Influence of crystal structure, ligand environment and morphology on Co L-edge XAS spectral characteristics in cobalt compounds.

The electronic structure of a material plays an important role in its functionality for different applications which can be probed using synchrotron-based spectroscopy techniques. Here, various cobalt-based compounds, differing in crystal structure, ligands surrounding the central metal ion and morphology, have been studied by soft X-ray absorption spectroscopy (XAS) at the Co L-edge in order to measure the effect of these parameters on the electronic structure. A careful qualitative analysis of the spectral branching ratio and relative intensities of the L3 and L2 peaks provide useful insight into the electronic properties of compounds such as CoO/Co(OH)2, CoCl2.6H2O/CoF2.4H2O, CoCl2/CoF2, Co3O4 (bulk/nano/micro). For further detailed analysis of the XAS spectra, quantitative analysis has been performed by fitting the spectral profile with simulated spectra for a number of cobalt compounds using crystal field atomic multiplet calculations.

Effects of rare-earth size on the electronic structure of La1−xLuxVO3.

The electronic structure of La(1-x)Lu(x)VO(3)(x = 0, 0.2, 0.6 and 1) single crystals has been investigated using soft x-ray absorption spectroscopy, soft x-ray emission spectroscopy, and resonant soft x-ray inelastic scattering to study the effects of rare-earth size. The x-ray absorption and emission spectra at the O K-edge present a progressive evolution with R-site cation, in agreement with local spin density approximation calculations. This evolution with R, together with the temperature dependence of the O K-edge spectra, is attributed to changes in the crystal structure of La(1-x)Lu(x)VO(3). The crystal-field dd. excitations probed by resonant inelastic x-ray scattering at the V L(3)-edge exhibit an increase in energy and enhanced intensity with the decrease of R-site ionic radius, which is mainly attributed to the increased tilting magnitude of the VO(6) octahedra. Upon cooling to ~95 K, the dd* excitations are prominently enhanced in relative Intensity, in agreement with the formation of the Jahn.Teller distortion int he orbital ordering phase. Additionally, the dd* transitions of the mixed compounds are noticeably suppressed with respect to those of the pure compounds, possibly owing to the formation of C-type orbital ordering induced by large R-site size variances.

Low-energy V t2g orbital excitations in NdVO3.

The electronic structure of NdVO(3) and YVO(3) has been investigated as a function of sample temperature using resonant inelastic soft x-ray scattering at the V L(3)-edge. Most of the observed spectral features are in good agreement with an atomic crystal-field multiplet model. However, a low energy feature is observed at ∼ 0.4 eV that cannot be explained by crystal-field arguments. The resonant behaviour of this feature establishes it as due to excitations of the V t(2g) states. Moreover, this feature exhibits a strong sample temperature dependence, reaching maximum intensity in the orbitally-ordered phase of NdVO(3), before becoming suppressed at low temperatures. This behaviour indicates that the origin of this feature is a collective orbital excitation, i.e. the bi-orbiton.

The band structure of WO3 and non-rigid-band behaviour in Na0.67WO3 derived from soft x-ray spectroscopy and density functional theory.

The electronic structure of single-crystal WO3 and Na0.67WO3 (a sodium-tungsten bronze) has been measured using soft x-ray absorption and resonant soft x-ray emission oxygen K-edge spectroscopies. The spectral features show clear differences in energy and intensity between WO3 and Na0.67WO3. The x-ray emission spectrum of metallic Na0.67WO3 terminates in a distinct Fermi edge. The rigid-band model fails to explain the electronic structure of Na0.67WO3 in terms of a simple addition of electrons to the conduction band of WO3. Instead, Na bonding and Na 3s-O 2p hybridization need to be considered for the sodium-tungsten bronze, along with occupation of the bottom of the conduction band. Furthermore, the anisotropy in the band structure of monoclinic γ-WO3 revealed by the experimental spectra with orbital-resolved geometry is explained via density functional theory calculations. For γ-WO3 itself, good agreement is found between the experimental O K-edge spectra and the theoretical partial density of states of O 2p orbitals. Indirect and direct bandgaps of insulating WO3 are determined from extrapolating separations between spectral leading edges and accounting for the core-hole energy shift in the absorption process. The O 2p non-bonding states show upward band dispersion as a function of incident photon energy for both compounds, which is explained using the calculated band structure and experimental geometry.

Electronic excitations in the correlated metal BaV(0.98)Ti(0.02)S(3) studied using resonant inelastic soft x-ray scattering.

Electronic excitations in the correlated metal BaTi(0.02)V(0.98)S(3) have been studied using resonant inelastic soft x-ray scattering at the V L edge. The intensities of the intra-atomic d-d(*) excitations and the elastic x-ray scattering feature are found to be temperature dependent, with the intensity increasing with decreasing temperature until saturation is reached near 100 K. The behavior of the spectral features is interpreted as evidence of a shift in the 3d electrons from more band-like states at higher temperature to more localized states at low temperature.

Comment on "Near-edge X-ray absorption fine-structure investigation of graphene".

A Comment on the Letter by D. Pacilé et al., Phys. Rev. Lett. 101, 066806 (2008)10.1103/PhysRevLett.101.066806. The authors of the Letter offer a Reply.

X-ray spectroscopic study of the charge state and local ordering of room-temperature ferromagnetic Mn-doped ZnO.

The charge state and local ordering of Mn doped into a pulsed laser deposited single-phase thin film of ZnO are investigated by using x-ray absorption spectroscopy at the O K-edge, Mn K-edge and L-edge, and x-ray emission spectroscopy at the O K-edge and Mn L-edge. This film is ferromagnetic at room temperature. EXAFS measurement shows that Mn(2+) replaces the Zn site in tetrahedral symmetry, and there is no evidence for either metallic Mn or MnO in the film. Upon Mn doping, the top of O 2p valence band extends into the bandgap, indicating additional charge carriers being created.

Electronic origins of structural distortions in post-transition metal oxides: experimental and theoretical evidence for a revision of the lone pair model.

Structural distortions in post-transition metal oxides are often explained in terms of the influence of sp hybrid "lone pairs." Evidence is presented here showing that this model must be revised. The electronic structures of prototypically distorted alpha-PbO and alpha-Bi2O3 have been measured by high-resolution x-ray photoemission and soft x-ray emission spectroscopies. In contrast with the expectations of the lone pair model, a high density of metal 6s states is observed at the bottom of the valence band. The measurements are consistent with the results of density functional theory calculations.

Quasiparticle spectra, charge-density waves, superconductivity, and electron-phonon coupling in 2H-NbSe2.

High-resolution photoemission has been used to study the electronic structure of the charge-density wave (CDW) and superconducting dichalcogenide, 2H-NbSe2. From the extracted self-energies, important components of the quasiparticle interactions have been identified. In contrast to previously studied TaSe2, the CDW transition does not affect the electronic properties significantly. The electron-phonon coupling is identified as a dominant contribution to the quasiparticle self-energy and is shown to be very anisotropic (k dependent) and much stronger than in TaSe2.