Atomic and Electronic Structure in MgO-SiO2.

Understanding disordered structure is difficult due to insufficient information in experimental data. Here, we overcome this issue by using a combination of diffraction and simulation to investigate oxygen packing and network topology in glassy (g-) and liquid (l-) MgO-SiO2 based on a comparison with the crystalline topology. We find that packing of oxygen atoms in Mg2SiO4 is larger than that in MgSiO3, and that of the glasses is larger than that of the liquids. Moreover, topological analysis suggests that topological similarity between crystalline (c)- and g-(l-) Mg2SiO4 is the signature of low glass-forming ability (GFA), and high GFA g-(l-) MgSiO3 shows a unique glass topology, which is different from c-MgSiO3. We also find that the lowest unoccupied molecular orbital (LUMO) is a free electron-like state at a void site of magnesium atom arising from decreased oxygen coordination, which is far away from crystalline oxides in which LUMO is occupied by oxygen's 3s orbital state in g- and l-MgO-SiO2, suggesting that electronic structure does not play an important role to determine GFA. We finally concluded the GFA of MgO-SiO2 binary is dominated by the atomic structure in terms of network topology.

Outstanding Energy-Storage Density Together with Efficiency of above 90% via Local Structure Design.

Dielectric ceramic capacitors with high recoverable energy density (Wrec) and efficiency (η) are of great significance in advanced electronic devices. However, it remains a challenge to achieve high Wrec and η parameters simultaneously. Herein, based on density functional theory calculations and local structure analysis, the feasibility of developing the aforementioned capacitors is demonstrated by considering Bi0.25Na0.25Ba0.5TiO3 (BNT-50BT) as a matrix material with large local polarization and structural distortion. Remarkable Wrec and η of 16.21 J/cm3 and 90.5% have been achieved in Bi0.25Na0.25Ba0.5Ti0.92Hf0.08O3 via simple chemical modification, which is the highest Wrec value among reported bulk ceramics with η greater than 90%. The examination results of local structures at lattice and atomic scales indicate that the disorderly polarization distribution and small nanoregion (∼3 nm) lead to low hysteresis and high efficiency. In turn, the drastic increase in local polarization activated via the ultrahigh electric field (80 kV/mm) leads to large polarization and superior energy storage density. Therefore, this study emphasizes that chemical design should be established on a clear understanding of the performance-related local structure to enable a targeted regulation of high-performance systems.

Achieving giant electrostrain of above 1% in (Bi,Na)TiO3-based lead-free piezoelectrics via introducing oxygen-defect composition.

Piezoelectric ceramics have been extensively used in actuators, where the magnitude of electrostrain is key indicator for large-stroke actuation applications. Here, we propose an innovative strategy based on defect chemistry to form a defect-engineered morphotropic phase boundary and achieve a giant strain of 1.12% in lead-free Bi0.5Na0.5TiO3 (BNT)-based ceramics. The incorporation of the hypothetical perovskite BaAlO2.5 with nominal oxygen defect into BNT will form strongly polarized directional defect dipoles, leading to a strong pinning effect after aging. The large asymmetrical strain is mainly attributed to two factors: The defect dipoles along crystallographic [001] direction destroy the long-range ordering of the ferroelectric and activate a reversible phase transition while promoting polarization rotation when the dipoles are aligned along the applied electric field. Our results not only demonstrate the potential application of BNT-based materials in low-frequency, large-stroke actuators but also provide a general methodology to achieve large strain.

Lorentz factor for time-of-flight neutron Bragg and total scattering.

The three fundamental origins of the Lorentz factor for neutron time-of-flight powder diffraction are revisited. A detailed derivation of the Lorentz factor is presented in the context of diffuse scattering modelling in reciprocal space when perfect periodicity is assumed, and the total scattering pattern is constructed in its discrete form - the factor in this case becomes 1/Q2 (or d2). Discussion is also presented with respect to practical data reduction where a vanadium measurement is usually taken as the normalization factor (to account for various factors such as detector efficiency), and it is shown that the existence of the Lorentz factor is independent of such a normalization process.

Orientational disorder in sulfur hexafluoride: a neutron total scattering and reverse Monte Carlo study.

