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At least 1,189 records · Page 66

The solidification of Al–Pd–Mn studied by high-energy X-ray diffraction from electrostatically levitated samples

Here, we report on the results of a high-energy x-ray diffraction study of Al–Pd–Mn to investigate the solidification products obtained during free-cooling using an electrostatic levitation furnace. The primary solidification product from the melt is i-Al–Pd–Mn which coexists with a significant remaining liquid component. As the sample cools further, we find that the solidification pathway is consistent with the liquidus projection and pseudo-binary cut through the ternary phase diagram reported previously. At ambient temperature we have identified the major phase to be the ξ'-phase orthorhombic approximant, along with minor phases identified as Al and, most likely, the R-phase orthorhombic approximant. We have also observed a distinct prepeak in the liquid at high temperature, signifying the presence of extended atomic order. Interestingly, this prepeak was not observed in previous neutron diffraction measurements on the Al–Pd–Mn system. No undercooling was observed preceding the solidification of the i-Al–Pd–Mn phase from the melt which may signal the close similarity of the short-range order in the solid and liquid. However, this can not be clearly determined because of the potential for heterogenous nucleation associated with the presence of an Al2O3 impurity at the surface of the sample.

36 MATERIALS SCIENCE↗

Improvements in the Sample Space for the Backscattering Silicon Spectrometer (BASIS)

The increase in neutron flux at the Oak Ridge National Laboratory (ORNL) Spallation Neutron Source (SNS), currently operating at 2.0 MW proton beam power, has created new opportunities for higher-throughput neutron scattering experiments while also increasing the importance of minimizing background scattering and optimizing sample-environment operations. To address these challenges on the Backscattering Silicon Spectrometer (BA-SIS), several upgrades were developed and evaluated, including boron carbide (B₄C) masking for flat-plate sample containers, multi-cell sample holders used with a vertically translating sample stick, and an automated helium pump and purge (HPP) system for closed-cycle refrigerators. Neutron diffraction measurements demonstrate that B₄C masks reduce background scattering by 49–67%, outperforming both borated aluminum and boron nitride masks while introducing no additional Bragg reflections within the instrument’s accessible Q-range. Commissioning tests of a double-cell flat-plate sample contain-er showed no measurable crosstalk between adjacent sample compartments and con-firmed stable thermal performance, enabling multiple samples to be measured without re-peated temperature cycling. In addition, the automated HPP system provided reproducible sample-space gas handling with approximately ±1 mbar precision while reducing the need for operator intervention and supporting remote operation. Together, these developments improve signal-to-noise performance, increase experimental throughput, and enhance operational efficiency at BASIS, supporting the instrument’s continued operation under higher neutron flux conditions.

Jalarvo, Niina [ORNL] (ORCID:0000000306446866)↗

Excess-iron driven spin glass phase in Fe 1 + y Te 1 – x Se x

The iron-chalcogenide superconductor FeTe 1– x Se x displays a variety of exotic features distinct from iron pnictides. Although much effort has been devoted to understanding the interplay between magnetism and superconductivity near x = 0.5, the existence of a spin glass phase with short-range magnetic order in the doping range ( x ~ 0.1–0.3) has rarely been studied. Here, we use DC/AC magnetization and (quasi) elastic neutron scattering to confirm the spin-glass nature of the short-range magnetic order in a Fe 1.07 Te 0.8 Se 0.2 sample. The AC-frequency dependent spin-freezing temperature T f generates a frequency sensitivity Δ T f ( ω )/[ T f ( ω )Δlog 10 ω ] ≈ 0.028 and the description of the critical slowing down with τ = τ 0 ( T f / T SG – 1) - z v gives T SG ≈ 22 K and zv ≈ 10, comparable to that of a classical spin-glass system. We have also extended the frequency-dependent T f to the smaller time scale using energy-resolution-dependent neutron diffraction measurements, in which the T N of the short-range magnetic order increases systematically with increasing energy resolution. We find that by removing the excess iron through annealing in oxygen, the spin-freezing behavior disappears, and bulk superconductivity is realized. Thus, the excess Fe is the driving force for the formation of the spin-glass phase detrimental to bulk superconductivity.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Helium Incorporation into Scandium Fluoride, a Model Negative Thermal Expansion Material

