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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.

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At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Probing Molecular Packing of Amorphous Pharmaceutical Solids Using X-ray Atomic Pair Distribution Function and Solid-State NMR

The structural investigation of amorphous pharmaceuticals is of paramount importance in comprehending their physicochemical stability. However, it has remained a relatively underexplored realm primarily due to the limited availability of high-resolution analytical tools. Here in this study, we utilized the combined power of X-ray pair distribution functions (PDFs) and solid-state nuclear magnetic resonance (ssNMR) techniques to probe the molecular packing of amorphous posaconazole and its amorphous solid dispersion at the molecular level. Leveraging synchrotron X-ray PDF data and employing the empirical potential structure refinement (EPSR) methodology, we unraveled the existence of a rigid conformation and discerned short-range intermolecular C–F contacts within amorphous posaconazole. Encouragingly, our ssNMR 19 F– 13 C distance measurements offered corroborative evidence supporting these findings. Furthermore, employing principal component analysis on the X-ray PDF and ssNMR data sets enabled us to gain invaluable insights into the chemical nature of the intermolecular interactions governing the drug–polymer interplay. These outcomes not only furnish crucial structural insights facilitating the comprehension of the underlying mechanisms governing the physicochemical stability but also underscore the efficacy of synergistically harnessing X-ray PDF and ssNMR techniques, complemented by robust modeling strategies, to achieve a high-resolution exploration of amorphous structures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

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↗
DOE OSTI2023

Pair distribution function analysis of nano-object assemblies

The atomic pair distribution function (aPDF) analysis technique, also known as the total scattering method, which considers both Bragg and diffuse scattering, has been used extensively to probe local atomic arrangements in crystalline and disordered materials. In contrast, there have been limited applications of the PDF in self-assembled nanomaterials, which represent a class of materials built from nanoscale objects, such as nano-colloids, micelles and proteins. As distinguished from atoms, nano-objects have polydispersity in size and shape, and such form-factor effects complicate the application of PDF analysis to nano-systems. Here, in this paper, the application of the PDF is extended to spherical nano-object assemblies and the formulae for the nano-PDF (nPDF) are derived, showing some differences from the aPDF. By numerical simulations, the properties of the nPDF (peak broadening and pattern profile) are studied systematically as a function of structural features, such as nano-object parameters (size and size polydispersity) and assembly structural features (size, shape, structure type and lattice disorder), and of data processing parameters ( q cut-off and `missing' data in ultra-small-angle regions). The nPDF analysis method is found to provide an effective route to revealing not only nanoscale but also mesoscale structural properties, for example the morphology of a nano-assembly.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2025

Solving disorder in (3D) real space: a comparative study of the three-dimensional difference pair distribution function and atomic resolution holography reconstructions

The quantitative analysis of local ordering principles in disordered crystalline systems has gained much attention over the past few years, as it is often considered crucial for optimizing material functionality. This development has been driven by significant advancements in computational and experimental methods, which have led to the establishment and widespread use of various analytical techniques. In this study, we perform model calculations to compare the effectiveness of atomic resolution holography and three-dimensional difference pair distribution function analysis (3D-ΔPDF). Using Cu 3 Au as a model system, we demonstrate an approach to derive local order parameters quantitatively and show that both techniques are well suited to quantifying chemical short-range order correlations and local bond-distance variations. By evaluating the strengths and limitations of both techniques, we advocate for their combined use to solve complex short-range order problems accurately.

3D-ΔPDF↗
DOE OSTI2025

Fast calculation of diffraction patterns from an ensemble of aligned molecules

We report an algorithm to calculate electron diffraction patterns for molecules with anisotropic angular distribution, which is significantly faster than existing methods. The algorithm uses a transform to convert the molecular orientation distribution, which is a function of three Euler angles, to the atom-pair distribution functions which depend on the polar and azimuthal angles. The diffraction signal can then be calculated from the atom-pair distributions. We demonstrate the computation method numerically by calculating electron diffraction patterns for a symmetric top molecule (trifluoroiodomethane) and an asymmetric top molecule (formaldehyde) and show that it reduces the calculation time by approximately two orders of magnitude compared to the standard brute-force method. Here, the method can also be applied to the calculation of x-ray diffraction patterns.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2023

Atomic Three-Dimensional Investigations of Pd Nanocatalysts for Acetylene Semi-hydrogenation

