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MnSb$_{2}$O$_{6}$ is based on the noncentrosymmetric $P321$ space group with magnetic Mn$^{2+}$ ($S={5/2}$, $L\approx 0$) spins ordering below $T_{\mathrm{N}}=12$ K in a helicoidal structure. The ground state magnetic structure, expected to be built and originate from 7 Heisenberg exchange constants, has been shown to be coupled to the underlying crystallographic chirality with polar domain switching being reported. We apply neutron spectroscopy to extract these symmetric exchange constants. Given the high complexity of the magnetic exchange network, crystallographic structure and complications fitting linear spin-wave models, we take advantage of multiplexed neutron instrumentation to use the first moment sum rule of neutron scattering to estimate the 7 exchange constants. We then use these parameters to calculate the low-energy spin-waves in the N\'eel state to reproduce the neutron response without strong antisymmetric coupling. Using Green's response functions, the stability of long-wavelength excitations in the context of proposed magnetic structures is then discussed. The results show the presence of strong exchange constants for the chiral exchange pathways and illustrate an underlying coupling between crystallographic and magnetic ``chirality" through predominantely symmetric exchange.

MnSb$_{2}$O$_{6}$ is based on the structural chiral $P$321 space group #150 where the magnetic Mn$^{2+}$ moments ($S=5/2$, $L\approx 0$) order antiferromagnetically at $T_\mathrm{N}=12$ K. Unlike the related iron based langasite (Ba$_3$NbFe$_3$Si$_2$O$_{14}$) where the low temperature magnetism is based on a proper helix characterized by a time-even pseudoscalar `magnetic' chirality, the Mn$^{2+}$ ions in MnSb$_{2}$O$_{6}$ order with a cycloidal structure at low temperatures, described instead by a time-even vector `magnetic' polarity. A tilted cycloidal structure has been found [M. Kinoshita et al. Phys. Rev. Lett. 117, 047201 (2016)] to facilitate ferroelectric switching under an applied magnetic field. In this work, we apply polarized and unpolarized neutron diffraction analyzing the magnetic and nuclear structures in MnSb$_{2}$O$_{6}$ with the aim of understanding this magnetoelectric coupling. We find no evidence for a helicoidal magnetic structure with one of the spin envelope axes tilted away from the cycloidal $c$-axis. However, on application of a magnetic field $\parallel$ $\vec{c}$ the spin rotation plane can be tilted, giving rise to a cycloid-helix admixture that evolves towards a distorted helix (zero cycloidal component) for fields great than $\approx$ 2 T. We propose a mechanism for the previously reported ferroelectric switching based on coupled structural and magnetic chiralities requiring only an imbalance of structural chiral domains.

The reliable calculation of electronic structures and understanding of electrical properties depends on an accurate model of the crystal structure. Here, we have reinvestigated the crystal structure of the high-zT thermoelectric material tin selenide, SnSe, between 4 and 1000 K using high-resolution neutron powder diffraction. Symmetry analysis reveals the presence of four active structural distortion modes, one of which is found to be active over a relatively wide range of more than +/-200 K around the symmetry-breaking Pnma-Cmcm transition at 800 K. Density functional theory calculations on the basis of the experimental structure parameters show that the unusual, step-like temperature dependencies of the electrical transport properties of SnSe are caused by the onset of intrinsic bipolar conductivity, amplified and shifted to lower temperatures by a rapid reduction of the band gap between 700 and 800 K. The calculated band gap is highly sensitive to small out-of-plane Sn displacements observed in the diffraction experiments. SnSe with a sufficiently controlled acceptor concentration is predicted to produce simultaneously a large positive and a large negative Seebeck effect along different crystal directions., Comment: 7 pages, 7 figures, accepted for publication in Phys. Rev. Materials

SnSe is a topical thermoelectric material with a low thermal conductivity which is linked to its unique crystal structure. We use low-temperature heat capacity measurements to demonstrate the presence of two characteristic vibrational energy scales in SnSe with Debye temperatures thetaD1 = 345(9) K and thetaD2 = 154(2) K. These hard and soft substructures are quantitatively linked to the strong and weak Sn-Se bonds in the crystal structure. The heat capacity model predicts the temperature evolution of the unit cell volume, confirming that this two-substructure model captures the basic thermal properties. Comparison with phonon calculations reveals that the soft substructure is associated with the low energy phonon modes that are responsible for the thermal transport. This suggests that searching for materials containing highly divergent bond distances should be a fruitful route for discovering low thermal conductivity materials., Comment: Accepted by Applied Physics Letters