Scandium trifluoride is a model negative thermal expansion (NTE) material. Its simple structure can be described as an A-site vacant perovskite, and it shows isotropic NTE over a very wide temperature range (up to ~1100 K), due to transverse vibrational motion of the fluoride. Like many framework NTE materials, it undergoes a phase transition at low pressures, adopting a rhombohedral (R3̅c) structure at >0.7 GPa and 300 K in commonly used nonpenetrating pressure media, such as silicone oil. High pressure X-ray diffraction data and gas uptake/release measurements indicate that, on compression in helium above ~200 K, helium is inserted into ScF 3 to form the defect perovskite He x ScF 3 . The incorporation of helium stiffens the structure and changes its phase behavior. At room temperature, complete filling of the structure with helium does not occur until >1.5 GPa. On compression, a cubic perovskite structure is maintained until ~5 GPa. As the pressure was increased to ~9.5 GPa, a further transition occurred at ~7 GPa. The first transition at ~5 GPa is likely to a tetragonal (P4/mbm) perovskite, but the detailed structure of the perovskite phase formed on compression above ~7 GPa is unclear. Cooling down from 300 to 100 K in helium at ~0.4 GPa leads to an approximate composition of He 0.1 ScF 3 . High pressure neutron diffraction measurements, in the temperature range 15–150 K show that the incorporation of helium increases the pressure at which the cubic (Pm3̅m) to rhombohedral (R3̅c) putative quantum structural phase transition occurs from close to 0 GPa to ~0.2 GPa at 0 K.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Spin dynamics of the centrosymmetric skyrmion material GdRu 2 Si 2

Magnetic skyrmion crystals are traditionally associated with non-centrosymmetric crystal structures; however, it has been demonstrated that skyrmion crystals can be stabilized by competing interactions in centrosymmetric crystals. To understand and optimize the physical responses associated with topologically nontrivial skyrmion textures, it is important to quantify their magnetic interactions by comparing theoretical predictions with spectroscopy data. Here, we present neutron diffraction and spectroscopy data on the centrosymmetric skyrmion material GdRu 2 Si 2 and show that the key spectroscopic features can be explained by magnetic interactions calculated using density functional theory. We further show that the recently proposed 2-q “topological spin stripe” structure yields better agreement with our data than a 1-q helical structure and identify how the magnetic structure evolves with temperature.

36 MATERIALS SCIENCE↗

Pyridoxal 5'-phosphate dependent reactions: Analyzing the mechanism of aspartate aminotransferase

Enzyme catalysis is the primary activity in energy and information metabolism and enzyme cofactors are key to the catalytic ability of most enzymes. Pyridoxal 5'-phosphate (PLP) cofactor, derived from Vitamin B6, is widely distributed in nature and has significant latitude in catalytic diversity. X-ray crystallography has revealed the structures of diverse PLP dependent enzymes from multiple families. But these structures are incomplete, lacking the positions of protons essential for understanding enzymatic mechanisms. Here, we review the diversity of PLP and discuss the use of neutron crystallography and joint X-ray/neutron refinement of Fold Type I aspartate aminotransferase to visualize the positions of protons in both the internal and external aldimine forms. Strategies used to prepare extremely large crystals required for neutron diffraction and the approach to data refinement including the PLP cofactor are discussed. The observed positions of protons, including one located in a previously unknown low-barrier hydrogen bond, have been used to create more accurate models for computational analysis. The results revealed a new mechanism for the transaminase reaction where hyperconjugation is key to reducing the energy barrier which finally provides a clear explanation of the Dunathan alignment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Physical properties and anisotropic magnetism of EuBi 2

