Pair Distribution Research Articles

Stereochemically Active Lone Pairs Stabilizing Intrinsic Vacancy Defects in Thermoelectric InTe.

Harvesting waste heat efficiently with thermoelectric energy conversion requires materials with low thermal conductivity. Recently, it was demonstrated how dynamic lone pair expression in thermoelectric InTe is responsible for giant anharmonicity leading to a very low lattice thermal conductivity. InTe also contains correlated disorder of intrinsic defects due to vacancies, and this contributes to additional lowering of the thermal conductivity. Here we use the three-dimensional difference pair distribution function (3D-ΔPDF) to analyze 25 K single crystal diffuse X-ray scattering from InTe to unravel the local defect structure, and propose a microscopic structural model. Extended off-centering of In+ ions induced by vacancies allows for the local expression of stereochemically active lone pairs. The associated electronic stabilization is proposed to be a driving force for the formation of In+ vacancy defects in InTe.

GIWAXS experimental methods at the NFPS-BL17B beamline at Shanghai Synchrotron Radiation Facility.

The BL17B beamline at the Shanghai Synchrotron Radiation Facility was first designed as a versatile high-throughput protein crystallography beamline and one of five beamlines affiliated to the National Facility for Protein Science in Shanghai. It was officially opened to users in July 2015. As a bending magnet beamline, BL17B has the advantages of high photon flux, brightness, energy resolution and continuous adjustable energy between 5 and 23 keV. The experimental station excels in crystal screening and structure determination, providing cost-effective routine experimental services to numerous users. Given the interdisciplinary and green energy research demands, BL17B beamline has undergone optimization, expanded its range of experimental methods and enhanced sample environments for a more user-friendly testing mode. Thesemethods include single-crystal X-ray diffraction, powder crystal X-ray diffraction, wide-angle X-ray scattering, grazing-incidence wide-angle X-ray scattering (GIWAXS), and fully scattered atom pair distribution function analysis, covering structure detection from crystalline to amorphous states. This paper primarily presents the performance of the BL17B beamline and the application of the GIWAXS methodology at the beamline in the field of perovskite materials.

Deciphering diffuse scattering with machine learning and the equivariant foundation model: the case of molten FeO

Bridging the gap between diffuse x-ray or neutron scattering measurements and predicted structures derived from atom–atom pair potentials in disordered materials, has been a longstanding challenge in condensed matter physics. This perspective gives a brief overview of the traditional approaches employed over the past several decades. Namely, the use of approximate interatomic pair potentials that relate three-dimensional structural models to the measured structure factor and its’ associated pair distribution function. The use of machine learned interatomic potentials has grown in the past few years, and has been particularly successful in the cases of ionic and oxide systems. Recent advances in large scale sampling, along with a direct integration of scattering measurements into the model development, has provided improved agreement between experiments and large-scale models calculated with quantum mechanical accuracy. However, details of local polyhedral bonding and connectivity in meta-stable disordered systems still require improvement. Here we leverage MACE-MP-0; a newly introduced equivariant foundation model and validate the results against high-quality experimental scattering data for the case of molten iron(II) oxide (FeO). These preliminary results suggest that the emerging foundation model has the potential to surpass the traditional limitations of classical interatomic potentials.

PyCSH: Automated atomic-level structure generation of bulk C-S-H and investigation of their intrinsic properties

A new Python code for the automated generation of realistic bulk calcium silicate hydrate (C-S-H) structures is introduced. The code was used to generate 400 structures with Ca/Si of 1.3, 1.5, 1.7, and 1.9. The generated structures are in excellent agreement with experimentally measured C-S-H properties (Ca/Si, 2H/Si, MCL, Si-OH/Si, and Ca-OH/Ca). Molecular dynamics was used to simulate the structures, which were then investigated for their structural features and energetic stability. The results indicate very similar short-range ordering and energetic stability between all 400 structures. Finally, it is shown how computational C-S-H models can be used to understand the experimentally measured pair distribution functions. The code, named pyCSH, is available as open source under GPL-2 license at GitHub https://github.com/hegoimanzano/pyCSH.git and https://github.com/akmiitm/pyCSH.git.

