Al-Pt intermetallic compounds: HAXPES study.

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.

Two types of magnetic shape-memory effects from twinned microstructure and magneto-structural coupling in Fe1+y Te.

A detailed experimental investigation of Fe1+y Te (y = 0.11, 0.12) using pulsed magnetic fields up to 60 T confirms remarkable magnetic shape-memory (MSM) effects. These effects result from magnetoelastic transformation processes in the low-temperature antiferromagnetic state of these materials. The observation of modulated and finely twinned microstructure at the nanoscale through scanning tunneling microscopy establishes a behavior similar to that of thermoelastic martensite. We identified the observed, elegant hierarchical twinning pattern of monoclinic crystallographic domains as an ideal realization of crossing twin bands. The antiferromagnetism of the monoclinic ground state allows for a magnetic-field-induced reorientation of these twin variants by the motion of one type of twin boundaries. At sufficiently high magnetic fields, we observed a second isothermal transformation process with large hysteresis for different directions of applied field. This gives rise to a second MSM effect caused by a phase transition back to the field-polarized tetragonal lattice state.

Interplay of Atomic Interactions in the Intermetallic Semiconductor Be5 Pt.

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 Be5 Pt 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.

Discovery of a superhard iron tetraboride superconductor.

Single crystals of novel orthorhombic (space group Pnnm) iron tetraboride FeB4 were synthesized at pressures above 8 GPa and high temperatures. Magnetic susceptibility and heat capacity measurements demonstrate bulk superconductivity below 2.9 K. The putative isotope effect on the superconducting critical temperature and the analysis of specific heat data indicate that the superconductivity in FeB4 is likely phonon mediated, which is rare for Fe-based superconductors. The discovered iron tetraboride is highly incompressible and has the nanoindentation hardness of 62(5) GPa; thus, it opens a new class of highly desirable materials combining advanced mechanical properties and superconductivity.

New antiferromagnetic perovskite CaCo3V4O12 prepared at high-pressure and high-temperature conditions.

A new perovskite, CaCo(2+)3V(4+)4O12, has been synthesized at high-pressure and high-temperature (HP-HT) conditions. The properties of this perovskite were examined by a range of techniques. CaCo3V4O12 was found to adopt a double-perovskite cubic lattice [a = 7.3428(6) Å] with Im3 symmetry. We have established that this new perovskite is stable at ambient conditions, and its oxidation and/or decomposition at ambient pressure begins above 500 °C. It undergoes an abrupt antiferromagnetic transition around 98 K. Electrical resistivity data suggest semimetallic conductivity in the temperature range of 1.6-370 K. We have established that the Co(2+) ions in CaCo3V4O12 are in the high-spin state with a sizable orbital moment, even though their square-planar oxygen coordination could be more suitable for the low-spin state, which is prone to Jahn-Teller distortion. Electrical resistivity curves also exhibit a distinct steplike feature around 100 K. CaCo3V4O12 is a first example of perovskite in which the sites A' are fully occupied by Co(2+) ions, and hence its synthesis opens the door to a new class of double perovskites, ACo3B4O12, that may be derived by chemical substitution of the A sublattice by lanthanides, sodium, strontium, and bismuth and by other elements and/or of the B sublattice by some other transition metals.

Single crystals of Rb4C60: synthesis and structure determination.

Single crystals of Rb(4)C(60) were obtained at 973 K in a closed niobium ampule, and the structure was determined by X-ray diffraction (I4/mmm, Z = 2, a = b = 11.9783(17) A, c = 11.035(2) A, and V = 1583.3(4) A(3)). The refinement was successful without any bond distance restraint and resulted in average C-C bond lengths of d(6:6) = 1.383(5) A and d(5:6) = 1.453(5) A. C(60)(4-) is rotationally disordered and has the shape of a distorted truncated icosahedron (D(2h)). Using the new structural data, density functional theory calculations obtain a metallic ground state.

Distortions in the cubic primitive high-pressure phases of calcium.

The superconductivity in highly compressed calcium involves the occurrence of closely related low-symmetry structural patterns with an exceptionally low coordination number. Earlier theoretical and experimental results are controversial and some findings are inconsistent with our later observations in the pressure range up to 60 GPa. This situation motivated the present concerted computational and experimental re-investigation of the structural arrangement of calcium slightly above the high-pressure limit of the bcc arrangement at low-temperatures. We report here reproducible experimental evidence for a monoclinic distortion (mC4, space group C2/c) of the calcium polymorph previously assigned to the tetragonal ß-Sn structure type. In accordance, the enthalpies calculated by electronic band structure calculations show the mC4 phase to be more stable than the undistorted ß-Sn type by about 100 meV in the entire phase space. The other low-temperature phase of calcium adopts space group Cmcm (oC4) rather than the earlier assigned Cmmm symmetry. These structural alterations substantially effect the density of states at the Fermi level and, thus, the electronic properties.

