Spontaneous redox continuum reveals sequestered technetium clusters and retarded mineral transformation of iron
Abstract not provided
Boglaienko, Daria↗
SEARCH · Engineering Papers
Results for “quantitative structure”
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Systematic electronic structure in the cuprate parent state from quantum many-body simulations
The quantitative description of correlated electron materials remains a modern computational challenge. We demonstrate a numerical strategy to simulate correlated materials at the fully ab initio level beyond the solution of effective low-energy models and apply it to gain a detailed microscopic understanding across a family of cuprate superconducting materials in their parent undoped states. We uncover microscopic trends in the electron correlations and reveal the link between the material composition and magnetic energy scales through a many-body picture of excitation processes involving the buffer layers. Our work illustrates a path toward a quantitative and reliable understanding of more complex states of correlated materials at the ab initio many-body level.
Science & Technology - Other Topics↗
Probing atom dynamics of excited Co-Mo-S nanocrystals in 3D
Advances in electron microscopy have enabled visualizations of the three-dimensional (3D) atom arrangements in nano-scale objects. The observations are, however, prone to electron-beam-induced object alterations, so tracking of single atoms in space and time becomes key to unravel inherent structures and properties. Here, we introduce an analytical approach to quantitatively account for atom dynamics in 3D atomic-resolution imaging. The approach is showcased for a Co-Mo-S nanocrystal by analysis of time-resolved in-line holograms achieving ~1.5 Å resolution in 3D. The analysis reveals a decay of phase image contrast towards the nanocrystal edges and meta-stable edge motifs with crystallographic dependence. These findings are explained by beam-stimulated vibrations that exceed Debye-Waller factors and cause chemical transformations at catalytically relevant edges. This ability to simultaneously probe atom vibrations and displacements enables a recovery of the pristine Co-Mo-S structure and establishes, in turn, a foundation to understand heterogeneous chemical functionality of nanostructures, surfaces and molecules.
36 MATERIALS SCIENCE↗
Structure and pressure dependence of the Fermi surface of lithium
Here, we report studies of the Fermi surface (FS) of isotopically pure polycrystalline 7 Li from ambient pressure to 4.7 GPa. Shubnikov–de Haas (SdH) oscillations at 300 mK in external magnetic fields up to 35 T are measured to map the spherical parts of the FS of lithium. Our ambient pressure data show that the principal SdH frequencies consist of three distinct peaks at 41.25 ± 0.05, 41.65 ± 0.05, and 42.05 ± 0.05 kT, which are theoretically consistent with the presence of two crystal structure domains exhibiting nearly spherical FS. The size of the spherical parts of the FS is compatible with bcc and fcc crystal structures. The measured frequencies at 41.25 and 42.65 kT present direct quantitative evidence for the spherical deformation of the FS in fcc Li. Our high-pressure data show that while the FS of Li deforms under compression, it remains mostly spherical up to 4.7 GPa and the pressure dependence of the SdH frequency is consistent with the theoretically calculated pressure dependence in the fcc structure. Finally, we find that the electron effective mass does not deviate under pressure significantly from its ambient pressure value.
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
Imaging and structure analysis of ferroelectric domains, domain walls, and vortices by scanning electron diffraction
Direct electron detectors in scanning transmission electron microscopy give unprecedented possibilities for structure analysis at the nanoscale. In electronic and quantum materials, this new capability gives access to, for example, emergent chiral structures and symmetry-breaking distortions that underpin functional properties. Quantifying nanoscale structural features with statistical significance, however, is complicated by the subtleties of dynamic diffraction and coexisting contrast mechanisms, which often results in a low signal-to-noise ratio and the superposition of multiple signals that are challenging to deconvolute. Here we apply scanning electron diffraction to explore local polar distortions in the uniaxial ferroelectric Er(Mn,Ti)O 3 . Using a custom-designed convolutional autoencoder with bespoke regularization, we demonstrate that subtle variations in the scattering signatures of ferroelectric domains, domain walls, and vortex textures can readily be disentangled with statistical significance and separated from extrinsic contributions due to, e.g., variations in specimen thickness or bending. The work demonstrates a pathway to quantitatively measure symmetry-breaking distortions across large areas, mapping structural changes at interfaces and topological structures with nanoscale spatial resolution.
