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Intermetallic compounds in the Al–Pt system were systematically studied via hard X-ray photoelectron spectroscopy, focusing on the positions of Pt 4f and Al 2s core levels and valence band features. On one hand, with increasing Al content, the Pt 4f core levels shift towards higher binding energies (BE), revealing the influence of the atomic interactions (chemical bonding) on the electronic state of Pt. On the other hand, the charge transfer from Al to Pt increases with increasing Al content in Al–Pt compounds. These two facts cannot be combined using the standard "chemical shift" approach. Computational analysis reveals that higher negative effective charges of Pt atoms are accompanied by reduced occupancy of Pt 5d orbitals, leading to the limited availability of these electrons for the screening of the 4f core hole and this in turn explains the experimentally observed shift of 4f core levels to higher BE. [ABSTRACT FROM AUTHOR]

For the inelastic electron scattering of atoms and molecules, a consensus has been reached that the first Born approximation is easily approached by decreasing the momentum transfer at the same impact electron energy or increasing the impact electron energy at the same momentum transfer. Although this consensus is applicable for the elastic electron scattering of most atoms and molecules, it is violated for helium where the experimental differential cross sections deviate from the first Born approximation prediction gradually with the decrease of squared momentum transfer at the same impact electron energy. Since this anomalous phenomenon was observed more than 40 years ago, the intrinsic mechanism is not explicit. In the present work, using the high-resolution x-ray scattering, we isolate the scattering contribution from the nucleus and directly obtain the pure electronic structure of helium. Then, the anomalous asymptotic behavior of the elastic electron scattering of helium has been elucidated, i.e., in the small squared momentum transfer region, the scattering contribution from the target's electrons is counteracted by the one from the atomic nucleus, which results in the residual contribution beyond the first Born approximation being drastically enlarged. [ABSTRACT FROM AUTHOR]

Laser-excited N and R fluorescence lines of heavily doped ruby have been studied up to 26 GPa at low temperatures. While the intensity of the R lines at ambient pressure significantly decreases with decreasing temperature, the intensity of N lines originating from exchange-coupled Cr ion pairs is enhanced at low temperatures. The pressure induced wavelength shift of the N lines at 19 K is well fitted with an empirical formula similar to the equation for the R1 line, showing that the intense N line could be used as an alternative pressure scale at low temperatures. We also observe continuous increase in non-hydrostaticity with increasing pressure at low temperatures when silicone oil and 4:1 mixture of methanol and ethanol are used as pressure media. [ABSTRACT FROM AUTHOR]

Semiconducting substances form one of the most important families of functional materials. However, semiconductors containing only metals are very rare. The chemical mechanisms behind their ground‐state properties are only partially understood. Our investigations have rather unexpectedly revealed the semiconducting behaviour (band gap of 190 meV) for the intermetallic compound Be5Pt formed at a very low valence‐electron count. Quantum‐chemical analysis shows strong charge transfer from Be to Pt and reveals a three‐dimensional entity of vertex‐condensed empty Be4 tetrahedrons with multi‐atomic cluster bonds interpenetrated by the framework of Pt‐filled vertex‐condensed Be4 tetrahedrons with two‐atomic polar Be−Pt bonds. The combination of strong Coulomb interactions with relativistic effects results in a band gap. [ABSTRACT FROM AUTHOR]

High-resolution partial-fluorescence-yield X-ray absorption and resonant X-ray emission spectra were used to characterize the temperature dependence of Sm 4f configurations and orbital/charge degree of freedom in SmB6. The variation of Sm 4f configurations responds well to the formed Kondo gap, below 140 K, and an in-gap state, below 40 K. The topological in-gap state is correlated with the fluctuating population of Sm 4f configurations that arises via carrier transfer between 3d94f6 and 3d94f5 states; both states are partially delocalized, and the mediating 5d orbital plays the role of a transfer path. Complementary results shown in this work thus manifest the importance of configuration fluctuations and orbital delocalization in the topological surface state of SmB6. [ABSTRACT FROM AUTHOR]

