Search NASA⌕ Search

SEARCH · Search NASA

Results for “MULTIPLE SCATTERING”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 649 records · Page 36
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Toward accurate measurement of electromagnetic field by retrieving and refining the center position of non-uniform diffraction disks in Lorentz 4D-STEM

Recent advancement in scanning transmission electron microscopy (STEM) allows the use of 4D-STEM, a technique that captures an electron diffraction pattern at each scan point in STEM, to measure electrostatic and magnetic potential and field in materials. However, accurate measurement, separation of the magnetic and electric signals, and removal of artifacts remain challenging, especially in the presence of complex non-uniform diffraction contrast within the disks. In this work, based on dynamic simulations of 4D-STEM patterns built upon superstructures consisting of millions of atoms to account for different sample thickness and edge geometries, we show how the shape and intensity distribution of the central disk are affected by multiple scattering. We propose a robust refinement procedure through iteration of the spin-sensitive peak position of the disk-center in the circular Hough transform filtered images from experimental Lorentz 4D-STEM dataset after minimizing the possible artifacts, such as those due to the change of thickness, dynamic scattering, and scanning process. We verify that caution must be taken as in practice the rigid-disk-shift model used to reconstruct induction maps can easily break down due to disk-protrusion when there exists a nonconstant phase gradient or thickness within the width of the probe. Through quantitative analysis and comparing experiment with calculation the effect of the non-spin-related intensity distribution inside the disk as well as that causes the disk shift due to the intensity-protrusion can be removed, and high-quality magnetic field mapping is possible.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2023

Circular dichroism in hard X-ray photoelectron diffraction observed by time-of-flight momentum microscopy

X-ray photoelectron diffraction (XPD) is a powerful technique that yields detailed structural information of solids and thin films that complements electronic structure measurements. Among the strongholds of XPD we can identify dopant sites, track structural phase transitions, and perform holographic reconstruction. High-resolution imaging of k ll -distributions (momentum microscopy) presents a new approach to core-level photoemission. It yields full-field k x -k y XPD patterns with unprecedented acquisition speed and richness in details. Here, we show that beyond the pure diffraction information, XPD patterns exhibit pronounced circular dichroism in the angular distribution (CDAD) with asymmetries up to 80%, alongside with rapid variations on a small k ll -scale (0.1 Å -1 ). Measurements with circularly-polarized hard X-rays (hν = 6 keV) for a number of core levels, including Si, Ge, Mo and W, prove that core-level CDAD is a general phenomenon that is independent of atomic number. The fine structure in CDAD is more pronounced compared to the corresponding intensity patterns. Additionally, they obey the same symmetry rules as found for atomic and molecular species, and valence bands. Further, the CD is antisymmetric with respect to the mirror planes of the crystal, whose signatures are sharp zero lines. Calculations using both the Bloch-wave approach and one-step photoemission reveal the origin of the fine structure that represents the signature of Kikuchi diffraction. To disentangle the roles of photoexcitation and diffraction, XPD has been implemented into the Munich SPRKKR package to unify the one-step model of photoemission and multiple scattering theory.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2018

Grains and Strains from Cepstral Analysis of 4D-STEM Nano-Diffraction Datasets

We report the availability of fast, high dynamic range pixel array detectors makes scanning convergent beam electron diffraction (CBED) a powerful tool for rapid, spatially resolved characterization of lattice structure over a wide range of length scales. However, to extract useful structural information from the large 4-dimensional datasets, especially for complex, 3D specimens, we must confront challenges with CBED intensity variations due to crystal mistilts and multiple scattering as well as challenges with precisely localizing diffracted disk centers.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Semi Transparent Three-Dimensional Macroporous Quaternary Oxynitride Photoanodes for Photoelectrochemical Water Oxidation

