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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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All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Correlated Dirac–Coulomb–Breit multiconfigurational self-consistent-field methods

The fully correlated frequency-independent Dirac–Coulomb–Breit Hamiltonian provides the most accurate description of electron–electron interaction before going to a genuine relativistic quantum electrodynamics theory of many-electron systems. In this work, we introduce a correlated Dirac–Coulomb–Breit multiconfigurational self-consistent-field method within the frameworks of complete active space and density matrix renormalization group. In this approach, the Dirac–Coulomb–Breit Hamiltonian is included variationally in both the mean-field and correlated electron treatment. Here, we also analyze the importance of the Breit operator in electron correlation and the rotation between the positive- and negative-orbital space in the no-virtual-pair approximation. Atomic fine-structure splittings and lanthanide contraction in diatomic fluorides are used as benchmark studies to understand the contribution from the Breit correlation.

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

Investigation of the fine structure of antihydrogen

At the historic Shelter Island Conference on the Foundations of Quantum Mechanics in 1947, Willis Lamb reported an unexpected feature in the fine structure of atomic hydrogen: a separation of the 2S 1/2 and 2P 1/2 states. The observation of this separation, now known as the Lamb shift, marked an important event in the evolution of modern physics, inspiring others to develop the theory of quantum electrodynamics. Quantum electrodynamics also describes antimatter, but it has only recently become possible to synthesize and trap atomic antimatter to probe its structure. Mirroring the historical development of quantum atomic physics in the twentieth century, modern measurements on anti-atoms represent a unique approach for testing quantum electrodynamics and the foundational symmetries of the standard model. Here we report measurements of the fine structure in the n = 2 states of antihydrogen, the antimatter counterpart of the hydrogen atom. Using optical excitation of the 1S–2P Lyman-α transitions in antihydrogen, we determine their frequencies in a magnetic field of 1 tesla to a precision of 16 parts per billion. Assuming the standard Zeeman and hyperfine interactions, we infer the zero-field fine-structure splitting (2P 1/2 –2P 3/2 ) in antihydrogen. The resulting value is consistent with the predictions of quantum electrodynamics to a precision of 2 per cent. Using our previously measured value of the 1S–2S transition frequency, we find that the classic Lamb shift in antihydrogen (2S 1/2 –2P 1/2 splitting at zero field) is consistent with theory at a level of 11 per cent. Our observations represent an important step towards precision measurements of the fine structure and the Lamb shift in the antihydrogen spectrum as tests of the charge–parity–time symmetry8 and towards the determination of other fundamental quantities, such as the antiproton charge radius, in this antimatter system.

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

Resolving the Atomic Structure of Sequential Infiltration Synthesis Derived Inorganic Clusters

Sequential infiltration synthesis (SIS) is a route to the precision deposition of inorganic solids in analogy to atomic layer deposition but occurs within (vs upon) a soft material template. SIS has enabled exquisite nanoscale morphological complexity in various oxides through selective nucleation in block copolymers templates. However, the earliest stages of SIS growth remain unresolved, including the atomic structure of nuclei and the evolution of local coordination environments, before and after polymer template removal. We employed In K-edge extended X-ray absorption fine structure and atomic pair distribution function analysis of high-energy X-ray scattering to unravel (1) the structural evolution of InO x H y clusters inside a poly(methyl methacrylate) (PMMA) host matrix and (2) the formation of porous In 2 O 3 solids (obtained after annealing) as a function of SIS cycle number. Early SIS cycles result in InO x H y cluster growth with high aspect ratio, followed by the formation of a three-dimensional network with additional SIS cycles. That the atomic structures of the InO x H y clusters can be modeled as multinuclear clusters with bonding patterns related to those in In 2 O 3 and In(OH) 3 crystal structures suggests that SIS may be an efficient route to 3D arrays of discrete-atom-number clusters. As a result, annealing the mixed inorganic/polymer films in air removes the PMMA template and consolidates the as-grown clusters into cubic In 2 O 3 nanocrystals with structural details that also depend on SIS cycle number.