We report the synthesis of EuBi 2 single crystals and their magnetic and electronic properties. Plate-like crystals were grown in excess bismuth, and X-ray diffraction data confirm the previously reported tetragonal space group, I 4 1 /amd (No. 141). A Néel temperature of T N = 18.6 K was determined from the specific heat data, and corresponding anomalies occur in the magnetization and resistivity. We only observe one magnetic transition in zero magnetic field. The magnetization data above 70 K are well described by a Curie-Weiss model with a Weiss temperature of Θ CW ≈ −35 K and an effective moment near that of the expected spin-only moment of Eu 2+ (S = 7/2). Isothermal magnetization measurements reveal field-induced transitions for H||[100], including a hysteretic spin-flop centered at 10.1 T and a change in slope at 12 T and 2 K. However, while the isothermal magnetization for H||[110] displays nonlinear behavior, discrete metamagnetic transitions are not observed for H||[110] or H||[001], indicating significant magnetic anisotropy. The magnetization does not saturate by 13.5 T for any orientation. EuBi 2 is metallic and our crystals possess an in-plane residual resistivity ratio of ⍴300 K/⍴2 K ≈ 40. Single crystal neutron diffraction data reveal a large magnetic unit cell and non-trivial antiferromagnetic ordering. These results demonstrate that strong antiferromagnetic coupling drives complex magnetism in EuBi 2 .

36 MATERIALS SCIENCE↗

The Convolutional Multiple Whole Profile (CMWP) Fitting Method, a Global Optimization Procedure for Microstructure Determination

The analysis of line broadening in X-ray and neutron diffraction patterns using profile functions constructed on the basis of well-established physical principles and TEM observations of lattice defects has proven to be a powerful tool for characterizing microstructures in crystalline materials. These principles are applied in the convolutional multiple-whole-profile (CMWP) procedure to determine dislocation densities, crystallite size, stacking fault and twin boundary densities, and intergranular strains. The different lattice defect contributions to line broadening are separated by considering the hkl dependence of strain anisotropy, planar defect broadening and peak shifts, and the defect dependent profile shapes. The Levenberg–Marquardt (LM) peak fitting procedure can be used successfully to determine crystal defect types and densities as long as the diffraction patterns are relatively simple. However, in more complicated cases like hexagonal materials or multiple-phase patterns, using the LM procedure alone may cause uncertainties. Here, we extended the CMWP procedure by including a Monte Carlo statistical method where the LM and a Monte Carlo algorithm were combined in an alternating manner. The updated CMWP procedure eliminated uncertainties and provided global optimized parameters of the microstructure in good correlation with electron microscopy methods.

36 MATERIALS SCIENCE↗

Spin-lattice coupling mediated multiferroicity in (ND 4 ) 2 FeCl 5 • D 2 O

In this paper, we report a neutron diffraction study of the multiferroic mechanism in (ND 4 ) 2 FeCl 5 • D 2 O, a molecular compound that exhibits magnetically induced ferroelectricity. This material exhibits two successive magnetic transitions on cooling: a long-range order transition to an incommensurate (IC) collinear sinusoidal spin state at T N = 7.3 K, followed by a second transition to an IC cycloidal spin state at T FE = 6.8 K, the latter of which is accompanied by spontaneous ferroelectric polarization. The cycloid structure is strongly distorted by spin-lattice coupling, as evidenced by the observations of both odd and even higher-order harmonics associated with the cycloid wave vector, and a weak commensurate phase that coexists with the IC phase. The second-order harmonic appears at T FE , thereby providing unambiguous evidence that the onset of the electric polarization is accompanied by a lattice modulation due to spin-lattice interaction. The neutron results, in conjunction with the negative thermal expansion and large magnetostriction observed, indicate that spin-lattice coupling plays a critical role in the ferroelectric mechanism of (ND 4 ) 2 FeCl 5 • D 2 O.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Local lattice strains in the system of cubic Zn{sub 0.999}Fe{sub 0.001}S{sub x}Se{sub 1-x} (0 {<=} x {<=} 1) crystals

The structure of cubic Zn{sub 0.999}Fe{sub 0.001}S{sub x}Se{sub 1-x} (0 {<=} x {<=} 1) crystals obtained by vapor-phase chemical transport has been investigated by thermal-neutron diffraction. The diffraction patterns of these crystals are found to exhibit previously unknown diffuse-scattering effects related to local static atomic displacements in the metastable fcc lattice. It is substantiated that the tendency to form polytypes, which is characteristic to a greater extent of zinc sulfide, can be a key factor of instability in the lattice of compounds belonging to the series of anion-substituted solid solutions under study.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Pseudospin-lattice coupling and electric control of the square-lattice iridate Sr2IrO4

