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At least 1,279 records · Page 71
All sourcesNASA NTRSDOE OSTI
DOE OSTI2017

Rapidly convergent cluster expansion and application to lithium ion battery materials

The convergence of a cluster expansion for lithium transition-metal (TM) oxides is improved by explicit treatment of TM magnetic moments. The approach is applied to layered LiC o y N i 1 - y O 2 (NC). The ground state and low-lying excited state structures are identified, and the distribution of TM ions and magnetic moment in those structures is investigated to explain the origin of Ni-antisite ions and Jahn-Teller distortion. In this work, the developed model also reveals the mechanisms governing the atomic arrangement of NC, including in-plane Co-Co vs Co-Ni competition, magnetic frustration vs disproportionation competition, and cationic interactions spanning adjacent layers.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2024

Time-resolved X-ray Spectroscopy from the Atomic Orbital Ground State Up

X-ray spectroscopy has been a key method to determine ground and excited state properties of quantum materials with atomic specificity. Now, new x-ray facilities are opening the door to the study of pump-probe x-ray spectroscopy - specifically time-resolved x-ray absorption (trXAS) and time-resolved resonant inelastic x-ray scattering (trRIXS). In this paper we will present simulations of each of these spectroscopies using a time-domain full atomic multiplet, charge transfer Hamiltonian, adapted to study the properties of a generalized cluster model including a central transition metal ion caged by ligand atoms in a planar geometry. The numerically evaluated trXAS and trRIXS cross-sections for representative electron configurations 3d9 and 3d8 demonstrate the insights that can be obtained from charge transfer pumping, and how this nonequilibrium process affects ground and excited state properties. The straightforward characterization of the excitations in these systems, based on our analysis of the simulations, can serve as a benchmark for future experiments, as access to these time-resolved spectroscopic techniques becomes more widely available.

Jost, Daniel↗
DOE OSTI2026

Distinguishing Leptothrix and Sphaerotilus genera by an integrated genomic-phenotypic analysis supported by new Leptothrix genomes

The Sphaerotilus-Leptothrix group of bacteria includes one of the first described microorganisms, Leptothrix ochracea, an uncultured type strain, plus isolates of Leptothrix and Sphaerotilus. This group is unified by the ability to form sheaths and oxidize metals, although L. ochracea exhibits obvious ecological, morphological, and functional differences from the rest of Sphaerotilus-Leptothrix. Recently, there have been calls to combine the group into one genus, Sphaerotilus; however, these studies lacked adequate genomic representation of L. ochracea. Here, we present a comprehensive comparative genomic analysis of the Sphaerotilus-Leptothrix group, including expanded representation of L. ochracea, a closely related novel species, Leptothrix toolikensis, and two new isolates (Leptothrix mechoopdaensis). Analysis of 38 genomes resolves three phylogenetic and functional groups: the ochracea-type Leptothrix (Group 1), the mobilis-type Leptothrix (Group 2), and Sphaerotilus (Group 3). Group 1 genomes form a separate genus based on average nucleotide identity and alignment fraction. The genomes clearly diverge from the rest of Sphaerotilus-Leptothrix in phylogeny, size, and metabolic potential. Group 1 genomes are much smaller (2.59–3.04 Mb) than those of Groups 2 (4.55–6.06 Mb) and 3 (3.94–5.07 Mb), while encoding more metal oxidases and fewer carbohydrate-active enzymes. Group 2 clusters with Group 3 phylogenetically and is similar in organic carbon metabolisms but maintains more metal oxidation genes. Group 2 members lack homogeneity in phenotype and genotype, suggesting that additional isolates and genomes are needed for confident classification. However, Group 1 genomes (L. ochracea and L. toolikensis) show clear divergence, precluding their inclusion in Sphaerotilus and supporting the retention of the genus Leptothrix.