The orientational disorder in crystalline sulfur hexafluoride, SF6, has been studied using a combination of neutron total scattering and the reverse Monte Carlo method. Analysis of the atomic configurations has shown the extent of the disorder through the evaluation of the S-F bond orientational distribution function, consistent with, but improving upon, the results of earlier neutron powder diffraction data. The correlations between orientations of neighbouring molecules have been studied through analysis of the distributions of F-F distances, showing that nearest-neighbour F-F close contacts are avoided, consistent with previous molecular dynamics simulation results. The results present a new case study of the application of neutron total scattering and the reverse Monte Carlo methods for the study of orientational disorder, where in this instance the disorder arises from orientational frustration rather than from a mismatch of molecular and site symmetries.

Intermolecular correlations of liquid and glassy CS2 studied by synchrotron radiation x-ray diffraction.

How is the orientation of molecular liquids ordered on cooling? What are the basic structures of molecular glasses, e.g., close to the crystalline structure or some special structures such as icosahedral cluster? These are long-standing questions in liquid and glass physics. We have constructed a novel cryostat to prepare simple molecular glasses by vapor deposition and performed in situ synchrotron radiation x-ray diffraction experiments. The glassy state of a simple molecule CS2, which cannot be vitrified by normal liquid quenching, was successfully prepared with this instrument, and its diffraction data were collected in a wide Q-range of 0.16-25.7 Å-1 with a high-energy diffractometer at BL04B2, SPring-8. The diffraction data of liquid CS2 were also recorded in a wide temperature range of 160-300 K. These diffraction data were analyzed with molecular dynamics simulations and reverse Monte Carlo modelings to investigate orientational correlation. From the obtained 3D structure models, the orientational correlation between neighboring CS2 molecules was investigated quantitatively as a function of temperature. At room temperature, the parallel and T-shaped arrangements are preferred for the nearest neighbor correlation. On cooling, these arrangements are developed gradually, and its rate became prominent below the melting temperature (162 K). In the glassy state, the slipped-parallel arrangement is dominant as well as the T-shaped arrangement. Both arrangements appear in the CS2 crystal, indicating that the structure of glassy CS2 is close to that of crystalline CS2.

Orientational order and phase transitions in deuterated methane: a neutron total scattering and reverse Monte Carlo study.

We report a study of the orientational order and phase transitions in crystalline deuterated methane, carried out using neutron total scattering and the reverse Monte Carlo method. The resultant atomic configurations are consistent with the average structures obtained from Rietveld refinement of the powder diffraction data, but additionally enable us to determine the C-D bond orientational distribution functions (ODF) for the disordered molecules in the high-temperature phase, and for both ordered and disordered molecules in the intermediate-temperature phase. We show that this approach gives more accurate information than can been obtained from fitting a bond ODF to diffraction data. Given the resurgence of interest in orientationally-disordered crystals, we argue that the approach of total scattering with the RMC method provides a unique quantification of orientational order and disorder.

A cloud platform for atomic pair distribution function analysis: PDFitc.

A cloud web platform for analysis and interpretation of atomic pair distribution function (PDF) data (PDFitc) is described. The platform is able to host applications for PDF analysis to help researchers study the local and nanoscale structure of nanostructured materials. The applications are designed to be powerful and easy to use and can, and will, be extended over time through community adoption and development. The currently available PDF analysis applications, structureMining, spacegroupMining and similarityMapping, are described. In the first and second the user uploads a single PDF and the application returns a list of best-fit candidate structures, and the most likely space group of the underlying structure, respectively. In the third, the user can upload a set of measured or calculated PDFs and the application returns a matrix of Pearson correlations, allowing assessment of the similarity between different data sets. structureMining is presented here as an example to show the easy-to-use workflow on PDFitc. In the future, as well as using the PDFitc applications for data analysis, it is hoped that the community will contribute their own codes and software to the platform.

Local structure and distortions of mixed methane-carbon dioxide hydrates.

