Pressure-induced valence anomaly in TmTe probed by resonant inelastic X-ray scattering

The pressure-induced valence transition in TmTe was investigated by resonant inelastic x-ray scattering at the Tm L3 edge, a powerful probe of the rare-earth valent state. The data are analyzed within the Anderson impurity model which yields key parameters such as the Tm 4f-5d hybridization. In addition to the general tendency of the f electrons towards delocalization, we find a plateau in both the Tm valence and hybridization pressure dependences between 4.3 and 6.5 GPa which is interpreted in terms of an n-channel Kondo (NCK) screening process. This behavior is at odds with the usually continuous, single-channel Kondo-like f delocalization while being supported by the seminal calculations of the NCK temperature in Tm ion by Saso et al. Our study raises the interesting possibility that an NCK effect realized in a compressed mixed-valent f system could impede the concomitant electron delocalization.     

Magnetic circular dichroism in soft X-ray resonant inelastic scattering

We discuss the application of resonant inelastic X-ray scattering to the study of magnetic systems in the soft X-ray range. To this end we distinguish two broad areas. In the first the layout of the experiment is such that the absorption magnetic circular dichroism (MCD) is not zero. In the second the magnetisation is perpendicular to the incident helical beam so that the absorption MCD is zero. In the first area we summarise published results on Fe-Co alloys and we present new data on Mn impurities in Ni together with calculations. In the second area we summarise published results on Ni in Ni-ferrite with final 3s shell excitation and we present new results on Co-metal and Co in Co-ferrite measured with a new approach. This is based on the incident energy dependence of the integral of the Raman spectrum in inner shell excitation (integrated resonant Raman scattering). The potentialities and the limitations of the above methods are critically presented. Received: 23 May 2001 / Accepted: 4 July 2001 / Published online: 5 October 2001     

硫化锰电子结构的软X射线共振非弹性散射研究

利用软X射线共振非弹性散射谱(resonant inelastic soft X-ray scattering, RIXS)对3d过渡金属硫化物中的硫化锰(MnS)电子结构进行了研究.通过分析Mn²⁺的2p⁶3d⁵→2p⁵3d⁶→2p⁶3d⁵二次光子过程，得到了共振非弹性散射谱中的两类非弹性峰，d-d电子跃迁和电荷转移(charge-transfer)跃迁.这两部分跃迁分别共振增强于L边附近及伴随峰附近.基于Hartree-Fock方法的多重态计算分别模拟了原子近似下和立方体O_h对称群下共振非弹性散射谱及吸收谱.计算得MnS实际晶体场10Dq值介于0.80eV—0.85eV之间.对MnS和MnO CT跃迁差异的讨论表明MnS较强的CT跃迁来源于其较窄的能隙宽度. 关键词： 软X射线共振非弹性散射 软X射线吸收谱 d-d跃迁 电荷转移     

Electronic structure of single-wall carbon nanotubes studied by resonant inelastic X-ray scattering

F in the nanotubes, indicating that metallic nanotubes are present in the sample. Received: 2 April 1998     

Many-particle effects in resonant inelastic scattering of an X-ray photon by an atom

The influence of many-particle effects on the shape and values of the double differential cross section for the resonant inelastic scattering of a linearly polarized X-ray photon by a free atom near the K and KL₂₃ ionization thresholds has been theoretically analyzed for the neon atom. The calculations have been performed using the nonrelativistic Hartree-Fock approximation for single-electron wavefunctions and the dipole approximation for the anomalous dispersion component of the cross section. The analytical structure of the contact part of the scattering cross section has been obtained beyond the dipole approximation. The effects of the radial relaxation of electron shells, spin-orbit and multiplet splitting, and configuration interaction in the doubly excited atomic states, as well as the Auger and radiative decays of the produced vacancies, are taken into account. The nature and role of the effect of correlation amplitudes, which is responsible for the appearance of the nonzero amplitudes of nonradiative transitions between intermediate and final single-electron states of the same symmetry that are obtained in different Hartree-Fock fields, have been analyzed also. The calculations are predictive and, for an incident-photon energy of 5.41 keV, agree well with experimental results for the Kα X-ray emission spectrum of the neon atom.     

A wavelength-dispersive X-ray spectrometer for in/ex situ resonant inelastic X-ray scattering studies

A wavelength-dispersive X-ray spectrometer based on von Hamos geometry for in/ex situ resonant inelastic X-ray scattering (RIXS) studies at BL14W1-X-ray absorption fine structure (XAFS) beamline of Shanghai Synchrotron Radiation Facility (SSRF) is reported. The design considerations and the operational characteristics of the spectrometer are described in detail. With a Si(444) bent crystal, the spectrometer provides an energy range from 8 to 9 keV, which enables the measurement of K-edge X-ray spectroscopy of some transition metal complexes and L-edge X-ray spectroscopy of some 5d transition metal complexes. Based on von Hamos geometry, the process of the collection of RIXS is considerably simplified. The collection of full RIXS planes of tungstic samples requiring spectral resolutions is presented, demonstrating the speciation capabilities of the instrument. Taking the series of oxide-derived copper catalysts for carbon dioxide electrochemical reduction as the research model, the in situ RIXS were measured to probe dynamic changes in electronic structure. Finally, the comparison between in situ RIXS and in situ conventional XAFS is presented, demonstrating more competitive spectral resolution of RIXS.     

