Complex magnetic order from multiple Ce-sites in Ce3Pd4Sn6.

Polycrystalline [Formula: see text] [Formula: see text] [Formula: see text] samples were synthesized by arc-melting and subsequent annealing at 970 K. Specific heat, electrical resistivity and magnetic susceptibility measurements are performed over a wide range in temperature and provide hints for the presence of a complex magnetic ordering below 3 K arising from three crystallographically independent Ce sites. This behaviour is driven by a complex interplay between ferro-, ferri-, and antiferromagnetic correlations among the Ce atoms.

On the nature of superconductivity in the anisotropic dichalcogenide NbSe2{CoCp2}x.

We present a detailed study of the superconducting properties of the weakly pinned, quasi-two-dimensional superconductor 2H-NbSe2, and its intercalated variant NbSe2{CoCp2}0.26. The intercalation of 2H-NbSe2 with the organometallic donor molecule cobaltocene (CoCp2) hardly affects the superconducting properties within the layers. However, the properties perpendicular to the layers change significantly due to the large expansion of the layer spacings of the host lattice in the c-direction by a factor of about two. In particular, the superconducting anisotropy factor Γ increases from 3.3 in the parent compound 2H-NbSe2 up to 4.4 in the intercalated species. Therefore, NbSe2{CoCp2}0.26 is an excellent candidate to analyze how the anisotropy effects the superconducting mechanism in layered dichalcogenides, and to evaluate the various models proposed in the literature to account for the anisotropy in 2H-NbSe2. While a two-gap model and an anisotropic single-gap model are competing concepts to describe the almost linear T(2)-dependence of ΔC/T in low-dimensional dichalcogenides, our comparative study suggests that a single-gap model with an anisotropic Fermi-surface is sufficient to capture the ΔC/T(T) behavior in our samples qualitatively.

Ultrasound study of FeCr2S4 in high magnetic fields.

We report on ultrasound studies of FeCr2S4 in static and pulsed magnetic fields exhibiting an orbital-order transition at 9 K. A longitudinal acoustic mode exhibits distinct features in the phase space of temperature and magnetic field due to magnetic and structural transformations. Pulsed-field measurements show significant differences in the sound velocity below and above the orbital-ordering transition as well as the spin-reorientation transition at 60 K. Our results indicate a reduction of the magnetocrystalline anisotropy on entering the orbitally ordered phase.

Interplay between crystal field splitting and Kondo effect in CeNi9Ge(4-x)Si(x).

The pseudo-ternary solid solution CeNi(9)Ge(4-x)Si(x) (0 ≤ x ≤ 4) has been investigated by means of x-ray diffraction, magnetic susceptibility, specific heat, electrical resistivity, thermopower and inelastic neutron scattering studies. The isoelectronic substitution of germanium by silicon atoms causes a dramatic change of the relative strength of competing Kondo, RKKY and crystal field (CF) energy scales. The strongest effect is the continuous elevation of the Kondo temperature T(K) from approximately 3.5 K for CeNi(9)Ge(4) to about 70 K for CeNi(9)Si(4). This increase of the Kondo temperature is attended by a change of the CF level scheme of the Ce ions. The interplay of the different energy scales results in an incipient reduction of the ground state degeneracy from an effectively fourfold degenerate non-magnetic Kondo ground state with unusual non-Fermi-liquid features of CeNi(9)Ge(4) to a lower one, followed by an increase towards a sixfold, fully degenerate ground state multiplet in CeNi(9)Si(4) (T(K) ∼ Δ(CF)).

A prototype hybrid 7π quinone-fused 1,3,2-dithiazolyl radical.

Reaction of 1,4-naphthoquinone and SNSMF(6) (M = As, Sb) in SO(2) solution in a 1 : 2 molar ratio led to the naphthoquinone fused 1,3,2-dithiazolylium salts, 3MF(6) quantitatively by multinuclear NMR (87% isolated yield of 3SbF(6)) via the cycloaddition and oxidative dehydrogenation chemistry of SNS(+) with formation of NH(4)SbF(6) and S(8). The product 3SbF(6) was fully characterized by IR, Raman, multinuclear {(1)H, (13)C, (14)N} NMR, elemental analysis, cyclic voltammetry and single crystal X-ray crystallography. The reduction of 3SbF(6) with ferrocene (Cp(2)Fe) in refluxing acetonitrile (CH(3)CN) led to the first isolation of a fused quinone-thiazyl radical, 3˙ in 73% yield. The prototype hybrid quinone-thiazyl radical 3˙ was fully characterized by IR, Raman microscopy, EI-MS, elemental analysis, solution and solid state EPR, magnetic susceptibility (2-370 K) and was found to form π*-π* dimers in the solid state as determined by single crystal X-ray crystallography. Furthermore, the thermal decomposition of 3˙ led to a novel quinone-fused 1,2,3,4-tetrathiine, 10 (x = 2) and the known 1,2,5-thiadiazole, 11. The energetics of the cycloadditon and oxidative dehydrogenation chemistry of SNS(+) and 1,4-naphthoquinone leading to 3SbF(6) were estimated in the gas phase and SO(2) solution by DFT calculations (PBE0/6-311G(d)) and lattice enthalpies obtained by the volume based thermodynamic (VBT) approach in the solid state. The gas phase ion energetics (ionization potential (IP) and electron affinity (EA)) of 3˙ are compared to related 1,3,2- and 1,2,3-dithiazolyl radicals.