Leptothrix↗
DOE OSTI2018

Calculation of Chemical Shifts of X-Ray-Emission Spectra of Niobium in Niobium(V) Oxides Relative to Metal

Chemical shifts of the K{sub α1} and K{sub β1} lines of X-ray-emission spectra of niobium in oxides (Nb{sub 2}O{sub 5}){sub n}, n = 1–4, relative to metal Nb have been calculated. Stoichiometric clusters (Nb2O5)n the electronic structure of which was calculated using accurate relativistic pseudopotentials and two-component version of the density functional theory are considered as prototypes for modeling different crystal forms of niobium(V) oxide. The chemical shifts were calculated using the method based on using the property of approximate proportionality of valence spinors in the core region of the heavy atom [11]. Corrections to values of chemical shifts have been determined with allowance for deviations from the abovementioned proportionality. Rapid convergence of results with respect to the size of the niobium oxide cluster has been demonstrated.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2013

The Populus Superoxide Dismutase Gene Family and Its Responses to Drought Stress in Transgenic Poplar Overexpressing a Pine Cytosolic Glutamine Synthetase (GS1a)

Glutamine synthetase (GS) plays a central role in plant nitrogen assimilation, a process intimately linked to soil water availability. We previously showed that hybrid poplar (Populus tremula X alba, INRA 717-1B4) expressing ectopically a pine cytosolic glutamine synthetase gene (GS1a) display enhanced tolerance to drought. Preliminary transcriptome profiling revealed that during drought, members of the superoxide dismutase (SOD) family were reciprocally regulated in GS poplar when compared with the wild-type control, in all tissues examined. SOD was the only gene family found to exhibit such patterns. In silico analysis of the Populus genome identified 12 SOD genes and two genes encoding copper chaperones for SOD (CCSs). The poplar SODs form three phylogenetic clusters in accordance with their distinct metal co-factor requirements and gene structure. Nearly all poplar SODs and CCSs are present in duplicate derived from whole genome duplication, in sharp contrast to their predominantly single-copy Arabidopsis orthologs. Drought stress triggered plant-wide down-regulation of the plastidic copper SODs (CSDs), with concomitant up-regulation of plastidic iron SODs (FSDs) in GS poplar relative to the wild type; this was confirmed at the activity level. We also found evidence for coordinated downregulation of other copper proteins, including plastidic CCSs and polyphenol oxidases, in GS poplar under drought conditions. Both gene duplication and expression divergence have contributed to the expansion and transcriptional diversity of the Populus SOD/CCS families. Coordinated down-regulation of major copper proteins in drought-tolerant GS poplars supports the copper cofactor economy model where copper supply is preferentially allocated for plastocyanins to sustain photosynthesis during drought. Our results also extend previous findings on the compensatory regulation between chloroplastic CSDs and FSDs, and suggest that this copper-mediated mechanism represents a common response to oxidative stress and other genetic manipulations, as in GS poplars, that affect photosynthesis.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2016

METALLICITY AND AGE OF THE STELLAR STREAM AROUND THE DISK GALAXY NGC 5907

Stellar streams have become central to studies of the interaction histories of nearby galaxies. To characterize the most prominent parts of the stellar stream around the well-known nearby ( d = 17 Mpc) edge-on disk galaxy NGC 5907, we have obtained and analyzed new, deep gri Subaru/Suprime-Cam and 3.6 μ m Spitzer /Infrared Array Camera observations. Combining the near-infrared 3.6 μ m data with visible-light images allows us to use a long wavelength baseline to estimate the metallicity and age of the stellar population along an ∼60 kpc long segment of the stream. We have fitted the stellar spectral energy distribution with a single-burst stellar population synthesis model and we use it to distinguish between the proposed satellite accretion and minor/major merger formation models of the stellar stream around this galaxy. We conclude that a massive minor merger (stellar mass ratio of at least 1:8) can best account for the metallicity of −0.3 inferred along the brightest parts of the stream.