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

Local ordering in Ge/Ge–Sn semiconductor alloy core/shell nanowires revealed by extended x-ray absorption fine structure (EXAFS)

Short-range atomic order in semiconductor alloys is a relatively unexplored topic that may promote design of new materials with unexpected properties. Here, local atomic ordering is investigated in Ge–Sn alloys, a group-IV system that is attractive for its enhanced optoelectronic properties achievable via a direct gap for Sn concentrations exceeding ≈10 at. %. The substantial misfit strain imposed on Ge–Sn thin films during growth on bulk Si or Ge substrates can induce defect formation; however, misfit strain can be accommodated by growing Ge–Sn alloy films on Ge nanowires, which effectively act as elastically compliant substrates. In this work, Ge core/Ge 1–x Sn x (x ≈ 0.1) shell nanowires were characterized with extended x-ray absorption fine structure (EXAFS) to elucidate their local atomic environment. Simultaneous fitting of high-quality EXAFS data collected at both the Ge K-edge and the Sn K-edge reveals a large (≈ 40%) deficiency of Sn in the first coordination shell around a Sn atom relative to a random alloy, thereby providing the first direct experimental evidence of significant short-range order in this semiconductor alloy system. Furthermore, comparison of path length data from the EXAFS measurements with density functional theory simulations provides alloy atomic structures consistent with this conclusion.

36 MATERIALS SCIENCE↗
DOE OSTI2023

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

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

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2021

Origin of the enhanced Nb3Sn performance by combined Hf and Ta doping

Abstract In recent years there has been an increasing effort in improving the performance of Nb 3 Sn for high-field applications, in particular for the fabrication of conductors suitable for the realization of the Future Circular Collider (FCC) at CERN. This challenging task has led to the investigation of new routes to advance the high-field pinning properties, the irreversibility and the upper critical fields ( H Irr and H c2 , respectively). The effect of hafnium addition to the standard Nb-4Ta alloy has been recently demonstrated to be particularly promising and, in this paper, we investigate the origins of the observed improvements of the superconducting properties. Electron microscopy, Extended X-ray Absorption Fine Structure Spectroscopy (EXAFS) and Atom Probe Tomography (APT) characterization clearly show that, in presence of oxygen, both fine Nb 3 Sn grains and HfO 2 nanoparticles form. Although EXAFS is unable to detect significant amounts of Hf in the A15 structure, APT does indeed reveal some residual intragrain metallic Hf. To investigate the layer properties in more detail, we created a microbridge from a thin lamella extracted by Focused Ion Beam (FIB) and measured the transport properties of Ta-Hf-doped Nb 3 Sn. H c2 (0) is enhanced to 30.8 T by the introduction of Hf, ~ 1 T higher than those of only Ta-doped Nb 3 Sn, and, even more importantly the position of the pinning force maximum exceeds 6 T, against the typical ~ 4.5–4.7 T of the only Ta-doped material. These results show that the improvements generated by Hf addition can significantly enhance the high-field performance, bringing Nb 3 Sn closer to the requirements necessary for FCC realization.

36 MATERIALS SCIENCE↗
DOE OSTI2024

R-matrix calculations for opacities: I. Methodology and computations

Abstract An extended version of the R -matrix methodology is presented for calculation of radiative parameters for improved plasma opacities. Contrast and comparisons with existing methods primarily relying on the distorted wave approximation are discussed to verify accuracy and resolve outstanding issues, particularly with reference to the opacity project (OP). Among the improvements incorporated are: (i) large-scale Breit–Pauli R -matrix calculations for complex atomic systems including fine structure, (ii) convergent close coupling wave function expansions for the ( e + ion) system to compute oscillator strengths and photoionization cross sections, (iii) open and closed shell iron ions of interest in astrophysics and experiments, (iv) a treatment for plasma broadening of autoionizing resonances as function of energy-temperature-density dependent cross sections, (v) a ‘top-up’ procedure to compare convergence with R -matrix calculations for highly excited levels, and (vi) spectroscopic identification of resonances and bound ( e + ion) levels. The present R -matrix monochromatic opacity spectra are fundamentally different from OP and lead to enhanced Rosseland and Planck mean opacities. An outline of the work reported in other papers in this series and those in progress is presented. Based on the present re-examination of the OP work, opacities of heavy elements might require revisions in high temperature-density plasma sources.