Pressure-induced transitions from ordered intermetallic phases to substitutional alloys to semi-ordered phases were studied in a series of bismuth tellurides. Using angle-dispersive x-ray diffraction, the compounds Bi4Te5, BiTe, and Bi2Te were observed to form alloys with the disordered body-centered cubic (bcc) crystal structure upon compression to above 14--19 GPa at room temperature. The BiTe and Bi2Te alloys and the previously discovered high-pressure alloys of Bi2Te3 and Bi4Te3 were all found to show atomic ordering after gentle annealing at very moderate temperatures of ~100{\deg}C. Upon annealing, BiTe transforms from the bcc to the B2 (CsCl) crystal structure type, and the other phases adopt semi-disordered variants thereof, featuring substitutional disorder on one of the two crystallographic sites. The transition pressures and atomic volumes of the alloy phases show systematic variations across the Bi_mTe_n series including the end members Bi and Te. First-principles calculations were performed to characterize the electronic structure and chemical bonding properties of B2-type BiTe and to identify the driving forces of the ordering transition. The calculated Fermi surface of B2-type BiTe has an intricate structure and is predicted to undergo three topological changes between 20 and 60 GPa., Comment: 8 pages, 11 figures, accepted for publication in Phys. Rev. B

The crystal structure of the thermoelectric material tin selenide has been investigated with angle-dispersive synchrotron x-ray powder diffraction under hydrostatic pressure up to 27 GPa. With increasing pressure, a continuous evolution of the crystal structure from the GeS type to the higher-symmetry TlI type was observed, with a critical pressure of 10.5(3) GPa. The orthorhombic high-pressure modification, beta'-SnSe, is closely related to the pseudo-tetragonal high-temperature modification at ambient pressure. The similarity between the changes of the crystal structure at elevated temperatures and at high pressures suggests the possibility that strained thin films of SnSe may provide a route to overcoming the problem of the limited thermal stability of beta-SnSe at high temperatures., Comment: 11 pages, 7 figures

The introduction of A-site vacancies in SrTiO3 results in a glass-like thermal conductivity while Nb substituted samples maintains good electrical conductivity. This unexpected result brings SrTiO3 one step closer to being a high-performing phonon-glass electron-crystal thermoelectric material.

Inelastic neutron scattering experiments were performed to investigate the crystalline electric field (CEF) excitations of Nd3+ (J = 9/2) in the iron pnictide NdFeAsO. The crystal field level structures for both the high-temperature paramagnetic phase and the low-temperature antiferromagnetic phase of NdFeAsO are constructed. The variation of CEF excitations of Nd3+ reflects not only the change of local symmetry but also the change of magnetic ordered state of the Fe sublattice. By analyzing the crystal field interaction with a crystal field Hamiltonian, the crystal field parameters are obtained. It was found that the sign of the fourth and sixth-order crystal field parameters change upon the magnetic phase transition at 140 K, which may be due to the variation of exchange interactions between the 4f and conduction electrons., Comment: 5 pages, 4 figures

We carried out AC magnetic susceptibility measurements and muon spin relaxation spectroscopy on the cubic double perovskite Ba2YMoO6, down to 50 mK. Below ~1 K the muon relaxation is typical of a magnetic insulator with a spin-liquid type ground state, i.e. without broken symmetries or frozen moments. However, the AC susceptibility revealed a dilute-spin-glass like transition below ~ 1 K. Antiferromagnetically coupled Mo5+ 4d1 electrons in triply degenerate t2g orbitals are in this material arranged in a geometrically frustrated fcc lattice. Bulk magnetic susceptibility data has previously been interpreted in terms of a freezing to a heterogeneous state with non-magnetic sites where 4d^1 electrons have paired in spin-singlets dimers, and residual unpaired Mo5+ 4d1 electrons. Based on the magnetic heat capacity data it has been suggested that this heterogeneity is the result of kinetic constraints intrinsic to the physics of the pure system (possibly due to topological overprotection), leading to a self-induced glass of valence bonds between neighbouring 4d1 electrons. The muSR relaxation unambiguously points to a static heterogeneous state with a static arrangement of unpaired electrons isolated by spin-singlet (valence bond) dimers between the majority of Mo5+ 4d electrons. The AC susceptibility data indicate that the residual magnetic moments freeze into a dilute-spin-glass-like state. This is in apparent contradiction with the muon-spin decoupling at 50 mK in fields up to 200 mT, which indicates that, remarkably, the time scale of the field fluctuations from the residual moments is ~ 5 ns. Comparable behaviour has been observed in other geometrically frustrated magnets with spin-liquid-like behaviour and the implications of our observations on Ba2YMoO6 are discussed in this context., Comment: 11 pages, 3 Figures. Published in New Journal of Physics

