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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 361 records · Page 20
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Effect of single atom Platinum (Pt) doping and facet dependent on the electronic structure and light absorption of Lanthanum Titanium Oxide (La 2 Ti 2 O 7 ): A Density Functional Theory study

Charge generation and separation are two key processes for semiconductor photocatalysis. Here, we use Pt as a single atom catalyst to systematically examine the facet-dependent electronic band structure and light absorption of the layered perovskite-type wide-gap semiconductor, lanthanum titanium oxide (La 2 Ti 2 O 7 , LTO) by means of density functional theory simulations. In this study, it is found that single Pt atom doping of different LTO surfaces (here, (100), (101) and (001)) can not only create states in the bandgap that would promote the formation of recombination centers, but also shift the optical absorption edge to the visible region. Interestingly, the Pt doping forms a heterojunction, with the valence band maximum consisting of Pt states and the conduction band minimum consisting of LTO states, respectively. To study the facet dependent surface activity, acetic acid (CH 3 COOH) was used as a model molecule to investigate the adsorption and charge transfer on the (101), (100) and (001) Pt-LTO surface facets. The results show that the (101) facet could enable stronger adsorption of CH 3 COOH by promoting more electron transfer during the interfacial interaction. Our theoretical findings aim to promote the design and optimization of the single atom catalysts (SACs) for photocatalytic applications and other broad catalysis systems.

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

Isospin-violating contributions to ϵ'/ϵ

The known isospin-breaking contributions to the K → ππ amplitudes are reanalyzed, taking into account our current understanding of the quark masses and the relevant non-perturbative inputs. We present a complete numerical reappraisal of the direct CP-violating ratio ϵ'/ϵ, where these corrections play a quite significant role. We obtain the Standard Model prediction Re (ϵ'/ϵ) = (14 ± 5) · 10 -4 , which is in very good agreement with the measured ratio. The uncertainty, which has been estimated conservatively, is dominated by our current ignorance about 1/N C -suppressed contributions to some relevant chiral-perturbation-theory low-energy constants.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2022

Strongly correlated itinerant magnetism near superconductivity in NiTa 4 Se 8

Metallic ferromagnets with strongly interacting electrons often exhibit remarkable electronic phases such as ferromagnetic superconductivity, complex spin textures, and nontrivial topology. Here, in this report, we discuss the synthesis of a layered magnetic metal NiTa 4 Se 8 (or Ni 1/4 TaSe 2 ) with a Curie temperature of 58 Kelvin. Magnetization data and density functional theory calculations indicate that the nickel atoms host uniaxial ferromagnetic order of about 0.7µ B per atom, while an even smaller moment is generated in the itinerant tantalum conduction electrons. Strong correlations are evident in flat bands near the Fermi level, a high heat capacity coefficient, and a high Kadowaki-Woods ratio. Density functional theory calculations suggest that electron and hole Fermi surfaces in the ferromagnetic phase are associated with opposite spin polarization. When the system is diluted of magnetic ions, the samples become superconducting below about 2 Kelvin. We discuss possible mechanisms for superconductivity in this family.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2020

Single Ru Atoms Stabilized by Hybrid Amorphous/Crystalline FeCoNi Layered Double Hydroxide for Ultraefficient Oxygen Evolution

Abstract In view of the sluggish kinetics suppressing the oxygen evolution reaction (OER), developing efficient and robust OER catalysts is urgent and essential for developing efficient energy conversion technologies. Herein, hybrid amorphous/crystalline FeCoNi layered double hydroxide (LDH)‐supported single Ru atoms (Ru SAs/AC‐FeCoNi) are developed for enabling a highly efficient electrocatalytic OER. The amorphous outer layer in Ru SAs/AC‐FeCoNi is composed of abundant defect sites and unsaturated coordination sites, which can serve as anchoring sites to stabilize single Ru atoms. The crystalline inner has a highly symmetric rigid structure, thereby strengthening the stability of support for a long‐lasting OER. The synergistic effects endow this hybrid catalyst with extremely low overpotential (205 mV at 10 mA cm −2 ). Density functional theory calculation indicates that single Ru atoms stabilized by hybrid amorphous/crystalline FeCoNi LDH facilitate the formation of Ru–O* (rate‐determining step), thus accelerating the OER process.

