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Superconductivity in the iron pnictides emerges from metallic parent compounds exhibiting intertwined stripe-type magnetic order and nematic order, with itinerant electrons suggested to be essential for both. Here we use x-ray and neutron scattering to show that a similar intertwined state is realized in semiconducting KFe_{0.8}Ag_{1.2}Te_{2} (K_{5}Fe_{4}Ag_{6}Te_{10}) without itinerant electrons. We find that Fe atoms in KFe_{0.8}Ag_{1.2}Te_{2} form isolated 2×2 blocks, separated by nonmagnetic Ag atoms. Long-range magnetic order sets in below T_{N}≈35  K, with magnetic moments within the 2×2 Fe blocks ordering into the stripe-type configuration. A nematic order accompanies the magnetic transition, manifest as a structural distortion that breaks the fourfold rotational symmetry of the lattice. The nematic orders in KFe_{0.8}Ag_{1.2}Te_{2} and iron pnictide parent compounds are similar in magnitude and in how they relate to the magnetic order, indicating a common origin. Since KFe_{0.8}Ag_{1.2}Te_{2} is a semiconductor without itinerant electrons, this indicates that local-moment magnetic interactions are integral to its magnetic and nematic orders, and such interactions may play a key role in iron-based superconductivity.

Single crystals of (Nd1−xCex)2Fe14B, some reaching ∼6×8×8mm3 in volume, are grown out of Fe-(Nd, Ce) flux. This crystal growth method allows for large (Nd1−xCex)2Fe14B single crystals to be synthesized using a simple flux growth procedure. Chemical and structural analyses of the crystals indicate that (Nd1−xCex)2Fe14B forms a solid solution until at least x=0.38 with a Vegard-like variation of the lattice constants with x. Refinements of single crystal neutron diffraction data indicate that Ce has a slight site preference (7:3) for the 4g rare earth site over the 4f site. Magnetization measurements at 300 K show only small decreases with increasing Ce content in saturation magnetization (Ms) and anisotropy field (HA), and Curie temperature (TC). First principles calculations are carried out to understand the effect of Ce substitution on the electronic and magnetic properties. For a multitude of applications, it is expected that the advantage of incorporating lower-cost and more abundant Ce will outweigh the small adverse effects on magnetic properties. Ce-substituted Nd2Fe14B is therefore a potential high-performance permanent magnet material with substantially reduced Nd content.

Single crystals of (Nd1-xCex)2Fe14B are grown out of Fe-(Nd,Ce) flux.Chemical and structural analysis of the crystals indicates that(Nd1-xCex)2Fe14B forms a solid solution until at least x = 0.38 with aVegard-like variation of the lattice constants with x. Refinements of singlecrystal neutron diffraction data indicate that Ce has a slight site preference(7:3) for the 4g rare earth site over the 4f site. Magnetization measurementsshow that for x = 0.38 the saturation magnetization at 400 K, a temperatureimportant to applications, falls from 29.8 for the parent Nd2Fe14B to 27.6(mu)B/f.u., the anisotropy field decreases from 5.5 T to 4.7 T, and the Curietemperature decreases from 586 to 543 K. First principles calculations carriedout within density functional theory are used to explain the decrease inmagnetic properties due to Ce substitution. Though the presence of thelower-cost and more abundant Ce slightly affects these important magneticcharacteristics, this decrease is not large enough to affect a multitude ofapplications. Ce-substituted Nd2Fe14B is therefore a potential high-performancepermanent magnet material with substantially reduced Nd content.

Li substitutes for Cu in (Formula presented)(Formula presented) up to the limiting stoichiometry (Formula presented)(Formula presented)(Formula presented)(Formula presented), which has superstructure order. The effects of this in-plane hole doping on the structural and magnetic properties of (Formula presented)(Formula presented) are very similar to those due to Sr substitution. The tetragonal-orthorhombic structural phase transition occurs, for a given amount of Sr or Li, at nearly the same temperature, and the in-plane lattice constant of (Formula presented)(Formula presented)(Formula presented)(Formula presented)(Formula presented) at room temperature depends only on the combined hole count (x+y) and not on the individual Sr or Li concentration. Long-range magnetic order is destroyed upon substituting 3% Li for Cu, analogous to the effect of Sr substitution on (Formula presented). However, the holes introduced by Li substitution are bound. The resistivity as a function of temperature is nonmetallic for all Li concentrations. © 1996 The American Physical Society.

