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High‐Pressure and High‐Temperature Single‐Crystal Elasticity of Cr‐Pyrope: Implications for the Density and Seismic Velocity of Subcontinental Lithospheric Mantle
Abstract Single‐crystal X‐ray diffraction and Brillouin spectroscopy experiments were performed on a natural Cr‐pyrope (Prp 71.0 Alm 12.6 Sps 0.7 Grs 3.5 Uvr 12.2 ) at high pressure and high temperature up to 11.0 GPa and 800 K. Fitting the collected data to the third‐order finite strain equation yields bulk modulus ( K S 0 ), shear modulus ( G 0 ), their pressure ((∂ K S /∂ P ) T and (∂ G /∂ P ) T ) and temperature (( ∂K S /∂T ) P and ( ∂G/∂T ) P ) derivatives, K S 0 = 167.7(8) GPa, G 0 = 91.5(5) GPa, (∂ K S /∂ P ) T = 4.3(1), (∂ G /∂ P ) T = 1.4(1), ( ∂K S /∂T ) P = − 0.0175(1) GPa/K and ( ∂G/∂T ) P = − 0.0073(1) GPa/K. Using the obtained results, we examined whether the elastic properties of the Cr‐pyrope can be accurately calculated from those of endmembers including pyrope, almandine, grossular, and uvarovite assuming a linear relationship between elastic properties and composition (end‐member model). The results indicate that the end‐member model provides a sufficient approximation for the elastic properties of Cr‐pyrope in calculating the density and velocity of the subcontinental lithospheric mantle (SCLM). We modeled the densities and velocities of three typical types of SCLM (Archon, Proton, and Tecton) in order to investigate how the variation of chemical composition influences the SCLM. We obtained that the compositional change from the Archon to the Tecton increases the density of the SCLM significantly, which can be an important prerequisite for SCLM delamination. However, the compositional variation only slightly changes the velocity of the SCLM and the change is within the uncertainty of the calculation. Moreover, in comparison to the velocity, ρ / V P and ρ / V S are much more sensitive to the compositional change of the SCLM.
Synthesis and Stability of an Eight‐Coordinated Fe 3 O 4 High‐Pressure Phase: Implications for the Mantle Structure of Super‐Earths
Abstract Super‐Earths ranging up to 10 Earth masses (M E ) with Earth‐like density are common among the observed exoplanets thus far, but their measured masses and radii do not uniquely elucidate their internal structure. Exploring the phase transitions in the Mg‐silicates that define the mantle‐structure of super‐Earths is critical to characterizing their interiors, yet the relevant terapascal conditions are experimentally challenging for direct structural analysis. Here we investigated the crystal chemistry of Fe 3 O 4 as a low‐pressure analog to Mg 2 SiO 4 between 45–115 GPa and up to 3000 K using powder and single crystal X‐ray diffraction in the laser‐heated diamond anvil cell. Between 60–115 GPa and above 2000 K, Fe 3 O 4 adopts an 8‐fold coordinated Th 3 P 4 ‐type structure ( I ‐43d, Z = 4) with disordered Fe 2+ and Fe 3+ into one metal site. This Fe‐oxide phase is isostructural with that predicted for Mg 2 SiO 4 above 500 GPa in super‐Earth mantles and suggests that Mg 2 SiO 4 can incorporate both ferric and ferrous iron at these conditions. The pressure‐volume behavior observed in this 8‐fold coordinated Fe 3 O 4 indicates a maximum 4% density increase across the 6‐ to 8‐fold coordination transition in the analog Mg‐silicate. Reassessment of the FeO—Fe 3 O 4 fugacity buffer considering the Fe 3 O 4 phase relationships identified in this study reveals that increasing pressure and temperature to 120 GPa and 3000 K in Earth and planetary mantles drives iron toward oxidation.