79 ASTRONOMY AND ASTROPHYSICS↗
NASA NTRS2003

Intermediate Element Abundances In Galaxy Clusters

We present the average abundances of the intermediate elements obtained by performing a stacked analysis of all the galaxy clusters in the archive of the X-ray telescope AKA. We determine the abundances of Fe, Si, S, and Ni as a function of cluster temperature (mass) from 1 - 10 keV, and place strong upper limits on the abundances of Ca and Ar. In general, Si and Ni are overabundant with respect to Fe, while Ar and Ca are very underabundant. The discrepancy between the abundances of Si, S , Ar, and Ca indicate that the alpha-elements do not behave homogeneously as a single group. We show that the abundances of the most well-determined elements Fe, Si, and S in conjunction with recent theoretical supernovae yields do not give a consistent solution for the fraction of material produced by Type Ia and Type II supernovae at any temperature or mass. The general trend is for higher temperature clusters to have more of their metals produced in Type II supernovae than in Type Ias. The inconsistency of our results with abundances in the Milky Way indicate that spiral galaxies are not the dominant metal contributors to the intracluster medium (ICM). The pattern of elemental abundances requires an additional source of metals beyond standard SNIa and SNII enrichment. The properties of this new source are well matched to those of Type II supernovae with very massive, metal-poor progenitor stars. These results are consistent with a significant fraction of the ICM metals produced by an early generation of population III stars.

White, Nicholas E.↗
DOE OSTI2015

X-ray tomography investigation of intensive sheared Al–SiC metal matrix composites

X-ray computed tomography (XCT) was used to characterise three dimensional internal structure of Al–SiC metal matrix composites. The alloy composite was prepared by casting method with the application of intensive shearing to uniformly disperse SiC particles in the matrix. Visualisation of SiC clusters as well as porosity distribution were evaluated and compared with non-shearing samples. Results showed that the average particle size as well as agglomerate size is smaller in sheared sample compared to conventional cast samples. Further, it was observed that the volume fraction of porosity was reduced by 50% compared to conventional casting, confirming that the intensive shearing helps in deagglomeration of particle clusters and decrease in porosity of Al–SiC metal matrix composites. - Highlights: • XCT was used to visualise 3D internal structure of Al-SiC MMC. • Al-SiC MMC was prepared by casting with the application of intensive shearing. • SiC particles and porosity distribution were evaluated. • Results show shearing deagglomerates particle clusters and reduces porosity in MMC.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Structure Sensitivity of Acetylene Semi-Hydrogenation on Pt Single Atoms and Subnanometer Clusters

Oxide-supported Pt-group single atoms and clusters in the subnanometer size regime maximize the metal utilization and have shown extraordinary catalytic properties for many reactions including selective hydrogenation. Establishing relations between the metal nuclearity and electronic and catalytic properties is crucial for catalyst design. Here, we varied the nuclearity of Pt supported on TiO 2 from single atoms to subnanometer clusters to larger nanoparticles to develop such relations for acetylene hydrogenation. We show that, in contrast to the low selectivity on large Pt nanoparticles, in the subnanometer size regime, Pt exhibits remarkably high selectivity to ethylene. Through a combination of X-ray photoelectron spectroscopy and calorimetry, we demonstrate that the origin of high selectivity is the decreased electron density on Pt and destabilization of C 2 H 4 as the Pt nuclearity decreases. However, as the Pt nuclearity decreased, the activity for H 2 activation and acetylene hydrogenation decreased, indicating a trade-off between activity and selectivity. Lastly, the results show that, while different properties emerge in the subnanometer regime, Pt supported on TiO 2 appears to be bound by similar scaling and Brønsted–Evans–Polanyi relationships as on metal surfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Detailed abundances for a large sample of giant stars in the globular cluster 47 Tucanae (NGC 104)