Deciphering the three-dimensional (3D) insight into nanocatalyst surfaces at the atomic level is crucial to understanding catalytic reaction mechanisms and developing high-performance catalysts. Nevertheless, better understanding the inherent insufficiency of a long-range ordered lattice in nanocatalysts is a big challenge. Here, in this work, we report the local structure of Pd nanocatalysts, which is beneficial for demonstrating the shape-structure-adsorption relationship in acetylene hydrogenation. The 5.27 nm spherical Pd catalyst (Pd sph ) shows an ethylene selectivity of 88% at complete acetylene conversion, which is much higher than those of the Pd octahedron and Pd cube and superior to other reported monometallic Pd nanocatalysts so far. By virtue of the local structure revelation combined with the atomic pair distribution function (PDF) and reverse Monte Carlo (RMC) simulation, the atomic surface distribution of the unique compressed strain of Pd-Pd pairs in Pd sph was revealed. Density functional theory calculations verified the obvious weakening of the ethylene adsorption energy on account of the surface strain of Pd sph . It is the main factor to avoid the over-hydrogenation of acetylene. The present work, entailing shape-induced surface strain manipulation and atomic 3D insight, opens a new path to understand and optimize chemical activity and selectivity in the heterogeneous catalysis process.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Three-dimensional charge density wave in the dual heavy fermion system UPt 2 Si 2

Heavy fermion liquids offer via their Kondo lattice diverse possibilities for exotic ground states. Using variable-temperature atomic pair distribution function analysis, we study the local atomic structure of the "dual" heavy fermion liquid UPt 2 Si 2 , which exhibits antiferromagnetism consistent with localized 5f-electron states and transport properties characteristic to itinerant 5f-"spd" hybridized electron systems. We show that UPt 2 Si 2 exhibits periodic lattice distortions (PLDs) involving both uranium and platinum atoms that are characteristic to three-dimensional charge density waves. Here, the temperature evolution of the PLDs tracks that of the transport and magnetic properties, suggesting the presence of little-known 5f-electron-lattice interactions. We argue that PLDs in heavy fermion liquids in general, and in particular in UPt 2 Si 2 , appear as new degrees of freedom that entangle competing electronic states and, as such, must be accounted for when their rich physics is considered.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Structural Characterization of the Platinum Nanoparticle Hydrogen-Evolving Catalyst Assembled on Photosystem I by Light-Driven Chemistry

Directed assembly of abiotic catalysts onto biological redox protein frameworks is of interest as an approach for the synthesis of biohybrid catalysts that combine features of both synthetic and biological materials. In this report, we provide a multiscale characterization of the platinum nanoparticle (NP) hydrogen-evolving catalysts that are assembled by light-driven reductive precipitation of platinum from an aqueous salt solution onto the photosystem I protein (PSI), isolated from cyanobacteria as trimeric PSI. The resulting PSI-NP assemblies were analyzed using a combination of X-ray energy-dispersive spectroscopy (XEDS), high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), small-angle X-ray scattering (SAXS), and high-energy X-ray scattering with atomic pair distribution function (PDF) analyses. The results show that the PSI-supported NPs are approximately 1.8 nm diameter disk-shaped particles that assemble at discrete sites with 145 Å separation. This separation is too large to be consistent with NP nucleation and growth at a site adjacent to the F B cofactor site. Instead, we suggest a mechanism for NP growth at hydrophobic sites on the PSI stromal surface. The NPs photoreductively assembled on the PSI stromal surface are found to be analogous to the nanostructures produced by successive cycles of atomic layer deposition (ALD) of platinum onto 40 nm porous anodic alumina oxide supports, although the mechanisms for nucleation appear to differ. In conclusion, this work establishes a foundation for the investigation of the reductive assembly of abiotic metal catalysts at sites connected to photochemically reducing equivalent production in PSI.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Chemical compression and ferroic orders in La substituted BiFe O 3

Chemical compression effects on the ferroic orders in La substituted BiFeO 3 are studied by atomic pair distribution function analysis and structure modeling. While rhombohedral BiFeO 3 exhibits ferroelectricity and antiferromagnetism (AF) with a cycloidal Fe spin arrangement leading to zero magnetization, La substituted BiFeO 3 exhibits a reduced lattice polarization, strengthened AF order, and an apparently suppressed spin cycloid leading to nonzero magnetization. Furthermore, the observed changes in the ferroic orders arise from the chemical compression induced changes in the octahedral rotation and ferroelectric displacement of Bi atoms, which appear as lattice degrees of freedom entangling the electronic and magnetic orders in BiFeO 3 .