Thermoelectric figures of merit, ZT > 0.5, have been obtained in arc-melted TiNiSn-based ingots. This promising conversion efficiency is due to a low lattice thermal conductivity, which is attributed to excess nickel in the half-Heusler structure.

The low-temperature magnetic structure of NdFeAsO has been revisited using neutron powder diffraction and symmetry analysis using the Sarah representational analysis program. Four magnetic models with one magnetic variable for each of the Nd and Fe sublattices were tested. The best fit was obtained using a model with Fe moments pointing along the c-direction, and Nd moments along the a-direction. This signals a significant interplay between rare-earth and transition metal magnetism, which results in a spin-reorientation of the Fe sublattice upon ordering of the Nd moments. All models that fit the data well, including collinear models with more than one magnetic variable per sublattice, were found to have an Fe moment of 0.5 BM and a Nd moment of 0.9 BM, demonstrating that the low-temperature Fe moment is not substantially enhanced compared to the spin-density wave (SDW) state., Comment: accepted to J. Phys.: Cond. Mat

The phase stability of the (Bi2)m(Bi2Te3)n natural superlattices has been investigated through the low temperature solid state synthesis of a number of new binary BixTe1-x compositions. Powder X-ray diffraction revealed that an infinitely adaptive series forms for 0.44 < x < 0.70, while an unusual 2-phase region with continuously changing compositions is observed for 0.41 < x < 0.43. For x > 0.70, mixtures of elemental Bi and an almost constant composition (Bi2)m(Bi2Te3)n phase are observed. Rietveld analysis of synchrotron X-ray powder diffraction data collected on Bi2Te (m = 2, n = 1) revealed substantial interchange of Bi and Te between the Bi2 and Bi2Te3 blocks, demonstrating that the block compositions are variable. All investigated phase pure compositions are degenerate semiconductors with low residual resistivity ratios and moderate positive magnetoresistances (R/R0 = 1.05 in 9 T). The maximum Seebeck coefficient is +80 muV K-1 for x = 0.63, leading to an estimated thermoelectric figure of merit, zT = 0.2 at 250 K., Comment: accepted to a special issue on thermoelectric materials in the Journal of Solid State Chemistry

We investigated the low energy excitations in the parent compound NdFeAsO of the Fe-pnictide superconductor in the $\mu$eV range by a back scattering neutron spectrometer. The energy scans on a powder NdFeAsO sample revealed inelastic peaks at E = 1.600 $ \pm 0.003 \mu$eV at T = 0.055 K on both energy gain and energy loss sides. The inelastic peaks move gradually towards lower energy with increasing temperature and finally merge with the elastic peak at about 6 K. We interpret the inelastic peaks to be due to the transition between hyperfine-split nuclear level of the $^{143}$Nd and $^{145}$Nd isotopes with spin $I = 7/2$. The hyperfine field is produced by the ordering of the electronic magnetic moment of Nd at low temperature and thus the present investigation gives direct evidence of the ordering of the Nd magnetic sublattice of NdFeAsO at low temperature.

