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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 379 records · Page 21
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Atomic-scale structure of ZrO 2 : Formation of metastable polymorphs

Metastable phases can exist within local minima in the potential energy landscape when they are kinetically “trapped” by various processing routes, such as thermal treatment, grain size reduction, chemical doping, interfacial stress, or irradiation. Despite the importance of metastable materials for many technological applications, little is known about the underlying structural mechanisms of the stabilization process and atomic-scale nature of the resulting defective metastable phase. Investigating ion-irradiated and nanocrystalline zirconia with neutron total scattering experiments, we show that metastable tetragonal ZrO 2 consists of an underlying structure of ferroelastic, orthorhombic nanoscale domains stabilized by a network of domain walls. The apparent long-range tetragonal structure that can be recovered to ambient conditions is only the configurational ensemble average of the underlying orthorhombic domains. This structural heterogeneity with a distinct short-range order is more broadly applicable to other nonequilibrium materials and provides insight into the synthesis and recovery of functional metastable phases with unique physical and chemical properties.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2015

Effects of rapid thermal annealing on the structural and local atomic properties of ZnO: Ge nanocomposite thin films

We have investigated the structural and local atomic properties of Ge nanocrystals (Ge-ncs) embedded ZnO (ZnO: Ge) thin films. The films were deposited by sequential sputtering of ZnO and Ge thin film layers on z-cut quartz substrates followed by an ex-situ rapid thermal annealing (RTA) at 600 °C for 30, 60, and 90 s under forming gas atmosphere. Effects of RTA time on the evolution of Ge-ncs were investigated by x-ray diffraction (XRD), scanning electron microscopy (SEM), hard x-ray photoelectron spectroscopy (HAXPES), and extended x-ray absorption fine structure (EXAFS). XRD patterns have clearly shown that fcc diamond phase Ge-ncs of sizes ranging between 18 and 27 nm are formed upon RTA and no Ge-oxide peak has been detected. However, cross-section SEM images have clearly revealed that after RTA process, Ge layers form varying size nanoclusters composed of Ge-ncs regions. EXAFS performed at the Ge K-edge to probe the local atomic structure of the Ge-ncs has revealed that as prepared ZnO:Ge possesses Ge-oxide but subsequent RTA leads to crystalline Ge structure without the oxide layer. In order to study the occupied electronic structure, HAXPES has been utilized. The peak separation between the Zn 2p and Ge 3d shows no significant change due to RTA. This implies little change in the valence band offset due to RTA.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2014

Atomic shell structure from the Single-Exponential Decay Detector

The density of atomic systems is analysed via the Single-Exponential Decay Detector (SEDD). SEDD is a scalar field designed to explore mathematical, rather than physical, properties of electron density. Nevertheless, it has been shown that SEDD can serve as a descriptor of bonding patterns in molecules as well as an indicator of atomic shells [P. de Silva, J. Korchowiec, and T. A. Wesolowski, ChemPhysChem 13, 3462 (2012)]. In this work, a more detailed analysis of atomic shells is done for atoms in the Li–Xe series. Shell populations based on SEDD agree with the Aufbau principle even better than those obtained from the Electron Localization Function, which is a popular indicator of electron localization. A link between SEDD and the local wave vector is given, which provides a physical interpretation of SEDD.

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

Modulating Electronic Structure of Atomically Dispersed Nickel Sites through Boron and Nitrogen Dual Coordination Boosts Oxygen Reduction

