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Results for “determining the coordination number”

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 OSTI2021

Benchmarking Coordination Number Prediction Algorithms on Inorganic Crystal Structures

Coordination numbers and geometries form a theoretical framework for understanding and predicting materials properties. Algorithms to determine coordination numbers automatically are increasingly used for machine learning and automatic structural analysis. In this work, we introduce MaterialsCoord, a benchmark suite containing 56 experimentally-derived crystal structures (spanning elements, binaries, and ternary compounds) and their corresponding coordination environments as described in the research literature. We also describe CrystalNN, a novel algorithm for determining near neighbors. We compare CrystalNN against 7 existing near-neighbor algorithms on the MaterialsCoord benchmark, finding CrystalNN to perform similarly to several well-established algorithms. For each algorithm, we also assess computational demand and sensitivity towards small perturbations that mimic thermal motion. Finally, we investigate the similarity between bonding algorithms when applied to the Materials Project database. Finally, we expect that this work will aid the development of coordination prediction algorithms as well as improve structural descriptors for machine learning and other applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Transformation of atomically dispersed platinum in SAPO-37 into platinum clusters: catalyst for ethylene hydrogenation

Atomically dispersed supported platinum catalysts were synthesized by the reaction of Pt(acac) 2 (acac = acetylacetonato) with the silicoaluminophosphate molecular sieve SAPO-37, with infrared spectra showing that the reaction involved SAPO OH groups. Extended X-ray absorption fine structure (EXAFS) spectra show that, after heating in air to 623 K, each platinum atom on average was bonded to approximately two oxygen atoms of the SAPO support, with no evidence of platinum clusters. X-ray absorption near edge spectra (XANES) indicate a platinum formal oxidation state of approximately +2. Here, these supported mononuclear species lacked catalytic activity for ethylene hydrogenation at 1 bar and room temperature, but activity arose during catalysis in a once-through flow reactor/X-ray absorption spectroscopy cell, as the XANES white line intensity decreased, indicating reduction of the platinum, and the EXAFS-determined Pt–Pt coordination number (CN) increased from essentially zero to 2.7 ± 0.5 after 2 h, indicating the formation of platinum clusters of only a few atoms each. The data indicate the almost instantaneous formation of the clusters and identify them as the catalytically active species. Subsequent exposure of the catalyst to ethylene as in situ EXAFS and XANES data were recorded led to a decrease in the Pt–Pt coordination number to 1.6 ± 0.3 and an increase in the white line intensity, indicating partial oxidative fragmentation of the clusters by ethylene. Platinum clusters in SAPO-37 formed in separate experiments by exposure to H 2 prior to catalysis were also catalytically active for ethylene hydrogenation. Here, the data thus show how to dial in the catalytic activity by forming platinum clusters by exposure of mononuclear platinum to H 2 and how to dial back the activity by oxidative fragmentation of the clusters by reaction with ethylene, all under mild conditions; the ethylene : H 2 ratio of the reactant gas determines the average platinum nuclearity and thus the catalytic activity.

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

Quantifying selective solvent transport under an electric field in mixed-solvent electrolytes

Electrolytes in lithium-ion batteries comprise solvent mixtures, but analysis of ion transport is always based on treating the solvents as a single-entity. We combine electrophoretic NMR (eNMR) measurements and molecular dynamics (MD) simulations to quantify electric-field-induced transport in a concentrated solution containing LiPF 6 salt dissolved in an ethylene carbonate/ethyl methyl carbonate (EC/EMC) mixture. The selective transport of EC relative to EMC is reflected in the difference between two transference numbers, defined as the fraction of current carried by cations relative to the velocity of each solvent species. This difference arises from the preferential solvation of cations by EC and its dynamic consequences. The simulations reveal the presence of a large variety of transient solvent-containing clusters which migrate at different velocities. Rigorous averaging over different solvation environments is essential for comparing simulated and measured transference numbers. Our study emphasizes the necessity of acknowledging the presence of four species in mixed-solvent electrolytes.