We introduce a computational framework that integrates artificial intelligence (AI), machine learning, and high-performance computing to enable real-time steering of neutron scattering experiments using an edge-to-exascale workflow. Focusing on time-of-flight neutron event data at the Spallation Neutron Source, our approach combines temporal processing of four-dimensional neutron event data with predictive modeling for multidimensional crystallography. At the core of this workflow is the Temporal Fusion Transformer model, which provides voxel-level precision in predicting 3D neutron scattering patterns. The system incorporates edge computing for rapid data preprocessing and exascale computing via the Frontier supercomputer for large-scale AI model training, enabling adaptive, data-driven decisions during experiments. This framework optimizes neutron beam time, improves experimental accuracy, and lays the foundation for automation in neutron scattering. Although real-time experiment steering is still in the proof-of-concept stage, the demonstrated potential of this system offers a substantial reduction in data processing time from hours to minutes via distributed training, and significant improvements in model accuracy, setting the stage for widespread adoption across neutron scattering facilities and more efficient exploration of complex material systems., Competing Interests: The authors have no conflicts to disclose., (© 2024 Author(s).)

Neutron diffraction and spectroscopy offer unique insight into structures and properties of solids and molecular materials. All neutron instruments located at the various neutron sources are distinct, even if their designs are based on similar principles, and thus, they are usually less familiar to the community than commercial X-ray diffractometers and optical spectrometers. Major neutron instruments in the USA, which are open to scientists around the world, and examples of their use in coordination chemistry research are presented here, along with a list of similar instruments at main neutron facilities in other countries. The reader may easily and quickly find from this minireview an appropriate neutron instrument for research. The instruments include single-crystal and powder diffractometers to determine structures, inelastic neutron scattering (INS) spectrometers to probe magnetic and vibrational excitations, and quasielastic neutron scattering (QENS) spectrometers to study molecular dynamics such as methyl rotation on ligands. Key and unique features of the diffraction and neutron spectroscopy that are relevant to inorganic chemistry are reviewed.

It is shown that structural disorder-in the form of anisotropic, picoscale atomic displacements-modulates the refractive index tensor and results in the giant optical anisotropy observed in BaTiS 3 , a quasi-1D hexagonal chalcogenide. Single-crystal X-ray diffraction studies reveal the presence of antipolar displacements of Ti atoms within adjacent TiS 6 chains along the c-axis, and threefold degenerate Ti displacements in the a-b plane. 47/49 Ti solid-state NMR provides additional evidence for those Ti displacements in the form of a three-horned NMR lineshape resulting from a low symmetry local environment around Ti atoms. Scanning transmission electron microscopy is used to directly observe the globally disordered Ti a-b plane displacements and find them to be ordered locally over a few unit cells. First-principles calculations show that the Ti a-b plane displacements selectively reduce the refractive index along the ab-plane, while having minimal impact on the refractive index along the chain direction, thus resulting in a giant enhancement in the optical anisotropy. By showing a strong connection between structural disorder with picoscale displacements and the optical response in BaTiS 3 , this study opens a pathway for designing optical materials with high refractive index and functionalities such as large optical anisotropy and nonlinearity., (© 2024 The Authors. Advanced Materials published by Wiley‐VCH GmbH.)

Cedrol-like compounds are of pharmacological interest due to their diverse range of medicinal effects and are used globally in traditional medicines and cosmetics. Many cedrol tautomers are known from molecular studies but few have been studied in crystalline form by X-ray diffraction. Acicular white crystals collected from the wood of eastern red cedar (Juniperus virginiana) are determined to be (+)-cedrol hemihydrate, namely, (1S,2R,5S,7R,8R)-2,6,6,8-tetramethyltricyclo[5.3.1.0 1,5 ]undecan-8-ol hemihydrate, C 15 H 26 O·0.5H 2 O, a novel packing of two unique cedrol molecules (Z' = 2) with a single water molecule [space group P2 1 2 1 2 1 ; a = 6.1956 (1), b = 14.5363 (1), and c = 30.9294 (4) Å]. The hydrogen bonding forms a one-dimensional spiral chain running along the a axis, following the chirality of the cedrol molecule, through hydrogen-bonding interactions with a right-handed helical configuration in graph-set notation Δ-C 3 3 (6) > a > c > b. The crystal packing and symmetry are different from crystalline isocedrol due to the different hydrogen-bonding geometry.