Abstract Atomically dispersed 3D transitional metal active sites with nitrogen coordination anchored on carbon support have emerged as a kind of promising electrocatalyst toward oxygen reduction reaction (ORR) in the field of fuel cells and metal–air cells. However, it is still a challenge to accurately modulate the coordination structure of single‐atom metal sites, especially first‐shell coordination, as well as identify the relationship between the geometric/electronic structure and ORR performance. Herein, a carbon‐supported single‐atom nickel catalyst is fabricated with boron and nitrogen dual coordination (denoted as Ni‐B/N‐C). The hard X‐ray absorption spectrum result reveals that atomically dispersed Ni active sites are coordinated with one B atom and three N atoms in the first shell (denoted as Ni‐B 1 N 3 ). The Ni‐B/N‐C catalyst exhibits a half‐wave potential ( E 1/2 ) of 0.87 V versus RHE, along with a distinguished long‐term durability in alkaline media, which is superior to commercial Pt/C. Density functional theory calculations indicate that the Ni‐B 1 N 3 active sites are more favorable for the adsorption of ORR intermediates relative to Ni‐N 4 , leading to the reduction of thermodynamic barrier and the acceleration of reaction kinetics, which accounts for the increased intrinsic activity.

Chemistry↗
DOE OSTI2014

Mesoscale Effects in Electrochemical Conversion: Coupling of Chemistry to Atomic- and Nanoscale Structure in Iron-Based Electrodes

The complex coupling of atomic, chemical, and electronic transformations across multiple length scales underlies the performance of electrochemical energy storage devices. Here, the coupling of chemistry with atomic- and nanoscale structure in iron conversion electrodes is resolved by combining pair distribution function (PDF) and small-angle X-ray scattering (SAXS) analysis for a series of Fe fluorides, oxyfluorides, and oxides. The data show that the anion chemistry of the initial electrode influences the abundance of atomic defects in the Fe atomic lattice. This, in turn, is linked to different atom mobilities and propensity for particle growth. Competitive nanoparticle growth in mixed anion systems contributes to a distinct nanostructure, without the interconnected metallic nanoparticles formed for single anion systems.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Efficient and interpretable graph network representation for angle-dependent properties applied to optical spectroscopy

Abstract Graph neural networks are attractive for learning properties of atomic structures thanks to their intuitive graph encoding of atoms and bonds. However, conventional encoding does not include angular information, which is critical for describing atomic arrangements in disordered systems. In this work, we extend the recently proposed ALIGNN (Atomistic Line Graph Neural Network) encoding, which incorporates bond angles, to also include dihedral angles (ALIGNN-d). This simple extension leads to a memory-efficient graph representation that captures the complete geometry of atomic structures. ALIGNN-d is applied to predict the infrared optical response of dynamically disordered Cu(II) aqua complexes, leveraging the intrinsic interpretability to elucidate the relative contributions of individual structural components. Bond and dihedral angles are found to be critical contributors to the fine structure of the absorption response, with distortions that represent transitions between more common geometries exhibiting the strongest absorption intensity. Future directions for further development of ALIGNN-d are discussed.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Magnetic control over the fundamental structure of atomic wires

When reducing the size of materials towards the nanoscale, magnetic properties can emerge due to structural variations. Here, we show the reverse effect, where the structure of nanomaterials is controlled by magnetic manipulations. Using the break-junction technique, we find that the interatomic distance in platinum atomic wires is shorter or longer by up to ~20%, when a magnetic field is applied parallel or perpendicular to the wires during their formation, respectively. The magnetic field direction also affects the wire length, where longer (shorter) wires are formed under a parallel (perpendicular) field. Our experimental analysis, supported by calculations, indicates that the direction of the applied magnetic field promotes the formation of suspended atomic wires with a specific magnetization orientation associated with typical orbital characteristics, interatomic distance, and stability. A similar effect is found for various metal and metal-oxide atomic wires, demonstrating that magnetic fields can control the atomistic structure of different nanomaterials when applied during their formation stage.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Regulating the product distribution of CO reduction by the atomic-level structural modification of the Cu electrode surface