Hu, Yidong↗
DOE OSTI2023

Stability and magnetic behavior of exfoliable nanowire one-dimensional materials

Low-dimensional materials can display enhanced electronic, magnetic, and quantum properties. Here we use the topological scaling algorithm to identify all sufficiently metastable materials in the Materials Project database to identify bulk crystals with one-dimensional (1D) structural motifs: Five hundred fifty-one crystals that are within 50 meV atom –1 of the thermodynamic hull display 1D motifs, where 293 of these contain d-valence elements, which we focus on in this work. After exfoliating nanowires from 263 of these materials and calculating their thermodynamic stability using density functional theory, 103 nanowires meet per-atom and per-Ångström thermodynamic stability criteria. We illustrate for three nanowire systems that a variety of local minima can be present in these systems, demonstrating one case of a Peierls distortion. The wires display a broad diversity of electronic and magnetic properties of these nanowires, with 14 metals, 7 half-metals, and 82 semiconductors and insulators, and 41 nanowires displaying magnetic moments ranging from 0.1 to 5μ B per d-valence species when assuming ferromagnetic order. A subset of these chains are investigated for the impact of magnetic ordering, identifying 1D FeCl 3 to be most stable in an antiferromagnetic state. The electronic and magnetic properties of the identified 1D materials could enable applications in spintronic and quantum devices.

36 MATERIALS SCIENCE↗
NASA NTRS1989

Oxygen evolution on a SrFeO3 anode - Mechanistic considerations from molecular orbital theory

Various pathways proposed in the literature for the evolution of O2 in electrochemical oxidations are explored using the atom superposition and electron delocalization molecular orbital (ASED-MO) theory and the cluster models of the SrFeO3 surface as a prototype material. Calculations indicate that oxygen atoms can be easily formed on the (100) surface as well as on the edge cation sites of a SrFeO3 anode by the discharge of OH(-), followed by its deprotonation and electron transfer to the electrode. The O atoms can form O2 on the edge and corner sites, where the Fe(4+) is coordinated to four and three bulk oxygen anions, respectively. The calculations strongly disfavor mechanisms involving coupling of oxygen atoms adsorbed on different cations as well as a mechanism featuring an ozone intermediate.

Mehandru, S. P.↗
DOE OSTI2020

Photoemission from hybrid states of Cl@C 60 before and after a stabilizing charge transfer

Photoionization calculations of the endofullerene molecule Cl@C 60 with an open-shell chlorine atom are performed in the linear response density functional theory based on a spherical jellium model of C 60 . Cross sections for atom–fullerene hybrid photoemission studied show the effects of the hybridization symmetry, the giant plasmon and the molecular cavity. Comparisons with the results of Ar@C 60 provide insights into the role of a shell-closing electron and its influence on the dynamics. The results for Cl@C 60 are further compared with those of a more stable configuration that results after a C 60 electron transfers to Cl forming Cl–@${{\text{C}}_{60}}^{+}$. This comparison reveals noticeable differences in the ionization properties of the antibonding hybrid state while the bonding hybrid remains nearly unaltered showing a magnification covering the entire giant plasmon energy range. Furthermore, these predictions should raise interest in probing the molecular configuration using photoelectron spectroscopy.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2023

