RESUMEN
Unconventional superconductivity in non-centrosymmetric superconductors has attracted a considerable amount of attention. While several lanthanide-based materials have been reported previously, the number of actinide-based systems remains small. In this work, we present the discovery of a novel cubic complex non-centrosymmetric superconductor [Formula: see text] ([Formula: see text] space group). This intermetallic cage compound displays superconductivity below [Formula: see text] K, as evidenced by specific heat and resistivity data. [Formula: see text] is a type-II superconductor, which has an upper critical field [Formula: see text] T and a moderate Sommerfeld coefficient [Formula: see text] mJ [Formula: see text] [Formula: see text]. A non-zero density of states at the Fermi level is evident from metallic behavior in the normal state, as well as from electronic band structure calculations. The isostructural [Formula: see text] compound is a paramagnet with a moderately enhanced electronic mass, as indicated by the electronic specific heat coefficient [Formula: see text] mJ [Formula: see text] [Formula: see text] and Kadowaki-Woods ratio [Formula: see text] [Formula: see text] [Formula: see text] cm [Formula: see text] [Formula: see text] (mJ)[Formula: see text]. Both [Formula: see text] and [Formula: see text] are crystallographically complex, each hosting 212 atoms per unit cell.
RESUMEN
CeOs_{4}Sb_{12} (COS) and PrOs_{4}Sb_{12} (POS) are two representative compounds that provide the ideal vantage point to systematically study the physics of multi-f-electron systems. COS with Ce 4f^{1}, and POS with Pr 4f^{2} configurations show distinct properties of Kondo insulating and heavy fermion superconductivity, respectively. We unveiled the underlying microscopic origin by angle-resolved photoemission spectroscopy studies. Their eV-scale band structure matches well, representing the common characters of conduction electrons in ROs_{4}Sb_{12} systems (R=rare earth). However, f electrons interact differently with conduction electrons in COS and POS. Strong hybridization between conduction electrons and f electrons is observed in COS with band dependent hybridization gaps, and the development of a Kondo insulating state is directly revealed. Although the ground state of POS is a singlet, finite but incoherent hybridization exists, which can be explained by the Kondo scattering with the thermally excited triplet crystalline electric field state. Our results help us to understand the intriguing properties in COS and POS, and provide a clean demonstration of the microscopic differences in heavy fermion systems with 4f^{1} and 4f^{2} configurations.
RESUMEN
New germanides with composition RE3Pt4Ge13 (RE = Y, Pr, Sm, Gd, Tb, Tm) have been prepared by high-pressure, high-temperature synthesis. Their crystal structures have been refined, and the relationship of this new rhombohedral and monoclinic structure types with the primitive cubic Yb3Rh4Sn13 prototype is discussed. Band structure calculations within density functional theory confirm the distorted rhombohedral and monoclinic structural arrangements to be energetically more favorable than the simple cubic one. X-ray absorption spectroscopy and magnetic susceptibility measurements indicate that the RE-atoms are in the +3 oxidation state in all studied compounds.
RESUMEN
The synthesis and a joint experimental and theoretical study of the crystal structure and physical properties of the new ternary intermetallic compound TiGePt are presented. Upon heating, TiGePt exhibits an unusual structural phase transition with a huge volume contraction of about 10 %. The transformation is characterized by a strong change in the physical properties, in particular, by an insulator-metal transition. At temperatures below 885 °C TiGePt crystallizes in the cubic MgAgAs (half-Heusler) type (LT phase, space group F43m, a = 5.9349(2)â Å). At elevated temperatures, the crystal structure of TiGePt transforms into the TiNiSi structure type (HT phase, space group Pnma, a = 6.38134(9)â Å, b = 3.89081(5)â Å, c = 7.5034(1)â Å). The reversible, temperature-dependent structural transition was investigated by in-situ neutron powder diffraction and dilatometry measurements. The insulator-metal transition, indicated by resistivity measurements, is in accord with band structure calculations yielding a gap of about 0.9â eV for the LT phase and a metallic HT phase. Detailed analysis of the chemical bonding in both modifications revealed an essential change of the Ti-Pt and Ti-Ge interactions as the origin of the dramatic changes in the physical properties.