A combination of synchrotron X-ray, neutron powder diffraction, magnetization, heat capacity and electrical resistivity measurements reveals that NdMnAsO is an antiferromagnetic semiconductor with large Neel temperature (TN = 359(2) K). At room temperature the magnetic propagation vector k = 0 and the Mn moments are directed along the crystallographic c-axis (mMn = 2.41(6) BM). Upon cooling a spin reorientation (SR) transition of the Mn moments into the ab-plane occurs (TSR = 23 K). This coincides with the long range ordering of the Nd moments, which are restricted to the basal plane. The magnetic propagation vector remains k = 0. At base temperature (1.6 K) the fitted moments are mab,Mn = 3.72(1) BM and mab,Nd = 1.94(1) BM. The electrical resistivity is characterized by a broad maximum at 250 K, below which it has a metallic temperature dependence but semiconducting magnitude (rho250K = 50 Ohm cm, residual resistivity ratio = 2), and a slight upturn at the SR transition.

We report on the unconventional magnetism in the cubic B-site ordered double perovskite Ba2YMoO6, using AC and DC magnetic susceptibility, heat capacity and muSR. No magnetic order is observed down to 2 K while the Weiss temperature is ~ -160 K. This is ascribed to the geometric frustration in the lattice of edge-sharing tetrahedra with orbitally degenerate Mo5+ s=1/2 spins. Our experimental results point to a gradual freezing of the spins into a disordered pattern of spin-singlets, quenching the orbital degeneracy while leaving the global cubic symmetry unaffected, and providing a rare example of a valence bond glass., Comment: 4 pages, 5 figures. Published in Phys. Rev. Lett.

The structural, electronic, and magnetic properties of the superconducting NdFeAsO$_{1-x}$F$_{x}$ phases ($T_C=43 {\rm K}$ for $x=0.15$) have been investigated experimentally by high-resolution synchrotron x-ray powder diffraction, magnetization and $^{75}$As NMR measurements. Density-functional calculations were performed to calculate and analyze the electric field gradient and the density of states. Compared to LaFeAsO family, the NdFeAsO family shows a contraction of the lattice parameters with shorter rare-earth (RE)-As bond distances, an increased thickness of the As-Fe$_2$-As layer, and less distorted Fe-As$_4$ tetrahedra. The $^{75}$As quadrupole frequencies are enhanced with respect to the La analogs. This is due to a more prolate As $4p$ electron distribution mainly caused by the reduced lattice parameters and not by the presence of Nd $4f$ electrons. A non-negligible hyperfine coupling between the $^{75}$As nuclei and the Nd $4f$ states indicates a weak coupling between the REO and FeAs layer and possibly opens the channel for a Ruderman-Kittel-Kasuya-Yosida (RKKY)-type interaction between localized Nd $4f$ moments mediated by itinerant Fe 3d and/or Nd $5d$ states., Comment: 7 pages, 6 figures, replaces 0806.1450

A suppression of superconductivity in the late rare earth RFeAsO1-xFx materials is reported. The maximum critical temperature (Tc) decreases from 51 K for R = Tb to 36 K for HoFeAsO0.9F0.1, which has been synthesised under 10 GPa pressure. This suppression is driven by a decrease in the Fe-As-Fe angle below an optimimum value of 110.6 degrees, as the angle decreases linearly with unit cell volume (V) across the RFeAsO1-xFx series. A crossover in electronic structure around this optimum geometry is evidenced by a change in sign of the compositional dTc/dV, from negative values for previously reported large R materials to positive for HoFeAsO0.9F0.1., Comment: accepted to PRB

We report measurements of the phonon density-of-states in iron oxypnictide superconductors by inelastic x-ray scattering. A good agreement with ab-initio calculations that do not take into account strong electronic correlations is found, and an unpredicted softening of phonon branches under F doping of these compounds is observed. Raman scattering experiments lead us to conclude that this softening is not related to zone center phonons, and consequently imply an important softening of the relevant phonon branches at finite momentum transfer Q., Comment: 4 pages, 4 figures. Originally submitted 07 Jul 08, accepted for publication in Phys. Rev. B (R)

The magnetic properties and structure of LixCoO2 for x between 0.5 and 1.0 are reported. Co4+ is found to be high-spin in LixCoO2 for x between 0.94 and 1.0 and low-spin for x between 0.50 and 0.78. Weak antiferromagnetic coupling is observed, increasing in strength as more Co4+ is introduced. At an x value of about 0.65, the temperature-independent contribution to the magnetic susceptibility and the electronic contribution to the specific heat are largest. Neutron diffraction analysis reveals that the lithium oxide layer expands perpendicular to the basal plane and the Li ions displace from their ideal octahedral sites with decreasing x. A comparison of the structures of the NaxCoO2 and LixCoO2 systems reveals that the CoO2 layer changes substantially with alkali content in the former but is relatively rigid in the latter. Further, the CoO6 octahedra in LixCoO2 are less distorted than those in NaxCoO2. We postulate that these structural differences strongly influence the physical properties in the two systems.