Pradhan, A. K. (ORCID:0000000187753643)↗
DOE OSTI2021

Electric-field-dependent g factor for the ground state of lead monofluoride, PbF

The electric field dependent g–factor and the electron electric dipole moment (eEDM)-induced Stark splittings for the lowest rotational levels of 207,208 PbF are calculated. Observed and calculated Zeeman shifts for 207 PbF are found to be in very good agreement. Furthermore, it is shown that the 207 PbF hyperfine sublevels provide a promising system for the eEDM search and related experiments.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2026

Gaunt and Breit two-electron contributions to mean-field transformations and fine structure splitting

Materials utilized by novel energy systems are often studied using weakly correlated mean-field theories. However, if these systems incorporate heavy elements, relativistic effects must be included. Therefore, a Kramers unrestricted coupled cluster with singles and doubles excitation formalism within a molecular mean-field exact two-component framework (X2C mmf ) using a four-component Dirac–Hartree–Fock (DHF) reference state is presented. The exact X2C mmf transformed normal-order Hamiltonian incorporates all one-electron and two-electron (2e) contributions from the Coulomb, Gaunt, and Breit operators and is used with the equation of motion method to calculate the excitation energies of the alkali group of elements. Using this framework, the effects of 2e Gaunt and Breit integrals are studied. Results demonstrate growing contributions from these integrals to the generated X2C mmf mean-fields and electronic fine structure calculations with increasing atomic number. Overall, this paper outlines the method, its effect within the X2C mmf approach, and lays the foundation for future theoretical development of relativistic calculations within this framework.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2020

Adsorption of Rare Earth Elements onto DNA-Functionalized Mesoporous Carbon

The recovery and separation of rare earth elements (REEs) are of national importance owing to the specific usages, high demand, and low supply of these elements. In this research, we have investigated the adsorption of rare earth elements onto DNA-functionalized mesoporous carbons with a BET surface area of 605 m2/g and a median mesopore width of 48 Å. Additionally, three types of single-stranded DNA, one with 100 base units of thymine, another with 20 units of thymine, and the third, a 2000 unit long DNA from salmon milt were grafted on the carboxylated mesoporous carbon surface. All of the DNA-functionalized mesoporous carbons demonstrated higher adsorption of REEs compared to pristine mesoporous carbon and DNA grafted with 100 units of thymine demonstrated slightly higher adsorbed amounts compared to others. Pure neodymium (Nd(III)) adsorption in the aqueous phase demonstrated an adsorbed amount of 110.4 mg/g with respect to the initial concentration of 500 mg/g. A pH variation study with pure Nd(III) demonstrated that the adsorbed amount is higher at elevated pH compared to that at lower pH, thereby suggesting possible recovery at lower pH. Adsorption of a mixture of 16 REEs, including Sc, Lu, Tm, Yb, Er, Ho, Tb, Dy, Y, Eu, Gd, Sm, Ce, Nd, Pr, and La revealed that the adsorbed amount increased with an increase in the atomic weight and metallic radii of elements within the lanthanides. The calculation of the distribution coefficients for all of the equilibrium adsorption amounts suggested that adsorption is more effective in the lower concentration region. The Nd L3-edge X-ray absorption near edge structure (XANES) confirmed a 3+ oxidation state of Nd in the adsorbed phase. The extended X-ray absorption fine structure (EXAFS) confirmed the local atomic structure relaxation of Nd complexes in the adsorbed phase and shortening of the Nd–O bond distance by about 0.03–0.04 Å, which may be associated with their local complexation at the carbon surface.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Complex concentrated alloys and chemical short-range ordering

Abstract Complex concentrated alloys (CCAs) are materials comprising three or more elements in similar proportions and possessing structural but no chemical long-range order. Fascination with CCAs has grown over the last 20 years and to date, CCAs have opened a new materials design paradigm and horizon for discovery of materials to meet the demands of applications in aggressive environments. Understanding the fundamental mechanisms controlling their response, however, is challenging due to the chemical and structural variations that wildly fluctuate over fine atomic and nanoscales. This issue focuses on the experimental, computational, and theoretical investigations that aim to uncover phenomena and processes determining the structure, kinetics, mechanics, or deformation mechanisms in CCAs at the atomic scale. At the atomic scale at which they operate, chemical short-range ordering can be influential. This issue further addresses the capabilities, as well as the debatable need, to characterize, predict, and relate short-range ordering to material performance. Collectively, the articles in this issue highlight the insights, understanding, and experimental and computational tools that attempt to create property-tunable CCAs “from the atom up” by treating short-range ordering and engineering atomic-scale mechanisms. Graphical abstract