Semi transparent three-dimensional macroporous (3DM) photoanodes based on quaternary oxynitrides have the potential to simultaneously realize superior light harvesting and efficient charge transfer in a tandem photoelectrochemical (PEC) cell. A 3DM CaTaO 2 N photoanode was prepared for the first time on a GaN/Al 2 O 3 substrate via a chemical route, and it exhibits a high transmittance of >60% in the wide solar spectrum and a photoresponse onset at −0.3 V versus the reversible hydrogen electrode (V RHE ) under simulated solar illumination. In particular, a plateau photocurrent density of 0.21 mA cm –2 was achieved at a low potential of 0.4 V RHE , which was 1.6-fold and more than 50-fold higher than a two-dimensional macroporous (2DM) CaTaO 2 N/GaN/Al 2 O 3 photoanode and a conventional particle-based CaTaO 2 N/GaN/Al 2 O 3 photoanode, respectively. The bicontinuous, interconnected pore structure within this 3DM film can improve charge carrier separation and collection by reducing the average diffusion distance for minority carriers toward the electrolyte. Optical measurements and simulations verified the enhanced sunlight harvesting in the 3DM photoanode, which was ascribed to the concentrated distribution of the electric field and multiple scattering. Furthermore, this study provides guidance for future synthesis of highly efficient semitransparent 3DM quaternary oxynitride-based photoanodes for a tandem PEC device.

Layers↗
DOE OSTI2021

Coordination Sphere of Lanthanide Aqua Ions Resolved with Ab Initio Molecular Dynamics and X-ray Absorption Spectroscopy

To resolve the fleeting structures of lanthanide Ln 3+ aqua ions in solution, we (i) performed the first ab initio molecular dynamics (AIMD) simulations of the entire series of Ln 3+ aqua ions in explicit water solvent using pseudopotentials and basis sets recently optimized for lanthanides and (ii) measured the symmetry of the hydrating waters about Ln 3+ ions (Nd 3+ , Dy 3+ , Er 3+ , Lu 3+ ) for the first time with extended X-ray absorption fine structure (EXAFS). EXAFS spectra were measured experimentally and generated from AIMD trajectories to directly compare simulation, which concurrently considers the electronic structure and the atomic dynamics in solution, with experiment. In this study, we performed a comprehensive evaluation of EXAFS multiple-scattering analysis (up to 6.5 Å) to measure Ln–O distances and angular correlations (i.e., symmetry) and elucidate the molecular geometry of the first hydration shell. This evaluation, in combination with symmetry-dependent L 3 - and L 1 -edge spectral analysis, shows that the AIMD simulations remarkably reproduces the experimental EXAFS data. The error in the predicted Ln–O distances is less than 0.07 Å for the later lanthanides, while we observed excellent agreement with predicted distances within experimental uncertainty for the early lanthanides. Our analysis revealed a dynamic, symmetrically disordered first coordination shell, which does not conform to a single molecular geometry for most lanthanides. This work sheds critical light on the highly elusive coordination geometry of the Ln 3+ aqua ions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Sensitivity of Solvation Environment to Oxidation State and Position in the Early Actinide Period

In this work, the aqueous solvation of U–Pu in the III–VI oxidation states has been examined using density functional theory and hydrated cluster models of the form An(H 2 O) 30 4+/3+ and AnO 2 (H 2 O) 30 2+/+ embedded within a polarizable continuum model to approximate the effect of bulk water. The structural features are compared to available data from extended X-ray absorption fine structure. Then, using a multiple-scattering approach, the X-ray absorption near-edge spectra (XANES) have been simulated and compared to experiment. These structural data are complemented by a detailed thermodynamic analysis using a recently benchmarked protocol. The structural, spectroscopic, and thermodynamic information has been used to assign the primary solvation environments in water, with an emphasis upon understanding how oxidation state and position in the period modifies the hydration number and equilibrium between different solvation shell environments. Tetravalent U is proposed to exist in equilibrium between the 8- and 9-coordinate species. Moving to the right of the period, Np(IV) and Pu(IV) exist solely as the octa-aquo species. Reduction to the trivalent ions leads to thermodynamic favorability for this solvation environment, whose features reproduce the XANES spectra. The actinyl dications (AnO 2 2+ ) of U and Np have a preferred environment in the equatorial plane consisting of 5 solvating waters; however, changes to the ionic radius and electronic structure at Pu leads to an equilibrium between the 4- and 5-coordinate species for PuO 2 2+ . Reduction of the dications to form the monocations generally leads to a preference for the 4-coordinate primary solvation shell, with an equilibrium existing for uranyl, while the neptunyl and plutonyl species exist solely as AnO 2 (H 2 O) 4 + . Finally, these data provide accurate thermodynamic information for several rare species and the combined thermodynamic, structural, and spectroscopic approach reveals trends in hydration behavior across actinide oxidation states and within the early actinide period.