A layered Sr2Co0.5Ir0.5O4 (space group I4/ mmm) perovskite of the K2NiF4 structure type was synthesized as a single-phase sample. Neutron powder diffraction measurements revealed full site occupancy of oxygen atoms. The Co3+/Ir5+ valence states were evaluated by a combination of X-ray absorption and X-ray photoemission spectroscopy as well as by magnetization measurements, and thus the differences to the parent compounds Sr2CoO4 and Sr2IrO4 with similar structures were confirmed. Co- K edge EXAFS studies indicated a long average Co-O distance of 1.967 Å suggesting a high-spin state of the Co3+ ion in Sr2Co0.5Ir0.5O4. No long-range magnetic ordering down to 4 K was detected by neutron powder diffraction, probably hindered by the random distribution of Co and Ir cations in the Sr2Co0.5Ir0.5O4 structure. High-pressure synchrotron powder diffraction studies showed stability of the Sr2Co0.5Ir0.5O4 structure up to at least 27 GPa at room temperature. A maximum in the c/a ratio at 10 GPa together with an anomaly in the pressure dependence of the unit-cell volume could be a sign of a change in the spin state of the Co ions under pressure. [ABSTRACT FROM AUTHOR]

In this study an analysis strategy towards using the resonant inelastic X-ray scattering (RIXS) technique more effectively compared with X-ray absorption spectroscopy (XAS) is presented. In particular, the question of when RIXS brings extra information compared with XAS is addressed. To answer this question the RIXS plane is analysed using two models: (i) an exciton model and (ii) a continuum model. The continuum model describes the dipole pre-edge excitations while the exciton model describes the quadrupole excitations. Applying our approach to the experimental 1 s2 p RIXS planes of VO2 and TiO2, it is shown that only in the case of quadrupole excitations being present is additional information gained by RIXS compared with XAS. Combining this knowledge with methods to calculate the dipole contribution in XAS measurements gives scientists the opportunity to plan more effective experiments. [ABSTRACT FROM AUTHOR]

The observed heavy-hole, light-hole and split-off band edges of a semiconductor are the well known consequence of two physical processes: atomic spin–orbital interaction and solid-state band–band anticrossing. In this work, we examined the four band-edge-like bands in great detail within the Ge space–charge layer with either Pb/Ge(111)- R30° or a 2 ML Pb film on Ge(111). Our results reveal that the conventional picture of band edges for a semiconductor is actually crude. In addition, momentum-dependent Rashba splitting effect can be included to explain the observed non-split-off band, indicating the Rashba effect as an intrinsic property near a semiconductor surface. [ABSTRACT FROM AUTHOR]

The epitaxial growth of Cu on Ag(111) was explored on monitoring the evolution of its surface states with angle-resolved photoemission spectroscopy; the chemical element on the top of Cu islands on Ag(111) with a (9×9) reconstruction was determined to be not Cu but Ag. Our result demonstrates a technique with which the chemical property associated with a surface state is explorable and an identification of the chemical element in the topmost layer of the surface becomes feasible. [ABSTRACT FROM AUTHOR]

We report a technique to determine the coverage of metallic thin films by analyzing layer-resolved surface states with photoemission by using atomically flat Ag/Au(111) thin films as a test system. We analyzed the surface state on Au(111) covered with Ag up to 4 ML with atomic resolution, and precisely determined the total Ag coverage of Ag/Au(111) through a line-shape analysis. With precise measurements of the absolute coverage of thin films becoming possible, one can calibrate the tooling factor of evaporators with unprecedented accuracy. [ABSTRACT FROM AUTHOR]

The structural characteristics of organically passivated CdSe nanocrystals (NCs) were investigated with x-ray diffraction and extended x-ray absorption fine structure. As the NC size decreases, the axial bond length R(1) for an atomic tetrahedron extends but the equatorial bond length R(2) contracts, with a similar tendency of distortion for the lattice parameters of the wurtzite structure. The authors suggest that the observed hexagonal distortion is attributed to the surface stress of the NCs related to the organic passivation effect and the relaxation of atomic positions at the stacking fault interface. [ABSTRACT FROM AUTHOR]

A topological insulator (TI) is a quantum material in a new class with attractive properties for physical and technological applications. Here we derive the electronic structure of highly crystalline Sb2Te2Se single crystals studied with angle-resolved photoemission spectra. The result of band mapping reveals that the Sb2Te2Se compound behaves as a p-type semiconductor and has an isolated Dirac cone of a topological surface state, which is highly favored for spintronic and thermoelectric devices because of the dissipation-less surface state and the decreased scattering from bulk bands. More importantly, the topological surface state and doping level in Sb2Te2Se are difficult to alter for a cleaved surface exposed to air; the robustness of the topological surface state defined in our data indicates that this Sb2Te2Se compound has a great potential for future atmospheric applications. [ABSTRACT FROM AUTHOR]