Magnetic and defect probes of the SmB6 surface state.

The impact of nonmagnetic and magnetic impurities on topological insulators is a central focus concerning their fundamental physics and possible spintronics and quantum computing applications. Combining scanning tunneling spectroscopy with transport measurements, we investigate, both locally and globally, the effect of nonmagnetic and magnetic substituents in SmB6, a predicted topological Kondo insulator. Around the so-introduced substitutents and in accord with theoretical predictions, the surface states are locally suppressed with different length scales depending on the substituent's magnetic properties. For sufficiently high substituent concentrations, these states are globally destroyed. Similarly, using a magnetic tip in tunneling spectroscopy also resulted in largely suppressed surface states. Hence, a destruction of the surface states is always observed close to atoms with substantial magnetic moment. This points to the topological nature of the surface states in SmB6 and illustrates how magnetic impurities destroy the surface states from microscopic to macroscopic length scales.

Magnetic properties of single nanomagnets: Electron energy-loss magnetic chiral dichroism on FePt nanoparticles.

Electron energy-loss magnetic chiral dichroism (EMCD) allows for the quantification of magnetic properties of materials at the nanometer scale. It is shown that with the support of simulations that help to identify the optimal conditions for a successful experiment and upon implementing measurement routines that effectively reduce the noise floor, EMCD measurements can be pushed towards quantitative magnetic measurements even on individual nanoparticles. With this approach, the ratio of orbital to spin magnetic moments for the Fe atoms in a single L10 ordered FePt nanoparticle is determined to be ml/ms=0.08±0.02. This finding is in good quantitative agreement with the results of XMCD ensemble measurements.

CeRu4Sn6: a strongly correlated material with nontrivial topology.

Topological insulators form a novel state of matter that provides new opportunities to create unique quantum phenomena. While the materials used so far are based on semiconductors, recent theoretical studies predict that also strongly correlated systems can show non-trivial topological properties, thereby allowing even the emergence of surface phenomena that are not possible with topological band insulators. From a practical point of view, it is also expected that strong correlations will reduce the disturbing impact of defects or impurities, and at the same increase the Fermi velocities of the topological surface states. The challenge is now to discover such correlated materials. Here, using advanced x-ray spectroscopies in combination with band structure calculations, we infer that CeRu4Sn6 is a strongly correlated material with non-trivial topology.

Quasi-one-dimensional magnetism driven by unusual orbital ordering in CuSb2O6.

Essentially all undoped cuprates exhibit a quasiplanar, fourfold Cu-O coordination responsible for the magnetically active antibonding 3d(x(2)-y(2)) like state. Here, we present an electronic structure study for CuSb(2)O(6) that reveals, in contrast, a half-filled 3d(3z(2)-r(2)) orbital. This hitherto unobserved ground state originates from a competition of in- and out-of-plaquette orbitals where the strong Coulomb repulsion drives the surprising and unique orbital ordering. This, in turn, gives rise to an unexpected quasi-one-dimensional magnetic behavior. Our results provide a consistent explanation of recent thermodynamical and neutron diffraction measurements.

Ferromagnetism induced by orbital order in the charge-transfer insulator Cs2AgF4: an electronic structure study.

Cs2AgF4 was proposed to be an orbitally ordered ferromagnet based on recent neutron scattering data. Here, we report a detailed electronic structure study within the local spin density approximation also including strong Coulomb repulsion U. We investigate the influence of an orthorhombic distortion of the Ag environment and the importance of the on-site Coulomb repulsion. We find good quantitative agreement with both the experimentally observed exchange coupling and structural changes. Thus, our results strongly support that Cs2AgF4 is a strongly correlated charge-transfer insulator where the ferromagnetism is driven by orbital order.

Destruction of the small Fermi surfaces in NaxCoO2 by disorder.

We show using density functional calculations that the small e'g Fermi surfaces in NaxCoO2 are destroyed by Na disorder. This provides a means to resolve the prediction of these sections in band structure calculations with their nonobservation in angle resolved photoemission experiments.

Superconductivity and lattice instability in compressed lithium from Fermi surface hot spots.

The highest superconducting temperature Tc observed in any elemental metal (Li with Tc approximately 18-20 K at pressure 35-48 GPa) is shown to arise from increasingly strong electron-phonon coupling concentrated along intersections of Kohn anomaly surfaces with the evolving Fermi surface. First-principles linear response calculations of the phonon spectrum and spectral function alpha2F(omega) reveal very strong Q- and phonon-polarization dependence of coupling strength, resulting in values of in the observed range. The sharp momentum dependence of the coupling even for the simple Li Fermi surface indicates more generally that a fine Q mesh is required for precise evaluation of lamda.