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At least 559 records · Page 31

Revealing the hidden structure of disordered materials by parameterizing their local structural manifold

Abstract Durable interest in developing a framework for the detailed structure of glassy materials has produced numerous structural descriptors that trade off between general applicability and interpretability. However, none approach the combination of simplicity and wide-ranging predictive power of the lattice-grain-defect framework for crystalline materials. Working from the hypothesis that the local atomic environments of a glassy material are constrained by enthalpy minimization to a low-dimensional manifold in atomic coordinate space, we develop a generalized distance function, the Gaussian Integral Inner Product (GIIP) distance, in connection with agglomerative clustering and diffusion maps, to parameterize that manifold. Applying this approach to a two-dimensional model crystal and a three-dimensional binary model metallic glass results in parameters interpretable as coordination number, composition, volumetric strain, and local symmetry. In particular, we show that a more slowly quenched glass has a higher degree of local tetrahedral symmetry at the expense of cyclic symmetry. While these descriptors require post-hoc interpretation, they minimize bias rooted in crystalline materials science and illuminate a range of structural trends that might otherwise be missed.

36 MATERIALS SCIENCE↗

A microstructure-based modeling approach to predict the mechanical properties of Zr alloy with hydride precipitates

In nuclear reactors, hydrides can form in fuel cladding due to hydrogen absorption in ZIrcaloy and cause embrittlement. This work presents a microstructure-based finite element model to predict the stress-strain response of Zircaloy containing hydrides. Quantitative microstructural details extracted from scanning electron microscopy (SEM) images were used to generate heterogeneous microstructures including the morphology and spatial distribution of hydrides. The constitutive material model for zircaloy in this study is based on crystal plasticity theory which considers the hexagonal close-packed (HCP) atomic structure of Zircaloy material. The hydrides were modeled as brittle material along with a damage model. Hydride formation inside the zircoloy matrix results in residual stress. This phenomenon is also captured in this model. A parametric study has been conducted to understand the effect of volume fraction, orientation, and lamellae thickness of the hydride phase on the mechanical properties of the overall material.

Kulkarni, Shank S.↗

High-pressure phase diagram and equation of state of solid helium from single-crystal X-ray diffraction to 23.3 GPa

Single-crystal X-ray diffraction measurements have been performed on solid He-4 from 15.6 to 23.3 GPa at 300 K with synchrotron radiation. The diffraction patterns demonstrate that the structure of the solid is hexagonal close packed over this pressure-temperature range, contrary to both the interpretation of high-pressure optical studies and to theoretical predictions. The solid is more compressible than is indicated by equations of state calculated with recently determined helium pair potentials. The results suggest that a significant revision of current views of the phase diagram and energetics of dense solid helium is in order.

Mao, H. K.↗

Towards the extraction of the crystal cell parameters from pair distribution function profiles

The approach based on atomic pair distribution function (PDF) has revolutionized structural investigations by X-ray/electron diffraction of nano or quasi-amorphous materials, opening up the possibility of exploring short-range order. However, the ab initio crystal structural solution by the PDF is far from being achieved due to the difficulty in determining the crystallographic properties of the unit cell. A method for estimating the crystal cell parameters directly from a PDF profile is presented, which is composed of two steps: first, the type of crystal cell is inferred using machine-learning approaches applied to the PDF profile; second, the crystal cell parameters are extracted by means of multivariate analysis combined with vector superposition techniques. The procedure has been validated on a large number of PDF profiles calculated from known crystal structures and on a small number of measured PDF profiles. The lattice determination step has been benchmarked by a comprehensive exploration of different classifiers and different input data. The highest performance is obtained using the k -nearest neighbours classifier applied to whole PDF profiles. Descriptors calculated from the PDF profiles by recurrence quantitative analysis produce results that can be interpreted in terms of PDF properties, and the significance of each descriptor in determining the prediction is evaluated. The cell parameter extraction step depends on the cell metric rather than its type. Monometric, dimetric and trimetric cells have top-1 estimates that are correct 40, 20 and 5% of the time, respectively. Promising results were obtained when analysing real nanocrystals, where unit cells close to the true ones are found within the top-1 ranked solution in the case of monometric cells and within the top-6 ranked solutions in the case of dimetric cells, even in the presence of a crystalline impurity with a weight fraction up to 40%.