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

The primary gas phase hydration shell of hydroxide

The number of water molecules in hydroxide’s primary hydration shell has been long debated to be three from the interpretation of experimental data and four from theoretical studies. Here, we provide direct evidence for the presence of a fourth water molecule in hydroxide’s primary hydration shell from a combined study based on high-resolution cryogenic experimental photoelectron spectroscopy and high-level quantum chemical computations. Well-defined spectra of OH - (H 2 O) n clusters (n = 2 to 5) yield accurate electron binding energies, which are, in turn, used as key signatures of the underlying molecular conformations. Although the smaller OH - (H 2 O) 3 and OH - (H 2 O) 4 clusters adopt close-lying conformations with similar electron binding energies that are hard to distinguish, the OH - (H 2 O) 5 cluster clearly has a predominant conformation with a four-coordinated hydroxide binding motif, a finding that unambiguously determines the gas phase coordination number of hydroxide to be four.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Modeling Heterogeneity in UO 2 Nanoparticles Using X‐ray Absorption Spectroscopy

Abstract EXAFS provides the capability to interrogate nanoparticle (NP) structure in atomistic detail without relying on long‐range crystallinity. There is a limitation in that EXAFS provides averaged structural information, making it difficult to separate a small amount of heterogeneous structure from bulk. In this work, models were developed to extract surface‐specific information from conventional EXAFS measurements collected on UO 2 NPs of varying size. Specifically, the surface terminating species of UO 2 NPs was determined from comparison of coordination numbers with geometric models while the origin of static disorder was interrogated from user‐defined simulations. Results show that the degree of oxygenation on the NP surface does not significantly deviate from bulk surface and that static disorder is highly enhanced in NP surface layers but cannot be attributed to surface relaxation effects alone. The approach described herein has the potential to be adapted to a range of inorganic NP systems to interrogate surface structure.

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

FY24 Progress Report on Viscosity and Thermal Conductivity Measurements of Nuclear Industry Relevant Chloride Salts: An Experimental and Computational Study

As presented in this report, experimental and computational techniques were performed to assess the viscosity and thermal conductivity of key alkali and actinide chloride mixtures for molten salt reactor developers. These mixtures were pure LiCl, NaCl-KCl, LiCl-NaCl, LiCl-KCl, LiCl-NaCl-KCl, and NaCl-UCl 3 . Experimental measurements of viscosity were performed with a rolling ball viscometer, whereas experimental measurements of thermal conductivity were performed with a variable gap apparatus. Additional benchmarking work was performed using both property measurement systems to prepare for x-ray radiography in stainless-steel crucibles for viscosity and to ensure that calibration methods were accurate for thermal conductivity before assessing the NaCl-UCl 3 system. Validation data for the NaCl-UCl 3 in literature are minimal. Details on the calibration methods, salt measurement processes, and sources of error and uncertainty are discussed in detail for both property measurements. The computational methods described herein involved ab-initio molecular dynamics (AIMD) calculations using CP2K. The calculations were performed for the LiCl-KCl-NaCl and NaCl-UCl 3 systems. These calculations not only provided thermophysical property estimations for comparison to experimental data, but they also allowed for the determination of diffusion coefficients, coordination numbers, and radial distribution functions to provide insight into ion mobility and local coordination environments, which is linked to macroscopic property trends.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗
DOE OSTI2025

Cyclic Peptides for Lanthanide Binding

Lanthanide ions are difficult to separate from one another due to their similar chemical properties. The discovery of lanthanide-binding peptides and proteins in nature has led to an increased interest in the possibility of utilizing the strong binding of peptides to lanthanide ions for their separations; as such, there has been an effort to identify or design peptides with improved lanthanide binding and selectivity toward particular lanthanide ions. Here, in this study, we designed and characterized lanthanide-binding cyclic peptides (LBCPs) with molecular dynamics simulations, electronic structure calculations, and emission spectroscopy. Luminescent decay measurements were done to determine the number of water molecules coordinated to the Eu 3+ ion in Eu-LBCP complexes and compare to the predicted number of water molecules by computation to assess the lanthanide-binding affinity of LBCPs. Measured stability constants show binding of the LBCPs to the Eu 3+ ion with stronger than micromolar affinity. We were able to identify multiple peptides that selectively bind to middle lanthanides. We describe the structural basis of the lanthanide-binding selectivity trend with strongest binding to the middle lanthanides, followed by the heavier lanthanides, and finally to the lighter ions.

