Composition dependent polymorphism and superconductivity in Y3+x{Rh,Ir}4Ge13-x.

Polymorphism is observed in the Y3+xRh4Ge13-x series. The decrease of Y-content leads to the transformation of the primitive cubic Y3.6Rh4Ge12.4 [x = 0.6, space group Pm3̄n, a = 8.96095(9) Å], revealing a strongly disordered structure of the Yb3Rh4Sn13 Remeika prototype, into a body-centred cubic structure [La3Rh4Sn13 structure type, space group I4132, a = 17.90876(6) Å] for x = 0.4 and further into a tetragonal arrangement (Lu3Ir4Ge13 structure type, space group I41/amd, a = 17.86453(4) Å, a = 17.91076(6) Å) for the stoichiometric (i.e. x = 0) Y3Rh4Ge13. Analogous symmetry lowering is found within the Y3+xIr4Ge13-x series, where the compound with Y-content x = 0.6 is crystallizing with La3Rh4Sn13 structure type [a = 17.90833(8) Å] and the stoichiometric Y3Ir4Ge13 is isostructural with the Rh-analogue [a = 17.89411(9) Å, a = 17.9353(1) Å]. The structural relationships of these derivatives of the Remeika prototype are discussed. Compounds from the Y3+xRh4Ge13-x series are found to be weakly-coupled BCS-like superconductors with Tc = 1.25, 0.43 and 0.6, for x = 0.6, 0.4 and 0, respectively. They also reveal low thermal conductivity (<1.5 W K-1 m-1 in the temperature range 1.8-350 K) and small Seebeck coefficients. The latter are common for metallic systems. Y3Rh4Ge13 undergoes a first-order phase transition at Tf = 177 K, with signatures compatible to a charge density wave scenario. The electronic structure calculations confirm the instability of the idealized Yb3Rh4Sn13-like structural arrangements for Y3Rh4Ge13 and Y3Ir4Ge13.

Valence fluctuations in the 3D + 3 modulated Yb3Co4Ge13 Remeika phase.

Yb3Co4Ge13 is the first example of a Remeika phase with a 3D + 3 [space group P4̄3n(α,0,0)000(0,α,0)000(0,0,α)000; a = 8.72328(1) Å, α = 0.4974(2)] modulated crystal structure. A slight shift of the composition towards higher Yb-content (i.e. Yb3.2Co4Ge12.8) leads to the disappearance of the satellite reflections and stabilization of the disordered primitive cubic [space group Pm3̄n, a = 8.74072(2) Å] Remeika prototype structure. The stoichiometric structurally modulated germanide is a metal with hole-like charge carriers, where Yb-ions are in a temperature-dependent intermediate valence state varying from +2.60 to +2.66 for the temperature range 85-293 K. The valence fluctuations have been investigated by means of temperature dependent X-ray absorption spectroscopy, magnetic susceptibility and thermopower measurements.

ROBL-II at ESRF: a synchrotron toolbox for actinide research.

ROBL-II provides four different experimental stations to investigate actinide and other alpha- and beta-emitting radionuclides at the new EBS storage ring of ESRF within an energy range of 3 to 35 keV. The XAFS station consists of a highly automatized, high sample throughput installation in a glovebox, to measure EXAFS and conventional XANES of samples routinely at temperatures down to 10 K, and with a detection limit in the sub-p.p.m. range. The XES station with its five bent-crystal analyzer, Johann-type setup with Rowland circles of 1.0 and 0.5 m radii provides high-energy resolution fluorescence detection (HERFD) for XANES, XES, and RIXS measurements, covering both actinide L and M edges together with other elements accessible in the 3 to 20 keV energy range. The six-circle heavy duty goniometer of XRD-1 is equipped for both high-resolution powder diffraction as well as surface-sensitive CTR and RAXR techniques. Single crystal diffraction, powder diffraction with high temporal resolution, as well as X-ray tomography experiments can be performed at a Pilatus 2M detector stage (XRD-2). Elaborate radioprotection features enable a safe and easy exchange of samples between the four different stations to allow the combination of several methods for an unprecedented level of information on radioactive samples for both fundamental and applied actinide and environmental research.

Crystal structure, chemical bonding, and electrical and thermal transport in Sc5Rh6Sn18.

Single crystals of Sc5Rh6Sn18 were grown from Sn-flux. The crystal structure (SG: I41/acd, a = 13.5529(2) Å, c = 27.0976(7) Å) was studied by high-resolution X-ray diffraction on powder and single crystal material as well as by TEM. All methods confirm it to crystallize with a Sc5Ir6Sn18 (space group I41/acd) type structure. The performed structural studies also suggest the presence of local domains with a broken average translational symmetry. An analysis of the chemical bonding situation reveals highly polar covalent Sc2-Sn1, Sn-Rh and Sc2-Rh bonds, two- and three-centre bonds involving Sn-atoms as well as the ionic nature of Sc1 bonding. The thermopower of Sc5Rh6Sn18 is isotropic, small and negative (i.e. dominance of electron-like charge carriers). Due to structural disorder, the thermal conductivity is lower in comparison with regular metallic systems.

Crystal structure and superconducting properties of Sc5Ir6Sn18.

Sc5Ir6Sn18 crystallizes with a split variant of the Tb5Rh6Sn18 structure type (space group I41/acd, [Formula: see text] [Formula: see text], [Formula: see text] [Formula: see text]). DFT calculations confirmed the instability of the structural arrangement with the fully occupied and unsplit crystallographic sites. High quality single crystals were grown from a Sn melt. Sc5Ir6Sn18 is a diamagnetic metal showing a superconducting transition at a critical temperature [Formula: see text] K. The relatively low critical magnetic field [Formula: see text] 3.2 T as well as the obtained values of the specific heat ratio [Formula: see text] and energy-gap ratio [Formula: see text] suggest this system to be a weakly coupled BCS-like superconductor.

Two-gap superconductivity in Ag1-x Mo6S8 Chevrel phase.

The superconducting properties of [Formula: see text]Mo6S8 [[Formula: see text]] Chevrel phase [[Formula: see text] K] are studied on a sample compacted by spark plasma sintering. Both lower ([Formula: see text] mT) and the upper [[Formula: see text] T] critical magnetic fields are obtained from magnetization and electrical resistivity measurements for the first time. The analysis of the low-temperature electronic specific heat indicates [Formula: see text]Mo6S8 to be a two band superconductor with the energy gaps [Formula: see text] meV (95%) and [Formula: see text] meV (5%). Theoretical DFT calculations reveal a much stronger electron-phonon coupling in the studied Chevrel phase compared to earlier reports. Similar to MgB2, the Fermi surface of studied Chevrel phase is formed by two hole-like and one electron-like bands.