36 MATERIALS SCIENCE↗

Cryogenic temperatures promote the pressure-induced polymorphic transition in CoCrFeMnNi high entropy alloy

Pressure-induced polymorphism has recently been demonstrated in several high entropy alloys. This offers a new window into the much-debated issue of phase selection and stability in these systems. Here, we examine the effect of cryogenic temperatures on the pressure-induced transition from face centered cubic to hexagonal close-packed structures of the prototype CoCrFeMnNi (Cantor) alloy. We observe a reduction in the critical pressure for the onset of the polymorphic transition as the temperature decreases, confirming the progressive stabilization of the hexagonal phase with decreasing temperature previously predicted by ab initio calculations accounting for magnetic interactions. We argue that in situ high-pressure experiments at cryogenic temperatures, which suppress time-dependent transformation triggered at higher temperatures, present a unique opportunity to significantly improve our understanding of these complex alloys.

alloys↗

Cubic Crystal Structure Formation and Optical Properties within the Ag–B II –M IV –X (B II = Sr, Pb; M IV = Si, Ge, Sn; X = S, Se) Family of Semiconductors

Quaternary chalcogenide semiconductors are promising materials for energy conversion and nonlinear optical applications, with properties tunable primarily by varying the elemental composition and crystal structure. Here, we first analyze the connections among several cubic crystal structure types, as well as the orthorhombic Ag 2 PbGeS 4 -type structure, reported for select members within the Ag–B II –M IV –X (B II = Sr, Pb; M IV = Si, Ge, Sn; X = S, Se) compositional space. Focusing on the Ag–Pb–Si–S and Ag–Sr–Sn–S systems, we show that one structure type, with the formulas Ag 2 Pb 3 Si 2 S 8 and Ag 2 Sr 3 Sn 2 S 8 , is favored. We have prepared powder and single-crystal samples of Ag 2 Pb 3 Si 2 S 8 and Ag 2 Sr 3 Sn 2 S 8 , showing that each takes on the noncentrosymmetric cubic space group I$\bar{43}$d and is isostructural to the previously reported compound Ag 2 Sr 3 Ge 2 Se 8 . Through hybrid density functional theory calculations, these cubic compounds are demonstrated to be (quasi-)direct band gap semiconductors with high densities of states at the band maxima. Furthermore, the band-gap energies are measured by reflectance spectroscopy as 1.95(3) and 2.66(4) eV for Ag 2 Pb 3 Si 2 S 8 and Ag 2 Sr 3 Sn 2 S 8 , respectively. We further measure the optical properties and show the electronic band structures of three other isostructural A I –B II –M IV –X-type materials, i.e., Ag 2 Sr 3 Si 2 S 8 , Ag 2 Sr 3 Ge 2 S 8 , and Ag 2 Sr 3 Ge 2 Se 8 , showing that the band gaps can be predictably tuned by element substitution. Detailed visual analyses of the different structures and of their relationships with other members of the Ag–B II –M IV –X compositional family provide a basis for a broader understanding of the structure formation and optoelectronic properties within the quaternary chalcogenide semiconductor family.