Here, Cu catalyzes the electrochemical reduction of CO 2 or CO to an assortment of products, a behavior that is a detriment when only one reduced compound is desired. The present article provides an example in which, through the atomic-level control of the structure of the Cu electrode surface, the yield distribution is regulated to generate only one product. The reaction investigated was the preferential reduction of CO to C 2 H 5 OH on Cu at a low overpotential in alkaline solution. Experimental measurements combined electrochemical scanning tunneling microscopy (ECSTM) and differential electrochemical mass spectrometry (DEMS). An atomically ordered Cu(100) surface, prepared from either a single crystal or by Cu(pc)-to-Cu(100) reconstruction, did not produce ethanol. When the surfaces were subjected to monolayer-limited Cu↔Cu 2 O cycles, only the reconstructed surface underwent an additional structural transformation that spawned the selective production of ethanol at a potential 645 mV lower than that which generates multiple products. Quasi-operando ECSTM indicated transformation to an ordered stepped surface, Cu(S) [3(100)×(111)], or Cu(511). The non-selective, multiple-product Cu-catalyzed reduction of CO had thus been regulated to yield only one liquid fuel by an atomic-level structural modification of the electrode surface.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Composition–Structure–Activity Correlation of Platinum–Ruthenium Nanoalloy Catalysts for Ethanol Oxidation Reaction

Understanding the evolution of the composition and atomic structure of nanoalloy catalysts in the ethanol oxidation reaction (EOR) is essential for the design of active and robust catalysts for direct ethanol fuel cells. This article describes a study of carbon-supported platinum–ruthenium electrocatalysts (PtRu/C) with different bimetallic compositions and their activities in the EOR, an important anode reaction in direct ethanol fuel cells (DEFCs). The study focused on establishing the relationship between the catalyst’s composition, atomic structure, and catalytic activity for the EOR. Ex situ and in situ synchrotron high-energy X-ray diffraction (HE-XRD) experiments coupled with atomic pair distribution function (PDF) analysis and in situ energy-dispersive X-ray (EDX) analysis were employed to probe the composition and structural evolution of the catalysts during the in situ EOR inside a membrane electrode assembly (MEA) in the fuel cell. The results revealed an intriguing composition–structure–activity relationship for the PtRu electrocatalysts under EOR experimental conditions. In particular, the alloy with a Pt/Ru ratio of ~50:50 was found to exhibit a maximum EOR activity as a function of the bimetallic composition. This composition–activity relationship coincides with the relationship between the Pt interatomic distances and coordination numbers and the bimetallic composition. Notably, the catalytic activities of the PtRu electrocatalysts showed a significant improvement during the EOR, which can be related to atomic-level structural changes in the nanoalloys occurring during the EOR, as indicated by in situ HE-XRD/PDF/EDX data. Here, the findings shed some new light on the mechanism of the ethanol oxidation reaction over bimetallic alloy nanocatalysts, which is important for the rational design and synthesis of active nanoalloy catalysts for DEFCs.

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

Structure of Carbon Nanotube Porins in Lipid Bilayers: An in Situ Small-Angle X-ray Scattering (SAXS) Study [Atomic-level structure of carbon nanotube porins in lipid bilayers: an in-situ small-angle x-ray scattering (SAXS) study]

Carbon nanotube porins (CNTPs), small segments of carbon nanotubes capable of forming defined pores in lipid membranes, are important future components for bionanoelectronic devices as they could provide a robust analog of biological membrane channels. Furthermore, in order to control the incorporation of these CNT channels into lipid bilayers, it is important to understand the structure of the CNTPs before and after insertion into the lipid bilayer as well as the impact of such insertion on the bilayer structure. Here we employed a noninvasive in situ probe, small-angle X-ray scattering, to study the integration of CNT porins into dioleoylphosphatidylcholine bilayers. These results show that CNTPs in solution are stabilized by a monolayer of lipid molecules wrapped around their outer surface. We also demonstrate that insertion of CNTPs into the lipid bilayer results in decreased bilayer thickness with the magnitude of this effect increasing with the concentration of CNTPs.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Pushing the limits of the periodic table — A review on atomic relativistic electronic structure theory and calculations for the superheavy elements