Atomic resolution coherent x-ray imaging with physics-based phase retrieval
Coherent x-ray imaging and scattering from accelerator based sources such as synchrotrons continue to impact biology, medicine, technology, and materials science. Many synchrotrons around the world are currently undergoing major upgrades to increase their available coherent x-ray flux by approximately two orders of magnitude. The improvement of synchrotrons may enable imaging of materials in operando at the atomic scale which may revolutionize battery and catalysis technologies. Current algorithms used for phase retrieval in coherent x-ray imaging are based on the projection onto sets method. These traditional iterative phase retrieval methods will become more computationally expensive as they push towards atomic resolution and may struggle to converge. Additionally, these methods do not incorporate physical information that may additionally constrain the solution. In this work, we present an algorithm which incorporates molecular dynamics into Bragg coherent diffraction imaging (BCDI). This algorithm, which we call PRAMMol (Phase Retrieval with Atomic Modeling and Molecular Dynamics) combines statistical techniques with molecular dynamics to solve the phase retrieval problem. We present several examples where our algorithm is applied to simulated coherent diffraction from 3D crystals and show convergence to the correct solution at the atomic scale.
Suppressed-moment 2-k order in the canonical frustrated antiferromagnet Gd 2 Ti 2 O 7
In partially ordered magnets, order and disorder coexist in the same magnetic phase, distinct from both spin liquids and spin solids. Here, we determine the nature of partial magnetic ordering in the canonical frustrated antiferromagnet Gd 2 Ti 2 O 7 , in which Gd 3+ spins occupy a pyrochlore lattice. Using single-crystal neutron-diffraction measurements in applied magnetic field, magnetic symmetry analysis, inelastic neutron-scattering measurements, and spin-wave modeling, we show that its low-temperature magnetic structure involves two propagation vectors (2-k structure) with suppressed ordered magnetic moments and enhanced spin-wave fluctuations. Our experimental results are consistent with theoretical predictions of thermal fluctuation-driven order in Gd 2 Ti 2 O 7 , and reveal that inelastic neutron-scattering measurements on powder samples can solve the longstanding problem of distinguishing single-k and multi-k magnetic structures.
Effects of interlayer confinement and hydration on capacitive charge storage in birnessite
Nanostructured birnessite exhibits high specific capacitance and nearly ideal capacitive behaviour in aqueous electrolytes, rendering it an important electrode material for low-cost, high-power energy storage devices. The mechanism of electrochemical capacitance in birnessite has been described as both Faradaic (involving redox) and non-Faradaic (involving only electrostatic interactions). To clarify the capacitive mechanism, we characterized birnessite’s response to applied potential using ex situ X-ray diffraction, electrochemical quartz crystal microbalance, in situ Raman spectroscopy and operando atomic force microscope dilatometry to provide a holistic understanding of its structural, gravimetric and mechanical responses. These observations are supported by atomic-scale simulations using density functional theory for the cation-intercalated structure of birnessite, ReaxFF reactive force field-based molecular dynamics and ReaxFF-based grand canonical Monte Carlo simulations on the dynamics at the birnessite–water–electrolyte interface. We show that capacitive charge storage in birnessite is governed by interlayer cation intercalation. We conclude that the intercalation appears capacitive due to the presence of nanoconfined interlayer structural water, which mediates the interaction between the intercalated cation and the birnessite host and leads to minimal structural changes.
Zero-field magnetic ground state of EuMg 2 Bi 2
Layered trigonal EuMg 2 Bi 2 is reported to be a topological semimetal that hosts multiple Dirac points that may be gapped or split by the onset of magnetic order. In this study, we report zero-field single-crystal neutron-diffraction and bulk magnetic susceptibility measurements versus temperature χ ( T ) of EuMg 2 Bi 2 that show the intraplane ordering is ferromagnetic ( Eu 2 + , S = 7 / 2 ) with the moments aligned in the a b plane while adjacent layers are aligned antiferromagnetically (i.e., A-type antiferromagnetism) below the Néel temperature.
