual atomic orbitals, especially of the outer shells involved in transport. However, no experimental techniques have so far shown the required sensitivity to probe single atoms with orbital selectivity. Here we resolve the magnetism of individual orbitals in Gd and Ho single atoms on MgO/Ag(100) by combining X-ray magnetic circular dichroism with multiplet calculations and density functional theory. In contrast to the usual assumption of bulk-like occupation of the different electronic shells, we establish a charge transfer mechanism leading to an unconventional singly ionized configuration. Our work identifies the role of the valence electrons in determining the quantum level structure and spin-dependent transport properties of lanthanide-based nanomagnets.

Tuning the Magnetic Anisotropy of Lanthanides on a Metal Substrate by Metal-Organic Coordination.

Taming the magnetic anisotropy of lanthanides through coordination environments is crucial to take advantage of the lanthanides properties in thermally robust nanomaterials. In this work, the electronic and magnetic properties of Dy-carboxylate metal-organic networks on Cu(111) based on an eightfold coordination between Dy and ditopic linkers are inspected. This surface science study based on scanning probe microscopy and X-ray magnetic circular dichroism, complemented with density functional theory and multiplet calculations, reveals that the magnetic anisotropy landscape of the system is complex. Surface-supported metal-organic coordination is able to induce a change in the orientation of the easy magnetization axis of the Dy coordinative centers as compared to isolated Dy atoms and Dy clusters, and significantly increases the magnetic anisotropy. Surprisingly, Dy atoms coordinated in the metallosupramolecular networks display a nearly in-plane easy magnetization axis despite the out-of-plane symmetry axis of the coordinative molecular lattice. Multiplet calculations highlight the decisive role of the metal-organic coordination, revealing that the tilted orientation is the result of a very delicate balance between the interaction of Dy with O atoms and the precise geometry of the crystal field. This study opens new avenues to tailor the magnetic anisotropy and magnetic moments of lanthanide elements on surfaces.

Electronic structure comparison of Cu 2p and O 1s X-Ray photoelectron spectra for CuxO nanofibers (x = 1, 2, i)

This article reports the evaluation and comparison the electronic structure of Cu 2p and O 1s spectra, using x-ray photoelectron spectroscopy (XPS) and the charge transfer multiplet calculation by the CTM4XAS (software). This research is relevant in the study of CuO - Cu2O and CuO nanofibers (NFs) that were synthesized with temperatures of 600 °C (CuO600) and 700 °C (CuO700), through the electrospinning method (EM). The NFs are analyzed with x-ray diffraction, scanning electron microscopy and high-resolution-scanning electron transmission microscopy. The expected results are innovative because the sample exhibits multivalent states (Cu1+, Cu2+, Cui+) and the reproducibility of the stoichiometry Cu2.0O0.88, Cu2.0O2.73, and Cu2.0O0.9 , Cu1.0O1.76, with uncertainties in the fittings, 3.7282 x 10−5 eV and 4.05987 x 10−5 eV. This was possible by doing peak fittings with modern parameters. The NFs present mixtures of oxides and charge transfer generated by oxygen vacancies (Vo).

Resonant photoemission spectroscopy of the ferromagnetic Kondo system CeAgSb2

We study the electronic structure of single crystal CeAgSb2, a low T c ferromagnetic Kondo system, using synchrotron radiation photoemission spectroscopy (PES) and x-ray absorption spectroscopy (XAS). We have carried out Ce 5s, Ce 5p, Sb 4d core level PES as well as Ce 4d–4f resonant PES of the valence band states of CeAgSb2. We also report the resonant PES behavior of Ce 5s and 5p core-levels and the simultaneous intensity suppression of Sb 4d core-level and Ag 4d valence band states across the Ce 4d–4f threshold. The Ce 4d–4f resonant valence band spectra show typical f 0 and f 1 features associated with Kondo behavior. The constant initial state spectra of the f 0 and f 1 features show maxima at different incident photon energies, arising from different relative contributions of surface and bulk character Ce 4f partial density of states. XAS across the Ce 3d–4f M-edge also shows the corresponding final state f 1 and f 2 features. The weak temperature dependence of the XAS spectra between T = 25 K and 300 K could be simulated using a full multiplet calculation combined with a simplified single-impurity Anderson model approach. The calculations confirm the Kondo screening and allows quantification of the bulk Ce 4f electron count in CeAgSb2. The Ce 5s states show an exchange splitting which reflects the local magnetic moment of Ce 4f states. The overall results characterize the bulk and surface sensitive Ce 4f states, and indicate the role of Kondo effect in forming the moderately enhanced heavy-fermion carriers in CeAgSb2.

