Localized electronic excitations in NiO studied with resonant inelastic X-Ray scattering at the Ni M threshold: evidence of spin flip

We studied the neutral electronic excitations of NiO localized at the Ni sites by measuring the resonant inelastic x-ray scattering (RIXS) spectra at the Ni M2,3 edges. The good energy resolution allows an unambiguous identification of several spectral features due to excitations. The dependence of the RIXS spectra on the excitation energy gives evidence of local spin flip and yields a value of 125 +/- 15 meV for the antiferromagnetic exchange interaction. Accurate crystal field parameters are also obtained.     

Electronic excitations in hole-doped La1−xSrxMnO3 studied by resonant inelastic X-ray scattering

We report a resonant inelastic X-ray scattering (RIXS) study on perovskite manganese oxides La_1−xSr_xMnO₃ (x=0, 0.2, and 0.4) at Mn K-absorption edge. Hole-doping effect on the electronic excitations in the strongly correlated electron systems is elucidated by comparing with undoped LaMnO₃. The scattering spectra of metallic La_0.6Sr_0.4MnO₃ show that a salient peak appears in low energies indicating the persistence of the Mott gap. At the same time, the energy gap is partly filled by doping holes and the spectral weight shifts toward lower energies. Though the peak position of the excitations shows weak dispersion in momentum dependence, RIXS intensity changes as a function of the scattering angle (2θ), which is related to the anisotropy. Furthermore, anisotropic temperature dependence is observed in La_0.8Sr_0.2MnO₃ which shows a metal-insulator transition associated with a ferromagnetic transition. We consider that the anisotropy in the RIXS spectra is possibly attributed to the correlation of the orbital degrees of freedom. The anisotropy is large in LaMnO₃ with long-range orbital order, while it is small but finite in hole-doped La_1−xSr_xMnO₃ which indicates persistence of short-range orbital correlation.     

Spectator and participator processes in the resonant photon-in and photon-out spectra at the Ce L3 edge of CeO2

We study both theoretically and experimentally the photon-in and photon-out spectra of CeO₂, which are caused by the Ce 2p to Ce 5d excitation followed by the three different de-excitation channels: (i) Ce 3d to Ce 2p (denoted by 3d-RXES), (ii) O 2p to Ce 2p (v-RXES), and (iii) Ce 5d to Ce 2p (RIXS). In 3d- and v-RXES, the 5d electron plays a role of a spectator, but in RIXS it is a participator. By extending our single impurity Anderson model (SIAM), which was used recently for our calculations of v- and 3d-RXES spectra of CeO₂, we study the polarization dependence in the spectator and participator spectra, and we perform more detailed calculations for 3d- and v-RXES spectral features, as well as new calculations for the RIXS spectrum with charge transfer excitations. The polarization dependence is different for the spectator and participator spectra; we have no polarization correlation between the incident and emitted photons for the spectator spectra but a strong polarization correlation for the participator spectrum. The theoretical calculations predict that the charge transfer excitations in RIXS occur in the transfer-energy range overlapped with v-RXES, but the RIXS and v-RXES spectra can be discriminated by taking advantage of the different polarization dependence. The overlapped RIXS and v-RXES spectra are observed successfully by our experiments and well reproduced by our SIAM calculations.     

d-d excitations in manganites probed by resonant inelastic x-ray scattering

We report a study of electronic excitations in manganites exhibiting a range of ground states, using resonant inelastic x-ray scattering (RIXS) at the Mn K edge. Excitations with temperature dependent changes correlated with the magnetism were observed as high as 10 eV. By calculating Wannier functions, and finite-q response functions, we associate this dependence with intersite d-d excitations. The calculated dynamical structure factor is found to be similar to the RIXS spectra.     

Resonant inelastic X-ray scattering (RIXS) spectroscopy at the Mn K absorption pre-edge—a direct probe of the 3d orbitals

A study of the Mn K absorption pre-edges in oxides using resonant inelastic X-ray scattering (RIXS) spectroscopy is presented. The energy transfer dimension enhances the separation of the pre-edge (predominantly 1s to 3d transitions) from the main K-edge and a detailed analysis is thus possible. The RIXS spectra are sensitive to the Mn spin state. The technique thus yields detailed information on the electronic structure that is not accessible in conventional K-edge absorption spectroscopy. The line splittings can be understood within a ligand field multiplet model, showing the importance of (2p,3d) two-electron interactions that give rise to the spin-sensitivity.     

The sub-bandgap energy loss satellites in the RIXS spectra of beryllium compounds

Resonant X-ray inelastic scattering spectra have been measured in BeO, phenakite (Be₂SiO₄) and chrysoberyl (BeAl₂O₄) with the excitation energy near the beryllium K edge.The RIXS spectra excited in the vicinity of the Be 1s core resonance show two principal features: the scattering on a valence excitation (which at higher excitation energies verges into the characteristic K_α emission), and a remarkably strong energy loss sideband to the elastic scattering peak. The energy loss shoulder appears to result from lattice relaxation in the absorption site. The comparison of the RIXS spectra of phenakite, chrysoberyl and BeO shows that the strength of the low energy sideband differs greatly; it is strongest in BeO and weakest in phenakite. The Si 2p RIXS spectra of phenakite also display a similar strong sub-bandgap energy loss tail.To gain further insight to this process, transitions in a system with a single vibrational mode have been modelled. The phonon relaxation has been simulated empirically by “smearing” the photoabsortion-populated vibrational levels with lower levels. This simple model is able to qualitatively explain this wide energy loss shoulder.     