ions↗
DOE OSTI2020

Experimental determination of the temperature-dependent Van Hove function in a Zr 80 Pt 20 liquid

Even though the viscosity is one of the most fundamental properties of liquids, the connection with the atomic structure of the liquid has proven elusive. By combining inelastic neutron scattering with the electrostatic levitation technique, the time-dependent pair-distribution function (i.e., the Van Hove function) has been determined for liquid Zr 80 Pt 20 . We show that the decay time of the first peak of the Van Hove function is directly related to the Maxwell relaxation time of the liquid, which is proportional to the shear viscosity. This result demonstrates that the local dynamics for increasing or decreasing the coordination number of local clusters by one determines the viscosity at high temperature, supporting earlier predictions from molecular dynamics simulations.

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

Local atomic configurations in mechanically alloyed amorphous (FeCoNi) 70 Ti 10 B 20 powders

Here, the atomic structure of amorphous (FeCoNi) 70 Ti 10 B 20 alloy synthesized by mechanical alloying was investigated using high energy synchrotron X-ray diffraction and inverse Monte Carlo simulations of pair distribution functions. Empirical potential structure refinement indicates a chemical short-range order at the length scales of 2.1–2.5 Å via local atomic arrangements forming deformed bcc-like clusters. The structural model obtained was described by bond lengths, coordination numbers, and bond angle distribution functions determined for the first neighbor atoms by x-ray scattering supplemented with 3D Monte Carlo simulations.

36 MATERIALS SCIENCE↗
DOE OSTI2025

The construction of large-scale structure catalogs for the Dark Energy Spectroscopic Instrument

We present the technical details on how large-scale structure (LSS) catalogs are constructed from redshifts measured from spectra observed by the Dark Energy Spectroscopic Instrument (DESI). The LSS catalogs provide the information needed to determine the relative number density of DESI tracers as a function of redshift and celestial coordinates and, e.g., determine clustering statistics. We produce catalogs that are weighted subsamples of the observed data, each matched to a weighted `random' catalog that forms an unclustered sampling of the probability density that DESI could have observed those data at each location. Precise knowledge of the DESI observing history and associated hardware performance allows for a determination of the DESI footprint and the number of times DESI has covered it at sub-arcsecond level precision. This enables the completeness of any DESI sample to be modeled at this same resolution. The pipeline developed to create LSS catalogs has been designed to easily allow robustness tests and enable future improvements. We describe how it allows ongoing work improving the match between galaxy and random catalogs, such as including further information when assigning redshifts to randoms, accounting for fluctuations in target density, accounting for variation in the redshift success rate, and accommodating blinding schemes.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2020

Imaging the kinetics of anisotropic dissolution of bimetallic core–shell nanocubes using graphene liquid cells

Chemical design of multicomponent nanocrystals requires atomic-level understanding of reaction kinetics. Here, we apply single-particle imaging coupled with atomistic simulation to study reaction pathways and rates of Pd@Au and Cu@Au core-shell nanocubes undergoing oxidative dissolution. Quantitative analysis of etching kinetics using in situ transmission electron microscopy (TEM) imaging reveals that the dissolution mechanism changes from predominantly edge-selective to layer-by-layer removal of Au atoms as the reaction progresses. Dissolution of the Au shell slows down when both metals are exposed, which we attribute to galvanic corrosion protection. Morphological transformations are determined by intrinsic anisotropy due to coordination-number-dependent atom removal rates and extrinsic anisotropy induced by the graphene window. Our work demonstrates that bimetallic coreshell nanocrystals are excellent probes for the local physicochemical conditions inside TEM liquid cells. Furthermore, single-particle TEM imaging and atomistic simulation of reaction trajectories can inform future design strategies for compositionally and architecturally sophisticated nanocrystals.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2025