Structural and elastic properties of zirconium silicate glasses: Insight from molecular dynamic simulation

Using Morse potentials, we performed molecular dynamics simulations to study the effect of ZrO2/SiO2 substitution on the structure and mechanical properties of SiO2-ZrO2 glasses with various ZrO2 concentrations (5, 10, 20, 30, 40, and 50 mol%). We computed the pair distribution function (PDF) for all atomic pairs and extracted the cation-oxygen coordination number and bond distance as a function of composition for Zr4+ and other cations. We found that Zr entered the glass network as distorted [ZrO6] octahedra. Our results showed that the ZrO2 content was positively associated with the number of non-bridging oxygens and the emergence of tricluster oxygens, which consequently reduced the glass transition temperature. The elastic constants such as Young’s, bulk and shear modulus, increase with rising zirconium content.

Efficient source-independent quantum conference key agreement

Quantum conference key agreement (QCKA) enables the unconditional secure distribution of conference keys among multiple participants. Due to challenges in high-fidelity preparation and long-distance distribution of multi-photon entanglement, entanglement-based QCKA is facing severe limitations in both key rate and scalability. Here, we propose a source-independent QCKA scheme utilizing the post-matching method, feasible within the entangled photon pair distribution network. We introduce an equivalent distributing virtual multi-photon entanglement protocol for providing unconditional security proof even in the case of coherent attacks. For the symmetry star network, compared with the previous n-photon entanglement protocol, the conference key rate is improved from O(η n ) to O(η2), where η is the transmittance from the entanglement source to one participant. Simulation results show that the performance of our protocol has multiple orders of magnitude advantages in the intercity distance. We anticipate that our approach will demonstrate its potential in the implementation of quantum networks.

Evidence for double resonant Raman decay from a Ag surface

We have investigated the electron pair emission from a Ag(100) surface upon photon absorption which leads to the emission of a 4p photoelectron. The subsequent Auger decay proceeds in a single-step process as shown previously. Key finding was the emergence of a diagonal intensity feature in a two-dimensional kinetic energy distribution of the electron pair whose width reveals a characteristic time of 30 as for the dynamics of the core-hole decay process. We utilize this observation as a tool to identify an unexpected pathway of electron pair emission. Once the photon energy is at the threshold of a double 4p core hole creation we notice a sizeable broadening of the energy sharing distribution. We associate this process to the excitation of two 4p electrons between the Fermi and vacuum level followed by radiation less double electron excitation. This feature is characterized by an energy sum of the pair which disperses linearly with the photon energy. Therefore, we regard it as a double resonant Raman decay. Published by the American Physical Society 2024

High-throughput and high-resolution powder X-ray diffractometer consisting of six sets of 2D CdTe detectors with variable sample-to-detector distance and innovative automation system.

The demand for powder X-ray diffraction analysis continues to increase in a variety of scientific fields, as the excellent beam quality of high-brightness synchrotron light sources enables the acquisition of high-quality measurement data with high intensity and angular resolution. Synchrotron powder diffraction has enabled the rapid measurement of many samples and various in situ/operando experiments in nonambient sample environments. To meet the demands for even higher throughput measurements using high-energy X-rays at SPring-8, a high-throughput and high-resolution powder diffraction system has been developed. This system is combined with six sets of two-dimensional (2D) CdTe detectors for high-energy X-rays, and various automation systems, including a system for automatic switching among large sample environmental equipment, have been developed in the third experimental hutch of the insertion device beamline BL13XU at SPring-8. In this diffractometer system, high-brilliance and high-energy X-rays ranging from 16 to 72 keV are available. The powder diffraction data measured under ambient and various nonambient conditions can be analysed using Rietveld refinement and the pair distribution function. Using the 2D CdTe detectors with variable sample-to-detector distance, three types of scan modes have been established: standard, single-step and high-resolution. A major feature is the ability to measure a whole powder pattern with millisecond resolution. Equally important, this system can measure powder diffraction data with high Q exceeding 30 Å-1 within several tens of seconds. This capability is expected to contribute significantly to new research avenues using machine learning and artificial intelligence by utilizing the large amount of data obtained from high-throughput measurements.

