Orbital frustration in the S = ½ kagome magnet vesignieite, BaCu3V2O8(OH)2

Here we report crystallographic and magnetic studies on high quality samples of the magnetically frustrated S = ½ kagome antiferromagnet vesignieite, BaCu3V2O8(OD)2. Powder neutron diffraction data collected from samples obtained by a new hydrothermal synthetic route reveal a previously unobserved trigonal P3121 structure, similar to the isoelectronic mineral SrCu3V2O8(OH)2. The refined structure is consistent with orbital frustration of the eg d-orbitals in a sublattice of the Cu2+ kagome network due to a dynamic Jahn–Teller effect, which persists below the magnetic transition at TN = 9 K and makes the material an interesting candidate for exploring concomitant spin and orbital frustration. A combination of crystallographic strain analysis and magnetisation measurements indicate strong magnetostructural coupling which may explain the varied magnetic behaviour between samples of vesignieite in the literature. The revised orbital structure is similar to that found in volborthite, rather than the quantum spin liquid herbertsmithite, and provides a convincing argument for the differing magnetic properties found in these frustrated magnets

High-temperature order–disorder transitions in the skutterudites CoGe1.5Q1.5 (Q=S, Te)

The temperature dependence of anion ordering in the skutterudites CoGe1.5Q1.5 (Q=S, Te) has been investigated by powder neutron diffraction. Both materials adopt a rhombohedral structure at room temperature (space group R-3 ) in which the anions are ordered trans to each other within Ge2Q2 rings. In CoGe1.5S1.5, anion ordering is preserved up to the melting point of 950 °C. However, rhombohedral CoGe1.5Te1.5 undergoes a phase transition at 610 °C involving a change to cubic symmetry (space group Im-3). In the high-temperature modification, there is a statistical distribution of anions over the available sites within the Ge2Te2 rings. The structural transition involves a reduction in the degree of distortion of the Ge2Te2 rings which progressively transform from a rhombus to a rectangular shape. The effect of this transition on the thermoelectric properties has been investigated

Thermoelastic and structural properties of ionically conducting cerate perovskites: (II) SrCeO₃ between 1273 K and 1723 K

Thermodynamic grüneisen parameter and bond valence parameters for strontium cerate perovskite.</p

Structural and dielectric studies of the phase behaviour of the topological ferroelectric La1-xNdxTaO4

We thank the University of St Andrews and EPSRC (via DTG studentships to CALD and JG) for funding,The layered perovskite LaTaO4 has been prepared in its polar orthorhombic polymorphic form at ambient temperature. Although no structural phase transition is observed in the temperature interval 25° C < T < 500 °C, a very large axial thermal contraction effect is seen, which can be ascribed to an anomalous buckling of the perovskite octahedral layer. The non-polar monoclinic polymorph can be stabilised at ambient temperature by Nd-doping. A composition La0.90Nd0.10TaO4 shows a first-order monoclinic-orthorhombic (non-polar to polar) transition in the region 250° C < T < 350 °C. Dielectric responses are observed at both the above structural events but, despite the ‘topological ferroelectric’ nature of orthorhombic LaTaO4, we have not succeeded in obtaining ferroelectric P–E hysteresis behaviour. Structural relationships in the wider family of AnBnX3n+2 layered perovskites are discussed.Publisher PDFPeer reviewe

Comprehensive determination of the high-pressure structural behaviour of BaTiO₃

We have mapped the phase diagram of BaTiO3 more extensively than previous attempts using high-pressure neutron-powder diffraction. The mapping of the phase diagram has been performed using isothermal compression at fixed temperatures (175, 225, 290, 480 K) within each of the known crystallographic phases, up to ∼6 GPa using a large volume press. The crystallographic structure of each phase has been measured, and the determined absolute atomic displacements of all atoms within the cell have provided detailed information on the order of the phase transitions observed, and the behaviour of the ferroelectric dipole moment.Publisher PDFPeer reviewe

Low temperature structure and the ferroelectric phase transitions in the CdTiO3 perovskite

The paraelectric-ferroelectric transition in CdTiO3 has been monitored using high resolution neutron diffraction data. This necessitated preparing a sample enriched in 114Cd. A subtle, but significant, anisotropy in the thermal expansion of the lattice parameters for CdTiO3 associated with the transition to the polar structure was observed. First-principles calculations are presented to understand energies, phonon dispersion, and structures of possible phases with different symmetries.Australian Research Counci

Thermal evolution of the crystal structure of the orthorhombic perovskite LaFeO3

CALD and CMK were supported by EPSRC DTA studentships (EP/L505079/1).The thermal evolution of the crystal structure of the prototypical orthorhombic perovskite LaFeO3 has been studied in detail by powder neutron diffraction in the temperature range 25<T<1285 K. A conventional bond length/bond angle analysis, combined with an analysis in terms of symmetry-adapted modes, allows key aspects of the thermal behavior to be understood. In particular, the largest-amplitude symmetry modes (viz. in-phase and out-of-phase octahedral tilts, and A-site cation displacements) are shown to display relatively ‘normal’ behavior, increasing with decreasing temperature, which contrasts with the anomalous behavior previously shown by the derivative Bi0.5La0.5FeO3. However, an unexpected behavior is seen in the nature of the intra-octahedral distortion, which is used to rationalize the unique occurrence of a temperature dependent crossover of the a and c unit cell metrics in this compound.PostprintPeer reviewe

The impact of anion ordering on octahedra distortion and phase transitions in SrTaO2N and BaTaO2N

In this work, we synthesized BaTaO2N and SrTaO2N using a two-step high temperature solid state reaction method and analysed the structural distortions, relative to the ideal cubic perovskite structure, according to group theory. From a complete distortion analysis/refinement using high resolution neutron diffraction data in the temperature range 8 K to 613 K, we identified tetragonal structures for BaTaO2N [P4/mmm (No 123)] and SrTaO2N [I4/mcm (No 140)]. In contrast to an anion-disordered cubic perovskite (Pm3 ̅m No 221) with Ta at the cell center, both systems show a site preference for oxygen anions in the two opposite corners (along the c axis) of the Ta-O/N octahedra rather than the four square corners in the ab plane (Γ3+ occupancy distortion), which induces a tetragonal elongation of the unit cell with the c axis being longer than the a axis. A further Ta-O/N octahedra displacement [R5-(a,0,0), rotation about the c axis] distortion was observed in SrTaO2N. This distortion mode is accompanied by an increased unit cell distortion that decreases as the temperature increases. Ultimately a second-order phase transition caused by the loss of the R5-(a,0,0) mode was observed at 400 – 450 K.Australian Synchrotron Australian Research Counc