A vast source of methane is found in gas hydrate deposits, which form naturally dispersed throughout ocean sediments and arctic permafrost. Methane may be obtained from hydrates by exchange with hydrocarbon byproduct carbon dioxide. It is imperative for the development of safe methane extraction and carbon dioxide sequestration to understand how methane and carbon dioxide co-occupy the same hydrate structure. Pair distribution functions (PDFs) provide atomic-scale structural insight into intermolecular interactions in methane and carbon dioxide hydrates. We present experimental neutron PDFs of methane, carbon dioxide and mixed methane-carbon dioxide hydrates at 10 K analyzed with complementing classical molecular dynamics simulations and Reverse Monte Carlo fitting. Mixed hydrate, which forms during the exchange process, is more locally disordered than methane or carbon dioxide hydrates. The behavior of mixed gas species cannot be interpolated from properties of pure compounds, and PDF measurements provide important understanding of how the guest composition impacts overall order in the hydrate structure.

Predicting short-range order and correlated phenomena in disordered crystalline materials.

Disordered crystalline materials are used in a wide variety of energy-related technologies. Recent results from neutron total scattering experiments have shown that the atomic arrangements of many disordered crystalline materials are not random nor are they represented by the long-range structure observed from diffraction experiments. Despite the importance of disordered materials and the impact of disorder on the expression of physical properties, the underlying fundamental atomic-scale rules of disordering are not currently well understood. Here, we report that heterogeneous disordering (and associated structural distortions) can be understood by the straightforward application of Pauling's rules (1929). This insight, corroborated by first principles calculations, can be used to predict the short-range, atomic-scale changes that result from structural disordering induced by extreme conditions associated with energy-related applications, such as high temperature, high pressure, and intense radiation fields.

Structure-mining: screening structure models by automated fitting to the atomic pair distribution function over large numbers of models.

A new approach is presented to obtain candidate structures from atomic pair distribution function (PDF) data in a highly automated way. It fetches, from web-based structural databases, all the structures meeting the experimenter's search criteria and performs structure refinements on them without human intervention. It supports both X-ray and neutron PDFs. Tests on various material systems show the effectiveness and robustness of the algorithm in finding the correct atomic crystal structure. It works on crystalline and nanocrystalline materials including complex oxide nanoparticles and nanowires, low-symmetry and locally distorted structures, and complicated doped and magnetic materials. This approach could greatly reduce the traditional structure searching work and enable the possibility of high-throughput real-time auto-analysis PDF experiments in the future.

Neutron scattering study of the orientational disorder and phase transitions in barium carbonate.

Orientational disorder of the molecular [Formula: see text] anions in BaCO3, which occurs naturally as the mineral witherite, has been studied using a combination of neutron total scattering analysed by the reverse Monte Carlo method and molecular dynamics simulations. The primary focus is on the phase transition to the cubic phase, which assumes a rocksalt structure (Strukturbericht type B1) with highly disordered orientations consistent with the mismatch between the site ([Formula: see text]) and molecular (3/m) symmetries. Both experiment and simulation show a high degree of disorder, with the C-O bond orientation distribution never exceeding 25% variation from that of a completely uniform distribution, although there are differences between the two methods regarding the nature of these variations. Molecular dynamics simulations are also reported for the analogous phase transitions in the very important mineral calcite, CaCO3. The combination of the simulations and comparison with BaCO3 shows that the properties of calcite at all temperatures within its stability field are affected mostly by the onset of orientational disorder associated with the high-temperature cubic phase, even though this lies outside the stability field of calcite. This is a new understanding of calcite, which previously had been interpreted purely in terms of the phase transition to an intermediate partially-disordered phase. Finally, we also found that witherite itself appears to support the development of orientational disorder on heating, with the simulations showing a sequence of phase transitions that explain the much larger thermal expansion of one axis.

High-Pressure Study of the Elpasolite Perovskite La2NiMnO6.