High-order finite element method for atomic structure calculations

We introduce featom, an open source code that implements a high-order finite element solver for the radial Schrödinger, Dirac, and Kohn-Sham equations. The formulation accommodates various mesh types, such as uniform or exponential, and the convergence can be systematically controlled by increasing the number and/or polynomial order of the finite element basis functions. The Dirac equation is solved using a squared Hamiltonian approach to eliminate spurious states. Here, to address the slow convergence of the $κ=±1$ states due to divergent derivatives at the origin, we incorporate known asymptotic forms into the solutions. We achieve a high level of accuracy (10 -8 Hartree) for total energies and eigenvalues of heavy atoms such as uranium in both Schrödinger and Dirac Kohn-Sham solutions. We provide detailed convergence studies and computational parameters required to attain commonly required accuracies. Finally, we compare our results with known analytic results as well as the results of other methods. In particular, we calculate benchmark results for atomic numbers (Z) from 1 to 92, verifying current benchmarks. We demonstrate significant speedup compared to the state-of-the-art shooting solver dftatom. An efficient, modular Fortran 2008 implementation, is provided under an open source, permissive license, including examples and tests, wherein particular emphasis is placed on the independence (no global variables), reusability, and generality of the individual routines.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
NASA NTRS1983

Testing for a cosmological influence on local physics using atomic and gravitational clocks

The existence of a possible influence of the large-scale structure of the universe on local physics is discussed. A particular realization of such an influence is discussed in terms of the behavior in time of atomic and gravitational clocks. Two natural categories of metric theories embodying a cosmic infuence exist. The first category has geodesic equations of motion in atomic units, while the second category has geodesic equations of motion in gravitational units. Equations of motion for test bodies are derived for both categories of theories in the appropriate parametrized post-Newtonian limit and are applied to the Solar System. Ranging data to the Viking lander on Mars are of sufficient precision to reveal (1) if such a cosmological influence exists at the level of Hubble's constant, and (2) which category of theories is appropriate for a descripton of the phenomenon.

Adams, P. J.↗
DOE OSTI2026

Theory Guided Fine‐Tune of Strain Effects in Pt Ternary Alloy via Rare Earth Templating: Achieving High Performance PEMFCs Catalysts

The sluggish kinetics and insufficient durability of platinum-based catalysts remain crucial barriers limiting proton-exchange-membrane fuel cells (PEMFCs) deployment. Here, we report a theory-guided synthesis combined with rare-earth templating to realize a previously inaccessible Pt 5 Co-like phase with tailored atomic-scale strain. Guided by density functional theory (DFT) calculations, we identified that a Pt 5 Co-like sublayer can induce a unique mild compressive strain (−1.24%) to the Pt(111) shell and an optimal *OH binding energy shift (ΔE ≈ 0.11 eV). This shift positions the alloy catalyst near the apex of the oxygen reduction reaction activity volcano. This prediction guided the synthesis of ternary alloy Pt 5 (Ce)Co@Pt multilayer nanoparticles, featuring a Ce-stabilized core, a Pt 5 Co-like sublayer, and a Pt-rich shell. This catalyst demonstrates both exceptionally high activity and durability, achieving a mass activity of 2.6 A∙mg Pt −1 in rotating disk electrode testing. In fuel cell membrane electrode assembly tests, Pt 5 (Ce)Co@Pt achieves a current density of 1.9 A∙cm −2 at 0.7 V under heavy-duty vehicle conditions. Remarkably, it maintains 1.2 A∙cm −2 after 1 80 000 AST cycles, doubling the U.S. DOE 2025 target. This work demonstrates a rational design strategy that DFT-guided strain engineering integrates with rare-earth templating to advance Pt-based catalysts for fuel cell applications.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2020

Graph theory approach to determine configurations of multidentate and high coverage adsorbates for heterogeneous catalysis

Abstract Heterogeneous catalysts constitute a crucial component of many industrial processes, and to gain an understanding of the atomic-scale features of such catalysts, ab initio density functional theory is widely employed. Recently, growing computational power has permitted the extension of such studies to complex reaction networks involving either high adsorbate coverages or multidentate adsorbates, which bind to the surface through multiple atoms. Describing all possible adsorbate configurations for such systems, however, is often not possible based on chemical intuition alone. To systematically treat such complexities, we present a generalized Python-based graph theory approach to convert atomic scale models into undirected graph representations. These representations, when combined with workflows such as evolutionary algorithms, can systematically generate high coverage adsorbate models and classify unique minimum energy multidentate adsorbate configurations for surfaces of low symmetry, including multi-elemental alloy surfaces, steps, and kinks. Two case studies are presented which demonstrate these capabilities; first, an analysis of a coverage-dependent phase diagram of absorbate NO on the Pt 3 Sn(111) terrace surface, and second, an investigation of adsorption energies, together with identifying unique minimum energy configurations, for the reaction intermediate propyne (CHCCH 3 *) adsorbed on a PdIn(021) step surface. The evolutionary algorithm approach reproduces high coverage configurations of NO on Pt 3 Sn(111) using only 15% of the number of simulations required for a brute force approach. Furthermore, the screening of potentially hundreds of multidentate adsorbates is shown to be possible without human intervention. The strategy presented is quite general and can be applied to a spectrum of complex atomic systems.