Evolution of quantum criticality in CeNi(9-x)Cu(x)Ge(4).

Crystal structure, specific heat, thermal expansion, magnetic susceptibility and electrical resistivity studies of the heavy fermion system CeNi(9-x)Cu(x)Ge(4) (0≤x≤1) reveal a continuous tuning of the ground state by Ni/Cu substitution from an effectively fourfold-degenerate non-magnetic Kondo ground state of CeNi(9)Ge(4) (with pronounced non-Fermi-liquid features) towards a magnetically ordered, effectively twofold-degenerate ground state in CeNi(8)CuGe(4) with T(N) = 175 ± 5 mK. Quantum critical behavior, [Formula: see text], is observed for [Formula: see text]. Hitherto, CeNi(9-x)Cu(x)Ge(4) represents the first system where a substitution-driven quantum phase transition is connected not only with changes of the relative strength of the Kondo effect and RKKY interaction, but also with a reduction of the effective crystal field ground state degeneracy.

Orbital freezing and orbital glass state in FeCr2S4.

Low-temperature specific heat measurements and dielectric spectroscopy have been performed on polycrystalline and single-crystalline FeCr2S4, the single crystals showing a transition into a low-temperature orbital glass phase. The freezing of the orbital moments is revealed by a glasslike specific heat anomaly and by a clear relaxational behavior of the dielectric permittivity, exhibiting several hallmark features of glassy dynamics. The orbital relaxation dynamics continuously slows down over six decades in time, before at the lowest temperatures the glass transition becomes suppressed by quantum tunneling.

Unusual single-ion non-fermi-liquid behavior in Ce(1-x)LaxNi9Ge4.

We report on specific heat, magnetic susceptibility, and resistivity measurements on the compound Ce(1-x)LaxNi9Ge4 for various concentrations ranging from the stoichiometric system with x = 0 to the dilute limit x = 0.95. Our data reveal single-ion scaling with the Ce concentration and the largest ever recorded value of the electronic specific heat Deltac/T approximately 5.5 J K-2 mol(-1) at T = 0.08 K for the stoichiometric compound x = 0 without any trace of magnetic order. While in the doped samples Deltac/T increases logarithmically below 3 K down to 50 mK, their magnetic susceptibility behaves Fermi-liquid-like below 1 K. These properties make the compound Ce(1-x)LaxNi9Ge4 a unique system on the borderline between Fermi-liquid and non-Fermi-liquid physics.

Grüneisen ratio divergence at the quantum critical point in CeCu(6-x)Agx.

The heavy-fermion system CeCu6-xAgx is studied at its antiferromagnetic quantum critical point, xc=0.2, by low-temperature (T> or =50 mK) specific heat, C(T), and volume thermal expansion, beta(T), measurements. Whereas C/T proportional to log((T0/T) would be compatible with the predictions of the itinerant spin-density-wave (SDW) theory for two-dimensional critical spin fluctuations, beta(T)/T and the Grüneisen ratio, Gamma(T) proportional to beta/C, diverge much weaker than expected, in strong contrast to this model. Both C and beta, plotted as a function of the reduced temperature t=T/T0 with T0=4.6 K, are similar to what was observed for YbRh2(Si(0.95)Ge(0.05))2 (T0=23.3 K), indicating a striking discrepancy to the SDW prediction in both systems.

Spin and orbital frustration in MnSc2S4 and FeSc2S4.

Crystal structure, magnetic susceptibility, and specific heat were measured in the normal cubic spinel compounds MnSc2S4 and FeSc2S4. Down to the lowest temperatures, both compounds remain cubic and reveal strong magnetic frustration. Specifically the Fe compound is characterized by a Curie-Weiss (CW) temperature ThetaCW = -45 K and does not show any indications of order down to 50 mK. In addition, the Jahn-Teller ion Fe2+ is orbitally frustrated. Hence, FeSc2S4 belongs to the rare class of spin-orbital liquids. MnSc2S4 is a spin liquid for temperatures T>TN approximately 2 K.

Heavy fermion superconductivity and magnetic order in noncentrosymmetric CePt3Si.

CePt3Si is a novel heavy fermion superconductor, crystallizing in the CePt3B structure as a tetragonally distorted low symmetry variant of the AuCu3 structure type. CePt3Si exhibits antiferromagnetic order at T(N) approximately 2.2 K and enters into a heavy fermion superconducting state at T(c) approximately 0.75 K. Large values of H(')(c2) approximately -8.5 T/K and H(c2)(0) approximately 5 T refer to heavy quasiparticles forming Cooper pairs. Hitherto, CePt3Si is the first heavy fermion superconductor without a center of symmetry.