Ions↗
DOE OSTI2024

Toward a Machine Learning Approach to Interpreting X-ray Spectra of Trace Impurities by Converting XANES to EXAFS

The fact that the photoabsorption spectrum of a material contains information about the atomic structure, commonly understood in terms of multiple scattering theory, is the basis of the popular extended X-ray absorption spectroscopy (EXAFS) technique. How much of the same structural information is present in other complementary spectroscopic signals is not obvious. Here we use a machine learning approach to demonstrate that within theoretical models that accurately predict the EXAFS signal, the extended near-edge region does indeed contain the EXAFS-accessible structural information. We do this by exhibiting deep operator neural networks (DeepONets) that have learned the relationship between the extended and near edge portions of the X-ray absorption spectrum to predict the former from the latter. We find that we can accurately predict the EXAFS spectrum between 6 and 14 Å –1 from the first 6 Å –1 (≈100 eV) of the absorption spectrum of Cu 2 + substitutional defects in the Fe 3+ mineral hematite (α-Fe 2 O 3 ). This surprising finding implies that theoretical analyses of X-ray absorption spectra could be implemented that extract the same conclusions as high-quality EXAFS studies from spectra collected over a much smaller range of photon energies. This relaxes a host of experimental limitations related to the X-ray source and measurement sample, including collection time, minimum dopant concentration, source brilliance, and energy range. We describe the theoretical data sets and DeepONet construction and show that the resulting DeepONets produce EXAFS that recovers linear combination fits to experimental data with accuracy approaching the original ab initio calculations. We discuss the implications of our findings for minor constituent characterization and for understanding the information content of spectroscopic data more broadly, including how this approach might be applied to measured experimental spectra. In conclusion, to encourage similar efforts, the simulated X-ray spectra, machine learning, and fitting code are publicly available.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Deciphering the Solvation Structure of Aqueous ZnCl 2 Solutions from X-ray Absorption Spectra Using the Interpretable Graph Neural Network

Machine learning (ML) provides powerful pathways for predicting spectroscopic observables from atomic structures, but its broader impact depends on making model predictions interpretable in terms of physical and chemical principles. Here, we introduce a physics-guided graph neural network (GNN) model that predicts Zn K-edge X-ray spectroscopy (XAS) spectra of aqueous ZnCl 2 solutions. Training data are generated from ab initio XAS calculations on molecular dynamics snapshots obtained using a machine learning interatomic potential. The GNN reproduces experimental spectra across concentrations from dilute (<0.1 m) to highly concentrated (30 m, “water-in-salt”) regimes and scales efficiently to large, disordered liquid systems beyond the reach of conventional ab initio approaches. Gradient-based attribution analysis reveals that the model learns physically meaningful structure-spectrum relationships. Ligand-specific attributions reflect orbital hybridization patterns and the origin of the excitations derived from the density functional theory. Bond-length attributions recover spectral shifts consistent with multiple-scattering theory. Finally, this work bridges data-driven prediction with electronic-structure theory, establishing a general paradigm for interpretable ML that links atomic structure, electronic structure, and spectroscopic observables.

25 ENERGY STORAGE↗
DOE OSTI2024

Electron Radiation-Induced Nickel Nanoparticle Formation in KCl-ZnCl 2 Eutectic Molten Salt Using X-ray Absorption Spectroscopy

Understanding the speciation and local structure of metal solutes in molten salts is essential for predicting thermal properties and the redox and corrosion potentials of molten salts for next-generation nuclear reactors and concentrated solar power plant applications. Here, we employ X-ray absorption spectroscopy combined with electron paramagnetic resonance (EPR) measurements to investigate the effects of electron irradiation on 0.1 wt % NiCl 2 dissolved in molten eutectic KCl-ZnCl 2 salt. Radiation-driven reduction of Ni 2+ leading to nucleation and growth of Ni nanoparticles is studied as a function of electron dose (3–15 MGy) and temperature. Quantitative X-ray absorption near edge structure and linear combination fitting are utilized to investigate the extent of reduction as a function of the electron dose and temperature. A multiple-scattering (MS) approach is used for extended X-ray absorption fine structure analysis to deduce the size of the Ni nanoparticles formed and to understand the effect of the dose on the local structure of the nanoparticles. EPR studies on solidified NiCl 2 dissolved in molten eutectic KCl-ZnCl 2 salt show the formation of magnetic Ni nanoparticles.