Label-semantics enhanced multi-layer heterogeneous graph convolutional network for Aspect Sentiment Quadruplet Extraction

Aspect-based sentiment analysis (ABSA) is a pivotal area within natural language processing (NLP) that focuses on extracting fine-grained sentiment information from text. A particularly demanding task within ABSA is Aspect Sentiment Quadruplet Extraction (ASQE), which aims to identify quadruplets comprising aspect terms, their corresponding opinion terms, sentiment polarity, and categories. This level of analysis is crucial for downstream applications such as sentiment monitoring and user experience research, offering nuanced insights into textual data. However, current methodologies fall short of fully leveraging the rich linguistic features of sentences and the semantic information of labels embedded within sentences. To address this gap, this paper introduces a novel framework, the Label-Semantics Enhanced Multi-layer Heterogeneous Graph Convolutional Network (LSEMH-GCN), specifically designed for ASQE. Our model integrates sentence linguistic features and label semantics to construct a graph neural network tailored for this task. It employs a multi-layer graph convolutional network that synergizes various linguistic features, and utilizes Biaffine attention to enrich the label probability distribution for token pairs with semantic label information. Furthermore, our approach introduces a token pair vector concatenation strategy alongside an advanced asymmetric label tagging scheme to enhance quadruplet extraction. Comprehensive evaluations on benchmark datasets reveal that LSEMH-GCN significantly surpasses existing state-of-the-art models, establishing a new benchmark for ASQE. Our model achieves an average F1 score improvement of 15.52% and 12.30% on the Restaurant-ACOS and Laptop-ACOS datasets, respectively.

Tracking copper nanofiller evolution in polysiloxane during processing into SiOC ceramic.

Polymer-derived ceramics (PDCs) remain at the forefront of research for a variety of applications including ultra-high-temperature ceramics, energy storage and functional coatings. Despite their wide use, questions remain about the complex structural transition from polymer to ceramic and how local structure influences the final microstructure and resulting properties. This is further complicated when nanofillers are introduced to tailor structural and functional properties, as nanoparticle surfaces can interact with the matrix and influence the resulting structure. The inclusion of crystalline nanofiller produces a mixed crystalline-amorphous composite, which poses characterization challenges. With this study, we aim to address these challenges with a local-scale structural study that probes changes in a polysiloxane matrix with incorporated copper nanofiller. Composites were processed at three unique temperatures to capture mixing, pyrolysis and initial crystallization stages for the pre-ceramic polymer. We observed the evolution of the nanofiller with electron microscopy and applied synchrotron X-ray diffraction with differential pair distribution function (d-PDF) analysis to monitor changes in the matrix's local structure and interactions with the nanofiller. The application of the d-PDF to PDC materials is novel and informs future studies to understand interfacial interactions between nanofiller and matrix throughout PDC processing.

Critical Role of Framework Flexibility and Disorder in Driving High Ionic Conductivity in LiNbOCl4.