Absence of a bulk signature of a charge density wave in hard x-ray measurements of UTe 2
The long-sought pair density wave (PDW) is an exotic phase of matter in which charge density wave (CDW) order is intertwined with the amplitude or phase of coexisting, superconducting order. Originally predicted to exist in copper-oxides, circumstantial evidence for PDW order now exists in a variety of materials. Recently, scanning tunneling microscopy (STM) studies have reported evidence for a three-component CDW at the surface of the heavy-fermion superconductor, UTe 2 , persisting below its superconducting transition temperature [Aishwarya et al., Nature 618, 928933 (2023); Gu et al., Nature 618, 921927 (2023); LaFleur et al., Nat. Commun. 15, 4456 (2024)]. Here, in this study, we use hard x-ray diffraction measurements on crystals of UTe 2 at 𝑇 = 1.9 and 12 K to search for a bulk signature of this CDW. Using STM measurements as a constraint, we calculate the expected locations of CDW superlattice peaks and sweep a large volume of reciprocal space in search of a signature. We fail to find any evidence for a CDW near any of the expected superlattice positions in many Brillouin zones. We estimate an upper bound on the CDW lattice distortion of 𝑢 max ≲ 4×10 −3 Å. Our results suggest that the CDW observed in STM is either purely electronic, somehow lacking a signature in the lattice, or is restricted to the material surface.
Unraveling structural, electronic, and magnetic ambiguities in Pb 1−𝛿 CrO 3 with an insulating charge-transfer band structure
As a recently identified Mott system, PbCrO 3 remains largely unexplored, especially for its band structure, leading to many contentious issues on its structural, electronic, and magnetic properties. Here we present a comprehensive study of two different Pb 1−𝛿 CrO 3 (δ = 0 and 0.15) samples involving atomic deficiency prepared under pressure. By means of state-of-the-art diffraction techniques, the crystal structure of PbCrO 3 is definitively determined to adopt the pristine 𝑃𝑚$\overline{3}$𝑚 symmetry, rather than other previously misassigned structures of M2-Pm$\overline{3}$𝑚 and Pmnm. The two materials exhibit a similar charge-transfer-type insulating band structure, and the charge-transfer effect splits both Cr 2𝑝 and Pb 4𝑓 orbitals, rationalizing doublet splitting of the associated spectral lines. Nearly identical nominal cationic valence states of Cr 4+ and Pb 2+ are identified for this oxide system, hence calling into question the validity of recently proposed charge disproportionation mechanisms. In addition, Pb 0.85 CrO 3 exhibits an anomalously higher Néel temperature of ∼240 K than that of PbCrO 3 (i.e., ∼200 K), likely due to the deficiency-induced enhancements of Cr3𝑑–O2𝑝 orbital overlap and magnetic exchange. In conclusion, these findings provide much solid evidence to look into the fundamental properties of this important material system.
Structure transition and zigzag magnetic order in Ir/Rh-substituted honeycomb lattice α - RuCl 3
Here, we report magnetization and neutron diffraction studies on crystal and magnetic structures of Ir- and Rh-substituted honeycomb lattice α-RuCl 3 . The iridium or rhodium atoms are distributed at the Ru site with little structural modification. Both systems undergo a room-temperature monoclinic C2/m to low-temperature trigonal $R\bar{3}$ phase transformation with a large recoverable hysteresis. At low temperature, a zigzag spin order is observed with the same characteristic wave vector (0,0.5,1) as in the parent α-RuCl 3 . Detailed magnetic structure refinement reveals an ordered moment of 0.32(5)µB/Ru and an upper boundary of canting angle of 15(4)º away from the basal plane at 5 K for the 10% Ir-substituted α-RuCl 3 , which is different from the 0.45–0.73 µB/Ru and 32°–48° canting angle reported in the parent compound α-RuCl 3 . The observation of unchanged RuCl 6 local octahedral environment, reduced ordered magnetic moment size and canting angle compared to previously reported highlights the potential to study quantum spin-liquid behavior through nonmagnetic ion doping.