We review the progress in atomic structure theory with a focus on superheavy elements and their predicted ground state configurations important for an element’s placement in the periodic table. To understand the electronic structure and correlations in the regime of large atomic numbers, it is essential to correctly solve the Dirac equation in strong Coulomb fields, and to take into account quantum electrodynamic effects. We specifically focus on the fundamental difficulties encountered when dealing with the many-particle Dirac equation. We further discuss the possibility for future many-electron atomic structure calculations going beyond the critical nuclear charge $Z_{crit}≈170$, where levels such as the $1s$ shell dive into the negative energy continuum ($E_{nκ} < –m_{e}c^2$). The nature of the resulting Gamow states within a rigged Hilbert space formalism is highlighted.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2023

Effect of a micro-scale dislocation pileup on the atomic-scale multi-variant phase transformation and twinning

In this paper, we perform concurrent atomistic–continuum (CAC) simulations to assess the contribution of the internal stress induced by the microscale dislocation pileup at an atomically structured interface to the atomic-scale phase transformations (PTs), reverse PTs, and twinning. The main novelty of this work is to unify the atomistic description of the interface and the coarse-grained (CG) description of the lagging dislocations away from the interface within one single framework. Our major findings are: (a) the interface dynamically responds to a pileup by forming steps/ledges, the height of which is proportional to the number of dislocations arriving at the interface; (b) the pileup-induced internal stress concentration profile follows neither the classical Eshelby model nor the super-dislocation model alone, but a combination of them; (c) when the pre-sheared sample is compressed, a direct square-to-hexagonal PT occurs ahead of the pileup tip and eventually grows into a wedge shape. The two variants of the hexagonal phases form a twin with respect to each other; (d) upon a further increase of the loading, part of the newly formed hexagonal phase transforms back to the square phase. The square product phase resulting from this reverse PT forms a twin with respect to the initial square phase. All phase boundaries (PBs) and twin boundaries (TBs) are stationary and correspond to zero thermodynamic Eshelby driving forces; and (e) the microscale dislocation pileup-induced internal shear stress and the structural change at the atomic-scale interface reduces the stress required for initiating a PT by a factor of 5.5, comparing with that in the sample containing no dislocations. This work is the first characterization of the behavior of PTs/twinning resulting from the reaction between a microscale dislocation slip and an atomically structured interface. In conclusion, the gained knowledge will advance our understanding of how the multi-phase material behaves in many complex physical processes, such as the synthesis of multi-phase high-entropy alloys or superhard ceramics under high-pressure torsion, deep mantle earthquakes in geophysics, and so on, which all involve dislocation slip, PTs, twinning, and their interactions across from the atomistic to the microscale and beyond.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Cooling rate dependence of structural order in Al{sub 90}Sm{sub 10} metallic glass

The atomic structure of Al{sub 90}Sm{sub 10} metallic glass is studied using molecular dynamics simulations. By performing a long sub-T{sub g} annealing, we developed a glass model closer to the experiments than the models prepared by continuous cooling. Using the cluster alignment method, we found that “3661” cluster is the dominating short-range order in the glass samples. The connection and arrangement of “3661” clusters, which define the medium-range order in the system, are enhanced significantly in the sub-T{sub g} annealed sample as compared with the fast cooled glass samples. Unlike some strong binary glass formers such as Cu{sub 64.5}Zr{sub 35.5}, the clusters representing the short-range order do not form an interconnected interpenetrating network in Al{sub 90}Sm{sub 10,} which has only marginal glass formability.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2020

Ptychographic atomic electron tomography: Towards three-dimensional imaging of individual light atoms in materials