Understanding Li-ion transport is key for the rational design of superionic solid electrolytes with exceptional ionic conductivities. LiNbOCl4 is reported to be one of the most highly conducting materials in the recently realized new class of soft oxyhalide solid electrolytes, exhibiting an ionic conductivity of ∼11 mS·cm-1. Here, we apply X-ray/neutron diffraction and pair distribution function analysis─coupled with density functional theory/ab initio molecular dynamics (AIMD)─to determine a structural model that provides a rationale for the high conductivity that we observe experimentally in this nanocrystalline solid. We show that it arises from unusually high framework flexibility at room temperature. This is due to isolated 1-D [NbOCl4]- anionic chains that exhibit energetically favorable orientational disorder that is─in turn─correlated to multiple, disordered, and equi-energetic Li+ sites in the lattice. As the Li ions sample the 3-D energy landscape with a fast predicted diffusion coefficient of 5.1 × 10-7 cm2/s at room temperature (σicalc = 17.4 mS·cm-1), the inorganic polymer chains can reorient or vice versa. The activation energy barrier for Li migration through the frustrated energy landscape is especially reduced by the elastic nature of the NbO2Cl4 octahedra evident from very widely dispersed Cl-Nb-Cl bond angles in AIMD simulations at 300 K. The phonon spectra are predominantly influenced by Cl vibrations in the low energy range, and there is a strong overlap between the framework (Cl, Nb) and Li partial density of states in the region between 1.2 and 4.0 THz. The framework flexibility is also reflected in a relatively low bulk modulus of 22.7 GPa. Our findings pave the way for the investigation of future "flex-ion" inorganic solids and open up a new direction for the design of high-conductivity, soft solid electrolytes for all-solid-state batteries.

Node Distortions in UiO-66 Inform Negative Thermal Expansion Mechanisms: Kinetic Effects, Frustration, and Lattice Hysteresis.

In metal-organic frameworks (MOFs) the interplay between the dynamics of individual components and how these are constrained by the extended lattice can yield unusual emergent phenomena. For the archetypal Zr-MOF, UiO-66, we explore the cooperative dynamics of a Zr-node transformation that gives rise to negative thermal expansion (NTE). Using in situ synchrotron X-ray scattering, with powder diffraction and pair distribution function (PDF) analyses, we identify lattice hysteresis and a thermal ramp-rate-dependence of the thermal expansion. Specifically, kinetic trapping of distorted node states formed at high temperature, leads to broad variability in the apparent thermal expansion which ranges from large positive to large negative thermal expansion with coefficients of thermal expansion (CTE) from +45 to -80 × 10-6K-1. Time-resolved relaxation studies at selected temperatures suggest that when equilibrated UiO-66 is intrinsically NTE, with a CTE of -35 × 10-6K-1. Kinetic trapping of the node-distorted state following high temperature activation has broad implications for characterization and applications of these Zr-MOFs; the nonequilibrium node state depends on the thermal history of the sample with quench vs slow cooling likely to impact gas binding, pore volume, and accessible catalytic sites.

Dissecting of Atomic Morphology of Superfine Pulverized Coal Based on X-ray Pair Distribution Function

Resolving the atomic structure information of the aromatic layers in coal plays a crucial role in understanding the generation mechanisms of NOx during coal combustion and further reducing the formation of NOx from the source. This study reveals the distribution of X-ray diffraction bands of superfine pulverized coal using a high-resolution synchrotron radiation X-ray Diffraction (HRXRD) facility, discussing the distribution of atomic distances and atomic density in aromatic layers through pair distribution function (PDF) methods. Furthermore, the influences of mechanochemistry on the evolution of atomic morphology are focused on. The results show that the PDF of coal gradually stabilizes when r > 8 Å, showing the short-range order of graphite-like structure. Additionally, due to the limitations of scanning angle and X-ray energy, atomic distances in aromatic layers for coal are significantly greater than that of pure graphene. Enhanced mechanochemical effects make the peaks 1, 2, and 3 of coal PDF more similar to graphene's by condensing alkyl side chains into smaller, regular aromatic layers when the particle size decreases. With the enhancement of mechanochemical effects, coals with different metamorphic degrees exhibit different aromatic evolution patterns. The aromaticity of NMG coal first decreases and then increases, while the aromaticity of YQ coal shows the opposite trend. The results can provide deeper insights into the atomic structure of coal macromolecular, which can facilitate the advancement of novel ultra-low NOx combustion methods and support the construction of precise coal macromolecular models.