Sr 2 IrO 4 is an archetypal spin-orbit-coupled Mott insulator and has been extensively studied in part because of a wide range of predicted states. Limited experimental characterization of these states thus far brings to light the extraordinary susceptibility of the physical properties to the lattice, particularly, the Ir-O-Ir bond angle. Here, we report a microscopic rotation of the IrO 6 octahedra below 50 K measured by single crystal neutron diffraction. Overall, this sharp lattice anomaly provides keys to understanding the anomalous low-temperature physics and a direct confirmation of a crucial role that the Ir-O-Ir bond angle plays in determining the ground state. Indeed, as also demonstrated in this study, applied electric current readily weakens the antiferromagnetic order via the straightening of the Ir-O-Ir bond angle, highlighting that even slight change in the local structure can disproportionately affect the physical properties in the spin-orbit-coupled system.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

High-pressure dynamics of hydrated protein in bioprotective trehalose environment

Here we present a pressure-dependence study of the dynamics of lysozyme protein powder immersed in deuterated , α-trehalose environment via quasielastic neutron scattering (QENS). The goal is to assess the baroprotective benefits of trehalose on biomolecules by comparing the findings with those of a trehalose-free reference study. While the mean-square displacement of the trehalose-free protein (hydrated to d D₂O ≃40 w%) as a whole, is reduced by increasing pressure, the actual observable relaxation dynamics in the picoseconds to nanoseconds time range remains largely unaffected by pressure up to the maximum investigated pressure of 2.78(2) Kbar. Our observation is independent of whether or not the protein is mixed with the deuterated sugar. This suggests that the hydrated protein s conformational states at atmospheric pressure remain unaltered by hydrostatic pressures, below 2.78 Kbar. We also found the QENS response to be totally recoverable after ambient pressure conditions are restored. Small-angle neutron diffraction measurements confirm that the protein-protein correlation remains undisturbed.We observe, however, a clear narrowing of the QENS response as the temperature is decreased from 290 to 230 K in both cases, which we parametrize using the Kohlrausch-Williams-Watts stretched exponential model. Finally, only the fraction of protons that are immobile on the accessible time window of the instrument, referred to as the elastic incoherent structure factor, is observably sensitive to pressure, increasing only marginally but systematically with increasing pressure.

59 BASIC BIOLOGICAL SCIENCES↗

Implementation of the riding hydrogen model in CCTBX to support the next generation of X-ray and neutron joint refinement in Phenix

A fundamental prerequisite for implementing new procedures of atomic model refinement against neutron diffraction data is the efficient handling of hydrogen atoms. The riding hydrogen model, which constrains hydrogen atom parameters to those of the non-hydrogen atoms, is a plausible parameterization for refinements. This work describes the implementation of the riding hydrogen model in the Computational Crystallography Toolbox and in Phenix. Riding hydrogen atoms can be found in several different configurations that are characterized by specific geometries. For each configuration, the hydrogen atom parameterization and the expressions for the gradients of refinement target function with respect to non-hydrogen parameters are described.

H atom parameterization↗

XY-like incommensurate magnetic order in Ce 2 ⁢SnS 5

We report the synthesis of single crystals of Ce 2 ⁢SnS 5 through a two-stage chemical vapor transport method. The Ce 2 ⁢SnS 5 system is a member of the orthorhombic Pbam (No. 55) space group and realizes a distorted trigonal tricapped prism (TTP) crystal field around each cerium site. We characterized the sample through orientation-dependent magnetization and heat capacity measurements to probe the magnetic anisotropy in the system characteristic of XY-like anisotropic Heisenberg model behavior. Ce 2 ⁢SnS 5 furthermore enters a zero-field ordered phase under 𝑇 𝑁 =2.4 K; powder neutron diffraction measurements reveal incommensurate magnetic order near 𝑇 𝑁 . Furthermore, the system then locks into a commensurate, two-𝑞 magnetic structure below approximately 1.2 K. This commensurate structure belongs to the Shubnikov group 𝑃⁢𝑏′⁢𝑎′⁢𝑚′ ⁡(MSG 55.359) and realizes the propagation vectors $\overrightarrow{𝑞}$ = (1/3, 0, 0) and $\overrightarrow{𝑞}$ = (0, 0, 0).