36 MATERIALS SCIENCE↗
A Frequency Domain Methodology for Quantitative Evaluation of Diffuse Wavefield With Applications to Seismic Imaging
Abstract Ambient Noise Imaging (ANI) of subsurface structures relies on seismic interferometry of diffuse seismic wavefields. However, the lack of effective methods to quantify and identify highly diffuse waves hampers applications of ANI, particularly in evaluating seismic attenuation and monitoring structural changes with high temporal resolution. Conventional ANI approaches require data normalization, which effectively suppresses the non‐diffuse component with large amplitude but also results in significant loss of amplitude and phase information in the continuous seismic records. In this study, we propose a frequency domain method to quantitatively evaluate the degree of diffuseness of seismic wavefields by analyzing their statistical characteristics of modal amplitudes for stationarity and randomness. Tests on synthetic waveform and field nodal records show that the proposed method can effectively distinguish between diffuse and non‐diffuse waveforms for either single‐ or three‐component data. As an application, we identify a 60‐s‐long diffuse coda of a local M 2.2 earthquake recorded by a dense nodal array on the San Jacinto Fault Zone, and successfully extract high‐quality dispersion curve andQ‐value without performing data normalization. These results are consistent with those obtained by conventional methods that assess the correlation between coherency and the Green's function, and by modeling ballistic waves generated by road traffic. Our proposed method can advance the imaging of subsurface velocity and attenuation structures as well as monitoring temporal changes for scientific studies and engineering applications.
Geochemistry & Geophysics↗
From Gargamelle to MINERvA: exploring the structure of the nucleon with neutrinos
Neutrino scattering experiments have been exploring the structure of the nucleon with Deep-Inelastic Scattering for over 50 years. Although hints of nucleon structure were available using CERN’s first neutrino beam in the 1960s, the study actually started quantitatively in the early 1970s with the Gargamelle heavy liquid bubble chamber that produced first neutrino confirmation of scaling. This study of nucleon structure continued with both bubble chambers and more massive electronic detectors that, with higher energy neutrino beams and $Q^2$ reach, examined the breaking of this scaling while testing Quantum Chromodynamics. Here, a significant factor when including neutrino explorations of nucleon structure in the overall picture is that to gather significant statistics, neutrino experiments have had to use heavier nuclear targets. It has been experimentally demonstrated that the structure of the nucleon in the nuclear environment is indeed different than the free nucleon structure. Understanding this modified structure has played an important part in the experimental and theoretical exploration of nucleon structure by neutrinos and is one of the important goals of the on-going MINERvA experiment at Fermilab.
72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
Psilocybin: crystal structure solutions enable phase analysis of prior art and recently patented examples
Psilocybin {systematic name: 3-[2-(dimethylamino)ethyl]-1 H -indol-4-yl dihydrogen phosphate} is a zwitterionic tryptamine natural product found in numerous species of fungi known for their psychoactive properties. Following its structural elucidation and chemical synthesis in 1959, purified synthetic psilocybin has been evaluated in clinical trials and has shown promise in the treatment of various mental health disorders. In a recent process-scale crystallization investigation, three crystalline forms of psilocybin were repeatedly observed: Hydrate A, Polymorph A, and Polymorph B. The crystal structure for Hydrate A was solved previously by single-crystal X-ray diffraction. This article presents new crystal structure solutions for the two anhydrates, Polymorphs A and B, based on Rietveld refinement using laboratory and synchrotron X-ray diffraction data, and density functional theory (DFT) calculations. Utilizing the three solved structures, an investigation was conducted via Rietveld method (RM) based quantitative phase analysis (QPA) to estimate the contribution of the three different forms in powder X-ray diffraction (PXRD) patterns provided by different sources of bulk psilocybin produced between 1963 and 2021. Over the last 57 years, each of these samples quantitatively reflect one or more of the hydrate and anhydrate polymorphs. In addition to quantitatively evaluating the composition of each sample, this article evaluates correlations between the crystal forms present, corresponding process methods, sample age, and storage conditions. Furthermore, revision is recommended on characterizations in recently granted patents that include descriptions of crystalline psilocybin inappropriately reported as a single-phase `isostructural variant.' Rietveld refinement demonstrated that the claimed material was composed of approximately 81% Polymorph A and 19% Polymorph B, both of which have been identified in historical samples. In this article, we show conclusively that all published data can be explained in terms of three well-defined forms of psilocybin and that no additional forms are needed to explain the diffraction patterns.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Thermodynamics–Structure–Dynamics Correlations and Nonuniversal Effects in the Elastically Collective Activated Hopping Theory of Glass-Forming Liquids