36 MATERIALS SCIENCE↗
DOE OSTI2020

Using Complementary Methods of Synchrotron Radiation Powder Diffraction and Pair Distribution Function to Refine Crystal Structures with High Quality Parameters—A Review

Determination of the atomic-scale structures of certain fine-grained minerals using single-crystal X-ray diffraction (XRD) has been challenging because they commonly occur as submicron and nanocrystals in the geological environment. Synchrotron powder diffraction and scattering techniques are useful complementary methods for studying this type of minerals. In this review, we discussed three example studies investigated by combined methods of synchrotron radiation XRD and pair distribution function (PDF) techniques: (1) low-temperature cristobalite; (2) kaolinite; and (3) vernadite. Powder XRD is useful to determine the average structure including unit-cell parameters, fractional atomic coordinates, occupancies and isotropic atomic displacement parameters. X-ray/Neutron PDF methods are sensitive to study the local structure with anisotropic atomic displacement parameters (ADP). The results and case studies suggest that the crystal structure and high-quality ADP values can be obtained using the combined methods. The method can be useful to characterize crystals and minerals that are not suitable for single-crystal XRD.

58 GEOSCIENCES↗
DOE OSTI2021

Recent progress and future prospects of atomic layer deposition to prepare/modify solid-state electrolytes and interfaces between electrodes for next-generation lithium batteries

Lithium ion batteries (LIBs) are encouraging electrochemical devices with remarkable properties including a high energy/power density, fast charging capability, and low self-discharge rate. Further increase in energy density as well as safe usage is needed for next-generation LIBs in electric transportation vehicles. Solid-state electrolytes (SSEs) are very promising for high-performance LIBs since they enable improved safety along with increased energy density compared to flammable liquid organic electrolytes. However, utilizing SSEs with a Li metal anode is very challenging due to the possibility of undesired side reactions and the formation of an unstable solid-electrolyte interphase. Therefore, it is critical to enhance the stability of SSEs against the Li anode. One feasible approach is to form a thin and conductive interlayer between the Li anode and solid-state electrolyte. Atomic layer deposition (ALD) is a unique technique for conformal coating of complex 3D structures with finely controlled film thickness (at the atomic scale). ALD coating on the surface of SSEs can be adopted for engineering solid-electrolyte interfaces with desired attributes and improved stability. In this review paper, we have discussed recent progress in implementing the ALD technique for depositing thin layers on various SSE configurations including lithium phosphorus oxynitride (LiPON), garnets, oxides, perovskites, sulphides, Li 3 BO 3 –Li 2 CO 3 (LBCO), and sodium super ionic conductors (NASICON). We have also highlighted the major areas for future research and development in the field. We believe that this review will be very helpful for directing future research on implementing ALD for synthesizing stable and high-performance SSEs with an engineered solid-electrolyte interface for next-generation electrochemical devices (e.g., Li-ion batteries, supercapacitors, and flow batteries).

36 MATERIALS SCIENCE↗
DOE OSTI2021

Full spectrum optical constant interface to the Materials Project

Optical constants characterize the interaction of materials with light and are important properties in material design. Here we present a Python-based Corvus workflow for simulations of full spectrum optical constants from the visible and ultraviolet to hard x-ray wavelengths based on the real-space Green’s function code FEFF10 and structural data from the Materials Project (MP). The Corvus workflow manager and its associated tools provide an interface to FEFF10 and the MP database. The workflow parallelizes the FEFF computations of optical constants over all absorption edges for each material in the MP database specified by a unique MP-ID. The workflow tools determine the distribution of computational resources needed for that case. Similarly, the optical constants for selected sets of materials can be computed in a single-shot. Additionally, to illustrate the approach, we present results for several elemental solids in the periodic table, as well as a sample compound, and compare our predictions with experimental results. In addition, we provide a database of calculated results for all elements for which there is a stable elemental solid at standard conditions available in the Materials Project database. As in x-ray absorption spectra, these results are interpreted in terms of an atomic-like background and fine-structure contributions.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Limits of Detection for EXAFS Characterization of Heterogeneous Single-Atom Catalysts