Polarization dependence of resonant inelastic X-ray scattering spectroscopy in correlated electron systems

Resonant inelastic X-ray scattering (RIXS) at the transition-metal K-edge is studied as a tool to detect the electronic structure in correlated electron systems. We, in particular, focus on the polarization dependence of RIXS intensity and symmetry of the electronic excitations. It is shown that by analyzing the polarization of the initial and scattered X-rays, the symmetry of the 4p orbitals are selected. Combined effects of the polarization of X-rays and the momentum transfer in the scattering are also studied.     

Low energy electronic excitations in the layered cuprates studied by copper L3 resonant inelastic x-ray scattering

We have measured the resonant inelastic x-ray scattering (RIXS) spectra at the Cu L3 edge in a variety of cuprates. Exploiting a considerably improved energy resolution (0.8 eV) we recorded significant dependencies on the sample composition and orientation, on the scattering geometry, and on the incident photon polarization. The RIXS final states correspond to two families of electronic excitations, having local (dd excitations) and nonlocal (charge-transfer) character. The dd energy splitting can be estimated with a simple crystal field model. The RIXS at the L3 edge demonstrates here a great potential, thanks to the resonance strength and to the large 2p spin-orbit splitting.     

Selective XANES spectroscopy from RIXS contour maps

Kβ resonant inelastic X-ray scattering (RIXS) spectra of Mn and Ga compounds are studied to examine different types of selective XANES. RIXS spectra of MnO in Mn Kβ_1,3 region and of GaCl₂ in Ga Kβ₂ region are plotted as contour maps over wide energy ranges in both excitation and emission. Through analyses of RIXS contour maps by the use of the Kramers-Heisenberg equation, spin-selective XANES spectra are deduced for MnO. In the case of a mixed valence compound GaCl₂ selective XANES of Ga³⁺ ion can be obtained by making use of a large difference in transition probabilities.     

Collapse of the magnetic gap of cuprate superconductors within a three-band model of resonant inelastic x-ray scattering

We present a three-band Hubbard Hamiltonian and the associated Cu Kappa-edge resonant inelastic x-ray scattering (RIXS) spectra for electron- and hole-doped cuprates over a wide range of energy and momentum transfers. By comparing computed spectra for the unfilled case with the corresponding results for 15% electron or hole doping at two different values of the effective Hubbard parameter , generic signatures of the collapse of the magnetic gap and the characteristic momentum dependencies and evolution of the spectra with doping are identified. Available RIXS data support the gap collapse scenario for electron-doped cuprates, but the situation in hole-doped systems is found to be less clear.     

Resonant inelastic x-ray scattering at the oxygen K resonance of NiO: nonlocal charge transfer and double-singlet excitations

We report high-resolution polarization-dependent resonant inelastic x-ray scattering (RIXS) at the O K resonance of NiO showing a rich excitation spectrum. We perform multisite Ni6O19 cluster model calculations, revealing that solid state effects are substantial. We identify a nonlocal charge transfer excitation at 4-5 eV and double-singlet creation at 1.75 eV, both exhibiting significant scattering geometry dependence. Apart from an intense band of local charge transfer excitations (above 5 eV) also dd excitations at 1 eV are observed. Finally, we point out that O K RIXS of correlated metal oxides allows a quantitative and consistent determination of the charge transfer energy delta and the Hund coupling energy J(H).     

Crystal field and low energy excitations measured by high resolution RIXS at the L3 edge of Cu, Ni and Mn

Resonant inelastic x-ray scattering in the soft x-ray regime has been profiting much from technical advances that have lowered considerably the instru- mental linewidth. At the ADRESS beam line of the Swiss Light Source the SAXES spectrometer can be used to measure RIXS spectra at the L edges of the 3d transition metals with unprecedented energy resolution, of the order of 100 meV for Mn, Ni and Cu. We present here some preliminary spectra on CuO, malachite, NiO, NiCl₂, MnO and LaMnO₃. The dd excitations are very well resolved allowing accurate experimental evaluation of 3d state energy splitting. The low energy scale becomes accessible opening the way to the study of collective excitations in strongly correlated electron systems, like magnons and orbitons.     

Momentum dependence of charge excitations in the electron-doped superconductor Nd1.85 Ce0.15 CuO4: a resonant inelastic x-ray scattering study

We report a resonant inelastic x-ray scattering (RIXS) study of charge excitations in the electron-doped high-T(c) superconductor Nd1.85 Ce0.15 CuO4. The intraband and interband excitations across the Fermi energy are separated for the first time by tuning the experimental conditions properly to measure charge excitations at low energy. A dispersion relation with q-dependent width emerges clearly in the intraband excitation, while the intensity of the interband excitation is concentrated around 2 eV near the zone center. The experimental results are consistent with theoretical calculation of the RIXS spectra based on the Hubbard model.     