Topological insulators (TIs) are interesting quantum matters that have a narrow bandgap for bulk and a Dirac-cone-like conducting surface state (SS). The recent discovered second Dirac surface state (SS) and bulk bands (BBs) located ~1.5 eV above the first SS are important for optical coupling in TIs. Here, we report on the time-domain measurements of THz radiation generated from TIs n-type Cu0.02Bi2Se3 and p-type Bi2Te3 single crystals by ultrafast optical pulse excitation. The observed polarity-reversal of the THz pulse originated from transient current is unusual, and cannot be reconciled with the photo-Dember effect. The second SS and BBs are found to be indispensable for the explanation of the unusual phenomenon. Thanks to the existence of the second SS and BBs, TIs manifest an effective wide band gap in THz generation. The present study demonstrates that time-domain THz spectroscopy provide rich information of the optical coupling and the electronic structure of TIs. [ABSTRACT FROM AUTHOR]

Highly ordered Ag films grown on cleaved mica with a two-step procedure were characterized in detail with several techniques for surface analysis, including low-energy electron diffraction, X-ray photoemission spectra, a scanning tunneling microscope and angle-resolved photoemission spectra. Silver films of a thickness ≥ 100 nm were deposited on mica substrates at 300 K and stored under ambient conditions. The Ag/mica films became atomically flat and free of contamination when they were transferred into ultra-high vacuum and prepared with sputtering and annealing. The experimental results indicate that the surfaces of the cleaned Ag/mica films have structural and electronic properties resembling those of a Ag(111) single crystal with ordered domains aligned over a macroscopic region, but the surfaces of the Ag/mica films became rough on annealing above 623 K. On the rough surfaces, the surface steps tended to bunch together, yielding flat terraces bound with steps of large heights. With the decreased thermal stability in mind, the Ag/mica film is adoptable as a cheap platform alternative to a Ag(111) single crystal for the growth of highly ordered overlayers. [ABSTRACT FROM AUTHOR]

A layered Sr2Co0.5Ir0.5O4 (space group I4/ mmm) perovskite of the K2NiF4 structure type was synthesized as a single-phase sample. Neutron powder diffraction measurements revealed full site occupancy of oxygen atoms. The Co3+/Ir5+ valence states were evaluated by a combination of X-ray absorption and X-ray photoemission spectroscopy as well as by magnetization measurements, and thus the differences to the parent compounds Sr2CoO4 and Sr2IrO4 with similar structures were confirmed. Co- K edge EXAFS studies indicated a long average Co-O distance of 1.967 Å suggesting a high-spin state of the Co3+ ion in Sr2Co0.5Ir0.5O4. No long-range magnetic ordering down to 4 K was detected by neutron powder diffraction, probably hindered by the random distribution of Co and Ir cations in the Sr2Co0.5Ir0.5O4 structure. High-pressure synchrotron powder diffraction studies showed stability of the Sr2Co0.5Ir0.5O4 structure up to at least 27 GPa at room temperature. A maximum in the c/a ratio at 10 GPa together with an anomaly in the pressure dependence of the unit-cell volume could be a sign of a change in the spin state of the Co ions under pressure. [ABSTRACT FROM AUTHOR]

An exfoliated Kish graphite sample on a heavily n -doped Si substrate covered with native oxide was prepared with a conventional micromechanical cleavage method. From angle-resolved photoemission spectra (ARPES), we measured the band structure of graphite over photon energies from 28 eV to 116 eV. The inner potential V 0 = 17.25 eV is determined with a period from the band dispersion in the KH direction. A set of parameters in the tight-binding method and the SWMcC model for graphite is extracted from the fitted results. A comparison of constant-energy mapping results at large binding energy indicates the reliability of the tight-binding parameters extracted from the ARPES results. [ABSTRACT FROM AUTHOR]