RESUMEN
The filled skutterudite compound CePt(4)Ge(12) is situated close to the border between the intermediate valence of Ce and heavy-fermion behavior. Substitution of Ge by Sb drives the system into a strongly correlated and, ultimately, upon further increasing the Sb concentration, an antiferromagnetically ordered state. Our experiments evidence a delicate interplay of emerging Kondo physics and the formation of a local 4f moment. An extended non-Fermi-liquid region, which can be understood in the framework of a Kondo-disorder model, is observed. Band-structure calculations support the conclusion that the physical properties are governed by the interplay of electron supply via Sb substitution and the concomitant volume effects.
RESUMEN
Electronic, magnetic, and transport properties of the filled platinum-germanium skutterudite CePt4Ge12 are investigated. High resolution x-ray absorption spectroscopy measurements at the cerium L(III) edge demonstrate that CePt4Ge12 in this compound has a temperature-independent valence close to three. However, magnetic susceptibility, thermopower, Hall effect, and electronic specific heat reveal a broad maximum at Tmax D 65-80 K, suggesting the presence of valence fluctuations. The Sommerfeld coefficient γ = 105 mJ mol⻹ K⻲, deduced from specific heat, indicates moderately enhanced band masses for CePt4Ge12. We discuss these findings and conclude that CePt4Ge12 represents a system at the border between intermediate valence (IV) and Kondo lattice behavior. In addition, the lattice specific heat and the thermal conductivity are discussed with respect to the vibrational dynamics of Ce in the [Pt4Ge12] framework.
RESUMEN
The discrepancy between Raman spectra of boron carbide obtained by Fourier transform Raman and conventional Raman spectrometry is systematically investigated. While at photon energies below the exciton energy (1.560 eV), Raman scattering of bulk phonons of boron carbide occurs, photon energies exceeding the fundamental absorption edge (2.09 eV) evoke additional patterns, which may essentially be attributed to luminescence or to the excitation of Raman-active processes in the surface region. The reason for this is the very high fundamental absorption in boron carbide inducing a very small penetration depth of the exciting laser radiation. Raman excitations essentially restricted to the boron carbide surface region yield spectra which considerably differ from bulk phonon ones, thus indicating structural modifications.
RESUMEN
The filled skutterudite superconductor PrPt4Ge12 was studied in muon-spin rotation (muSR), specific heat, and electrical resistivity experiments. The continuous increase of the superfluid density with decreasing temperature and the dependence of the magnetic penetration depth lambda on the magnetic field obtained by means of muSR, as well as the observation of a T3 dependence of the electronic specific heat indicate the presence of pointlike nodes in the superconducting energy gap. The gap and the specific heat are found to be well described by two models with point nodes, similar to results obtained for the unconventional heavy fermion skutterudite superconductor PrOs4Sb12.
RESUMEN
Using muon-spin rotation, we studied the in-plane (lambda_{ab}) and the out of plane (lambda_{c}) magnetic field penetration depth in SrFe_{1.75}Co_{0.25}As_{2} (T_{c} approximately 13.3 K). The penetration depth anisotropy gamma_{lambda} = lambda_{c}/lambda_{ab} increases from gamma_{lambda} approximately 2.1 at T_{c} to 2.7 at 1.6 K. The mean internal field in the superconducting state increases with decreasing temperature, just opposite to the diamagnetic response seen in magnetization experiments. This unusual behavior suggests that the external field induces a magnetic order which is maintained throughout the whole sample volume.
RESUMEN
In the strontium iron-cobalt arsenides SrFe2-xCoxAs2 (0.2 < or = x < or = 0.4) superconductivity with T_{c} up to 20 K is observed in magnetic susceptibility, electrical resistivity, and specific heat data. This first observation of bulk superconductivity induced by electron doping in this family of compounds-despite strong disorder in the Fe-As layer-favors an itinerant electronic theory in contrast to the strongly correlated cuprates and renders a p- or d-wave pairing unlikely. The magnetic ordering present in SrFe2As2 is rapidly suppressed by substitution of Fe by Co. Density functional theory calculations show that this is due to a rigid downshift of the Fe-3d_{x;{2}-y;{2}}-related band edge in the density of states.
RESUMEN
New germanium-platinum compounds with the filled-skutterudite crystal structure were synthesized. The crystal structure and composition were investigated by x-ray diffraction and microprobe analysis. Magnetic susceptibility, specific heat, and electrical resistivity measurements evidence superconductivity in LaPt4Ge12 and PrPt4Ge12 below 8.3 K. The parameters of the normal and superconducting states were established. Strong coupling and a crystal electric field singlet ground state is found for the Pr compound. Electronic structure calculations show a large density of states at the Fermi level. Similar behavior with lower Tc was observed for SrPt4Ge12 and BaPt4Ge12.