36 MATERIALS SCIENCE↗
DOE OSTI2019

EXAFS Spectroscopy of Fractional Mixed-Valence Charge Density Wave Systems

We present extended X-ray absorption fine structure (EXAFS) spectra and modeling of a series of structurally tunable quasi-one-dimensional mixed-valence platinum–halide linear chain materials, [Pt(en 2 )][Pt(en 2 )X 2 ](ClO 4 ) 4 with X = Cl, Br, I. The materials exhibit a commensurate charge density wave with fractional charge states on alternating platinum ions in the chain, as well as a Peierls distortion with alternating platinum–halide bond lengths. The amplitude of the charge density wave and, correspondingly, the extent of the Peierls distortion are controlled by the identity of the bridging halide ion. We have carried out ab initio multiple scattering calculations using the FEFF9 code to relate the oriented Pt L III EXAFS spectra to the tunable electronic and structural properties. The spectral modeling reveals distinct photoelectron threshold energy values for the two inequivalent platinum ions in each of the mixed-valence chains, with values that vary systematically with fractional valence state. The difference in the photoelectron threshold energies of the two inequivalent platinum ions within each material correlates directly with the amplitude of the charge density wave, reflecting the decrease in charge density wave strength through the halide series X = Cl, Br, and I. We use dynamical matrix modeling to relate the experimentally determined mean-square relative displacement parameters for the metal–halide bond distances to the chain–axis vibrational modes that modulate the charge density wave structure. In addition, we discuss the EXAFS fitting results for the Pt–I bond lengths in the [Pt(en 2 )][Pt(en 2 )I 2 ](ClO 4 ) 4 complex in comparison to previous, mutually inconsistent structural determinations for this material.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Toward Ultracold Organic Chemistry: Prospects of Laser Cooling Large Organic Molecules

Ultracold organic chemistry enables studies of reaction dynamics and mechanisms in quantum regime. Access to ultracold molecules hinges on the ability to efficiently scatter multiple photons via quasi-closed cycling transitions. Optical cycling in polyatomic molecules is challenging due to their complex electronic structure. Using equation-of-motion coupled-cluster calculations, we demonstrate that an alkaline earth metal attached to various aromatic ligands (such as benzene, phenol, cyclopentadienyl, and pyrrolide) offer nearly closed cycling transitions with only a few additional repump lasers. Here, we also show that aromatic ligands such as benzene can accommodate multiple cycling centers in various geometrical arrangements, opening new avenues in quantum information science, precision measurements, and ultracold chemistry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Strong Localization of Surface Plasmon Polaritons with Engineered Disorder

Here in this work, we experimentally demonstrate for the first time strong localization of surface plasmon polaritons (SPPs) at visible regime in metallic nanogratings with short-range correlated disorder. By increasing the degree of disorder, the confinement of SPPs is significantly enhanced, and the effective SPP propagation length dramatically shrinks. Strong localization of SPPs eventually emerges at visible regime, which is verified by the exponentially decayed fields and the vanishing autocorrelation function of the SPPs. Physically, the short-range correlated disorder induces strong interference among multiple scattered SPPs and provides an adequate fluctuation to effective permittivity, which leads to the localization effect. Finally, our study demonstrates a unique opportunity for disorder engineering to manipulate light on nanoscale and may achieve various applications in random nanolasing, solar energy, and strong light-matter interactions.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2018

Operando Structure Determination of Cu and Zn on Supported MgO/SiO 2 Catalysts during Ethanol Conversion to 1,3-Butadiene

Electronic structure and reactivity of Cu- and Zn-promoted wet kneaded MgO/SiO 2 catalysts was interrogated during ethanol reaction to 1,3-BD. A multimodal nature of characterization, including in situ or operando X-ray, electron, light spectroscopies and steady state reactivity measurements demonstrated critical new information on the temporal evolution of the catalyst active sites including key measurements performed operando using synchrotron source (EXAFS and XANES). In situ DRIFT spectroscopy allowed to decouple the aldol condensation and dehydrogenation reactive steps due to the promotion with enhanced ability to carry out aldol condensation, as correlated with the steady state reactivity experiments . In situ UV-Vis spectroscopy presented a complex picture of the adsorbates with π- π* electronic transitions due to the allylic cations, cyclic or aromatic species while also suggesting oligomeric CuO species were formed. Operando X-ray measurements combined with ab initio multiple scattering modelling performed as a function of temperature identified a new transient intermediate assigned to a 4-fold coordinate Cu species that was key leading to increase in Cu-Cu pair number. For the first time, two types of Zn pairs, namely Zn-O and Zn-Mg, were identified during X-ray analysis under operating conditions. With Zn nearly 6-coordinated when in the vicinity of Mg while Zn-O species coordinated to nearly 4 nearest neighbors. The data suggest that such supported catalyst deactivation might proceed not only via carbon coking mechanism but also through the dispersed Cu site diffusion and growth due to the nearest neighbor oxygen atoms loss. The results presented suggest intermediates for segregation/deactivation mechanisms for a broader set of supported Cu and Zn catalysts used for alcohol upgrading catalytic reactions.

