The electronic structure of LiNiO$_2$, a promising Li-ion battery cathode material, has remained a challenge to understand due to its highly covalent yet correlated nature. Here we elucidate the electronic structure in LiNiO$_2$ and the related compound NaNiO$_2$ using x-ray absorption spectra (XAS) and quantum many-body calculations. Notably, we use inverse partial fluorescence yield to correctly measure the Ni $L$-edge XAS, which is inaccurate using conventional methods. We show that the XAS are indicative of a strong Jahn-Teller effect in NaNiO$_2$ and a bond disproportionated state in LiNiO$_2$, supporting a theory of a high-entropy, glassy disproportionated state that stabilizes charging cycles in LiNiO$_2$.
We present a theory describing the local electronic properties of the perovskite rare earth nickelates--materials which have negative charge transfer energies, strong O $2p$ -- Ni $3d$ covalence, and breathing mode lattice distortions at the origin of highly studied metal-insulator and antiferromagnetic ordering transitions. Utilizing a full orbital, full correlation double cluster approach, we find strong charge fluctuations in agreement with a bond disproportionation interpretation. The unique double cluster formulation permits the inclusion of necessary orbital degeneracies and Coulomb inte…
We have measured the temperature dependence of the photoemission and x-ray absorption spectra of La$_{1-x}$Sr$_x$FeO$_3$ (LSFO) epitaxial thin films with $x=0.67$, where charge disproportionation ($3{Fe}^{3.67+}\to 2{Fe}^{3+}+ {Fe}^{5+}$) resulting in long-range spin and charge ordering is known to occur below $T_{CD}=190$ K. With decreasing temperature we observed gradual changes of the spectra with spectral weight transfer over a wide energy range of $\sim 5$ eV. Above $T_{CD}$ the intensity at the Fermi level ($E_F$) was relatively high compared to that below $T_{CD}$ but still much lower t…
Using \emph{ab initio} band structure methods and DFT+dynamical mean-field theory approach we explore the possible formation of spin and charge stripes in the Ni-O plane of hole-doped infinite-layer nickelates, $R$NiO$_2$. Our results reveal a remarkable instability of the $C$-type $(110)$ spin state with undistorted lattice towards the formation of the spin-density, charge- and bond-disproportionation stripe phases accompanied by in-plane``breathing''-like distortions of the crystal structure. Our work gives a comprehensive picture of competing charge and spin stripe states, with possible fru…
We develop a theory describing a parameter based phase diagram to be associated with materials incorporating skipped valence ions\cite{Varma}. We use a recently developed tight-binding approach for the bismuthates to study the phase diagram exhibiting the crossover from a bond disproportionated (BD) to a charge disproportionated (CD) system in addition to the presence of a new metallic phase. We argue that three parameters determine the underlying physics of the BD-CD crossover when electron correlation effects are small: the hybridization between O-2$p_σ$ and Bi-6$s$ orbitals ($t_{spσ}$), the…
We propose a simple theoretical description of the metal-insulator transition of rare-earth nickelates. The theory involves only two orbitals per nickel site, corresponding to the low-energy anti-bonding $e_g$ states. In the monoclinic insulating state, bond-length disproportionation splits the manifold of $e_g$ bands, corresponding to a modulation of the effective on-site energy. We show that, when subject to a local Coulomb repulsion $U$ and Hund's coupling $J$, the resulting bond-disproportionated state is a paramagnetic insulator for a wide range of interaction parameters. Furthermore, we …
The chiral magneto-electric compound Ni3TeO6 is investigated through temperature-dependent synchrotron-based powder x-ray diffraction and x-ray absorption spectroscopy between 15 to 300 K. Our work provides direct evidence for the exchange-striction in the material around the concomitant onset point of collinear antiferromagnetic and magneto-electric phases. The x-ray absorption near edge spectra and x-ray photoelectron spectra show that the sample consists of both Ni2+ and Ni3+ ions in the lattice. The ionic state of Ni is found to be quite robust, and it is largely independent of the prepara…
Understanding microscopic properties of LiNiO$_2$, a Li-ion battery cathode material with extraordinarily high reversible capacity, has remained a challenge for decades. Based on extensive electronic structure calculations, which reveal a large number of nearly degenerate phases involving local Jahn-Teller effect as well as bond and oxygen-based charge disproportionation, we propose that LiNiO$_2$ exists in a high-entropy charge-glass like state at and below ambient temperatures. Recognizing the glassy nature of LiNiO$_2$ does not only explain its key experimental features, but also opens a ne…
The crystal structure of layered metal IrTe2 is determined using single-crystal x-ray diffraction. At T=220 K, it exhibits Ir and Te dimers forming a valence-bond crystal. Electronic structure calculations reveal an intriguing quasi-two-dimensional electronic state, with planes of reduced density of states cutting diagonally through the Ir and Te layers. These planes are formed by the Ir and Te dimers, which exhibit a signature of covalent bonding character development. Evidence for significant charge disproportionation among the dimerized and non-dimerized Ir (charge order) is also presented.