Here we report a high-pressure investigation into the structural and magnetic properties of the double perovskite La2NiMnO6 using neutron scattering over a temperature range of 4.2-300 K at ambient pressure and over a temperature range of 120-1177 K up to a maximum pressure of 6.6 GPa. X-ray diffraction was also used up to a maximum pressure of 64 GPa, over a temperature range of 300-720 K. The sample was found to exist in a mixed rhombohedral/monoclinic symmetry at ambient conditions, the balance of which was found to be strongly temperature- and pressure-dependent. Alternating current magnetometry and X-ray absorption near-edge structure measurements were made at ambient pressure to characterize the sample, suggesting that the transition-metal sites exist in a mixed Ni3+/Mn3+ and Ni2+/Mn4+ state at ambient temperature and pressure. Analysis of the magnetic properties of the sample shows that the Curie temperature can be enhanced by ∼12 K with 2 GPa applied pressure, but it is highly stable at pressures beyond this. We report a pressure-volume-temperature equation of state for this material over this combined temperature and pressure range, with an ambient temperature bulk modulus of ∼179(8) GPa. The previously reported transition from monoclinic to rhombohedral symmetry upon heating to 700 K is seen to be encouraged with applied pressure, transforming fully by ∼1.5 GPa. Raman spectroscopy data were collected up to ∼8 GPa and show no clear changes or discontinuities over the reported phase transition to rhombohedral symmetry or any indication of further changes over the range considered. The ambient-pressure Grüneisen parameter γth was determined to be γth = 2.6 with a Debye temperature of 677 K. The individual modal parameters γj at ambient temperature were also determined from the high-pressure Raman data.

1 m long multilayer-coated deformable piezoelectric bimorph mirror for adjustable focusing of high-energy X-rays.

The Diamond Light Source (DLS) beamline I15-1 measures atomic pair distribution functions (PDF) using scattering of 40-80 keV X-rays. A unique focusing element was needed to condense these X-rays from an initial large cross section (11.0 mm H × 4.2 mm V) into a required spot size of FWHM ≈680 µm (H) × 20 µm (V) at a variable position between the sample and the detector. The large numerical aperture is achieved by coating a silicon substrate over 1 m long with three multilayer stripes of Bragg angle 4.2 mrad. One stripe selects X-rays of each energy 40.0, 65.4, and 76.6 keV. Sixteen piezoelectric bimorph actuators attached to the sides of the mirror substrate adjusted the reflecting surface's shape. Focal spots of vertical width < 15 µm were obtained at three positions over a 0.92 m range, with fast, easy switching from one focal position to another. Minimized root mean square slope errors were close to 0.5 µrad after subtraction of a uniform curvature. Reflectivity curves taken along each stripe showed consistent high peaks with generally small angular variation of peak positions. This is the first application of a 1 m long multilayer-coated bimorph mirror at a synchrotron beamline. Data collected with its help on a slice of a lithium ion battery's cathode are presented.

Hydrogen-bond-mediated structural variation of metal guanidinium formate hybrid perovskites under pressure.

The hybrid perovskites are coordination frameworks with the same topology as the inorganic perovskites, but with properties driven by different chemistry, including host-framework hydrogen bonding. Like the inorganic perovskites, these materials exhibit many different phases, including structures with potentially exploitable functionality. However, their phase transformations under pressure are more complex and less well understood. We have studied the structures of manganese and cobalt guanidinium formate under pressure using single-crystal X-ray and powder neutron diffraction. Under pressure, these materials transform to a rhombohedral phase isostructural to cadmium guanidinium formate. This transformation accommodates the reduced cell volume while preserving the perovskite topology of the framework. Using density-functional theory calculations, we show that this behaviour is a consequence of the hydrogen-bonded network of guanidinium ions, which act as struts protecting the metal formate framework against compression within their plane. Our results demonstrate more generally that identifying suitable host-guest hydrogen-bonding geometries may provide a route to engineering hybrid perovskite phases with desirable crystal structures. This article is part of the theme issue 'Mineralomimesis: natural and synthetic frameworks in science and technology'.

Mechanistic Insights into the Superexchange-Interaction-Driven Negative Thermal Expansion in CuO.

The negative thermal expansion (NTE) in CuO is explained via electron-transfer-driven superexchange interaction. The elusive connection between the spin-lattice coupling and NTE of CuO is investigated by neutron scattering and principal strain axes analysis. The density functional theory calculations show as the temperature decreases, the continuously increasing electron transfer accounts for enhancing the superexchange interaction along [101̅], the principal NTE direction. It is further rationalized that only when the interaction along [101̅] is preferably enhanced to a certain level compared to the other competing antiferromagnetic exchange pathways can the corresponding NTE occur. Outcomes from this work have implications for controlling the thermal expansion through superexchange interaction, via, for example, optical manipulation, electron or hole doping, etc.