We employ the microscopic Elastically Collective Nonlinear Langevin Equation (ECNLE) theory of activated dynamics in combination with crystal-avoiding simulations to study four inter-related questions for metastable monodisperse hard sphere fluids. The first is how significantly improved integral equation theory structural input (Modified-Verlet (MV) closure) changes the dynamical predictions of ECNLE theory. The main consequence is a modest enhancement of the importance of the collective elastic barrier relative to its local cage contribution, which increases the alpha relaxation time and fragility relative to prior results based on the Percus–Yevick closure. Second, ECNLE-MV theory predictions for the alpha time and self-diffusion constant in the metastable regime are quantitatively compared to our new simulations. The small adjustment of a numerical prefactor that enters the collective elastic barrier leads to quantitative agreement over three decades. Third, using the more accurate MV structural input, ECNLE theory is shown to predict thermodynamics–structure–dynamics “correlations” based on various long and short wavelength scalar properties all related to static two-point collective density fluctuations. The logarithm of the alpha relaxation time scales as a power law with these scalar metrics with an exponent that is significantly lower in the less dense noncooperative activated regime compared to the very dense highly cooperative regime. However, the discovered correlation of activated relaxation with a thermodynamic property (dimensionless compressibility) is not causal in ECNLE theory, but rather reflects a strong connection between the local structural quantities that quantify kinetic constraints in the theory with the amplitude of long wavelength density fluctuations. Fourth, the consequences of chemically specific nonuniversalities associated with the onset condition and relative importance of collective elasticity are studied. In conclusion, the predicted thermodynamics–structure–dynamics correlations are found to be robust, albeit with nontrivial shifts of the onset condition.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Efficient analysis of small-angle scattering curves for large biomolecular assemblies using Monte Carlo methods
Structure elucidation from small-angle scattering curves of large biomolecular assemblies is notoriously challenging. This is because the simulation of high-resolution features in the structure of large macromolecular assemblies, such as de novo protein assemblies, is computationally demanding when it needs to cover a broad range of length scales. Conventional methods, such as the numerical approximation to the Debye equation or the use of spherical harmonics, do not scale well as the size of the assembly increases, which limits their application to small structures (e.g. individual proteins). This work explores the effectiveness of a Monte Carlo method to simulate and fit scattering curves for large biomolecular assemblies spanning over ranges covering atomic and molecular detail (e.g. spacing and orientation of proteins in an assembly) as well as large-scale (hundreds of nanometres) features. Owing to its speed and scalability, it can be combined with a fitting algorithm to extract structural features from experimental small-angle scattering curves in biomolecular assemblies that are otherwise intractable for interpretation. This work first demonstrates the effectiveness of the tool using experimental small-angle X-ray scattering (SAXS) data from tile-like proteins that assemble into 1D tube-like macromolecular structures. Here, the diameter distribution of tubes is extracted from SAXS fits, and this is quantitatively compared with distributions from electron microscopy. SAXS data are also obtained from 2D sheet-like protein assemblies, and the proposed method is used to quantify structural features such as the separation distance between protein building blocks and the flexing of the sheet. An open-source implementation of the methodology is provided for use in a broad range of biological systems involving multi-scale scattering analysis.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Chitosan as a Canvas for Studies of Macromolecular Controls on CaCO 3 Biological Crystallization
A mechanistic understanding of how macromolecules, typically as an organic matrix, nucleate and grow crystals to produce functional biomineral structures remains elusive. Advances in structural biology indicate that polysaccharides (e.g., chitin) and negatively charged proteoglycans (due to carboxyl, sulfate, and phosphate groups) are ubiquitous in biocrystallization settings and play greater roles than currently recognized. This review highlights studies of CaCO 3 crystallization onto chitinous materials and demonstrates that a broader understanding of macromolecular controls on mineralization has not emerged. With recent advances in biopolymer chemistry, it is now possible to prepare chitosan-based hydrogels with tailored functional group compositions. By deploying these characterized compounds in hypothesis-based studies of nucleation rate, quantitative relationships between energy barrier to crystallization, macromolecule composition, and solvent structuring can be determined. Finally, this foundational knowledge will help researchers understand composition-structure-function controls on mineralization in living systems and tune the designs of new materials for advanced applications.