14 SOLAR ENERGY↗

Exciton Fine Structure in 2D Perovskites: The Out‐of‐Plane Excitonic State

2D Ruddlesden‐Popper metal‐halide perovskites feature particularly strong excitonic effects, making them a fascinating playground for studying exciton physics. A complete understanding of the properties of this quasi‐particle is crucial to fully exploit the tremendous potential of 2D perovskites (2DP) in light emission applications. Despite intense investigations, some of the exciton properties remain elusive to date, for example, the energy‐ordering of the exciton states within the so‐called fine structure manifold. Using optical spectroscopy, it demonstrates that in the archetypical 2DP (PEA) 2 PbI 4 , in contradiction to theoretical predictions, the energy of the bright out‐of‐plane exciton state is higher than that of two in‐plane states. Having elucidated the order of exciton fine structure, it determines the g ‐factor of the dark exciton transition, together with the values of the electron and hole g ‐factors in the direction parallel to the c ‐axis of the crystal. In this way, it provides for the first time, a complete picture of the exciton fine structure in (PEA) 2 PbI 4 2DP.

2D perovskites↗

A combined theoretical and experimental study of the phase coexistence and morphotropic boundaries in ferroelectric-antiferroelectric-antiferrodistortive multiferroics

The physical nature of the ferroelectric (FE), ferrielectric (FEI) and antiferroelectric (AFE) phases, their coexistence and spatial distributions underpins the functionality of antiferrodistortive (AFD) multiferroics in the vicinity of morphotropic phase transitions. In this work, using Landau-Ginzburg-Devonshire (LGD) phenomenology and a semi-microscopic four sublattice model (FSM), we explore the behavior of different AFE, FEI, and FE long-range orderings and their coexistence at the morphotropic phase boundaries in FE-AFE-AFD multiferroics. These theoretical predictions are compared with the experimental observations for dense Bi 1-y R y FeO 3 ceramics, where R is Sm or La atoms with the fraction 0 ≤ y ≤ 0.25, as confirmed by the X-ray diffraction (XRD) and Piezoresponse Force Microscopy (PFM). These complementary measurements were used to study the macroscopic and nanoscopic transformation of the crystal structure with doping. The comparison of the measured and calculated AFE/FE phase fractions demonstrate that the LGD-FSM approach well describes the experimental results obtained by XRD and PFM for Bi 1-y R y FeO 3 . Hence, this combined theoretical and experimental approach provides further insight into the origin of the morphotropic boundaries and coexisting FE and AFE states in model rare-earth doped multiferroics.

36 MATERIALS SCIENCE↗

Machine learning guided search for energetically favorable metal borocarbide ternary compounds

In this work, we employ machine-learning (ML) combined with first principles calculations to efficiently search for the energetically favorable metal borocarbide (M-B-C) ternary compounds with M being the group 1–3 metal elements. Using a crystal graph convolutional neural network (CGCNN) ML approach followed by first-principles calculations, we predicted 47 energetically favorable stable and metastable ternary Na-B-C, Ca-B-C, and La-B-C ternary compounds with their decomposition energy (E d ) below or within 100 meV/atom from the currently known convex hulls. Phonon spectra and electronic structures of the 14 energetically favorable stable structures are also investigated by first-principles calculations. By substituting the metal atoms in the 29 energetically favorable non-equivalent template structures of Na (Ca, La)-B-C with other group 1–3 elements in the periodic table, we further obtain 22 stable structures and 52 metastable structures (E d ≤100 meV/atom with respect to the known convex hulls) for Li-B-C, K-B-C, Rb-B-C, Mg-B-C, Sr-B-C, Ba-B-C, Sc-B-C and Y-B-C ternary compounds. New convex hulls including our newly predicted stable ternary structures and the known stable structures are constructed for the M-B-C systems. The results obtained by our ML guided first-principles calculations enrich our knowledge in the structure and energy landscape of metal borocarbide ternary compounds and provide useful guidance for further experimental synthesis and discovery.