The growth of Cu on Ag(1 1 1) under varied growth conditions was investigated with angle-resolved photoemission spectra. The evolution of Cu/Ag(1 1 1) during annealing was characterized on monitoring its surface states. The surface morphology of a Cu film on Ag(1 1 1) depends on the temperature and the Cu coverage. Islands or crystalline films develop when Cu is deposited at ∼300 K. Defects in the Cu films penetrate deeply into the Ag(1 1 1) substrate and expose the Ag(1 1 1) surface. The deposition of Cu at a low temperature results in disordered films. On annealing, the films become ordered with defects. Our results show the segregation of Ag on the Cu surface, which occurs at 300 K and becomes accelerated significantly at ∼380 K. After being annealed above 430 K, all islands and films of Cu are fully covered with Ag, showing a (9 × 9) reconstruction. Our results indicate also that the segregation of Ag on the Cu surface occurs only after the Ag(1 1 1) surface is exposed, indicating that Ag atoms migrate to the Cu(1 1 1) surface, not through bulk Cu, but along the walls of the islands and the defects in the films. [ABSTRACT FROM AUTHOR]

Abstract: The spin transition and substitution of Fe3+ in Mg0.85Fe3+ 0.15Al0.15Si0.85O3 post-Mg-perovskite (PPv) synthesized at 165–170GPa, 2100K were examined by X-ray emission spectroscopy (XES) and X-ray diffraction (XRD) during decompression to 37GPa without annealing. XRD showed that samples were single phase PPv down to 49GPa, although the samples may have partly become amorphous. The result of XES measurement indicates that Fe3+ is fully low spin (LS) for 165–100GPa and Fe3+ largely changes from LS to high spin (HS) between 80 and ∼40GPa. These results combined with previous reports indicate that Al and LS Fe3+ may occupy the A-(dodecahedral) and B-(octahedral) sites, respectively, as the favorable cation sites for 165–100GPa in Al-bearing PPv. Based on the present results on Fe3+ and recent theoretical reports on Fe2+, the spin states of iron in lower mantle PPv are discussed. [Copyright &y& Elsevier]

To investigate the surface diffusion of chemisorbed H on Ag/Au(lll) thin films with surface steps, we characterized the distribution of H atoms on the surface by measuring the Shockley states of these surfaces with angle-resolved photoelectron spectroscopy. Our results show that H atoms tend to diffuse and to remain on the terrace at the lower side of the surface steps during annealing. This diffusive behavior is explained qualitatively through the existence of an Ehrlich-Schwoebel potential barrier associated with the surface steps. [ABSTRACT FROM AUTHOR]

We performed an x-ray spectroscopic study combining resonant x-ray emission spectroscopy (RXES) and photoelectron spectroscopy on the superconducting ternary silicide YbGa1.15Si0.85 and nonsuperconducting ternary germanide YbGaxGe2-x (x = 1.0 and 1.1). The Yb valence for all three compounds is found to be about 2.3. In YbGa1.15Si0.85 no temperature dependence of the Yb valence is observed in the RXES spectra in the temperature range of 7–300 K, while the valence shows a drastic increase under pressure from the Yb2+ state partially including itinerant electrons to the localized Yb3+ state. Differences are observed in the valence-band spectra of the photoelectron spectroscopy between YbGa1.15Si0.85 and YbGaxGe2-x, which may be attributed to the difference of crystal structure. We conclude that both the crystal structure of the planar GaSi layer in YbGa1.15Si0.85 and the resultant electronic structure may have a crucial role in the occurrence of superconductivity. [ABSTRACT FROM AUTHOR]

CeRh_{2}As_{2} is a new multiphase superconductor with strong suggestions for an additional itinerant multipolar ordered phase. The modeling of the low-temperature properties of this heavy-fermion compound requires a quartet Ce^{3+} crystal-field ground state. Here, we provide the evidence for the formation of such a quartet state using x-ray spectroscopy. Core-level photoelectron and x-ray absorption spectroscopy confirm the presence of Kondo hybridization in CeRh_{2}As_{2}. The temperature dependence of the linear dichroism unambiguously reveals the impact of Kondo physics for coupling the Kramer's doublets into an effective quasiquartet. Nonresonant inelastic x-ray scattering data find that the |Γ_{7}^{-}⟩ state with its lobes along the 110 direction of the tetragonal structure (xy orientation) contributes most to the multiorbital ground state of CeRh_{2}As_{2}.