15 GEOTHERMAL ENERGY↗
Highly Asymmetric Graphene Layer Doping and Band Structure Manipulation in Rare Earth–Graphene Heterostructure by Targeted Bonding of the Intercalated Gadolinium
Heterostructures consisting of vertically stacked two-dimensional (2D) materials have recently gained large attention due to their highly controllable electronic properties and resulting quantum phases. In contrast to the mechanically stacked multilayered systems, which offer exceptional control over a stacking sequence or interlayer twist angles, the epitaxially grown 2D materials express unprecedented quality and stability over wafer-scale lengths. However, controlling the growth conditions remains a major obstacle toward the formation of complex, epitaxial heterostructures with well-defined electronic properties. Here, we synthesized a trilayer graphene heterostructure on the SiC(0001) substrate with two specific interlayer locations occupied by gadolinium. We applied multitechnique methodology based on low-temperature scanning tunneling microscopy/spectroscopy (STM/S) and angle-resolved photoelectron spectroscopy (ARPES) to determine the intercalant’s locations in the complex, epitaxial graphene heterostructure. Our approach relies on very high quality and large, micrometer-scale homogeneity of the synthesized system. The experimentally determined electronic structure is dominated by the two topmost graphene layers. Overall, our spectroscopic results show quantitative agreement between global ARPES, local STM/S, and density functional theory predictions. The characterized electronic properties primarily reflect highly anisotropic doping levels between the two corresponding graphene layers, which significantly affect the band structure topology. Two pairs of hybridized massive Dirac bands from our initial synthesis–the bilayer graphene on the SiC(0001) substrate–are transformed upon Gd intercalation into two pairs of massless Dirac bands with a new hybridization region in between. Our results open perspectives in the realization of exotic 2D quantum materials via atomically precise synthesis of epitaxial, multilayered graphene–rare earth heterostructures.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Data for Spatial Analysis of Cell Patterning to Aid Genetic and Phenotypic Understanding of Grass Stomatal Density: A Case Study in Maize
Biological processes involve complex hierarchies where composite traits result from multiple component traits. However, holistically understanding of how sets of component traits interact to underpin genotype-to-phenotype relationships is generally lacking. Stomatal density (SD) is a tractable model system for exploring how high-throughput phenotyping (HTP) data could be exploited by a new spatial analysis approach to better understand a developmentally and functionally important trait. SD is a composite trait, resulting from various components related to cell identity and size, which are themselves governed by a series of spatio-developmental processes. Data from 192 recombinant inbred lines of maize [Zea mays (L.)] were analyzed by a new stomatal patterning phenotype (SPP) to (1) describe the average spatial probability distribution of the nearest neighboring stomata; (2) derive a core set of component traits related to cell size, cell packing, and positional probabilities; (3) build a structural equation model of component traits underlying SD; and (4) identify stomatal patterning quantitative trait loci (QTL). The core set of SPP-derived traits explained 74% of the variation in SD. Analyzing SPP component traits allowed some loci previously identified as generic SD QTL to be recognized as specific to lateral versus longitudinal elements of stomatal patterning. Therefore, this study highlights how novel insights can be gained by decomposing a composite trait (e.g., SD) into a set of component traits that were present in HTP data but not previously exploited.
AI/ML↗
Structural and compositional complexities of hierarchical self-assembly: A hypergraph approach
Programmable self-assembly enables the construction of complex molecular, supramolecular, and crystalline architectures from well-designed building blocks. In this work, we introduce a hypergraph-based formalism, Blocks & Bonds (B&B), which generalizes classical chemical graph theory by incorporating directed and multicolored interactions, internal symmetries, and hierarchical organization. Within this framework, we develop the Structure Code (SC), a compact and versatile language for describing self-assembled architectures. We define a Kolmogorov-style structural complexity as the total information content of SC, obtained through its tokenization and Shannon information assignment. Complementing this encoding-based measure, we introduce a much simpler quantity, the compositional complexity, which depends only on the number and cumulative usage of block and bond types in the construction set. A central result of this work is a strong empirical correlation between the token-based structural complexity and the compositional complexity across all examined systems. Owing to this agreement, the compositional complexity emerges as the most practical and broadly applicable measure: it is easy to compute, requires no explicit encoding, and yet closely tracks the actual information content of structurally diverse architectures. Applications to molecular systems (ethylene glycol and glucose), DNA-origami lattices, and crystalline assemblies show that B&B hypergraphs provide a unified, scalable, and information-efficient representation of structural organization, naturally capturing symmetry, modularity, and stereochemistry. This framework establishes a quantitative foundation for complexity-aware classification and inverse design of programmable matter.