Theory of Cation Solvation in the Helmholtz Layer of Li-Ion Battery Electrolytes

The solvation environments of Li + in conventional nonaqueous battery electrolytes, such as LiPF 6 in mixtures of ethylene carbaronate (EC) and ethyl methyl carbonate (EMC), are often used to rationalize transport properties and solid electrolyte interphase (SEI) formation. Solvation environments in the compact electrical double layer (EDL) next to the electrode, also known as the Helmholtz layer, determine (partially) what species can react to form the SEI, with bulk solvation environments often being used as a proxy. Here, we develop and test a theory of cation solvation in the Helmholtz layer of nonaqueous Li-ion battery electrolytes. First, we validate the theory against bulk and diffuse EDL atomistic molecular dynamics (MD) simulations of LiPF 6 EC/EMC mixtures as a function of surface charge, where we find the theory can qualitatively capture the solvation environments. Next, we turn to the Helmholtz layer, where we find the main effect of the solvation structures next to the electrode is an apparent reduction in the number of binding sites between Li + and the solvents, again where we find reasonable agreement with our developed theory. Finally, by solving a simplified version of the theory, we find that the probability of Li + binding to each solvent remains equal to the bulk probability, suggesting that the bulk solvation environments are a reasonable place to start when understanding battery electrolytes. Our developed formalism can be parametrized from bulk MD simulations and used to predict the solvation environments in the Helmholtz layer through reducing the number of available coordination sites, which can be used to determine what could react and form the SEI.

Helmholtz↗
DOE OSTI2025

Local structure of zinc–indium–tin oxide films via grazing-incidence x-ray pair-distribution functions and theoretical methods

A detailed experimental and theoretical study on the local (r ≤ 4.5 Å) atomic structure of amorphous and crystalline zinc–indium–tin oxide (ZITO) thin films using grazing-incidence x-ray Pair-Distribution Functions (PDFs), ab initio Molecular Dynamics (MD), and Empirical Potential Structure Refinement (EPSR) Monte Carlo simulations is presented. High-energy synchrotron x rays, a two-dimensional detector, and different incident angles were used to probe the depth uniformity of five (ZnO) 0.15 (In 2 O 3 ) 0.70 (SnO 2 ) 0.15 films that were deposited via pulsed-laser deposition at growth temperatures (T G ) ranging from 25 to 300 °C. Films deposited at T G ≤ 150 °C were amorphous. The partially crystalline (T G = 200 °C) and fully crystalline (T G = 300 °C) films were highly textured. Both crystalline and amorphous structures were investigated using ab initio MD and EPSR Monte Carlo simulations. The density of the amorphous films determined from the experimental data agreed with MD calculations. Coordination numbers, bond lengths, and distortion for metal–oxygen and for both the edge- and corner-shared In–metal shells up to 4.5 Å obtained from PDF analysis closely agreed with MD and EPSR simulations. There is a pronounced decrease in the edge- and corner-shared In–Zn distances arising from the shorter Zn–O bond length, Zn–O tetrahedral coordination, and In–O–Zn angle in amorphous ZITO compared to its crystalline counterpart. A maximum in electrical mobility was observed for the amorphous film just before crystallization occurred. While the peak is broad, consistent with nearly unchanged overall cation–oxygen coordination in the amorphous films, ESPR results indicate that the tetrahedral coordination follows the conductivity trend.

Grazing Incidence X-ray↗
NASA NTRS1990

Clear air turbulence as a response to meso- and synoptic-scale dynamic processes

The paper presents both the Roach equation for the rate of energy dissipation due to clear air turbulence and Richardson number tendencies in isentropic coordinates and examines the implications of these formulations to determine whether there is a dynamic interdependence between Ri and the nonturbulent deformation processes. The equation representing the ln(Ri) tendency is applied diagnostically to grids from an isentropic analysis of archived soundings. The evolution of the Richardson number fields over 12-hour time periods is examined using a mechanistic model. It is suggested that the application of the Roach equation for the turbulent dissipation rate should have a more restricted use. Analyses of the meso-alpha scale Richardson number and of the Richardson number tendency fields reveal a phase relationship consistent with the theoretical predictions.