36 MATERIALS SCIENCE↗

Identifying $\textit{f}$-electron symmetries of UTe 2 with O-edge resonant inelastic x-ray scattering

The recent discovery of spin-triplet superconductivity emerging from a nonmagnetic parent state in UTe 2 has stimulated great interest in the underlying mechanism of Cooper pairing. Experimental characterization of short-range electronic and magnetic correlations is vital to understanding these phenomena. Here we use resonant inelastic x-ray scattering (RIXS), x-ray absorption spectroscopy (XAS), and atomic-multiplet-based modeling to shed light on the active debate between $5f^26d^1$-based models with singlet crystal field states versus $5f^3$-based models that predict atomic Kramers doublets and much greater $5\textit{f}$ itinerancy. In this work, the XAS and RIXS data are found to agree strongly with predictions for a $5f^26d^1$-like valence electron configuration with weak intradimer magnetic correlations, and provide a context for interpreting recent investigations of the electronic structure and superconducting pairing mechanism.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Burton-Cabrera-Frank theory for the influence of off-cut direction on the growth of hcp crystals

The precise direction of the off-cut of a vicinal crystal surface determines the azimuth (in-plane angle) of the surface steps and thus their kink density. Here we develop a Burton-Cabrera-Frank (BCF) theory for step-flow crystal growth that includes the effects of step azimuth. We focus on the basal-plane surfaces of hexagonal close-packed (hcp) and related crystal structures, for which surface steps have alternating properties that depend on azimuth. We build on a previous treatment that considered only a single-step azimuth, 𝜙 = 0, that gives alternating steps of pure A and B type. As 𝜙 increases from zero, the density of kinks on the steps increases. For hcp-type crystals, in addition the structural difference between alternating steps decreases, until they become equivalent at 𝜙 = 30°. We consider the azimuth dependence of the step transparency, attachment, and repulsion parameters of the BCF model, including the effects of both geometrically required and thermally generated kinks. Example calculations are presented that demonstrate the overall effect of step azimuth on BCF predictions for step spacings during steady-state growth and for their dynamics during growth transients. Effects of symmetric and asymmetric step-step repulsion are discussed.

Ju, Guangxu↗

Real-Time Alignment and Reorientation of Polymer Chains in Liquid Crystal Elastomers

Liquid crystal elastomers (LCEs) exhibit soft elasticity due to the alignment and reorientation of mesogens upon mechanical loading, which provides additional mechanisms to absorb and dissipate energy. This enhanced response makes LCEs potentially transformative materials for biomedical devices, tissue replacements, and protective equipment. However, there is a critical knowledge gap in understanding the highly rate-dependent dissipative behaviors of LCEs due to the lack of real-time characterization techniques that probe the microscale network structure and link it to the mechanical deformation of LCEs. In this work, we employ in situ optical measurements to evaluate the alignment and reorientation degree of mesogens in LCEs. The data are correlated to the quantitative physical analysis using polarized Fourier-transform infrared spectroscopy. The time scale of mesogen alignment is determined at different strain levels and loading rates. The mesogen reorientation kinetics is characterized to establish its relationship with the macroscale tensile strain, and compared to theoretical predictions. Overall, this work provides the first detailed study on the time-dependent evolution of mesogen alignment and reorientation in deformed LCEs. It also provides an effective and more accessible approach for other researchers to investigate the structural-property relationships of different types of polymers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

In situ microbeam surface X-ray scattering reveals alternating step kinetics during crystal growth

The stacking sequence of hexagonal close-packed and related crystals typically results in steps on vicinal {0001} surfaces that have alternating A and B structures with different growth kinetics. However, because it is difficult to experimentally identify which step has the A or B structure, it has not been possible to determine which has faster adatom attachment kinetics. Here we show that in situ microbeam surface X-ray scattering can determine whether A or B steps have faster kinetics under specific growth conditions. We demonstrate this for organo-metallic vapor phase epitaxy of (0001) GaN. X-ray measurements performed during growth find that the average width of terraces above A steps increases with growth rate, indicating that attachment rate constants are higher for A steps, in contrast to most predictions. Overall, our results have direct implications for understanding the atomic-scale mechanisms of GaN growth and can be applied to a wide variety of related crystals.