36 MATERIALS SCIENCE↗
NASA NTRS1979

Io's sodium cloud - Explanation of the east-west asymmetries

An explanation of the east-west asymmetries of Io's sodium clouds is suggested based upon the force experienced by sodium atoms as they resonantly scatter sunlight and upon the ability of this force to alter the cloud atom orbits, as determined by the gravitational fields of Io and Jupiter. Orbit calculations illustrating the time-dependent changes in the sodium atom trajectories produced by the solar radiation force as a function of Io's orbital location are presented in support of this explanation. This theory agrees with the idea that sodium atoms are emitted from the satellite nonisotropically and at a constant rate. These conclusions may be important in studying the global effects of active volcanoes and the intense satellite plasma torus discovered for Io from Voyager I spacecraft measurements.

Smyth, W. H.↗
DOE OSTI2024

State-Selective Double Photoionization of Atomic Carbon and Neon

Double photoionization (DPI) allows for a sensitive and direct probe of electron correlation, which governs the structure of all matter. For atoms, much of the work in theory and experiment that informs our fullest understanding of this process has been conducted on helium, and efforts continue to explore many-electron targets with the same level of detail to understand the angular distributions of the ejected electrons in full dimensionality. Expanding on previous results, we consider here the double photoionization of two 2p valence electrons of atomic carbon and neon and explore the possible continuum states that are connected by dipole selection rules to the coupling of the outgoing electrons in 3P, 1D, and 1S initial states of the target atoms. Carbon and neon share these possible symmetries for the coupling of their valence electrons. Results are presented for the energy-sharing single differential cross section (SDCS) and triple differential cross section (TDCS), further elucidating the impact of the initial state symmetry in determining the angular distributions that are impacted by the correlation that drives the DPI process.

Yip, Frank L. (ORCID:000000025409495X)↗
DOE OSTI2022

Hydrogen Localization and Cluster Formation in α-Zr from First-Principles Investigations

We report alpha-zirconium (α-Zr) is a hydrogen atom host material used in nuclear energy and semiconducting applications due to Zr's excellent properties such as corrosion resistance, low thermal neutrons cross-section, and thermodynamically favorable interstitial sequestering of H atoms. Herein we use density functional theory simulations to systematically analyze the initial stages of H insertion in the Zr matrix, and determine optimal hydrogen localization, distribution, and clustering tendencies from a thermodynamics and kinetics perspective. Our results suggest that H occupation of tetrahedral sites is strongly favored, consistent with previous experimental and theoretical studies. Further, a cooperative effect in H localization is shown where H atoms favor clustering. The H pair is found to be the most stable by occupying tetrahedral sites with pairs at second nearest-neighbor positions (TTn2). Among the four H atom clusters, the most favorable configuration has two TTn2 pairs forming "box " or "zig-zag" shaped-cluster with the pairs separated by 3.03 or 3.25 Å, respectively. Nudged elastic band simulations suggest that the formation of TTn2 is facile and is limited by the small diffusion barrier of the monomer of less than 0.1 eV. Further, the formation routes for the 4H atom clusters are also presented. The current study can serve as a foundation to systematically model H atom clustering in metals and alloys.