We compute the electronic structure, spin and charge state of Fe ions, and structural phase stability of paramagnetic CaFeO$_3$ under pressure using a fully self-consistent in charge density DFT+dynamical mean-field theory method. We show that at ambient pressure CaFeO$_3$ is a negative charge-transfer insulator characterized by strong localization of the Fe $3d$ electrons. It crystallizes in the monoclinic $P2_1/n$ crystal structure with a cooperative breathing mode distortion of the lattice. While the Fe $3d$ Wannier occupations and local moments are consistent with robust charge disproporti…
Perovskite-type BiNiO$_3$ is an insulating antiferromagnet in which a charge disproportionation occurs at the Bi site. La substitution for Bi suppresses the charge disproportionation and makes the system metallic. We have measured the photoemission and x-ray absorption (XAS) spectra of Bi$_{1-x}$La$_{x}$NiO$_{3}$ to investigate how the electronic structure changes with La doping. From Ni $2p$ XAS, we observed an increase of the valence of Ni from 2+ toward 3+. Combined with the core-level photoemission study, it was found that the average valence of Bi remains $\sim 4+$ and that the Ni valence…
We present a computational study of resonant inelastic x-ray scattering (RIXS) and x-ray absorption in a representative rare-earth nickelate LuNiO$_3$. We study the changes in the spectra across the metal-insulator/site-disproportionation transition. In particular, we address the question of site-selectivity of the two methods in the disproportionated insulating phase and the signature of metal-insulator transition in the fluorescence-like feature of the RIXS spectra. To this end we use the local density approximation + dynamical mean-field theory (LDA+DMFT) approach combined with configuratio…
The experimental Mn K-edge x-ray absorption spectra of La$_{1-x}$Sr$_x$MnO$_{3}$, $x$ = 0 - 0.7 are compared with the band structure calculations using spin polarized density functional theory. It is explicitly shown that there is a correspondence between the inflection point on the absorption edge and the centre of gravity of the unoccupied Mn 4$p$-band. This correspondence has been used to separate the doping and size contributions to edge shift due to variation in number of electrons in valence band and Mn-O bond lengths, respectively when Sr is doped into LaMnO$_3$. Such separation is help…
Elucidating the polymorphism of transition metal dichalcogenide layers and the interplay between structure and properties is a key challenge for the application of these materials. We identify a novel low energy metastable phase of monolayer VSe$_2$ and elucidate its magnetic and electronic properties. This structure is distinct from the previously identified charge density wave (CDW) phase. However, while having rather distinct properties it is very close in energy to the CDW phase and is likely to be realized in experiments. Importantly, local bonding instabilities, as characterized by recon…
With x-ray absorption spectroscopy we investigated the orbital reconstruction and the induced ferromagnetic moment of the interfacial Cu atoms in YBa$_2$Cu$_3$O$_{7}$/La$_{2/3}$Ca$_{1/3}$MnO$_3$ (YBCO/LCMO) and La$_{2-x}$Sr$_{x}$CuO$_4$/La$_{2/3}$Ca$_{1/3}$MnO$_3$ (LSCO/LCMO) multilayers. We demonstrate that these electronic and magnetic proximity effects are coupled and are common to these cuprate/manganite multilayers. Moreover, we show that they are closely linked to a specific interface termination with a direct Cu-O-Mn bond. We furthermore show that the intrinsic hole doping of the cuprat…
We use x-ray absorption spectroscopy to investigate the local structure and electronic properties of bulk La$_{1-y}$Sr$_{y}$Co$_{1-x}$Nb$_x$O$_3$ ($y=$ 2$x$ as LSCNO and $y=$ 0 as LCNO) samples. The x-ray absorption near-edge spectra (XANES) of LSCNO at Co K-edge affirm the valence state of Co in 3+. However, in the case of the LCNO, a subtle variation in the valence state of Co ions from 3+ to 2+ is evident with Nb substitution. The detailed analysis of the Fourier transform (FT) of the extended x-ray absorption fine structure (EXAFS) for the LSCNO samples exhibit the two groups of the bond-l…