Solvent organization in the ultrahigh-resolution crystal structure of crambin at room temperature
Ultrahigh-resolution structures provide unprecedented details about protein dynamics, hydrogen bonding and solvent networks. The reported 0.70 Å, room-temperature crystal structure of crambin is the highest-resolution ambient-temperature structure of a protein achieved to date. Sufficient data were collected to enable unrestrained refinement of the protein and associated solvent networks using SHELXL . Dynamic solvent networks resulting from alternative side-chain conformations and shifts in water positions are revealed, demonstrating that polypeptide flexibility and formation of clathrate-type structures at hydrophobic surfaces are the key features endowing crambin crystals with extraordinary diffraction power.
Nanocolumnar Pt:Ni Alloy Thin Films by High Pressure Sputtering for Oxygen Reduction Reaction
Self-supported nanocolumnar Pt:Ni thin films (TFs) with varying Pt:Ni atomic ratios and Pt mass loadings were produced on a microporous layer (MPL)-like surface composed of carbon particles by high pressure sputtering and examined as oxygen reduction reaction (ORR) electrocatalysts for polymer electrolyte membrane fuel cells. Cauliflower-like microstructures were observed from scanning electron microscopy imaging. Various Pt:Ni atomic ratios were obtained by simply changing the relative deposition power between Pt and Ni source and investigated by X-ray diffraction and quartz crystal microbalance analysis. Additionally, electrochemical characterization of the Pt:Ni-TF/MPL-like-layer/glassy-carbon samples was conducted through benchtop cyclic voltammetry and rotating disk electrode measurements. The electrochemically active surface area (ECSA) was found to be between 22–42 m 2 g -1 for different Pt:Ni atomic ratios. Lower Pt mass loadings exhibited a higher ECSA and the catalytic activity of all Pt:Ni ratios increased with the increase in Pt mass loading. The ORR activity of the Pt:Ni-TFs increased in the order of 3:1 < 1:1 < 1:3 with exhibiting a specific activity of 1781 μA cm -2 and mass activity of 0.66 A mg -1 for the Ni-rich film with 1:3 ratio. The catalytic performance of Pt:Ni-TFs were higher than traditional high surface area carbon supported Pt nanoparticles, elemental Pt nanorods, and Pt-Ni nanorods.
Pink-beam serial femtosecond crystallography for accurate structure factor determination at an X-ray free-electron laser
Diffraction images with crystal hits from the large bandwidth (2.2 % BW) data set (thaumatin 6), and nominal SASE (0.17 % BW) data set (thaumatin 8 + thaumatin 10) with bad pixel masks, online indexing results and CrystFEL stream files from final processing.
GSAS-II (GENERAL STRUCTURE AND ALAYSIS SYSTEM-II)
GSAS-II is a comprehensive data analysis and simulation software package for determining atomistic structures from single-crystal and powder diffraction data. X-ray, neutron and electron data may be used. Constant-wavelength, time-of-flight and pink-beam sources may be employed and analyses may combine different types of data. The package is oriented towards materials characterization problems, but protein crystallography, pair-distribution function analysis, small-angle scattering and reflectometry analysis are all included. GSAS-II provides tools for indexing and solving structures from powder diffraction data, in addition to structure, data and results visualization tools
Thermal Analysis, Compressibility, and Decomposition of Synthetic Bastnäsite-(La) to Lanthanum Oxyfluoride
Abstract not provided
Understanding the Chemical Complexity of Multicomponent Systems: Uranium Polyoxometalates as Nanosorbents