47 Tuc is an ideal target to study chemical evolution and globular cluster (GC) formation in massive more metal-rich GCs, as it is the closest massive GC. We present chemical abundances for O, Na, Al, Si, Ca, Ti, Fe, Ni, La, and Eu in 164 red giant branch stars in the massive GC 47 Tuc using spectra obtained with both the Hydra multifiber spectrograph at the Blanco 4 m telescope and the FLAMES multiobject spectrograph at the Very Large Telescope. We find an average [Fe/H] = –0.79 ± 0.09 dex, consistent with literature values, as well as overabundances of alpha-elements ([α/Fe] ∼ 0.3 dex). The n-capture process elements indicate that 47 Tuc is r process-dominated ([Eu/La] = +0.24), and the light elements O, Na, and Al exhibit star-to-star variations. The Na-O anticorrelation, a signature typically seen in Galactic GCs, is present in 47 Tuc, and extends to include a small number of stars with [O/Fe] ∼ –0.5. Additionally, the [O/Na] ratios of our sample reveal that the cluster stars can be separated into three distinct populations. A Kolmogorov-Smirnov test demonstrates that the O-poor/Na-rich stars are more centrally concentrated than the O-rich/Na-poor stars. The observed number and radial distribution of 47 Tuc's stellar populations, as distinguished by their light element composition, agrees closely with the results obtained from photometric data. We do not find evidence supporting a strong Na-Al correlation in 47 Tuc, which is consistent with current models of asymptotic giant branch nucleosynthesis yields.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2021

Transformation of Highly Stable Pt Single Sites on Defect Engineered Ceria into Robust Pt Clusters for Vehicle Emission Control

Engineering surface defects on metal oxide supports could help promote the dispersion of active sites and catalytic performance of supported catalysts. Herein, a strategy of ZrO 2 doping was proposed to create rich surface defects on CeO 2 (CZO) and, with these defects, to improve Pt dispersion and enhance its affinity as single sites to the CZO support (Pt/CZO). The strongly anchored Pt single sites on CZO support were initially not efficient for catalytic oxidation of CO/C 3 H 6 . However, after a simple activation by H 2 reduction, the catalytic oxidation performance over Pt/CZO catalyst was significantly boosted and better than Pt/CeO 2 . Pt/CZO catalyst also exhibited much higher thermal stability. The structural evolution of Pt active sites by H 2 treatment was systematically investigated on aged Pt/CZO and Pt/CeO 2 catalysts. With H 2 reduction, ionic Pt single sites were transformed into active Pt clusters. Much smaller Pt clusters were created on CZO (ca. 1.2 nm) than on CeO 2 (ca. 1.8 nm) due to stronger Pt-CeO 2 interaction on aged Pt/CZO. Consequently, more exposed active Pt sites were obtained on the smaller clusters surrounded by more oxygen defects and Ce 3+ species, which directly translated to the higher catalytic oxidation performance of activated Pt/CZO catalyst in vehicle emission control applications.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Cycling of block copolymer composites with lithium-conducting ceramic nanoparticles

Solid polymer and perovskite-type ceramic electrolytes have both shown promise in advancing solid-state lithium metal batteries. Despite their favorable interfacial stability against lithium metal, polymer electrolytes face issues due to their low ionic conductivity and poor mechanical strength. Highly conductive and mechanically robust ceramics, on the other hand, cannot physically remain in contact with redox-active particles that expand and contract during charge-discharge cycles unless excessive pressures are used. To overcome the disadvantages of each material, polymer-ceramic composites can be formed; however, depletion interactions will always lead to aggregation of the ceramic particles if a homopolymer above its melting temperature is used. In this study, we incorporate Li 0.33 La 0.56 TiO 3 (LLTO) nanoparticles into a block copolymer, polystyrene- b -poly (ethylene oxide) (SEO), to develop a polymer-composite electrolyte (SEO-LLTO). TEMs of the same nanoparticles in polyethylene oxide (PEO) show highly aggregated particles whereas a significant fraction of the nanoparticles are dispersed within the PEO-rich lamellae of the SEO-LLTO electrolyte. We use synchrotron hard x-ray microtomography to study the cell failure and interfacial stability of SEO-LLTO in cycled lithium-lithium symmetric cells. Three-dimensional tomograms reveal the formation of large globular lithium structures in the vicinity of the LLTO aggregates. Encasing the SEO-LLTO between layers of SEO to form a “sandwich” electrolyte, we prevent direct contact of LLTO with lithium metal, which allows for the passage of seven-fold higher current densities without signatures of lithium deposition around LLTO. We posit that eliminating particle clustering and direct contact of LLTO and lithium metal through dry processing techniques is crucial to enabling composite electrolytes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Mechanistic study of methanol synthesis from CO₂ and H₂ on a modified model Mo₆S₈ cluster