We present the single-crystalline x-ray diffraction study on the Ba4Ru3O10 consisting of the corner-shared Ru3O12 trimers. The crystal structure is re-determined from 78 to 300 K across an antiferromagnetic transition at 105 K. The orthorhombic symmetry (Cmca, space group No. 64) is preserved at all temperatures measured. This structure presents exceptionally long Ru-O distances characterized by a significant distribution within the Ru3O12 trimer. A bond valence sum calculation suggests that the charge disproportionation within the Ru3O12 trimer emerges even at room temperature, which we ascri…
Using a combination of spectroscopic ellipsometry and DC transport measurements, we determine the temperature dependence of the optical conductivity of NdNiO$_3$ and SmNiO$_{3}$ films. The optical spectra show the appearance of a characteristic two-peak structure in the near-infrared when the material passes from the metal to the insulator phase. Dynamical mean-field theory calculations confirm this two-peak structure, and allow to identify these spectral changes and the associated changes in the electronic structure. We demonstrate that the insulating phase in these compounds and the associat…
Electronic structure and chemical bonding in TiX2 (X=S, Se, Te), TMxTiSe2 (TM=Cr, Mn, Cu) and CrxTi1-xSe2 were studied by x-ray resonance photoemission and absorption spectroscopy. These methods are detected to be strong sensitive to chemical bonding. Charge transfer from the intercalated atoms to Ti 3d band is detected. Narrow Ti 3d and Cu 3d bands are observed under Fermi level in CuxTiSe2.
$Li_{2}RuO_{3}$ with a honeycomb structure undergoes a drastic transition from a regular honeycomb lattice with the $C2/m$ space group to a valence bond solid state of the $P2_{1}/m$ space group with an extremely strong dimerization at 550 K. We synthesized $Li_{2}Ru_{1-x}Mn_{x}O_{3}$ with a full solid solution and investigated doping effects on the valence bond solid state as a function of Mn content. The valence bond solid state is found to be stable up to $x = 0.2$, based on our extensive experiments: structural studies, resistivity, and magnetic susceptibility. On the other hand, the exten…
We report results of an electron spin resonance (ESR) study of a spin-gap antiferromagnet (C$_4$H$_{12}$N$_2$)(Cu$_2$Cl$_6$) (nicknamed PHCC) with chlorine ions partially substituted by bromine. We found that up to 10% of nominal doping the contribution of the random defects to the absorption spectra remains at about 0.1% per copper ion, almost the same as in the pure system. Instead, a particular kind of ESR absorption corresponding to gapless S=1 triplets is observed at low temperatures in samples with high nominal bromine content x>5%. Increase of bromine concentration also leads to the sys…
Temperature dependent extended x-ray absorption fine structure (EXAFS) spectra were measured for a 3.3 at% Ga stabilized Pu alloy over the range T= 20 - 300 K at both the Ga K-edge and the Pu L_III-edge. The temperature dependence of the pair-distance distribution widths, σ(T) was accurately modeled using a correlated-Debye model for the lattice vibrational properties, suggesting Debye-like behavior in this material. We obtain pair- specific correlated-Debye temperatures, Θ_cD, of 110.7 +/- 1.7 K and 202.6 +/- 3.7 K, for the Pu-Pu and Ga-Pu pairs, respectively. These results represent the firs…
We study energetics and the nature of both homogeneous and mixed spin (MS) states in LaCoO$_3$ incorporating structural changes of the crystal volume expansion and the Co-O bond disproportionation (BD) during the spin-state transition using the density functional theory plus dynamical mean field theory (DFT+DMFT) method. DFT+DMFT predicts that energetics of both excited spin states are almost the same while DFT+U calculations of the same structures energetically favor the MS states and produce various metastable solutions whose energetics depend sensitively on final spin states. Within DFT+DMF…