A high temperature gas flow environment for neutron total scattering studies of complex materials.

We present the design and capabilities of a high temperature gas flow environment for neutron diffraction and pair distribution function studies available at the Nanoscale Ordered Materials Diffractometer instrument at the Spallation Neutron Source. Design considerations for successful total scattering studies are discussed, and guidance for planning experiments, preparing samples, and correcting and reducing data is defined. The new capabilities are demonstrated with an in situ decomposition study of a battery electrode material under inert gas flow and an in operando carbonation/decarbonation experiment under reactive gas flow. This capability will aid in identifying and quantifying the atomistic configurations of chemically reactive species and their influence on underlying crystal structures. Furthermore, studies of reaction kinetics and growth pathways in a wide variety of functional materials can be performed across a range of length scales spanning the atomic to the nanoscale.

In situ neutron diffraction study of the formation of Ho2Ge2O7 pyrochlore at high temperature and pressure.

The formation of the spin-ice pyrochlore Ho2Ge2O7 by two different high temperature, high pressure routes has been explored using in situ neutron diffraction. The first route involves the solid-state reaction of Ho2O3 and GeO2, and formation of the pyrochlore phase is observed at 994(27) °C and 3.81(2) GPa, which are significantly milder conditions than those previously reported. The second route involves the hydrothermal synthesis of the tetragonal Ho2Ge2O7 pyrogermanate from Ho(NO3)3·5H2O and GeO2 and its subsequent transformation to the pyrochlore phase, which is observed at 683(23) °C and 3.89(3) GPa. The lowering of the formation temperature of high pressure phases by employment of a precursor of appropriate stoichiometry may also have applications in the wider field of solid-state chemistry.

ζ-Glycine: insight into the mechanism of a polymorphic phase transition.

Glycine is the simplest and most polymorphic amino acid, with five phases having been structurally characterized at atmospheric or high pressure. A sixth form, the elusive ζ phase, was discovered over a decade ago as a short-lived intermediate which formed as the high-pressure ∊ phase transformed to the γ form on decompression. However, its structure has remained unsolved. We now report the structure of the ζ phase, which was trapped at 100 K enabling neutron powder diffraction data to be obtained. The structure was solved using the results of a crystal structure prediction procedure based on fully ab initio energy calculations combined with a genetic algorithm for searching phase space. We show that the fate of ζ-glycine depends on its thermal history: although at room temperature it transforms back to the γ phase, warming the sample from 100 K to room temperature yielded ß-glycine, the least stable of the known ambient-pressure polymorphs.

Orbital Dimer Model for the Spin-Glass State in Y_{2}Mo_{2}O_{7}.

The formation of a spin glass generally requires that magnetic exchange interactions are both frustrated and disordered. Consequently, the origin of spin-glass behavior in Y_{2}Mo_{2}O_{7}-in which magnetic Mo^{4+} ions occupy a frustrated pyrochlore lattice with minimal compositional disorder-has been a longstanding question. Here, we use neutron and x-ray pair-distribution function (PDF) analysis to develop a disorder model that resolves apparent incompatibilities between previously reported PDF, extended x-ray-absorption fine structure spectroscopy, and NMR studies, and provides a new and physical explanation of the exchange disorder responsible for spin-glass formation. We show that Mo^{4+} ions displace according to a local "two-in-two-out" rule on each Mo_{4} tetrahedron, driven by orbital dimerization of Jahn-Teller active Mo^{4+} ions. Long-range orbital order is prevented by the macroscopic degeneracy of dimer coverings permitted by the pyrochlore lattice. Cooperative O^{2-} displacements yield a distribution of Mo-O-Mo angles, which in turn introduces disorder into magnetic interactions. Our study demonstrates experimentally how frustration of atomic displacements can assume the role of compositional disorder in driving a spin-glass transition.