The structures and thermoelectric properties of the (Bi2)m(Bi2Te3)n homologous series, derived from stacking hexagonal Bi2 and Bi2Te3 blocks, are reported. The end-members of this series are metallic Bi and semiconducting Bi2Te3; nine members of the series have been studied. The structures form an infinitely adaptive series and a unified structural description based on a modulated structure approach is presented. The as-synthesized samples have thermopowers (S) that vary from n-type for Bi2Te3 to p-type for phases rich in Bi2 blocks but with some Bi2Te3 blocks present, to n-type again for Bi metal. The thermoelectric power factor (S2/rho) is highest for Bi metal (43 muW/K2 cm at 130 K), followed by Bi2Te3 (20 muW/K2 cm at 270 K), while Bi2Te (m:n = 5:2) and Bi7Te3 (m:n = 15:6) have 9 muW/K2 cm (at 240 K) and 11 muW/K2 (at 270 K), respectively. The results of doping studies with Sb and Se into Bi2Te are reported., Comment: accepted for publication in PRB

Ferromagnetism is observed below 10 K in [Bi0.75Te0.125Mn0.125]Te. This material has the BiTe structure, which is made from the stacking of two Te-Bi-Te-Bi-Te blocks and one Bi-Bi block per unit cell. Crystal structure analysis shows that Mn is localized in the Bi2 blocks, and is accompanied by an equal amount of TeBi anti-site occupancy in the Bi2Te3 blocks. These TeBi anti-site defects greatly enhance the Mn solubility. This is demonstrated by comparison of the [Bi1-xMnx]Te and [Bi1-2xTexMnx]Te series; in the former, the solubility is limited to x = 0.067, while the latter has xmax = 0.125. The magnetism in [Bi1-xMnx]Te changes little with x, while that for [Bi1-2xTexMnx]Te shows a clear variation, leading to ferromagnetism for x > 0.067. Magnetic hysteresis and the anomalous Hall Effect are observed for the ferromagnetic samples., Comment: Accepted for publication in Phys. Rev. B

Charge density waves (CDWs) are periodic modulations of the conduction electron density in solids. They are collective states that arise from intrinsic instabilities often present in low dimensional electronic systems. The layered dichalcogenides are the most well-studied examples, with TiSe_2 one of the first CDW-bearing materials known. The competition between CDW and superconducting collective electronic states at low temperatures has long been held and explored, and yet no chemical system has been previously reported where finely controlled chemical tuning allows this competition to be studied in detail. Here we report how, upon controlled intercalation of TiSe_2 with Cu to yield Cu_xTiSe_2, the CDW transition is continuously suppressed, and a new superconducting state emerges near x = 0.04, with a maximum T_c of 4.15 K found at x = 0.08. Cu_xTiSe_2 thus provides the first opportunity to study the CDW to Superconductivity transition in detail through an easily-controllable chemical parameter, and will provide new insights into the behavior of correlated electron systems., Comment: Accepted to Nature Physics

The crystal structures of the NaxCoO2 phases based on three-layer NaCoO2, with x=0.32, x=0.51, x=0.60, x=0.75 and x=0.92, determined by powder neutron diffraction, are reported. The structures have triangular CoO2 layers interleaved by sodium ions, and evolve with variation in Na content in a more complex way than has been observed in the two-layer NaxCoO2 system. The highest and lowest Na containing phases studied (x=0.92 and x=0.32) are trigonal, with three CoO2 layers per cell and octahedral Na ion coordination. The intermediate compositions have monoclinic structures. The x=0.75 compound has one CoO2 layer per cell, with Na in octahedral coordination and an incommensurate superlattice. The x=0.6 and x=0.5 phases are also single-layer, but the Na is found in trigonal prismatic coordination. The magnetic behavior of the phases is similar to that observed in the two-layer system. Both the susceptibility and the electronic contribution to the specific heat are largest for x=0.6., Comment: 24 pages, 14 figures, submitted to Phys.Rev. B