As one of the most fundamental physical phenomena, charge density wave (CDW) order predominantly occurs in metallic systems such as quasi-1D metals, doped cuprates, and transition metal dichalcogenides, where it is well understood in terms of Fermi surface nesting and electron-phonon coupling mechanisms. On the other hand, CDW phenomena in semiconducting systems, particularly at the low carrier concentration limit, are less common and feature intricate characteristics, which often necessitate the exploration of novel mechanisms, such as electron-hole coupling or Mott physics, to explain. In this study, an approach combining electrical transport, synchrotron X-ray diffraction, and density-functional theory calculations is used to investigate CDW order and a series of hysteretic phase transitions in a dilute d-band semiconductor, BaTiS 3 . These experimental and theoretical findings suggest that the observed CDW order and phase transitions in BaTiS 3 may be attributed to both electron-phonon coupling and non-negligible electron-electron interactions in the system. This work highlights BaTiS 3 as a unique platform to explore CDW physics and novel electronic phases in the dilute filling limit and opens new opportunities for developing novel electronic devices., (© 2023 The Authors. Advanced Materials published by Wiley-VCH GmbH.)

Materials with large birefringence (Δn, where n is the refractive index) are sought after for polarization control (e.g., in wave plates, polarizing beam splitters, etc.), nonlinear optics, micromanipulation, and as a platform for unconventional light-matter coupling, such as hyperbolic phonon polaritons. Layered 2D materials can feature some of the largest optical anisotropy; however, their use in most optical systems is limited because their optical axis is out of the plane of the layers and the layers are weakly attached. This work demonstrates that a bulk crystal with subtle periodic modulations in its structure-Sr 9/8 TiS 3 -is transparent and positive-uniaxial, with extraordinary index n e = 4.5 and ordinary index n o = 2.4 in the mid- to far-infrared. The excess Sr, compared to stoichiometric SrTiS 3 , results in the formation of TiS 6 trigonal-prismatic units that break the chains of face-sharing TiS 6 octahedra in SrTiS 3 into periodic blocks of five TiS 6 octahedral units. The additional electrons introduced by the excess Sr form highly oriented electron clouds, which selectively boost the extraordinary index n e and result in record birefringence (Δn > 2.1 with low loss). The connection between subtle structural modulations and large changes in refractive index suggests new categories of anisotropic materials and also tunable optical materials with large refractive-index modulation., (© 2023 The Authors. Advanced Materials published by Wiley-VCH GmbH.)

Accurate structural models are of paramount importance for elucidating structure-property relationships in functional materials. Spinels (AB 2 O 4 ) form a highly important family of materials with complex crystal structures, and subtle structural details have a critical bearing on understanding their physical properties. In some spinels, the space group symmetry is debated, and in general, point defects such as cation inversion and interstitials add complexity. Most studies of spinels concern powder materials, and this challenges deep structural characterization. In fact, most published spinel structures have dubious atomic displacement parameters (ADPs), which is a typical sign of problematic structural description in the refinement of diffraction data. Here, we use various X-ray and neutron diffraction techniques to establish a benchmark crystal structure for the essentially defect-free spinel ferrite ZnFe 2 O 4 , which is a widely studied frustrated magnet. It is shown that the appearance of Fd 3̅ m forbidden reflections in the ZnFe 2 O 4 single-crystal neutron diffraction data is an artifact of multiple scattering rather than the loss of inversion symmetry. We then provide benchmark ADPs and demonstrate how strongly these parameters affect the refined cation inversion. The ADPs reported here may be used as reference data to test the soundness of refined structural models, possibly to constrain those based on suboptimal data quality, and thereby provide a more accurate fundamental understanding of the structure-property relationship in spinel-type materials.

Magnetic materials with the spinel structure (A 2+ B 3+ 2 O 4 ) form the core of numerous magnetic devices, and ZnFe 2 O 4 constitutes a peculiar example where the nature of the magnetism is still unresolved. Susceptibility measurements revealed a cusp around T c  = 13 K resembling an antiferromagnetic transition, despite the positive Curie-Weiss temperature determined to be Θ CW  = 102.8(1) K. Bifurcation of field-cooled and zero-field-cooled data below T c in conjunction with a frequency dependence of the peak position and a non-zero imaginary component below T c shows it is in fact associated with a spin-glass transition. Highly structured magnetic diffuse neutron scattering from single crystals develops between 50 K and 25 K revealing the presence of magnetic disorder which is correlated in nature. Here, the 3D-mΔPDF method is used to visualize the local magnetic ordering preferences, and ferromagnetic nearest-neighbor and antiferromagnetic third nearest-neighbor correlations are shown to be dominant. Their temperature dependence is extraordinary with some flipping in sign and a strongly varying correlation length. The correlations can be explained by orbital interaction mechanisms for the magnetic pathways and a preferred spin cluster. This study demonstrates the power of the 3D-mΔPDF method in visualizing complex quantum phenomena thereby providing a way to obtain an atomic-scale understanding of magnetic frustration., (© 2022 The Authors. Advanced Materials published by Wiley-VCH GmbH.)