Keller, John L.↗
DOE OSTI2024

Enhanced Hydrogen Evolution Catalysis of Pentlandite due to the Increases in Coordination Number and Sulfur Vacancy during Cubic‐Hexagonal Phase Transition

Abstract The search for new phases is an important direction in materials science. The phase transition of sulfides results in significant changes in catalytic performance, such as MoS 2 and WS 2 . Cubic pentlandite [cPn, (Fe, Ni) 9 S 8 ] can be a functional material in batteries, solar cells, and catalytic fields. However, no report about the material properties of other phases of pentlandite exists. In this study, the unit‐cell parameters of a new phase of pentlandite, sulfur‐vacancy enriched hexagonal pentlandite (hPn), and the phase boundary between cPn and hPn are determined for the first time. Compared to cPn, the hPn shows a high coordination number, more sulfur vacancies, and high conductivity, which result in significantly higher hydrogen evolution performance of hPn than that of cPn and make the non‐nano rock catalyst hPn superior to other most known nanosulfide catalysts. The increase of sulfur vacancies during phase transition provides a new approach to designing functional materials.

Chemistry↗
NASA NTRS1992

Conservative-variable average states for equilibrium gas multi-dimensional fluxes

Modern split component evaluations of the flux vector Jacobians are thoroughly analyzed for equilibrium-gas average-state determinations. It is shown that all such derivations satisfy a fundamental eigenvalue consistency theorem. A conservative-variable average state is then developed for arbitrary equilibrium-gas equations of state and curvilinear-coordinate fluxes. Original expressions for eigenvalues, sound speed, Mach number, and eigenvectors are then determined for a general average Jacobian, and it is shown that the average eigenvalues, Mach number, and eigenvectors may not coincide with their classical pointwise counterparts. A general equilibrium-gas equation of state is then discussed for conservative-variable computational fluid dynamics (CFD) Euler formulations. The associated derivations lead to unique compatibility relations that constrain the pressure Jacobian derivatives. Thereafter, alternative forms for the pressure variation and average sound speed are developed in terms of two average pressure Jacobian derivatives. Significantly, no additional degree of freedom exists in the determination of these two average partial derivatives of pressure. Therefore, they are simultaneously computed exactly without any auxiliary relation, hence without any geometric solution projection or arbitrary scale factors. Several alternative formulations are then compared and key differences highlighted with emphasis on the determination of the pressure variation and average sound speed. The relevant underlying assumptions are identified, including some subtle approximations that are inherently employed in published average-state procedures. Finally, a representative test case is discussed for which an intrinsically exact average state is determined. This exact state is then compared with the predictions of recent methods, and their inherent approximations are appropriately quantified.

Iannelli, G. S.↗
NASA NTRS1980

Geophysical parameters of the earth-moon system

Doppler tracking data from Lunar Orbiter 4 have been combined with laser ranging data from lunar retroreflectors to yield a number of geophysical and geodetic parameters for the earth and moon. This joint solution gives values of (1) the lunar principal polar moment C/M R squared = 0.3905 plus or minus 0.0023, (2) GM(E) = 398600.461 plus or minus 0.026 cu km/sq s, and (3) an earth/moon mass ratio at 81.300587 plus or minus 0.000049. Also determined are the harmonics of a complete lunar gravity field through degree and order 5, the obliquity of the lunar pole, selenocentric coordinates of the lunar retroreflectors, geocentric coordinates of the McDonald Observatory, and the lunar secular acceleration. The lunar potential Love number is weakly determined at 0.022 plus or minus 0.013, and a suprisingly large dissipation of rotational energy is inferred, though either solid body tidal dissipation or liquid core mantle interactions could be causes.

Ferrari, A. J.↗