Room temperature Co K-edge extended x-ray absorption fine structure (EXAFS), x-ray absorption near edge structure (XANES) including pre-edge and x-ray diffraction (XRD) studies are carried out on LaCoO3 and PrCoO3. The Co-O, Co-La/Pr and Co-Co bond lengths are obtained from EXAFS analysis and compared with those obtained from XRD. The EXAFS analysis of data indicates that CoO6 octahedron is distorted in both LaCoO3 and PrCoO3. Such distortion is expected in orthorhombic PrCoO3 but not in rhombohedral LaCoO3. This distortion in CoO6 octahedron is attributed to Jahn-Teller active Co3+ ion in int…
The coupled electronic-structural modulations of the ligand states in IrTe$_2$ have been studied by x-ray absorption spectroscopy (XAS) and resonant elastic x-ray scattering (REXS). Distinctive pre-edge structures are observed at the Te-$M_{4,5}$ (3$d$ $\rightarrow$ 5$p$) absorption edge, indicating the presence of a Te 5$p$-Ir 5$d$ covalent state near the Fermi level. An enhancement of the REXS signal near the Te 3$d$ $\rightarrow$ 5$p$ resonance at the $Q\!=\!(1/5,0,-1/5)$ superlattice reflection is observed below the structural transition temperature $T_s\sim$ 280 K. The analysis of the ene…
The Fe K X-ray absorption near edge structure (XANES) of BaFe2-xCoxAs2 superconductors was investigated. No appreciable alteration in shape or energy position of this edge was observed with Co substitution. This result provides experimental support to previous ab initio calculations in which the extra Co electron is concentrated at the substitute site and do not change the electronic occupation of the Fe ions. Superconductivity may emerge due to bonding modifications induced by the substitute atom that weakens the spin-density-wave ground state by reducing the Fe local moments and/or increasin…
We address the concomitant metal-insulator transition (MIT) and antiferromagnetic ordering in the novel pyrochlore iridate Eu2Ir2O7 by combining x-ray absorption spectroscopy, x-ray and neutron diffractions and density functional theory (DFT) based calculations. The temperature dependent powder x-ray diffraction clearly rules out any change in the lattice symmetry below the MIT, nevertheless a clear anomaly in the Ir-O-Ir bond angle and Ir-O bond length is evident at the onset of MIT. From the x-ray absorption near edge structure (XANES) spectroscopic study of Ir-L3 and L2 edges, the effective…
Ruthenium trichloride is the subject of many recent experimental and theoretical studies. Johnson et al. infer a candidate for the magnetic structure (Cc2/m) from results gathered in an extensive set of experiments on an untwined sample of alpha-RuCl3 [R. D. Johnson et al., Phys. Rev. B 92, 235119 (2015)]. The proposed zigzag antiferromagnetic ground state of Ru ions does not respond to bulk magnetic probes. Properties of the candidate magnetic structure not previously explored include polar magnetism that supports Ru Dirac multipoles, e.g., a ruthenium anapole. In a general case, Dirac dipole…
The electronic structure and the chemical state in Am binary oxides and Am-doped UO$_2$ were studied by means of x-ray absorption spectroscopy at shallow Am core ($4d$ and $5d$) edges. In particular, the Am $5f$ states were probed and the nature of their bonding to the oxygen states was analyzed. The interpretation of the experimental data was supported by the Anderson impurity model (AIM) calculations which took into account the full multiplet structure due to the interaction between $5f$ electrons as well as the interaction with the core hole. The sensitivity of the branching ratio of the Am…
The orbital symmetries of electron doped iron-arsenide superconductors Ba(Fe1-xCox)2As2 have been measured with x-ray absorption spectroscopy. The data reveal signatures of Fe d electron itinerancy, weak electronic correlations, and a high degree of Fe-As hybridization related to the bonding topology of the Fe dxz+yz states, which are found to contribute substantially at the Fermi level. The energies and detailed orbital character of Fe and As derived unoccupied s and d states are found to be in remarkably good agreement with the predictions of standard density functional theory.