Resolving length-scale-dependent transient disorder through an ultrafast phase transition

Material functionality can be strongly determined by structure extending only over nanoscale distances. The pair distribution function presents an opportunity for structural studies beyond idealized crystal models and to investigate structure over varying length scales. Applying this method with ultrafast time resolution has the potential to similarly disrupt the study of structural dynamics and phase transitions. Here we demonstrate such a measurement of CuIr2S4 optically pumped from its low-temperature Ir-dimerized phase. Dimers are optically suppressed without spatial correlation, generating a structure whose level of disorder strongly depends on the length scale. The redevelopment of structural ordering over tens of picoseconds is directly tracked over both space and time as a transient state is approached. This measurement demonstrates the crucial role of local structure and disorder in non-equilibrium processes as well as the feasibility of accessing this information with state-of-the-art XFEL facilities.

Intercalated Water Drives Anomalous Thermal Expansion in the Tetragonal Zircon Structured Bismuth Vanadate BiVO4 Photocatalyst.

The thermal transformation of the tetragonal-zircon (tz-) to tetragonal-scheelite (ts-)BiVO4 was studied by in situ synchrotron X-ray diffraction, thermogravimetric analysis, and Fourier-transformed infrared spectroscopy. Upon heating, the tetragonal zircon polymorph of BiVO4 (tz-BiVO4) transitioned to the ts-polymorph between 693-773 K. Above 773 K, single phase ts-BiVO4 was observed before transitioning to the monoclinic fergusonite (mf-) polymorph upon cooling. An anomaly in thermal expansion was observed between 400-500 K, associated with the loss of intercalated H2O/NH4 + from the coprecipitation procedure. Heating tz-BiVO4 resulted in contraction of the V-O bond distance and VO4 polyhedra volume, ascribed to rotation of the tetrahedra groups. Attempts to study this by neutron diffraction failed due to the large incoherent scatter from the hydrogenous species. Efforts to remove these species while maintaining the tz-BiVO4 structure were unsuccessful, suggesting they play a role in stabilizing the tz-polymorph. The local structure of both mf-BiVO4 and tz-BiVO4 were investigated by X-ray pair distribution function analysis, revealing local distortions.

Local structural modelling and local pair distribution function analysis for Zr–Pt metallic glass

In disordered glass structures, the structural modelling and analyses based on local experimental data are not yet established. Here we investigate the icosahedral short-range order (SRO) in a Zr–Pt metallic glass using local structural modelling, which is a reverse Monte Carlo simulation dedicated to two-dimensional angstrom-beam electron diffraction (ABED) patterns, and local pair distribution function (PDF) analysis. The local structural modelling invariably leads to the icosahedral SRO atomic configurations that are similarly distorted by starting from some different initial configurations. Furthermore, the SRO configurations with 11–13 coordination numbers reproduce almost identical ABED patterns, indicating that these SRO structures are similar to each other. Further local PDF analysis explicitly indicates the presence of the wide distribution of atomic bond distances, which is comparable to the global PDF profile, even at the SRO level. The SRO models based on the conventional MD simulation can be strengthened by comparison with those obtained by the present local structural modelling and local PDF analysis based on the ABED data.

Superadiabatic dynamical density functional theory for colloidal suspensions under homogeneous steady-shear.

The superadiabatic dynamical density functional theory (superadiabatic-DDFT) is a promising new method for the study of colloidal systems out-of-equilibrium. Within this approach, the viscous forces arising from interparticle interactions are accounted for in a natural way by explicitly treating the dynamics of the two-body correlations. For bulk systems subject to spatially homogeneous shear, we use the superadiabatic-DDFT framework to calculate the steady-state pair distribution function and the corresponding viscosity for low values of the shear-rate. We then consider a variant of the central approximation underlying this superadiabatic theory and obtain an inhomogeneous generalization of a rheological bulk theory due to Russel and Gast. This paper thus establishes for the first time a connection between DDFT approaches, formulated to treat inhomogeneous systems, and existing work addressing nonequilibrium microstructure and rheology in bulk colloidal suspensions.

Dilepton Polarization as a Signature of Plasma Anisotropy.