Single-atom catalysts (SACs), consisting of individual metal atoms dispersed on a support, attract attention due to their unique reactivity, efficient use of precious metals, and precise chemical tunability. Characterization of the metal species is crucial to substantiate structure–function relationships. Authors often use—and referees often require—X-ray absorption spectroscopy (XAS) data to prove the absence of clustered metal (or metal oxide) structures after pre-treatment and under in situ or operando conditions. However, there has been no critical assessment of the limitations of XAS in substantiating such conclusive statements, which is particularly important given the potential outsized influence of minority catalyst structures in dictating catalytic activity. Here, in this article, we quantitatively assess the detection limits of XAS to identify metal (or metal oxide) clusters in samples containing predominantly single atoms by modeling the extended X-ray absorption fine structure (EXAFS) of mixtures of structures. We identified that a significant fraction of clusters can coexist with SAC active sites (e.g., ~10% metallic Pt or ~40% oxidized Pt clusters in Pt/CeO 2 SACs), while eluding detection via EXAFS with any statistical significance. To generalize these conclusions, a descriptor-based screening of bulk metal oxides using a continuous Cauchy wavelet transform was proposed that suggests certain materials for which differentiating atomically dispersed metal species and metal oxide clusters would be infeasible by EXAFS (e.g., ReO x ). Based on this analysis, we suggest best practices for the study of SACs using EXAFS and provide recommendations to ensure that conclusions do not outpace the evidence used to support them. In this rapidly expanding research area, rigorous characterization will lead to greater understanding of the behavior of SACs and ultimately improved catalytic materials.

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

Cobalt ferrite nanoparticle intercalated carbon nanotubes for a nanomagnetic ultrasensitive sensor of Cr-VI in water

Nanocomposites of cobalt ferrite (CFO) magnetic nanoparticles intercalated on carbon nanotubes (CNTs) are evaluated as a nanomagnetic ultrasensitive sensor for the environmental toxin, hexavalent chromium (Cr-VI). Specifically, the structural and magnetic changes that accompany the infiltration of the CFO/CNTs by Cr-VI are presented. Extended x-ray absorption fine structure (EXAFS) shows that the atomic spacing within the CFO structure changes in the presence of Cr, suggesting that the Cr is incorporated into the nanoparticles. Vibrating sample magnetometry (VSM) reveals that CFO/CNTs composite infiltrated with Cr-VI have a 71% enhancement in saturation magnetization compared with the uninfiltrated CFO/CNTs, while small-angle neutron scattering (SANS) suggests that this magnetic enhancement is not associated with the nanoparticle lengthscales, but may arise from longer-ranged clusters. Both VSM and SANS clearly demonstrate that the Cr-doped CFO/CNTs are hysteretic with a net magnetization at remanence that is about 1/3 that of saturation, while this hysteresis is absent in the undoped CFO/CNTs. These magnetic differences at either remanence or saturation are promising for the magnetic detection of Cr-VI using CFO/CNTs sensors.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Sluggish atomic dynamics in a Y-Sc-Co-Al high entropy bulk metallic glass

We present how 20 at% Sc addition affects the atomic packing and dynamics in a Y-Co-Al metallic glass (MG) and find that it greatly suppresses the dynamics of Co atoms by reducing the atomic packing difference in their surroundings. The Co atoms tending to be mobile or static depend on their nearest neighbors, i.e., possessing more Y/Y+Sc atoms but fewer Co atoms or vice versa. The X-ray absorption fine structure results confirm that Sc addition mainly changes the local environment around Co atoms, forming more Co-Co and Co-Sc pairs but significantly fewer Co-Y pairs than in the ternary counterpart, which can seriously slow the atomic dynamics and stabilize the competing phases. Our findings shed new light on the understanding of strong glass forming ability of the Sc-added Y-based high entropy MG from its local structure and dynamics and will be helpful in developing new bulk MGs.

36 MATERIALS SCIENCE↗