Electronic structure of Tb0.5Sr0.5MnO3

We study the electronic structure of single-crystal ${\mathrm{Tb}}_{0.5}{\mathrm{Sr}}_{0.5}{\mathrm{MnO}}_{3}$, a non-charge-ordered mixed-valent semiconductor which exhibits a glassy magnetic ground state. We use the techniques of soft x-ray photoemission, hard x-ray photoemission, x-ray absorption, and resonant photoemission spectroscopy to investigate the occupied and unoccupied electronic states of ${\mathrm{Tb}}_{0.5}{\mathrm{Sr}}_{0.5}{\mathrm{MnO}}_{3}$. Core level photoemission and x-ray absorption spectroscopy allow us to determine the valence states of Tb, Sr, and Mn ions in ${\mathrm{Tb}}_{0.5}{\mathrm{Sr}}_{0.5}{\mathrm{MnO}}_{3}$. Model charge transfer multiplet calculations of core level photoemission and x-ray absorption spectra are employed to separate out the ${\mathrm{Mn}}^{3+}$ and ${\mathrm{Mn}}^{4+}$ states and confirm their relative concentrations. Resonant photoemission spectroscopy across the Mn $2p\text{\ensuremath{-}}3d$ threshold shows clear resonant enhancement of the Mn $3d$ partial density of states and two-hole correlation satellites. A Cini-Sawatzky analysis gives on-site Coulomb energy ${U}_{dd}\phantom{\rule{4pt}{0ex}}\ensuremath{\sim}\phantom{\rule{4pt}{0ex}}5.5\ifmmode\pm\else\textpm\fi{}0.2$ eV for the Mn $3{d}^{n}$ states and ${U}_{pd}$ = 0.7 $\mathrm{eV}\ifmmode\pm\else\textpm\fi{}0.2$ eV for the Mn $3{d}^{n+1}{\underline{L}}^{1}$ states. The O $1s\text{\ensuremath{-}}2p$ resonant photoemission is used to identify the O $2p$ two-hole correlation satellite which provides ${U}_{pp}\phantom{\rule{4pt}{0ex}}\ensuremath{\sim}\phantom{\rule{4pt}{0ex}}3.4\ifmmode\pm\else\textpm\fi{}0.2$ eV for the O $2p$ states. Valence band photoemission indicates a small-gap semiconductor ($<100$ meV) consistent with electrical transport measurements. The estimated electronic structure parameters of the on-site Coulomb energies, in combination with the charge transfer energy and the hybridization strength obtained from the model calculations, indicate that ${\mathrm{Tb}}_{0.5}{\mathrm{Sr}}_{0.5}{\mathrm{MnO}}_{3}$ is a strongly correlated charge transfer type semiconductor.