We report the methanol synthesis from CO₂ and H₂ on metal (M = K, Ti, Co, Rh, Ni, and Cu)-modified model Mo₆S₈ catalyst using density functional theory (DFT). The results show that the catalytic behavior of a Mo₆S₈ cluster is changed significantly due to the modifiers, via the electron transfer from M to Mo₆S₈ and therefore the reduction of the Mo cation (ligand effect) and the direct participation of M in the reaction (ensemble effect) to promote some elementary steps. With the most positively charged modifier, the ligand effect in the case of K-Mo₆S₈ is the most obvious among the systems studied; however it cannot compete with the ensemble effect, which plays a dominate role in determining activity via the electrostatic attraction in particular to stabilize the CH x O y species adsorbed at the Mo sites of Mo₆S₈. In comparison, the ligand effect is weaker and the ensemble effect is more important when the other modifiers are used. In addition, the modifiers also vary the optimal reaction pathway for methanol synthesis on Mo₆S₈, ranging from the reverse water-gas shift (RWGS) + CO hydrogenation as that of Mo₆S₈ to the formate pathway. Finally, K is able to accelerate the methanol synthesis on Mo₆S₈ the most; while the promotion by Rh is relatively small. Using the modifiers like Ti, Co, Ni, and Cu, the activity of Mo₆S₈ is decreased instead. The relative stability between *HCOO and *HOCO is identified as a descriptor to capture the variation in mechanism and scales well with the estimated activity. Our study not only provides better understanding of the reaction mechanism and actives on the modified Mo₆S₈, but also predicts some possible candidates, which can be used a promoter to facilitate the CH₃OH synthesis on Mo sulfides.

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

The APOGEE Library of Infrared SSP Templates (A-LIST): High-resolution Simple Stellar Population Spectral Models in the H Band

Integrated light spectroscopy from galaxies can be used to study the stellar populations that cannot be resolved into individual stars. This analysis relies on stellar population synthesis (SPS) techniques to study the formation history and structure of galaxies. However, the spectral templates available for SPS are limited, especially in the near-infrared (near-IR). We present A-LIST (APOGEE Library of Infrared SSP Templates), a new set of high-resolution, near-IR SSP spectral templates spanning a wide range of ages (2–12 Gyr), metallicities ( − 2.2 < [M/H] < + 0.4) and α abundances ( − 0.2 < [α/M] < + 0.4). This set of SSP templates is the highest resolution (R ∼ 22, 500) available in the near-IR, and the first such based on an empirical stellar library. Our models are generated using spectra of ∼300,000 stars spread across the Milky Way, with a wide range of metallicities and abundances, from the APOGEE survey. We show that our model spectra provide accurate fits to M31 globular cluster spectra taken with APOGEE, with best-fit metallicities agreeing with those of previous estimates to within ∼0.1 dex. We also compare these model spectra to lower-resolution E-MILES models and demonstrate that we recover the ages of these models to within ∼1.5 Gyr. This library is available in https://github.com/aishashok/ALIST-library.