RESUMEN
The new ternary magnesium rhodium boride Mg2Rh1-xB6+2x has been prepared by the reaction of the mixture of Mg powder, RhB, and crystalline boron in a Ta container sealed under argon. The crystal structure of Mg2Rh0.75(1)B6.50(4) is determined using single-crystal X-ray diffraction, electron diffraction, and high-resolution electron microscopy (space group Pbam, a=8.795(2) A, b=11.060(2) A, c=3.5279(5) A, Z=4, 630 reflections, RF=0.045). It represents a modified Y2ReB6 structure type with an unusual replacement of part of the Rh atoms by boron pairs located in the pentagonal channels parallel to the c axis. The pairs interconnect the neighboring planar boron nets into the 3D framework. The variation of the lattice parameters reveals a homogeneity range Mg2Rh1-xB6+2x. The random distribution of the Rh atoms and boron pairs and the stabilizing effect of the boron pairs on the Y2ReB6 type structure motif are discussed using electronic band structure calculations and chemical bonding analysis with the electron localization function (ELF).
RESUMEN
Optical investigations are presented of the filled skutterudites AFe4Sb12 with divalent cations A=Yb, Ca, Ba. For each of these compounds a very similar pseudogap structure in the optical conductivity develops in the far-infrared spectral region at temperatures below 90 K. Highly accurate local-density approximation electronic band structure calculations can consistently explain the origin of the pseudogap structure generated largely by transition metal 3d states. In particular, a 4f-conduction electron hybridization or strong correlations can be ruled out as origin for the pseudogap.
RESUMEN
New alkali-metal compounds with the filled-skutterudite structure were synthesized and their chemical and physical properties investigated. X-ray diffraction, microprobe, and chemical analysis established the structure and the composition without defects on the cation site. Magnetization, ac susceptibility, specific heat, resistivity, and NMR or NQR demonstrated NaFe4Sb12 to be ferromagnetic below approximately 85 K and to exhibit an additional magnetic anomaly around 40 K. Band structure calculations find a large density of states at the Fermi energy and a ferromagnetic ground state. Similar behavior was observed for KFe4Sb12.
RESUMEN
The crystal structure of a layered compound Sc(2)B(1.1)C(3.2), scandium boride carbide (M(r) = 140.43), has been re-refined as a commensurate composite crystal using 1795 single-crystal X-ray diffraction intensities with I > 2 sigma(I) collected by Shi, Leithe-Jasper, Bourgeois, Bando & Tanaka [(1999), J. Solid State Chem. 148, 442--449]. The crystal is composed of two layered subsystem structures, i.e. Sc--C--Sc sandwiches and graphite-like layers of the composition B(1/3)C(2/3). The structure refinement was performed in a five-dimensional formalism based on the trigonal superspace group P3m1(p00)(0p0)0m0. The unit cell and other crystal data are a = b = 3.387 (1), c = 6.703 (2) A, V = 66.59 (1) A(3), sigma(1) = (9/7 0 0), sigma(2) = (0 9/7 0), Z = 1, D(x) = 3.501 Mg m(-3). Two different three-dimensional sections through the superspace were analyzed, corresponding to two different superstructure models, one with P3m1 and the other with P3m1. A random distribution of B and C was assumed in the graphite-like layer and 41 structural parameters were introduced. R(F)/wR(F) were 0.0533/0.0482 and 0.0524/0.0476, respectively, for the first and second models. Although the difference between these R(F) or wR(F) values was too fine to exclude one of the models definitely, the advantages of using a superspace group were obvious. It not only brought about better convergence of refinement cycles by virtue of fewer parameters, but also gave an insight into the problem of symmetry of the superstructure.
RESUMEN
We have found a series of new rare earth boron-rich solids in REBC(N) (RE: Y, Ho, Er, Tm, and Lu), systems and their structures are solved from single crystal and/or powder X-ray diffraction data. Structure analysis results show that they are homologous with B(4)C and also show trigonal symmetry. As the two basic structural units, boron icosahedra and octahedra in the new phases form in layers and stack in different sequences which form different phases. With increasing number of icosahedral layers stacking between two neighboring octahedral layers, the c-axis of the unit cell is increased and the other two edges of the unit cell are only changed slightly. Three monophases of the series have been synthesized both in powders and as single crystals. The vibrational modes of the homologous phases are analyzed from the Raman spectra and compared with that of B(4)C.