PIONEER is a high Q-resolution, single-crystal, polarized neutron diffractometer at the Second Target Station (STS), Oak Ridge National Laboratory. It will provide the unprecedented capability of measuring tiny crystals (0.001 mm 3 , i.e., x-ray diffraction size), ultra-thin films (10 nm thickness), and weak structural and magnetic transitions. PIONEER benefits from the increased peak brightness of STS cold-neutron sources and uses advanced Montel mirrors that are able to deliver a focused beam with a high brilliance transfer, a homogeneous profile, and a low background. Monte Carlo simulations suggest that the optimized instrument has a high theoretical peak brilliance of 2.9 × 10 12 n cm -2 sr -1 Å -1 s -1 at 2.5 Å at the sample position, within a 5 × 5 mm 2 region and a ±0.3° divergence range. The moderator-to-sample distance is 60 m, providing a nominal wavelength band of 4.3 Å with a wavelength resolution better than 0.2% in the wavelength range of 1.0-6.0 Å. PIONEER is capable of characterizing large-scale periodic structures up to 200 Å. With a sample-to-detector distance of 0.8 m, PIONEER accommodates various sample environments, including low/high temperature, high pressure, and high magnetic/electric field. A large cylindrical detector array (4.0 sr) with a radial collimator is planned to suppress the background scattering from sample environments. Bottom detector banks provide an additional 0.4 sr coverage or can be removed if needed to accommodate special sample environments. We present virtual experimental results to demonstrate the scientific performance of PIONEER in measuring tiny samples.

Otoliths are frequently used to infer environmental conditions or fish life history events based on trace-element concentrations. However, otoliths can be comprised of any one or combination of the three most common polymorphs of calcium carbonate-aragonite, calcite, and vaterite-which can affect the ecological interpretation of otolith trace-element results. Previous studies have reported heterogeneous calcium carbonate compositions between left and right otoliths but did not provide quantitative assessments of polymorph abundances. In this study, neutron diffraction and Raman spectroscopy were used to identify and quantify mineralogical compositions of Chinook salmon Oncorhynchus tshawytscha otolith pairs. We found mineralogical compositions frequently differed between otoliths in a pair and accurate calcium carbonate polymorph identification was rarely possible by visual inspection alone. The prevalence of multiple polymorphs in otoliths is not well-understood, and future research should focus on identifying otolith compositions and investigate how variations in mineralogy affect trace-element incorporation and potentially bias environmental interpretations., (© 2022. The Author(s).)

A user-friendly program has been developed to analyze diffuse scattering from single crystals with the reverse Monte Carlo method. The approach allows for refinement of correlated disorder from atomistic supercells with magnetic or structural (occupational and/or displacive) disorder. The program is written in Python and optimized for performance and efficiency. Refinements of two user cases obtained with legacy neutron-scattering data demonstrate the effectiveness of the approach and the developed program. It is shown with bixbyite, a naturally occurring magnetic mineral, that the calculated three-dimensional spin-pair correlations are resolved with finer real-space resolution compared with the pair distribution function calculated directly from the reciprocal-space pattern. With the triangular lattice Ba 3 Co 2 O 6 (CO 3 ) 0.7 , refinements of occupational and displacive disorder are combined to extract the one-dimensional intra-chain correlations of carbonate molecules that move toward neighboring vacant sites to accommodate strain induced by electrostatic interactions. The program is packaged with a graphical user interface and extensible to serve the needs of single-crystal diffractometer instruments that collect diffuse-scattering data., (© Zachary J. Morgan et al. 2021.)

Changes to calcium carbonate (CaCO 3 ) biomineralization in aquatic organisms is among the many predicted effects of climate change. Because otolith (hearing/orientation structures in fish) CaCO 3 precipitation and polymorph composition are controlled by genetic and environmental factors, climate change may be predicted to affect the phenotypic plasticity of otoliths. We examined precipitation of otolith polymorphs (aragonite, vaterite, calcite) during early life history in two species of sturgeon, Lake Sturgeon, (Acipenser fulvescens) and White Sturgeon (A. transmontanus), using quantitative X-ray microdiffraction. Both species showed similar fluctuations in otolith polymorphs with a significant shift in the proportions of vaterite and aragonite in sagittal otoliths coinciding with the transition to fully exogenous feeding. We also examined the effect of the environment on otolith morphology and polymorph composition during early life history in Lake Sturgeon larvae reared in varying temperature (16/22 °C) and pCO 2 (1000/2500 µatm) environments for 5 months. Fish raised in elevated temperature had significantly increased otolith size and precipitation of large single calcite crystals. Interestingly, pCO 2 had no statistically significant effect on size or polymorph composition of otoliths despite blood pH exhibiting a mild alkalosis, which is contrary to what has been observed in several studies on marine fishes. These results suggest climate change may influence otolith polymorph composition during early life history in Lake Sturgeon.