1,3-butadiene↗
DOE OSTI2022

Modeling Structural Colors from Disordered One-Component Colloidal Nanoparticle-Based Supraballs Using Combined Experimental and Simulation Techniques

Bright, saturated structural colors in birds have inspired synthesis of self-assembled, disordered arrays of assembled nanoparticles with varied particle spacings and refractive indices. However, predicting colors of assembled nanoparticles, and thereby guiding their synthesis, remains challenging due to the effects of multiple scattering and strong absorption. In this work, we use a computational approach to first reconstruct the nanoparticles’ assembled structures from small-angle scattering measurements and then input the reconstructed structures to a finite-difference time-domain method to predict their color and reflectance. This computational approach is successfully validated by comparing its predictions against experimentally measured reflectance and provides a pathway for reverse engineering colloidal assemblies with desired optical and photothermal properties.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Anisotropic high-harmonic generation in bulk crystals

The microscopic valence electron density determines the optical, electronic, structural and thermal properties of materials. However, current techniques for measuring this electron charge density are limited: for example, scanning tunnelling microscopy is confined to investigations at the surface, and electron diffraction requires very thin samples to avoid multiple scattering. Therefore, an optical method is desirable for measuring the valence charge density of bulk materials. Since the discovery of high-harmonic generation (HHG) in solids, there has been growing interest in using HHG to probe the electronic structure of solids. Here, using single-crystal MgO, we demonstrate that high-harmonic generation in solids is sensitive to interatomic bonding. We find that harmonic efficiency is enhanced (diminished) for semi-classical electron trajectories that connect (avoid) neighbouring atomic sites in the crystal. Finally, these results indicate the possibility of using materials’ own electrons for retrieving the interatomic potential and thus the valence electron density, and perhaps even wavefunctions, in an all-optical setting.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Correspondence: Reply to ‘Phantom phonon localization in relaxors’

The Correspondence by Gehring et al. mistakes Anderson phonon localization for the concept of an atomic-scale local mode. An atomic-scale local mode refers to a single atom vibrating on its own within a crystal. Such a local mode will have an almost flat intensity profile, but this is not the same as phonon localization. Anderson localization is a wave interference effect in a disordered system that results in waves becoming spatially localized. The length scale of the localized waves is set by the wavelength, which is approximately 2 nm in this case. This larger length scale in real space means narrower intensity profiles in reciprocal space. Here, we conclude that the claims in the Correspondence by Gehring et al. are incorrect because they mistakenly assume that the length scale for Anderson localization is atomic, and because the experimental observations rule out multiple scattering as the origin.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Ion complexation waves emerge at the curved interfaces of layered minerals

Abstract Visualizing hydrated interfaces is of widespread interest across the physical sciences and is a particularly acute need for layered minerals, whose properties are governed by the structure of the electric double layer (EDL) where mineral and solution meet. Here, we show that cryo electron microscopy and tomography enable direct imaging of the EDL at montmorillonite interfaces in monovalent electrolytes with ångstrom resolution over micron length scales. A learning-based multiple-scattering reconstruction method for cryo electron tomography reveals ions bound asymmetrically on opposite sides of curved, exfoliated layers. We observe conserved ion-density asymmetry across stacks of interacting layers in cryo electron microscopy that is associated with configurations of inner- and outer-sphere ion-water-mineral complexes that we term complexation waves. Coherent X-ray scattering confirms that complexation waves propagate at room-temperature via a competition between ion dehydration and charge interactions that are coupled across opposing sides of a layer, driving dynamic transitions between stacked and aggregated states via layer exfoliation.

36 MATERIALS SCIENCE↗