36 MATERIALS SCIENCE↗
DOE OSTI2022

A metal-supported single-atom catalytic site enables carbon dioxide hydrogenation

Nitrogen-doped graphene-supported single atoms convert CO 2 to CO, but fail to provide further hydrogenation to methane – a finding attributable to the weak adsorption of CO intermediates. To regulate the adsorption energy, here we investigate the metal-supported single atoms to enable CO 2 hydrogenation. We find a copper-supported iron-single-atom catalyst producing a high-rate methane. Density functional theory calculations and in-situ Raman spectroscopy show that the iron atoms attract surrounding intermediates and carry out hydrogenation to generate methane. The catalyst is realized by assembling iron phthalocyanine on the copper surface, followed by in-situ formation of single iron atoms during electrocatalysis, identified using operando X-ray absorption spectroscopy. The copper-supported iron-single-atom catalyst exhibits a CO 2 -to-methane Faradaic efficiency of 64% and a partial current density of 128 mA cm –2 , while the nitrogen-doped graphene-supported one produces only CO. The activity is 32 times higher than a pristine copper under the same conditions of electrolyte and bias.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1985

Mechanism for chelated sulfate formation from SO2 and bis (triphenylphosphine) platinum

Structure and energy surface calculations using the atom superposition and electron delocalization molecular orbital theory show that the first step in the reaction between SO2 and the dioxygen complex (PPh3)2PtO2 is the coordination of SO2 with one oxygen atom of the complex, followed by metal-oxygen bond breaking and reorientation, leading to a five-membered cyclic structure. This then rearranges to form the bidentate coordinated sulfate. Alternative pathways are considered and are found to be less favorable.

Mehandru, S. P.↗
DOE OSTI2023

Discovery and construction of surface kagome electronic states induced by p-d electronic hybridization in Co3Sn2S2

Abstract Kagome-lattice materials possess attractive properties for quantum computing applications, but their synthesis remains challenging. Herein, based on the compelling identification of the two cleavable surfaces of Co 3 Sn 2 S 2 , we show surface kagome electronic states (SKESs) on a Sn-terminated triangular Co 3 Sn 2 S 2 surface. Such SKESs are imprinted by vertical p-d electronic hybridization between the surface Sn (subsurface S) atoms and the buried Co kagome-lattice network in the Co 3 Sn layer under the surface. Owing to the subsequent lateral hybridization of the Sn and S atoms in a corner-sharing manner, the kagome symmetry and topological electronic properties of the Co 3 Sn layer is proximate to the Sn surface. The SKESs and both hybridizations were verified via qPlus non-contact atomic force microscopy (nc-AFM) and density functional theory calculations. The construction of SKESs with tunable properties can be achieved by the atomic substitution of surface Sn (subsurface S) with other group III-V elements (Se or Te), which was demonstrated theoretically. This work exhibits the powerful capacity of nc-AFM in characterizing localized topological states and reveals the strategy for synthesis of large-area transition-metal-based kagome-lattice materials using conventional surface deposition techniques.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2022

Machine learning for design principles for single atom catalysts towards electrochemical reactions

Machine learning (ML) integrated density functional theory (DFT) calculations have recently been used to accelerate the design and discovery of heterogeneous catalysts such as single atom catalysts (SACs) through the establishment of deep structure–activity relationships. Here, this review provides recent progress in the ML-aided rational design of heterogeneous catalysts with the focus on SACs in terms of structure–activity relationships, feature importance analysis, high-throughput screening, stability, and metal–support interactions for electrochemistry. Support vector machine (SVM), random forest regression (RFR), and deep neural networks (DNN) along with atomic properties are mainly used for the design of SACs. The ML results have shown that the number of electrons in the d orbital, oxide formation enthalpy, ionization energy, Bader charge, d-band center, and enthalpy of vaporization are mainly the most important parameters for the defining of the structure–activity relationships for electrochemistry. However, the black-box nature of ML techniques occasionally makes a physical interpretation of descriptors, such as the Bader charge, d-band center, and enthalpy of vaporization, non-trivial. At the current stage, ML application is limited by the lack of a large and high-quality database. Future prospects for the development of a large database and a generalized ML algorithm for SAC design are discussed to give insights for further studies in this field.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