Spin-valley locking in monolayer transition metal dichalcogenides has attracted enormous interest, since it offers potential for valleytronic and optoelectronic applications. Such an exotic electronic state has sparsely been seen in bulk materials. Here, we report spin-valley locking in a Dirac semimetal BaMnSb 2 . This is revealed by comprehensive studies using first principles calculations, tight-binding and effective model analyses, angle-resolved photoemission spectroscopy measurements. Moreover, this material also exhibits a stacked quantum Hall effect (QHE). The spin-valley degeneracy extracted from the QHE is close to 2. This result, together with the Landau level spin splitting, further confirms the spin-valley locking picture. In the extreme quantum limit, we also observed a plateau in the z-axis resistance, suggestive of a two-dimensional chiral surface state present in the quantum Hall state. These findings establish BaMnSb 2 as a rare platform for exploring coupled spin and valley physics in bulk single crystals and accessing 3D interacting topological states.

We provide up-to-date morphological and compositional data on otoliths of the osteoglossomorph Goldeye (Hiodon alosoides). Using computed tomography (CT) X-ray, we documented the location of each of the three pairs of otoliths (lapilli, sagittae, and asterisci) in relation to the swim bladder, which extended forward in close proximity to the sagittae and asterisci. The lappili were the largest otoliths in terms of surface area and volume, but the sagittae were highly modified, appearing spiral in shape when viewed dorsally, with a surface area to volume ratio more than double that of the lapilli. Using scanning electron microscopy, the surface of each otolith was viewable in great detail, and small otoconia (~10.5 μm diameter) were observed on each, but were most numerous on the sagittae. On scanning electron micrographs, the sagittae appeared to be bi-lobed, with asymmetrical lobes each oriented in the same general direction. Using neutron and X-ray diffraction methods, we found three polymorphs of calcium carbonate crystals (aragonite, vaterite, and calcite), sometimes all within the same otolith. However, in general, lapilli and sagittae were composed predominately of aragonite whereas asterisci were composed chiefly of vaterite. With these results, we provide information on a unique species, whose inclusion in future studies would benefit our understanding of fish hearing, fish evolution, and fisheries ecology., (© 2021 Wiley Periodicals LLC. This article has been contributed to by US Government employees and their work is in the public domain in the USA.)

Polar van der Waals chalcogenophosphates exhibit unique properties, such as negative electrostriction and multi-well ferrielectricity, and enable combining dielectric and 2D electronic materials. Using low temperature piezoresponse force microscopy, we revealed coexistence of piezoelectric and non-piezoelectric phases in CuInP 2 Se 6 , forming unusual domain walls with enhanced piezoelectric response. From systematic imaging experiments we have inferred the formation of a partially polarized antiferroelectric state, with inclusions of structurally distinct ferrielectric domains enclosed by the corresponding phase boundaries. The assignment is strongly supported by optical spectroscopies and density-functional-theory calculations. Enhanced piezoresponse at the ferrielectric/antiferroelectric phase boundary and the ability to manipulate this entity with electric field on the nanoscale expand the existing phenomenology of functional domain walls. At the same time, phase-coexistence in chalcogenophosphates may lead to rational strategies for incorporation of ferroic functionality into van der Waals heterostructures, with stronger resilience toward detrimental size-effects.

Fish otoliths, or ear bones, are comprised of the CaCO 3 polymorphs (aragonite, calcite and vaterite), which can occur either alone or in combination. The polymorph phase abundance in an otolith depends on, as yet, unexplained genetic and environmental factors. Most fish otoliths are comprised of the densest CaCO 3 polymorph, aragonite. Sturgeon otoliths, on the other hand, contain significant amounts of the rare and the structurally enigmatic polymorph, vaterite. Sturgeon otoliths are frequently comprised of agglomerations of small microcrystalline vaterite spherulites (<300 μm in diameter), that range in shape from nearly perfect spheres to oblate spheroids. These spherulites are similar to the synthetic vaterite microspheres employed in laser trapping applications. Vaterite spherulites from both hatchery-reared (juvenile) and wild (adult) Lake Sturgeon exhibit extreme crystallographic texture as evidenced by X-ray diffraction patterns and their reconstructed pole-figures determined here. The vaterite crystallites making up the spherulites have excellent registry in both the axial and equatorial directions. Whether synthesized or natural, the texture manifested in these spherulites suggests that vaterite nucleates and grows similarly in vivo otolith formation as well as from laboratory synthesis. The uniaxial optical character of the vaterite spherulites, confirmed by these diffraction experiments and combined with their large birefringence, makes them well suited for laser trapping applications.