The overarching objective of this project was to develop a molecular-scale understanding of chemical interactions of the transuranic (TRU) elements with uranyl-based polyoxometalate nanoclusters (UPOMs). The specific goals that supported this overarching objective were to: (i) quantify TRU interactions with UPOMs as a function of TRU, carbonate, and UPOM concentration, pH, and temperature; (ii) examine the molecular-level bonding environment of TRU-UPOM complexes; and (iii) develop a rate expression capable of describing the sorption and reduction of TRU by UPOMs. The published literature suggests several potential interactions can occur in TRU-UPOM systems: (i) encapsulation of TRU and coordination with the internal ‘-yl’ oxygens of the UPOM, (ii) coordination of TRU with the external ‘-yl’ oxygens of the UPOM, and (iii) coordination of TRU with the bridging ligands (e.g., peroxo, hydroxo, oxalate) of the UPOM. The latter two may induce aggregation of the UPOMs. The concept of encapsulation is demonstrated by the X-ray diffraction structure of crystallized U 20 , which reveals a Na + cation under each pentagonal face (Sigmon et al., 2009). Computational modeling shows that, while the negative charge of U 20 is spread among all the oxygen atoms, the internal ‘-yl’ oxygens host the most negative charge (Miro and Bo, 2012). This negative charge is reduced through the complexation of the templating sodium ions in the interior of the UPOM. Furthermore, Nyman et al. (2011) shows that cesium can exit through the pentagonal window of U 28 in the aqueous phase, suggesting that the TRU elements, which are smaller than cesium, may be capable of entering a UPOM through these windows in an exchange reaction. Under this project, we focused on hafnium, neptunium, and plutonium interactions with UPOMs.
A new layered kagome strip structure Na 2 Co 3 (AsO 4 ) 2 (OH) 2 : static and dynamic magnetic properties
One-dimensional kagome strip chains share much of the same frustrated structural motif as two-dimensional kagome antiferromagnets, making them valuable for deepening our understanding of kagome lattice magnetism. In this paper, we report the hydrothermal synthesis and detailed structural and property characterization of Na 2 Co 3 (AsO 4 ) 2 (OH) 2 , a striped kagome system. The crystal structure was characterized using single crystal X-ray diffraction which reveals that Na 2 Co 3 (AsO 4 ) 2 (OH) 2 crystallizes in monoclinic crystal system C2/m. The structure features a one-dimensional kagome strip lattice built from Co 2+ ions and undergoes an antiferromagnetic transition at T N = 14 K. The magnetic ground state at zero field was characterized using neutron powder diffraction. Below the magnetic transition, Na 2 Co 3 (AsO 4 ) 2 (OH) 2 orders into an antiferromagnetic structure with a k-vector (0.5, 0.5, 0.5). In the proposed model, the Co1 moment is predominantly confined to the ac-plane while the Co2 moment is primarily aligned along the b-axis. Two flat bands were observed in the inelastic neutron spectra below the magnetic transition, 5 and 10 meV. Inelastic neutron spectra were modeled with a Heisenberg Hamiltonian including three nearest-neighbor exchange interactions (J 1 , J 2 , J 3 ) and strong single-ion anisotropy to stabilize the observed magnetic structure. Our study highlights the complexity of Co 2+ -based kagome strip magnetic lattice compound Na 2 Co 3 (AsO 4 ) 2 (OH) 2 which provides an excellent platform to broaden our understanding of the frustrated kagome magnetic lattice space.
Reaching the potential of electron diffraction
Microcrystal electron diffraction (MicroED) is an emerging structural technique in which submicron crystals are used to generate diffraction data for structural studies. Structures allow for the study of molecular-level architecture and drive hypotheses about modes of action, mechanisms, dynamics, and interactions with other molecules. Combining cryoelectron microscopy (cryo-EM) instrumentation with crystallographic techniques, MicroED has led to three-dimensional structural models of small molecules, peptides, and proteins and has generated tremendous interest due to its ability to use vanishingly small crystals. In this perspective, we describe the current state of the field for MicroED methodologies, including making and detecting crystals of the appropriate size for the technique, as well as ways to best handle and characterize these crystals. Our perspective provides insight into ways to unlock the full range of potential for MicroED to access previously intractable samples and describes areas of future development.