Low-temperature properties of magnetically frustrated rare-earth zirconatesA2Zr2O7.

Rare-earthA2Zr2O7zirconates have attracted considerable attention of the scientific community for their complex magnetic, electronic and material properties applicable in modern technologies. The light rare-earth members of the series, crystallising in the pyrochlore variant of cubic crystal structure, have been studied in detail. The heavierA2Zr2O7compounds have been investigated mainly from the material properties viewpoint, focussing on their thermal properties and stability at high temperature and pressure. Low-temperature studies were mostly missing until recently. We present the low-temperature magnetic and thermodynamic properties ofA2Zr2O7withA= Y, La, Nd, Eu, Gd, Tb, Dy, Ho, Tm, Yb, and Lu, well covering the whole series, newly synthesised by high-temperature sintering and melting methods. X-ray diffraction reveals and confirms the ordered pyrochlore structure in the light members, the disordered cubic structure of the defect-fluorite type inA2Zr2O7withA= Y, Gd-Yb, and finally the lower symmetry rhombohedral structure in the end-member Lu2Zr2O7. The specific heat of the investigated compounds is dominated by a low-temperature anomaly associated with magnetic ordering: long-range in light rare-earth zirconates; and short-range in heavier members. The effective magnetic moment in the studied compounds, determined by fitting the magnetisation data to the Curie-Weiss formula, is in good agreement with the expected value of theA3+free ion. The magnetic properties have been revealed to be strongly influenced by the geometric frustration of the magnetic moments of both the pyrochlore structure, as well as the face centred cubic lattice created by the cations of the defect-fluorite structure, but connected also to intrinsic atomic disorder. The experimental results are discussed in the framework of previous studies onA2Zr2O7zirconates, as well as otherA2B2O7compounds.

Kapellasite: a kagome quantum spin liquid with competing interactions.

Magnetic susceptibility, NMR, muon spin relaxation, and inelastic neutron scattering measurements show that kapellasite, Cu3Zn(OH)6Cl2, a geometrically frustrated spin-1/2 kagome antiferromagnet polymorphic with herbertsmithite, is a gapless spin liquid showing unusual dynamic short-range correlations of noncoplanar cuboc2 type which persist down to 20 mK. The Hamiltonian is determined from a fit of a high-temperature series expansion to bulk susceptibility data and possesses competing exchange interactions. The magnetic specific heat calculated from these exchange couplings is in good agreement with experiment. The temperature dependence of the magnetic structure factor and the muon relaxation rate are calculated in a Schwinger-boson approach and compared to experimental results.

Upper critical field reaches 90 tesla near the Mott transition in fulleride superconductors.

Controlled access to the border of the Mott insulating state by variation of control parameters offers exotic electronic states such as anomalous and possibly high-transition-temperature (Tc) superconductivity. The alkali-doped fullerides show a transition from a Mott insulator to a superconductor for the first time in three-dimensional materials, but the impact of dimensionality and electron correlation on superconducting properties has remained unclear. Here we show that, near the Mott insulating phase, the upper critical field Hc2 of the fulleride superconductors reaches values as high as ∼90 T-the highest among cubic crystals. This is accompanied by a crossover from weak- to strong-coupling superconductivity and appears upon entering the metallic state with the dynamical Jahn-Teller effect as the Mott transition is approached. These results suggest that the cooperative interplay between molecular electronic structure and strong electron correlations plays a key role in realizing robust superconductivity with high-Tc and high-Hc2.

Redox-controlled potassium intercalation into two polyaromatic hydrocarbon solids.

Alkali metal intercalation into polyaromatic hydrocarbons (PAHs) has been studied intensely after reports of superconductivity in a number of potassium- and rubidium-intercalated materials. There are, however, no reported crystal structures to inform our understanding of the chemistry and physics because of the complex reactivity of PAHs with strong reducing agents at high temperature. Here we present the synthesis of crystalline K2Pentacene and K2Picene by a solid-solid insertion protocol that uses potassium hydride as a redox-controlled reducing agent to access the PAH dianions, and so enables the determination of their crystal structures. In both cases, the inserted cations expand the parent herringbone packings by reorienting the molecular anions to create multiple potassium sites within initially dense molecular layers, and thus interact with the PAH anion π systems. The synthetic and crystal chemistry of alkali metal intercalation into PAHs differs from that into fullerenes and graphite, in which the cation sites are pre-defined by the host structure.