We propose the angular distribution of lepton pairs produced in ultrarelativistic heavy-ion collisions as a probe of thermalization of the quark-gluon plasma. We focus on dileptons with invariant masses large enough that they are produced through quark-antiquark annihilation in the early stages of the collision. The angular distribution of the lepton in the rest frame of the pair then reflects the angular distribution of quark momenta. At early times, the transverse pressure of the quark-gluon plasma is larger than its longitudinal pressure as a result of the fast longitudinal expansion, which results in an oblate lepton distribution. By contrast, direct (Drell-Yan) production by quarks and antiquarks from incoming nuclei, whose momenta are essentially longitudinal, results in a prolate distribution. As the invariant mass increases, Drell-Yan gradually becomes the dominant source of dilepton production, and the lepton distribution evolves from oblate to prolate. The invariant mass at which the transition occurs is highly sensitive to the equilibration time of the quark-gluon plasma or, equivalently, the shear viscosity over entropy ratio η/s in the early stages of the collision.

Vacancy Mediated Electrooxidation of 5‐Hydroxymethyl Furfuryl Using Defect Engineered Layered Double Hydroxide Electrocatalysts

AbstractElectrochemical biomass oxidation coupled with hydrogen evolution offers a promising route to generate value‐added chemicals and clean energy. The complex adsorption behavior of 5‐hydroxymethyl furfural (HMF) and hydroxyl ions (OH−) on the electrocatalyst surface during HMF electrooxidation reaction (HMFOR) necessitates an in‐depth understanding of active sites available for adsorption. Herein, oxygen vacancy (VO) defects are introduced in NiFe layered double hydroxide (LDH) using Ce dopants to manipulate electronic structure. Synchrotron‐based HE‐XRD and XAS indicate negligible VO in La‐doped NiFe while Ce doping leads to VO defects due to flexible Ce redox (Ce3+↔ Ce4+). The VO‐rich Ce‐NiFe exhibits higher Faradic efficiency of ≈90% to produce 2,5‐furan dicarboxylic acid (FDCA), far greater than ≈60% for NiFe VO in Ce‐NiFe act as alternative active sites for OH− adsorption, hence reducing adsorption competition for the same metal sites. DFT calculation results corroborate experimental findings by showcasing that the presence of VO in Ce‐NiFe manipulates the adsorption energies and facilitates the chemical adsorption OH− in VO to improve HMFOR. In situ HE‐XRD derived pair distribution function coupled to RMC simulations confirm OH− trapping in VO and HMF adsorption on metal centers as evident by interlayer distance evolution. Taken together, this work showcases routes for dual‐site electrocatalyst design for improved biomass electrooxidation.

Molybdenum-Oxysulfide-Functionalized MgAl-Layered Double Hydroxides─A Sorbent for Selenium Oxoanions.

Effective removal of chemically toxic selenium oxoanions at high-capacity and trace levels from contaminated water remains a challenge in current scientific pursuits. Here, we report the functionalization of the MgAl layered double hydroxide with molybdenum-oxysulfide (MoO2S2) anion, referred to as LDH-MoO2S2, and its potential to sequester SeVIO42- and SeIVO32- from aqueous solution. LDH-MoO2S2 nanosheets were synthesized by an ion exchange method in solution. Synchrotron X-ray pair distribution function (PDF) and extended X-ray absorption fine structure (EXAFS) revealed an unexpected transformation of the MoO2S22- to Mo2O2S62- like species during the intercalation process. LDH-MoO2S2 is remarkably efficient in removing SeO42- and SeO32- ions from the ppm to trace level (≤10 ppb), with distribution constant (Kd) ranging from 104 to 105 mL/g. This material showed exceptionally high sorption capacities of 237 and 358 mg/g for SeO42- and SeO32-, respectively. Furthermore, LDH-MoO2S2 demonstrates substantial affinity and efficiency to remove SeO32-/SeO42- even in the presence of competitive ions from contaminated water. Hence, the removal of selenium (VI/IV) oxoanions collectively occurs through reductive precipitation and ion exchange mechanisms. This work provides significant insights into the chemical structure of the MoO2S2 anion into LDH and emphasizes its exceptional potential for high-capacity selenium removal and positioning it as a premier sorbent for selenium oxoanions.