36 MATERIALS SCIENCE↗
DOE OSTI2026

Short and medium range structure in elastic deformation of metallic and covalent glasses

Here, we present a concise methodology to analyze structural response to the applied stress in amorphous solids, including metallic glasses (MG), glassy selenium, silica and polycarbonate, using high energy x-ray diffraction and atomic pair distribution function (PDF) analysis. To assess the structural anisotropy induced by applied axial stress, diffraction data were expanded into spherical harmonics. Using Bessel transformation, components of the structure function were converted into isotropic and anisotropic PDFs. The PDFs were compared to the expected model behavior for ideal elastic deformation to separate homogeneous affine strain from local non-affine strains. In metallic glass the range of non-affine deformation is limited to the nearest neighbor shell, suggesting local strain relaxation under stress that occurs even in the elastic regime. Beyond the second atomic shell strain is uniform. However, in glassy silica, polycarbonate and selenium strong local bonding inhibits local displacements and strain in short range order is accommodated by rotation of local units. Interestingly, beyond a molecular unit, deformation in covalent systems is similar to MG, and response of the medium range order scales with the macroscopic stress.

glassy structure↗
DOE OSTI2023

Extended q -Range X-Ray Scattering Reveals High-Resolution Structural Details of Biomacromolecules in Aqueous Solutions

Here, we communicate a feasibility study for high-resolution structural characterization of biomacromolecules in aqueous solution from X-ray scattering experiments measured over a range of scattering vectors (q) that is approximately two orders of magnitude wider than used previously for such systems. Scattering data with such an extended q-range enables the recovery of the underlying real-space atomic pair distribution function, which facilitates structure determination. We demonstrate the potential of this method for biomacromolecules using several types of cyclodextrins (CD) as model systems. We successfully identified deviations of the tilting angles for the glycosidic units in CDs in aqueous solutions relative to their values in the crystalline forms of these molecules. Such level of structural detail is inaccessible from standard small angle scattering measurements. Our results call for further exploration of ultra-wide-angle X-ray scattering measurements for biomacromolecules.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Structure and phase transitions in niobium and tantalum derived nanoscale transition metal perovskites, Ba(Ti,MV)O3, M=Nb,Ta

The prospect of creating ferroelectric or high permittivity nanomaterials provides motivation for investigating complex transition metal oxides of the form Ba(Ti, MV)O3, where M = Nb or Ta. Solid state processing typically produces mixtures of crystalline phases, rarely beyond minimally doped Nb/Ta. Using a modified sol-gel method, we prepared single phase nanocrystals of Ba(Ti, M)O3. Compositional and elemental analysis puts the empirical formulas close to BaTi0.5Nb0.5O3−δ and BaTi0.5Ta0.5O3−δ. For both materials, a reversible temperature dependent phase transition (non-centrosymmetric to symmetric) is observed in the Raman spectrum in the region 533–583 K (260–310 °C); for Ba(Ti, Nb)O3, the onset is at 543 K (270 °C); and for Ba(Ti, Ta)O3, the onset is at 533 K (260 °C), which are comparable with 390–393 K (117–120 °C) for bulk BaTiO3. The crystal structure was resolved by examination of the powder x-ray diffraction and atomic pair distribution function (PDF) analysis of synchrotron total scattering data. It was postulated whether the structure adopted at the nanoscale was single or double perovskite. Double perovskites (A2B′B″O6) are characterized by the type and extent of cation ordering, which gives rise to higher symmetry crystal structures. PDF analysis was used to examine all likely candidate structures and to look for evidence of higher symmetry. The feasible phase space that evolves includes the ordered double perovskite structure Ba2(Ti, MV)O6 (M = Nb, Ta) Fm-3m, a disordered cubic structure, as a suitable high temperature analog, Ba(Ti, MV)O3Pm-3m, and an orthorhombic Ba(Ti, MV)O3Amm2, a room temperature structure that presents an unusually high level of lattice displacement, possibly due to octahedral tilting, and indication of a highly polarized crystal.