Temperature dependence of the electronic structure of Sr14Cu24O41 studied by resonant inelastic X-ray scattering

We report a resonant inelastic X-ray scattering (RIXS) study of charge excitations in the two-leg ladder Sr₁₄Cu₂₄O₄₁. RIXS spectra at 1–5 eV are found to be dependent on temperature. An intraband excitation of the ladder, which appears as a continuum intensity below the Mott gap, decreases in intensity with temperature. Because the intraband excitation is related to the dynamics of doped holes in the ladder, its decrease of the intraband excitation is attributed to the reduction of the mobile holes in the ladder at low temperature.     

Spatial quantum beats in vibrational resonant inelastic soft x-ray scattering at dissociating states in oxygen

Resonant inelastic soft x-ray scattering (RIXS) spectra excited at the 1σ(g) → 3σ(u) resonance in gas-phase O2 show excitations due to the nuclear degrees of freedom with up to 35 well-resolved discrete vibronic states and a continuum due to the kinetic energy distribution of the separated atoms. The RIXS profile demonstrates spatial quantum beats caused by two interfering wave packets with different momenta as the atoms separate. Thomson scattering strongly affects both the spectral profile and the scattering anisotropy.     

Optical properties of sol-gel fabricated Ni/SiO2 glass nanocomposites

Nickel nanoparticles were grown in silica glass by annealing of the sol-gel prepared silicate matrices doped with nickel nitrate. TEM characterization of Ni/SiO₂ glass proves the formation of isolated spherical nickel nanoparticles with mean sizes 6.7 and 20 nm depending on annealing conditions. The absorption and photoluminescence spectra of Ni/SiO₂ glasses were measured. In the absorption spectra, we observed the band related to the surface plasmon resonance (SPR) in Ni nanoparticles. The broadening of SPR was observed with decrease of Ni nanoparticle size. The width of the surface plasmon band decreases 1.5 times at the lowering of temperature from 293 to 2 K because of strong electron-phonon interaction. The spectra proved the creation of nickel oxide NiO clusters and Ni²⁺ ions in silica glass as well.     

Spin-exchange dynamical structure factor of the S=1/2 Heisenberg chain

We determine the spin-exchange dynamical structure factor of the Heisenberg spin chain, as is measured by indirect resonant inelastic x-ray scattering (RIXS). We find that two-spin RIXS excitations nearly entirely fractionalize into two-spinon states. These share the same continuum lower bound as single-spin neutron scattering excitations, even if the relevant final states belong to orthogonal symmetry sectors. The RIXS spectral weight is mainly carried by higher-energy excitations, and is beyond the reach of the low-energy effective theories of Luttinger liquid type.     

A first-principles theoretical simulation on the electronic structures and optical absorption properties for O vacancy and Ni impurity in TiO2 photocatalysts

The band structures and optical absorption spectra of O vacancy and Ni ion doped anatase TiO₂ were successfully calculated and simulated by a plane wave pseudopotential method based on density functional theory (DFT). From the calculated results, a phenomenon of “impurity compensation” was found: the lower formation energy for O vacancy than Ni impurity indicated that introducing the intrinsic defect of O vacancy into Ni ion doped TiO₂ sample was very possible; the positive binding energy for the combination of O vacancy and Ni impurity indicated that two defects were apt to bind to each other; While Ni impurity produced the donor levels in the forbidden band of TiO₂, Ni impurity with O vacancy produced the acceptor levels upon which the excitation led to the photogenerated electrons with high energy and transferability. The combination of absorption spectra for O vacancy and Ni impurity with O vacancy models could reproduce the experimental measurement very well.     

Probing the transition in bulk Ce under pressure: a direct investigation by resonant inelastic X-ray scattering

We report on the most complete investigation to date of the -electron properties at the transition in elemental Ce by resonant inelastic x-ray scattering (RIXS). The Ce 2p3d-RIXS spectra were measured directly in the bulk material as a function of pressure through the transition. The spectra were simulated within the Anderson impurity model. The occupation number n(f) and f double occupancy were derived from the calculations in both gamma and alpha phases in the ground state. We find that the electronic structure changes result mainly from band formation of 4f electrons which concurs with reduced electron correlation and increased Kondo screening at high pressure.     

Charge-transfer excitations in the model superconductor HgBa(2)CuO(4+delta)

We report a Cu -edge resonant inelastic x-ray scattering (RIXS) study of charge-transfer excitations in the 2-8 eV range in the structurally simple compound HgBa(2)CuO(4+delta) at optimal doping (T(c)=96.5 K). The spectra exhibit a significant dependence on the incident photon energy which we carefully utilize to resolve a multiplet of weakly dispersive (<0.5 eV) electron-hole excitations, including a mode at 2 eV. The observation of this 2 eV excitation suggests the existence of a remnant charge-transfer gap deep in the superconducting phase. Quite generally, our results, which include additional data for the Mott insulator La(2)CuO(4), demonstrate the importance of exploring the incident photon-energy dependence of the RIXS cross section.