Antiferromagnetism↗

Magnetic structure, excitations and short-range order in honeycomb Na 2 Ni 2 TeO 6

Na 2 Ni 2 TeO 6 has a layered hexagonal structure with a honeycomb lattice constituted by Ni 2+ and a chiral charge distribution of Na + that resides between the Ni layers. In the present work, the antiferromagnetic transition temperature of Na 2 Ni 2 TeO 6 is confirmed at TN˜ 27 K, and further, it is found to be robust up to 8 T magnetic field and 1.2 GPa external pressure; and, without any frequency-dependence. Slight deviations from nominal Na-content (up to 5%) does not seem to influence the magnetic transition temperature, TN. Isothermal magnetization curves remain almost linear up to 13 T. Our analysis of neutron diffraction data shows that the magnetic structure of Na 2 Ni 2 TeO 6 is faithfully described by a model consisting of two phases described by the commensurate wave vectors vec kc, (0.5 0 0) and (0.5 0 0.5), with an additional short-range order component incorporated in to the latter phase. Consequently, a zig-zag long-range ordered magnetic phase of Ni 2+ results in the compound, mixed with a short-range ordered phase, which is supported by our specific heat data. Theoretical computations based on density functional theory (DFT) predict predominantly in-plane magnetic exchange interactions that conform to a J1-J2-J3 model with a strong J3 term. The computationally predicted parameters lead to a reliable estimate for TN and the experimentally observed zig-zag magnetic structure. A spin wave excitation in Na 2 Ni 2 TeO 6 at E ˜ 5 meV at T = 5 K is mapped out through inelastic neutron scattering experiments, which is reproduced by linear spin wave theory calculations using the J values from our computations. Our specific heat data and inelastic neutron scattering data strongly indicate the presence of short-range spin correlations, at T > TN, stemming from incipient antiferromagnetic clusters.

36 MATERIALS SCIENCE↗

Structure evolution and thermoelectric properties of carbonized polydopamine thin films

Carbonization of nature-inspired polydopamine can yield thin films with high electrical conductivity. Understanding of the structure of carbonized PDA (cPDA) is therefore highly desired. In this study, neutron diffraction, Raman spectroscopy, and other techniques indicate that cPDA samples are mainly amorphous with some short-range ordering and graphite-like structure that emerges with increasing heat treatment temperature. The electrical conductivity and the Seebeck coefficient show different trends with heat treatment temperature, while the thermal conductivity remains insensitive. Finally, the largest room-temperature ZT of 2 × 10 –4 was obtained on samples heat-treated at 800 °C, which is higher than that of reduced graphene oxide.

36 MATERIALS SCIENCE↗

Spin-orbital order and excitons in magnetoresistive HoBi

The magnetism of the rocksalt fcc rare-earth monopnictide HoBi, a candidate topological material with extreme magnetoresistance, is investigated. From the Ho 3+ non-Kramers J=8 spin-orbital multiplet, the cubic crystal electric field yields six nearly degenerate low-energy levels. These constitute an anisotropic magnetic moment with a Jahn-Teller-like coupling to the lattice. In the cubic phase for T>T N =5.72(1)K, the paramagnetic neutron scattering is centered at k=($\frac{1}{2}$$\frac{1}{2}$$\frac{1}{2}$) and was fit to dominant antiferromagnetic interactions between Ho spins separated by {100} and ferromagnetic interactions between spins displaced by {$\frac{1}{2}$ $\frac{1}{2}$ 0}. For T < T N , a type-II AFM long-range order with k=($\frac{1}{2}$$\frac{1}{2}$$\frac{1}{2}$) develops along with a tetragonal lattice distortion. While neutron diffraction from a multidomain sample cannot unambiguously determine the spin orientation within a domain, the bulk magnetization, structural distortion, and our measurements of the magnetic excitations all show the easy axis coincides with the tetragonal axis. Finally, the weakly dispersive excitons for T < T N can be accounted for by a spin Hamiltonian that includes the crystal electric field and exchange interactions within the random phase approximation.

36 MATERIALS SCIENCE↗