Chemistry↗
DOE OSTI2024

Two-step charge density wave transition and hidden transient phase in 1 T – TiSe 2

Using variable temperature atomic pair distribution function analysis, we study the emergence of charge density wave (CDW) order in 1T-TiSe 2 and find that it takes place via a two-step transition. First, upon decreasing temperature to about 235(3) K, CDW related lattice distortions emerge in the individual TiSe 2 layers alone. Then, upon further decreasing the temperature, the two-dimensional distortions in the layers couple and the widely recognized three-dimensional 2a o x 2a o x 2c o superstructure emerges at about 205(3) K. Because two different band gaps are known to emerge at the same temperatures, the finding indicates the presence of strong electron-phonon coupling. The transient phase between the two steps lacks inversion symmetry and may serve as a precursor of the debated chiral 1T-TiSe 2 phase. Finally, our findings are important for the understanding of the enigmatic CDW transition in 1T-TiSe 2 and CDW instabilities in van der Waals materials in general.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2023

Multielectrode electrochemical cell for in situ structural characterization of amorphous thin-film catalysts using high-energy X-ray scattering

A multielectrode-based electrochemical cell allows the structural characterization of an amorphous thin-film water oxidation catalyst under various electrochemical potentials using high-energy X-ray scattering and atomic pair distribution function (PDF) techniques. A multielectrode with five electrodes provides a sufficiently low background signal to enable high-energy X-ray scattering (HEXS) measurements and amplifies the extremely low HEXS signals from samples for high-resolution PDF analysis of in situ data from thin-film catalysts. Glassy carbon (GC) creates a relatively low intensity HEXS pattern and is used as a working electrode. Instead of a three-dimensional (3D) porous electrode architecture, the flat geometry of the electrode enables various deposition techniques to be used for the preparation of a highly conductive metal oxide layer. PDF analysis demonstrates high spatial resolution for a 230 nm thick amorphous iridium oxide film deposited on two roughened 60 µm thick GC electrodes. The PDF analysis resolves the domain size and distinguishes changes in fine structure which are directly correlated with the structure and function of the catalysts. In conclusion, the results bring the opportunity to analyze the structure of nanometre-scale amorphous thin-film catalysts in an electrolyte-compatible and compact 3D-printed electrochemical cell in a three-electrode configuration.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Resolving Atomic-Scale Structure and Chemical Coordination in High-Entropy Alloy Electrocatalysts for Structure–Function Relationship Elucidation

The recent breakthrough in confining five or more atomic species in nanocatalysts, referred to as high-entropy alloy nanocatalysts (HEAs), has revealed the possibilities of multielemental interactions that can surpass the limitations of binary and ternary electrocatalysts. The wide range of potential surface configurations in HEAs, however, presents a significant challenge in resolving active structural motifs, preventing the establishment of structure-function relationships for rational catalyst design and optimization. Here, we present a methodology for creating sub-5 nm HEAs using an aqueous-based peptide-directed route. Using a combination of pair distribution function and X-ray absorption spectroscopy, HEA structure models are constructed from reverse Monte Carlo modeling of experimental data sets and showcase a clear peptide-induced influence on atomic-structure and chemical miscibility. Coordination analysis of our structure models facilitated the construction of structure-function correlations applied to electrochemical methanol oxidation reactions, revealing the complex interplay between multiple metals that leads to improved catalytic properties. Our results showcase a viable strategy for elucidating structure-function relationships in HEAs, prospectively providing a pathway for future materials design.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Towards scanning nanostructure X-ray microscopy

This article demonstrates spatial mapping of the local and nanoscale structure of thin film objects using spatially resolved pair distribution function (PDF) analysis of synchrotron X-ray diffraction data. This is exemplified in a lab-on-chip combinatorial array of sample spots containing catalytically interesting nanoparticles deposited from liquid precursors using an ink-jet liquid-handling system. A software implementation is presented of the whole protocol, including an approach for automated data acquisition and analysis using the atomic PDF method. The protocol software can handle semi-automated data reduction, normalization and modeling, with user-defined recipes generating a comprehensive collection of metadata and analysis results. By slicing the collection using included functions, it is possible to build images of different contrast features chosen by the user, giving insights into different aspects of the local structure.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2025

Medium-range order and compositional correlation in metallic glasses

The compositional atomic ordering in metallic glasses was studied by simulation focusing on the medium-range order (MRO). Many metallic alloy liquids and glasses show MRO characterized by the oscillations in the atomic pair-distribution function (PDF) beyond the first peak, which decay exponentially with distance. To study the effects of the local chemical order on MRO, we examine the compositionally resolved PDF and its MRO for models of various binary metallic alloy glasses. We show that compositional ordering is limited mostly to the nearest-neighbor atoms and the MRO is largely independent of the compositional order. For some elements that strongly repel each other in the alloy, a second MRO periodicity is observed owing to the distinct correlations among them. These results are discussed in light of the idea that the MRO oscillations in the PDF describe the correlations in the atomic density fluctuations, rather than the detailed local atomic structure.

Atomic structure↗