Multi-k multipole order analyzed by resonant X-ray scattering in the electric quadrupole transition

We introduce a convenient expression of the resonant X-ray scattering (RXS) amplitude, which is appropriate for the investigation of the multipole ordering phase in localized f electron system. The expression is applied to the calculation of the RXS spectra in the electric quadrupole transition around the Np M_2,3 edges from the longitudinal triple-k antiferrooctupolar ordering phase in NpO₂. The results demonstrate a possibility that analyzing the energy profile of the RXS spectrum is effective to identify the type of the order parameter.     

Theory of resonant inelastic X-ray scattering spectrum for Ni impurities in cuprates

We perform the numerically exact diagonalization calculation for small Cu-O clusters with a Ni impurity site, representing the Ni-substituted cuprate, to examine the single-particle excitation spectra as well as the resonant inelastic X-ray scattering (RIXS) spectra. We clarify relations between low-energy electronic structures near the Ni site and excitations seen in the RIXS spectra.     

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.     

Polarization dependence of L- and M-edge resonant inelastic X-ray scattering in transition-metal compounds

The resonant inelastic x-ray scattering (RIXS) cross section at the L and M edges of transition-metal compounds is studied using an effective scattering operator. The intensities of the elastic peak and for spin-flip processes are derived. It is shown how the polarization dependence can be used to select transitions. Comparisons are made with experiment. A detailed analysis of the polarization and angular dependence of L- and M-edge RIXS for divalent copper compounds, such as the high-Tc superconductors, is given.     

Electron correlation effects in resonant inelastic X-ray scattering of NaV2O5

Element- and site-specific resonant inelastic x-ray scattering spectroscopy (RIXS) is employed to investigate electron correlation effects in NaV2O5. In contrast to single photon techniques, RIXS at the vanadium L3 edge is able to probe d-d* transitions between V d-bands. A sharp energy loss feature is observed at -1.56 eV, which is well reproduced by a model calculation including correlation effects. The calculation identifies the loss feature as excitation between the lower and upper Hubbard bands and permits an accurate determination of the Hubbard interaction term U = 3.0 +/- 0.2 eV.     

Charge-orbital ordering and Verwey transition in magnetite measured by resonant soft X-ray scattering

We report experimental evidence for the charge-orbital ordering in magnetite below the Verwey transition temperature T(V). Measurements of O K-edge resonant x-ray scattering on magnetite reveal that the O 2p states in the vicinity of the Fermi level exhibit a charge-orbital ordering along the c axis with a spatial periodicity of the doubled lattice parameter of the undistorted cubic phase. Such a charge-orbital ordering vanishes abruptly above T(V) and exhibits a thermal hysteresis, correlating closely with the Verwey transition in magnetite.     

Momentum‐resolved resonant inelastic X‐ray scattering on a single crystal under high pressure

A single‐crystal momentum‐resolved resonant inelastic X‐ray scattering (RIXS) experiment under high pressure using an originally designed diamond anvil cell (DAC) is reported. The diamond‐in/diamond‐out geometry was adopted with both the incident and scattered beams passing through a 1 mm‐thick diamond. This enabled us to cover wide momentum space keeping the scattering angle condition near 90°. Elastic and inelastic scattering from the diamond was drastically reduced using a pinhole placed after the DAC. Measurement of the momentum‐resolved RIXS spectra of Sr_2.5Ca_11.5Cu₂₄O₄₁ at the Cu K‐edge was thus successful. Though the inelastic intensity becomes weaker by two orders than the ambient pressure, RIXS spectra both at the center and the edge of the Brillouin zone were obtained at 3 GPa and low‐energy electronic excitations of the cuprate were found to change with pressure.     

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.     

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.     

Stationary and dispersive features in resonant inelastic soft X-ray scattering at the Ge 3p resonances

Resonant inelastic soft X-ray scattering at the 3p resonances in crystalline Ge is presented. Both stationary and dispersive features are observed in a wide energy range above as well as below the ionization limits. These observations are in agreement with theoretical predictions based on a two-step model where the initially excited electron has no influence on the emission step. Excess population of states in the conduction band is found, and discussed in terms of attosecond electron dynamics.     

X-ray diffraction investigation of the hexagonal-fcc structural transition in yttrium trihydride under hydrostatic pressure

Pressure induced structural transition of yttrium hydride has been investigated using synchrotron radiation X-ray diffraction measurement up to 24 GPa at room temperature. A reversible hexagonal-fcc transition with a wide intermediate region from 11 to 20 GPa is confirmed, which is consistent with previously reported X-ray results. The diffraction patterns measured for the intermediate state are not interpreted in terms of a hexagonal-fcc coexisting state or as rare-earth structures with various metal-layer stacking sequences. The equation of state determined for the hexagonal-YH₃ provides a bulk modulus B₀ of 71.9 GPa, which is nearly half of the previously reported value, but is within the range of values reported for other rare-earth metal trihydrides with hexagonal structures.