36 MATERIALS SCIENCE↗

Interface velocity dependent solute trapping and phase selection during rapid solidification of laser melted hypo-eutectic Al-11at.%Cu alloy

Microstructure formation of a hypo-eutectic Al-11Cu (atom percent) alloy during solidification after laser melting has been studied by transmission electron microscopy (TEM). The evolution of the solid-liquid-interface velocity, V SL , during the solidification process has been determined from direct observation by in-situ TEM. This enabled correlating V SL with development of four distinct microstructure zones. Crystal growth mode transitions from planar to cellular, cellular to dendritic, dendritic to cellular, and cellular to planar, have been observed for the accelerating solid-liquid-interface. The transition from coupled two-phase growth to the single-phase growth occurred for V SL = V a = (0.80±0.05) m/s, where V a is the velocity of absolute stability, at the onset of banded morphology grain formation. The in-situ and post-mortem TEM uniquely permitted determination of the non-equilibrium solidus for the rapidly solidifying Al-11Cu alloy. Experimental evidence for solute clustering and chemical ordering tendencies at length scales on the order of ≤ 5nm has been detected in the single-phase regions of the banded grains. The structural features of the single-phase bands have been interpreted as signatures of ‘frozen in’ configurations present in the liquid boundary layer adjacent to the growing crystal, which has a width of about 3nm. Finally, the nano-scale spatiotemporal resolution experimental TEM studies performed here provided quantitative metrics, e.g. the solidification interface velocity dependent solute concentration of the α-Al phase and the near-atomic scale structure in the single-phase bands, that are uniquely suitable for comparison with theory and model predictions for solidification microstructure development in multicomponent alloys after laser melting.

36 MATERIALS SCIENCE↗

Monte Carlo Simulations of Crystal Defects in Open Ensembles

Zero- and two-dimensional crystal defects form in open statistical ensembles, such as the grand canonical, that are usually inaccessible with conventional simulation techniques. This longstanding challenge is overcome with a new Hamiltonian Monte Carlo method that samples energy-biased gradual transformations. In conclusion, the method enables free energy calculations for nonideal point defects and the direct prediction of finite-temperature interface structures.

Grain boundaries↗

AlphaFold -assisted structure determination of a bacterial protein of unknown function using X-ray and electron crystallography

Macromolecular crystallography generally requires the recovery of missing phase information from diffraction data to reconstruct an electron-density map of the crystallized molecule. Most recent structures have been solved using molecular replacement as a phasing method, requiring an a priori structure that is closely related to the target protein to serve as a search model; when no such search model exists, molecular replacement is not possible. New advances in computational machine-learning methods, however, have resulted in major advances in protein structure predictions from sequence information. Methods that generate predicted structural models of sufficient accuracy provide a powerful approach to molecular replacement. Taking advantage of these advances, AlphaFold predictions were applied to enable structure determination of a bacterial protein of unknown function (UniProtKB Q63NT7, NCBI locus BPSS0212) based on diffraction data that had evaded phasing attempts using MIR and anomalous scattering methods. Using both X-ray and micro-electron (microED) diffraction data, it was possible to solve the structure of the main fragment of the protein using a predicted model of that domain as a starting point. The use of predicted structural models importantly expands the promise of electron diffraction, where structure determination relies critically on molecular replacement.

molecular replacement↗

Structure-Aware Unsupervised, Transformational Machine Learning for Drug Discovery (DTRA Basic Research Final Report)

The major goal of this project is to develop machine learning (ML) methods to enable improved predictive power on real drug discovery for novel targets. More specifically, we planned to demonstrate the capability and effectiveness of ML tools utilizing unlabeled large-volume protein-ligand datasets. We investigated multiple pre-training approaches for 3D protein-ligand structure-based foundation models, without relying on experimental binding data. We also addressed scenarios in which crystal structures are unavailable or binding data are limited. We also planned to develop a complete pipeline to screen novel compounds as well as to demonstrate the capability and effectiveness of the developed methods by testing on a realistic drug discovery task such as SARS-CoV-2. While the major goals and milestones remain consistent with the original proposal, certain technical details have been adjusted, based on the experimental results and related outcomes.

97 MATHEMATICS AND COMPUTING↗