Through numerical simulations, we demonstrate the combination of ptychography and atomic electron tomography as an effective method for low dose imaging of individual low-Z atoms in three dimensions. After generating noisy diffraction patterns with multislice simulations of an aberration-corrected scanning transmission electron microscope through a 5-nm zinc-oxide nanoparticle, we have achieved three-dimensional (3D) imaging of individual zinc and oxygen atoms and their defects by performing tomography on ptychographic projections. The methodology has also been simulated in 2D materials, resolving individual sulfur atoms in vertical WS 2 /WSe 2 van der Waals heterostructure with a low total electron dose where annular-dark-field images fail to resolve. Overall, we envision that the development of this method could be instrumental in studying the precise 3D atomic structures of radiation sensitive systems and low-Z atomic structures such as 2D heterostructures, catalysts, functional oxides, and glasses.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

Surface facet dependence of competing alloying mechanisms

Metal alloys are ubiquitous in many branches of heterogeneous catalysis, and it is now fairly well established that the local atomic structure of an alloy can have a profound influence on its chemical reactivity. While these effects can be difficult to probe in nanoparticle catalysts, model studies using well defined single crystal surfaces alloyed with dopants enable these structure–function correlations to be drawn. The first step in this approach involves understanding the alloying mechanism and the type of ensembles formed. In this study, we examined the atomic structure of RhCu single-atom alloys formed on Cu(111), Cu(100), and Cu(110) surfaces. Our results show a striking difference between Rh atoms alloying in Cu(111) vs the more open Cu(100) and Cu(110) surface facets. Unlike Cu(111) on which Rh atoms preferentially place-exchange with Cu atoms in the local regions above step edges leaving the majority of the Cu surface free of Rh, highly dispersed, homogeneous alloys are formed on the Cu(100) and (110) surfaces. These dramatically different alloying mechanisms are understood by quantifying the energetic barriers for atomic hopping, exchange, swapping, and vacancy filling events for Rh atoms on different Cu surfaces through theoretical calculations. Density functional theory results indicate that the observed differences in the alloying mechanism can be attributed to a faster hopping rate, relatively high atomic exchange barriers, and stronger binding of Rh atoms in the vicinity of step edges on Cu(111) compared to Cu(110) and Cu(100). Furthermore, these model systems will serve as useful platforms for examining structure sensitive chemistry on single-atom alloys.

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

Local conditions for the Pauli potential in order to yield self-consistent electron densities exhibiting proper atomic shell structure

The local conditions for the Pauli potential that are necessary in order to yield self-consistent electron densities from orbital-free calculations are investigated for approximations that are expressed with the help of a local position variable. It is shown that those local conditions also apply when the Pauli potential is given in terms of the electron density. An explicit formula for the Ne atom is given, preserving the local conditions during the iterative procedure. The resulting orbital-free electron density exhibits proper shell structure behavior and is in close agreement with the Kohn-Sham electron density. This study demonstrates that it is possible to obtain self-consistent orbital-free electron densities with proper atomic shell structure from simple one-point approximations for the Pauli potential at local density level.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2025

Atomic-resolution structural and spectroscopic evidence for the synthetic realization of two-dimensional copper boride

Since the first realization of borophene on Ag(111), two-dimensional (2D) boron nanomaterials have attracted substantial interest because of their polymorphic diversity and potential for hosting solid-state quantum phenomena. Here, we use atomic-resolution scanning tunneling microscopy (STM) and field-emission resonance (FER) spectroscopy to elucidate the structure and properties of atomically thin boron phases grown on Cu(111). Specifically, FER spectroscopy reveals charge transfer and electronic states that strongly differ from the decoupled borophene phases observed on silver, suggesting that the deposition of boron on copper results in strong covalent bonding characteristic of a 2D copper boride. This conclusion is reinforced by detailed STM characterization of line defects that are consistent with density functional theory calculations for atomically thin Cu8B14. This evidence for 2D copper boride is likely to motivate future synthetic efforts aimed at expanding the relatively unexplored family of atomically thin metal boride materials.

Science & Technology - Other Topics↗