In this study we quantified the percent CaCO 3 polymorph composition in otoliths of larval and juvenile Lake Sturgeon Acipenser fulvescens via X-ray microdiffraction. Sagittal otoliths of sub-adults were primarily composed of aragonite (> 90%) while the lapilli otoliths were 100% vaterite. This is the first time the presence of aragonite in otoliths has been reported in an acipenseriform and is surprising given that the ability to form aragonite otoliths was not thought to have evolved until the separation of teleost and holostean species from other Actinopterygian fishes (e.g., sturgeon, paddlefish, gar)., (© 2019 The Fisheries Society of the British Isles.)

Wide Angle Neutron Diffractometer Squared is a high-flux versatile diffractometer with a 2-Dimensional Position Sensitive Detector at the High Flux Isotope Reactor. The instrument has strengths in both powder and single crystal diffraction. It is a unique instrument in the neutron scattering landscape of North America, and its capabilities are at least equal to similar instruments in the world.

The nascent suite of single-crystal neutron diffractometers at the Oak Ridge National Laboratory has no equal at any other neutron scattering facility worldwide and offers the potential to re-assert single-crystal diffraction using neutrons as a significant tool to study nuclear and magnetic structures of small unit cell crystals, nuclear structures of macromolecules, and diffuse scattering. Signature applications and features of single-crystal neutron diffraction are high resolution nuclear structure analysis, magnetic structure and spin density determinations, contrast variation (particularly D 2 O/H 2 O) for nuclear structural studies, lack of radiation damage when using crystals of biological molecules such as proteins, and the fidelity to measure nuclear and magnetic diffuse scattering with elastic discrimination.

Frustrated magnetic systems exhibit extraordinary physical properties, but quantification of their magnetic correlations poses a serious challenge to experiment and theory. Current insight into frustrated magnetic correlations relies on modelling techniques such as reverse Monte-Carlo methods, which require knowledge about the exact ordered atomic structure. Here, we present a method for direct reconstruction of magnetic correlations in frustrated magnets by three-dimensional difference pair distribution function analysis of neutron total scattering data. The methodology is applied to the disordered frustrated magnet bixbyite, (Mn 1- x Fe x ) 2 O 3 , which reveals nearest-neighbor antiferromagnetic correlations for the metal sites up to a range of approximately 15 Å. Importantly, this technique allows for magnetic correlations to be determined directly from the experimental data without any assumption about the atomic structure.

Multiferroics materials, which exhibit coupled magnetic and ferroelectric properties, have attracted tremendous research interest because of their potential in constructing next-generation multifunctional devices. The application of single-phase multiferroics is currently limited by their usually small magnetoelectric effects. Here, we report the realization of giant magnetoelectric effects in a Y-type hexaferrite Ba 0.4 Sr 1.6 Mg 2 Fe 12 O 22 single crystal, which exhibits record-breaking direct and converse magnetoelectric coefficients and a large electric-field-reversed magnetization. We have uncovered the origin of the giant magnetoelectric effects by a systematic study in the Ba 2-x Sr x Mg 2 Fe 12 O 22 family with magnetization, ferroelectricity and neutron diffraction measurements. With the transverse spin cone symmetry restricted to be two-fold, the one-step sharp magnetization reversal is realized and giant magnetoelectric coefficients are achieved. Our study reveals that tuning magnetic symmetry is an effective route to enhance the magnetoelectric effects also in multiferroic hexaferrites.Control of the electrical properties of materials by means of magnetic fields or vice versa may facilitate next-generation spintronic devices, but is still limited by their intrinsically weak magnetoelectric effect. Here, the authors report the existence of an enhanced magnetoelectric effect in a Y-type hexaferrite, and reveal its underlining mechanism.

Otoliths, calcium carbonate (CaCO 3 ) ear bones, are among the most commonly used age and growth structures of fishes. Most fish otoliths are comprised of the most dense CaCO 3 polymorph, aragonite. Sturgeon otoliths, in contrast, have been characterized as the rare and structurally enigmatic polymorph, vaterite-a metastable polymorph of CaCO 3 . Vaterite is an important material ranging from biomedical to personal care applications although its crystal structure is highly debated. We characterized the structure of Lake Sturgeon otoliths using thermal analysis and neutron powder diffraction, which is used non-destructively. We confirmed that while Lake Sturgeon otoliths are primarily composed of vaterite, they also contain the denser CaCO 3 polymorph, calcite. For the vaterite fraction, neutron diffraction data provide enhanced discrimination of the carbonate group compared to x-ray diffraction data, owing to the different relative neutron scattering lengths, and thus offer the opportunity to uniquely test the more than one dozen crystal structural models that have been proposed for vaterite. Of those, space group P6 5 22 model, a = 7.1443(4)Å, c = 25.350(4)Å, V = 1121.5(2)Å 3 provides the best fit to the neutron powder diffraction data, and allows for a structure refinement using rigid carbonate groups.