Dynamical spin susceptibility in La2CuO4 studied by resonant inelastic x-ray scattering

Resonant inelastic x-ray scattering (RIXS) is a powerful probe of elementary excitations in solids. It is now widely applied to study magnetic excitations. However, its complex cross section means that RIXS has been more difficult to interpret than inelastic neutron scattering (INS). Here we report $\ensuremath{\sim}37$ meV resolution RIXS measurements of the magnetic excitations in ${\mathrm{La}}_{2}{\mathrm{CuO}}_{4}$, the antiferromagnetic parent of one system of high-temperature superconductors. At high energies ($\ensuremath{\sim}2$ eV), the RIXS spectra show angular-dependent $dd$ orbital excitations in agreement with previous RIXS studies but show new structure. They are interpreted with single-site multiplet calculations. At low energies ($\ensuremath{\lesssim}0.3$ eV), we model the wave-vector-dependent single magnon RIXS intensity as the product of the calculated single-ion spin-flip RIXS cross section and the dynamical structure factor $S(\mathbf{Q},\ensuremath{\omega})$ of the spin-wave excitations. When $S(\mathbf{Q},\ensuremath{\omega})$ is extracted from our data, the wave-vector-dependence of the single-magnon pole intensity shows a similar variation to that observed by INS. Our results confirm that suitably corrected RIXS data can yield the genuine wave-vector and energy dependence of $S(\mathbf{Q},\ensuremath{\omega})$ for a cuprate antiferromagnet. In addition to spin waves, our data show structured multimagnon excitations with dispersing peaks in the intensity at energies higher than the single-magnon excitations.

X-Ray Spectroscopy of Cobaltites

The ability of cobalt to take, depending on the temperature, pressure, and doping, various charge and spin states in oxide compounds periodically becomes the topic of scientific controversy and is a frequent cause of ambiguity in the interpretation of experimental results. In this review, we will discuss cobaltites, i.e., oxide compounds of cobalt, in which cobalt is in an oxidation state (charge state) of 3+. In these compounds, Co3+ ions can take the following spin configurations: high-spin, low-spin, and intermediate-spin configurations. The conditions for the formation of various spin states are given on the basis of the Tanabe–Sugano diagrams. It is shown how X-ray spectral methods, such as X-ray photoelectron spectroscopy, X-ray emission spectroscopy, X-ray absorption spectroscopy, and X-ray magnetic dichroism, can be used to study cobaltites. By using Co L2,3 X-ray absorption spectra that have a rich structure, one can determine the charge and spin states of cobalt ions. These spectra can be reproduced by atom-like multiplet calculations that involve many electrons and use the energy splitting of atomic orbitals by the ligand field as a free parameter. Absorption K spectra of oxygen are of a band nature, i.e., these spectra can be used, by mixing the 3d states of cobalt with the 2p states of oxygen, to estimate the spin state of cobalt ions and to analyze cobaltite phases after external influences. It is shown that the spin states of cobalt ions can be determined from Co Kβ X‑ray emission spectra (electronic transition $$3p \to 1s$$ ) that are sensitive to the spin state of 3d electrons because of the strong exchange interaction between the 3p hole and 3d orbitals in the final state of the emission process. A classic example of cobaltites with a low-spin configuration of cobalt ions is lithium cobaltite LiCoO2 that is a well-known material for power source cathodes. The nature of holes in defective cobaltites of the LixCoO2 (x < 1) type is considered. It is shown that holes arising from defects in the lithium sublattice are of an oxygen nature. In cobaltite LaCoO3 that also contains trivalent cobalt ions, a transition from a low-spin state to a high-spin state occurs at temperatures above 90 K. The feasibility of an intermediate-spin state in this compound is also considered. The results of X-ray spectral studies of double substitution perovskites Ln1 – xAxCo1 – yMyO3 (Ln is a lanthanide, A is Ca or Sr, and M is a transition element) are given, and changes in the charge states of cobalt ions upon doping of perovskites are shown. The results of experimental determination of spin states in octahedrons and pyramids of cobaltites LnBaCo2O6 – δ ( $$0 \leqslant \delta \leqslant 1$$ ) at temperatures below and above the temperature of the metal-insulator transition are systematized. Methods for determining spin states on the basis of X-ray spectral data are discussed. It is shown in the last section of the article how the charge state and concentration of cobalt ions in doped layered cobaltites LnBaCo4O7 can be determined using X-ray absorption spectroscopy. In these compounds, cobalt ions are in tetrahedral positions and, consequently, trivalent cobalt ions should be exclusively in the high-spin state.