An observation of electron phase transition in SmB6 at low temperatures

In order to reveal the nature of the ground state of archetypal intermediate-valence compound SmB₆, a comprehensive study of its transport and magnetic properties was carried out on high-quality single crystals at temperatures of 1.8-300 K in magnetic fields up to 7 T. A drastic enhancement of negative magnetoresistance was observed below 14 K, with the maximum absolute value of Δρ/ρB²∼2.2×10⁻³ T⁻² at T≈5.2 K. This effect seems to be attributable to anomalous magnetic scattering of many-body (exciton-polaronic) complexes induced by fast valence fluctuations on Sm sites. The observed anomalies of magnetotransport, thermoelectric and magnetic characteristics are discussed in terms of electron phase transition to the coherent state of interacting many-body complexes occurring at T^*∼5 K.     

Mass spectrometric identification of cyclic polysulfides in sediment of the Eastern Gulf of Finland. I

Structures of six cyclic polysulfides, previously unknown as organic environmental pollutants, were analyzed from a sediment sample from the Eastern Gulf of Finland. The determinations were done by gas chromatography connected to mass spectrometry. High resolution (HRMS) measurements of the isotopic composition of four compounds could be done to confirm their molecular formulae. Total low resolution (LRMS) spectra were used to elucidate structures of all six compounds by thermochemical approach, application of fragmentation rules and by ICLU simulation of the spectra. The compounds were deduced to be (in the order of GC- retention) 1,2,4-trithiacycloheptane, tetrathiacyclopentane, 1,2,4,5-tetrathia-cyclohexane, 1,2,3,4- tetrathiacycloheptane, 1,2,3,4-tetrathiacyclohexane and 1,2,4,6-tetrathiacyclooctane.     

Thermal properties of rare earth dodecaborides

We have measured heat capacity and thermal expansion of rare earth dodecaborides REB₁₂ (RE=Y, Tb-Tm, Lu). YB₁₂ and LuB₁₂ are diamagnetics whereas the other dodecaborides are ordered antiferromagnetically. The amplitude of the heat capacity discontinuity at the Néel temperature and the shape of the heat capacity variation in the critical region for all these antiferromagnetics are characteristics for amplitude-modulated magnetic structures. In the ordered state TbB₁₂ reveals two first-order phase transitions, most likely due to magnetic structure changes. The heat capacity of ErB₁₂ just below the Néel point shows an anomaly of unclear origin. From the Schottky contribution to the heat capacity we have determined crystal field parameters. They are completely different than that is estimated from Point Charge Model.     

Stereoselective Synthesis and Retentive Trapping of α‐Chiral Secondary Alkyllithiums Leading to Stereodefined α,β‐Dimethyl Carboxylic Esters

The treatment of α‐chiral secondary alkyl iodides with tBuLi at ?100 °C leads to the corresponding secondary alkyllithiums with high retention of configuration. Subsequent quenching with various electrophiles such as Bu₂S₂, DMF, MeOB(OR)₂, or Et₂CO provides the desired products with retention of configuration. Furthermore, a transmetalation with CuBr?P(OEt)₃ also allows retentive trapping with acid chlorides and ethylene oxide. The quenching of the resulting alkyllithiums with ClCO₂Et furnishes stereoselectively syn‐ and anti‐ethyl‐2,3‐dimethyl ester carboxylates (d.r.>94 %). Related esters bearing three adjacent stereo‐controlled centers (stereotriads) have also been prepared. This method has been applied to the synthesis of the ant pheromone (±)‐lasiol in 26 % overall yield (four steps) with d.r.=97:3 starting from commercially available cis‐2,3‐epoxybutane.     

Magnetic structure of rare-earth dodecaborides

We have investigated the magnetic structure of HoB₁₂, ErB₁₂ and TmB₁₂ by neutron diffraction on isotopically enriched single-crystalline samples. Results in zero field as well as in magnetic field up to 5 T reveal modulated incommensurate magnetic structures in these compounds. The basic reflections can be indexed with q=(1/2±δ, 1/2±δ, 1/2±δ), where δ=0.035 both for HoB₁₂ and TmB₁₂ and with q=(3/2±δ, 1/2±δ, 1/2±δ), where δ=0.035, for ErB₁₂. In an applied magnetic field, new phases are observed. The complex magnetic structure of these materials seems to result from the interplay between the RKKY and dipole-dipole interaction. The role of frustration due to the fcc symmetry of dodecaborides and the crystalline electric field effect is also considered.     

Quantum oscillations and the Sermi surface of LuB12

To examine the Fermi surface of LuB₁₂, measurements of the de Haas-van Alphen (dHvA) effect were made at temperatures between 0.35 and 2 K in magnetic fields up to 12 Tesla. Oscillations in the susceptibility occurred above 5 Tesla in any field direction relative to the single crystal sample. From the Fourier transform of the data obtained, we conclude the Fermi surface of both conduction bands to have multiple extremal cross sections. For some of these orbits, the temperature dependence of the dHvA signal was investigated to determine the corresponding cyclotron mass. For a better understanding, a Full Potential Linearized Augmented Plane Wave-(FLAPW-) band structure calculation was carried out and the shapes of the Fermi surfaces were determined. In addition, we investigated the transverse magnetoresistance as a function of the field and the field direction. Its anisotropy, as well as the Shubnikov-de Haas (SdH) oscillations occurring in certain geometries, are in agreement with the results of the dHvA measurements.     

Vibrational spectra of the YbB<Subscript>12</Subscript> Kondo insulator

The density of phonon states for the YbB₁₂ Kondo insulator is calculated from the inelastic neutron scattering spectra of this compound. It is established that thermal vibrations of rare-earth atoms predominantly occur in the low-energy range. These atoms are most weakly bound in the crystal structure of the YbB₁₂ Kondo insulator. The high-energy part of the vibrational spectrum is determined by thermal vibrations of the boron atoms forming a rigidly connected structure of the compound. It is revealed that the temperature dependence of the intensity of the phonon peak attributed to thermal vibrations of the ytterbium atoms exhibits an anomalous behavior. This circumstance suggests that the magnetoelastic coupling occurring in the structure of the YbB₁₂ Kondo insulator is relatively strong and can contribute to the magnetic excitation spectrum of this compound.