The first high-resolution neutron protein structure of perdeuterated rubredoxin from Pyrococcus furiosus (PfRd) determined using the new IMAGINE macromolecular neutron crystallography instrument at the Oak Ridge National Laboratory is reported. Neutron diffraction data extending to 1.65 Å resolution were collected from a relatively small 0.7 mm(3) PfRd crystal using 2.5 d (60 h) of beam time. The refined structure contains 371 out of 391, or 95%, of the D atoms of the protein and 58 solvent molecules. The IMAGINE instrument is designed to provide neutron data at or near atomic resolution (1.5 Å) from crystals with volume <1.0 mm(3) and with unit-cell edges <100 Å. Beamline features include novel elliptical focusing mirrors that deliver neutrons into a 2.0 × 3.2 mm focal spot at the sample position with full-width vertical and horizontal divergences of 0.5 and 0.6°, respectively. Variable short- and long-wavelength cutoff optics provide automated exchange between multiple-wavelength configurations (λmin = 2.0, 2.8, 3.3 Å to λmax = 3.0, 4.0, 4.5, ∼20 Å). These optics produce a more than 20-fold increase in the flux density at the sample and should help to enable more routine collection of high-resolution data from submillimetre-cubed crystals. Notably, the crystal used to collect these PfRd data was 5-10 times smaller than those previously reported.

Six members of a new family of cerium-halide-based materials with promising scintillation behavior have been synthesized in single crystal form, and their crystal structures were determined. Specifically, these new compounds are [(CeCl(3))(7)(BuOH)(16)(H(2)O)(2)]·(BuOH)(2) (1), (CeBr(3))(14)(BuOH)(36) (2), [(CeCl(3))(7)(1-PrOH)(16)(H(2)O)(2)]·(1-PrOH)(2) (3), [(CeBr(3))(7)(1-PrOH)(18)]·(1-PrOH)(2) (4), [(CeCl(3))(6)(iBuOH)(15)]·(iBuOH)(2) (5), and CeCl(3)(sec-BuOH)(2)(H(2)O) (6). Additionally, the scintillation ability of compound 1 was established. The structures of these cerium-halide-based materials consist of catenated tetradecanuclear rings that arrange themselves into three distinct structural motifs which contain the largest lanthanide-based ring structures reported to date; the different motifs are obtained by involving specific alcohols during synthesis. Specifically, n-butanol and n-propanol lead to 1-D chains of tetradecanuclear rings, and iso-butanol leads to 2-D parquet-patterned sheets of rectangular tetradecanuclear rings, while sec-butanol results in a zigzag 1-D chain structure. One of the compounds, [(CeCl(3))(6)(iBuOH)(15)]·(iBuOH)(2), has been shown to scintillate with a light yield of up to 1920 photons/MeV, and due to the presence of protons, it should be capable of detecting high energy neutrons without the necessity of prior thermalization. Furthermore, it also appears to be the first cerium-based compound that scintillates in spite of the fact that water coordinates to two of the Ce(III) centers within the structure.

The relationship between vacancy ordering and magnetism in TlFe(1.6)Se(2) has been investigated via single crystal neutron diffraction, nuclear forward scattering, and transmission electron microscopy. The examination of chemically and structurally homogeneous crystals allows the true ground state to be revealed, which is characterized by Fe moments lying in the ab plane below 100 K. This is in sharp contrast to crystals containing regions of order and disorder, where a competition between c axis and ab plane orientations of the moments is observed. The properties of partially disordered TlFe(1.6)Se(2) are, therefore, not associated with solely the ordered or disordered regions. This contrasts the viewpoint that phase separation results in independent physical properties in intercalated iron selenides, suggesting a coupling between ordered and disordered regions may play an important role in the superconducting analogues.