36 MATERIALS SCIENCE↗
Visualization of dynamic polaronic strain fields in hybrid lead halide perovskites
Excitation localization involving dynamic nanoscale distortions is a central aspect of photocatalysis, quantum materials and molecular optoelectronics. Experimental characterization of such distortions requires techniques sensitive to the formation of point-defect-like local structural rearrangements in real time. Here, we visualize excitation-induced strain fields in a prototypical member of the lead halide perovskites via femtosecond resolution diffuse X-ray scattering measurements. Here, this enables momentum-resolved phonon spectroscopy of the locally distorted structure and reveals radially expanding nanometre-scale strain fields associated with the formation and relaxation of polarons in photoexcited perovskites. Quantitative estimates of the magnitude and shape of this polaronic distortion are obtained, providing direct insights into the dynamic structural distortions that occur in these materials. Optical pump–probe reflection spectroscopy corroborates these results and shows how these large polaronic distortions transiently modify the carrier effective mass, providing a unified picture of the coupled structural and electronic dynamics that underlie the optoelectronic functionality of the hybrid perovskites.
36 MATERIALS SCIENCE↗
Covalent Organic Framework (COF) Derived Ni–N–C Catalysts for Electrochemical CO 2 Reduction: Unraveling Fundamental Kinetic and Structural Parameters of the Active Sites
Electrochemical CO 2 reduction is a potential approach to convert CO 2 into valuable chemicals using electricity as feedstock. Abundant and affordable catalyst materials are needed to upscale this process in a sustainable manner. Nickel-nitrogen-doped carbon (Ni-N-C) is an efficient catalyst for CO 2 reduction to CO, and the single-site Ni-N x motif is believed to be the active site. However, critical metrics for its catalytic activity, such as active site density and intrinsic turnover frequency, so far lack systematic discussion. In this work, we prepared a set of covalent organic framework (COF)-derived Ni-N-C catalysts, for which the Ni-N x content could be adjusted by the pyrolysis temperature. The combination of high-angle annular dark-field scanning transmission electron microscopy and extended X-ray absorption fine structure evidenced the presence of Ni single-sites, and quantitative X-ray photoemission addressed the relation between active site density and turnover frequency.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Imaging moiré flat bands in three-dimensional reconstructed WSe 2 /WS 2 superlattices
Moiré superlattices in transition metal dichalcogenide (TMD) heterostructures can host novel correlated quantum phenomena due to the interplay of narrow moiré flat bands and strong, long-range Coulomb interactions. However, microscopic knowledge of the atomically reconstructed moiré superlattice and resulting flat bands is still lacking, which is critical for fundamental understanding and control of the correlated moiré phenomena. Here we quantitatively study the moiré flat bands in three-dimensional (3D) reconstructed WSe 2 /WS 2 moiré superlattices by comparing scanning tunnelling spectroscopy (STS) of high-quality exfoliated TMD heterostructure devices with ab initio simulations of TMD moiré superlattices. A strong 3D buckling reconstruction accompanied by large in-plane strain redistribution is identified in our WSe 2 /WS 2 moiré heterostructures. STS imaging demonstrates that this results in a remarkably narrow and highly localized K-point moiré flat band at the valence band edge of the heterostructure. A series of moiré flat bands are observed at different energies that exhibit varying degrees of localization. Our observations contradict previous simplified theoretical models but agree quantitatively with ab initio simulations that fully capture the 3D structural reconstruction. Furthermore, our results reveal that the strain redistribution and 3D buckling in TMD heterostructures dominate the effective moiré potential and the corresponding moiré flat bands at the Brillouin zone K points.
36 MATERIALS SCIENCE↗
Dynamic modeling for heavy-ion collisions
Recent theory progress in (3+1)D dynamical descriptions of relativistic nuclear collisions at finite baryon density are reviewed. Heavy-ion collisions at different collision energies produce strongly coupled nuclear matter to probe the phase structure of Quantum Chromodynamics (QCD). Dynamical frameworks serve as a quantitative tool to study properties of hot QCD matter and map collisions to the QCD phase diagram. Outstanding challenges are highlighted when confronting theoretical models with the current and forthcoming experimental measurements from the RHIC beam energy scan program.
73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