Samples with the type I clathrate structure and composition Ba(8)Al(x)Si(46-x), where x = 8, 10, 12, 14, and 15, were examined by neutron powder diffraction at 35 K. The clathrate type I structure contains Ba cations as guests in a framework derived from tetrahedrally coordinated Al/Si atoms. The framework is made up of five- and six-membered rings that form dodecahedral and tetrakaidecahedral cages. The change in distances between tetrahedral sites across the series is used to develop a model for the mixed Al/Si occupancy observed in the framework. The calculated volumes of the cages that contain the Ba atoms display a linear increase with increasing Al composition. In the smaller dodecahedral cages, the Ba atomic displacement parameter is symmetry constrained to be isotropic for all compositions. In the larger tetrakaidecahedral cages, the anisotropic atomic displacement of the Ba atom depends upon the composition: the displacement is perpendicular (x = 8) and parallel (x = 15) to the six-membered ring. This difference in direction of the displacement parameter is attributed to interaction with the Al in the framework and not to the size of the cage volume as x increases from 8 to 15. The influence of the site occupation of Al in the framework on displacement of the cation at the 6d site is demonstrated.

Atoms and molecules <0.9 nm in diameter can be incorporated in the cages formed by hydrogen-bonded water molecules making up the crystalline solid clathrate hydrates. For these materials crystallographic structures generally fall into 3 categories, which are 2 cubic forms and a hexagonal form. A unique clathrate hydrate structure, previously known only hypothetically, has been synthesized at high pressure and recovered at 77 K and ambient pressure in these experiments. These samples contain Xe as a guest atom and the details of this previously unobserved structure are described here, most notably the host-guest ratio is similar to the cubic Xe clathrate starting material. After pressure quench recovery to 1 atmosphere the structure shows considerable metastability with increasing temperature (T <160 K) before reverting back to the cubic form. This evidence of structural complexity in compositionally similar clathrate compounds indicates that the reaction path may be an important determinant of the structure, and impacts upon the structures that might be encountered in nature.

Mössbauer-effect and microwave absorption experimental evidence unambiguously demonstrates the presence of slow, approximately 450 MHz, tunneling of magnetic europium between four equivalent sites in Eu8Ga16Ge30, a stoichiometric clathrate. Remarkably, six of the eight europium atoms, or 11% of the constituents in this solid, tunnel between these four sites separated by 0.55 A. The off centering of the atoms or ions in crystalline clathrates appears to be a promising route for producing Rabi oscillators in solid-state materials.

Mean-square atomic displacements in lanthanum triiron cobalt dodecaantimonide, determined as a function of temperature using single-crystal neutron diffraction, show that the La atom exhibits an anomalously large displacement at room temperature, U(eq) = 0.0196 (9) Å(2), because it is too small to fill the atomic cage formed by the corner-linked octahedral framework of M(4)Sb(12), M = Fe, Co. Site-occupancy refinements show 25% vacancies on the La site and an actual Fe:Co ratio of 2.17:1. Analysis of the temperature dependence of the atomic displacements identifies a significant temperature-independent component for the La atom ascribed to static disorder, which amounts to 19% of the room-temperature value. The large-amplitude rattling of the La atom can be effectively linked to the dramatic decrease of the lattice contribution to the thermal conductivity, which is a key factor for improving the thermoelectric behavior of these materials. This structure-property relationship offers a new paradigm for the exploration of thermoelectric materials.

Pulsed-laser deposition was used to synthesize artificially layered high-temperature superconductors. Thin-film compounds were formed when the constraint of epitaxy was used to stabilize SrCuO(2)-BaCuO(2) superlattices in the infinite layer structure. Using this approach, two new structural families, Ba(2)Srn-1,Cun+1 O2n+2+delta and Ba(4)Srn-1 Cun+3O2n+6+delta have been synthesized; these families superconduct at temperatures as high as 70 kelvin.

A natural single crystal of zircon, ZrSiO(4,) from Sri Lanka exhibited zonation due to alpha-decay damage. The zones vary in thickness on a scale from one to hundreds of micrometers. The uranium and thorium concentrations vary from zone to zone such that the alpha-decay dose is between 0.2 x 10(16) and 0.8 x 10(16) alpha-events per milligram (0.15 to 0.60 displacement per atom). The transition from the crystalline to the aperiodic metamict state occurs over this dose range. Differential expansion of individual layers due to variations in their alpha-decay dose caused a systematic pattern of fractures that do not propagate across aperiodic layers. High-resolution transmission electron microscopy revealed a systematic change in the microstructure from a periodic atomic array to an aperiodic array with increasing alpha-decay dose. At doses greater than 0.8 x 10(16) alpha-events per milligram there is no evidence for long-range order. This type of damage will accumulate in actinide-bearing, ceramic nuclear waste forms. The systematic pattern of fractures would occur in crystalline phases that are zoned with respect to actinide radionuclides.