47 OTHER INSTRUMENTATION↗
NASA NTRS2000

The Heavy Element Abundance in Groups of Galaxies

Over the past few years we have analyzed a sample of clusters observed by the Advanced Spacecraft for Cosmology Astrophysics (ASCA) X-ray satellite. We performed spatially resolved X-ray spectroscopy of a sample of 18 relaxed clusters of galaxies with gas temperatures below 4 keV. The spectral analysis was done using ASCA/SIS (Solid state Imaging Spectrometer) data combined with imaging data from ROSAT/PSPC (German acronym for X-ray satellite/Position Sensitive Proportional Counter) and Einstein/IPC (Imaging Proportional Counter) observations. We derived temperature profiles using single-temperature fits for all of the clusters in the sample, and also corrected for the presence of cold gas in the center of so-called 'cooling flow' clusters. For all of the clusters in the sample we derived Si and Fe abundance profiles. For a few of the clusters we also were able to derive Ne and S abundance profiles. We compared the elemental abundances derived at similar overdensities in all of the clusters in the sample. We also compared element mass-to-light ratios for the entire sample. We concluded that the preferential accretion of low entropy, low abundance gas into the potentials of groups and cold clusters can explain most of the observed trends in metallicity. In addition, we discussed the importance of preheating of the intracluster medium by Type II supernovae on the cluster scaling relations.

David, Laurence↗
NASA NTRS2013

Perspectives on Intracluster Enrichment and the Stellar Initial Mass Function in Elliptical Galaxies

The amount of metals in the Intracluster Medium (ICM) in rich galaxy clusters exceeds that expected based on the observed stellar population by a large factor. We quantify this discrepancy--which we term the "cluster elemental abundance paradox"--and investigate the required properties of the ICM-enriching population. The necessary enhancement in metal enrichment may, in principle, originate in the observed stellar population if a larger fraction of stars in the supernova-progenitor mass range form from an initial mass function (IMF) that is either bottom-light or top-heavy, with the latter in some conflict with observed ICM abundance ratios. Other alternatives that imply more modest revisions to the IMF, mass return and remnant fractions, and primordial fraction, posit an increase in the fraction of 3-8 solar mass stars that explode as SNIa or assume that there are more stars than conventionally thought--although the latter implies a high star formation efficiency. We discuss the feasibility of these various solutions and the implications for the diversity of star formation, the process of elliptical galaxy formation, and the nature of this hidden source of ICM metal enrichment in light of recent evidence of an elliptical galaxy IMF that, because it is skewed to low masses, deepens the paradox.

Lowenstein, Michael↗
DOE OSTI2019

Age and origin of IIE iron meteorites inferred from Hf-W chronology

Non-magmatic iron meteorites, including the IIE group, can provide important insights into the history of metal-silicate differentiation and collisions on planetesimals. To better constrain the evolution of metal segregation and impacts on the IIE parent body, W isotopic data are reported for 10 IIE iron meteorites and a metal vein from the Portales Valley H6 chondrite. In addition, Pt isotopic data were obtained to quantify cosmic ray-induced neutron capture effects on W isotopes. After correction for these effects, the IIE iron meteorites exhibit variable pre-exposure 182W compositions, translating into Hf-W model age clusters of ~4–5 million years (Ma), ~10 Ma, ~15 Ma, and ~27 Ma after CAI formation. These distinct 182 W clusters likely represent samples from several discrete metallic melt pools on the IIE parent asteroid. The earliest metal segregation event at ~4–5 Ma was likely facilitated by 26 Al decay as an internal heat source. By contrast, the younger Hf-W model ages may not be chronologically meaningful, and probably reflect the effects of secondary mixing and re-equilibration of metal and silicates, likely facilitated by impacts on the IIE parent body. Thus, contrary to prior work, the Hf-W systematics of IIE iron meteorites do not require a protracted history of metal-silicate separation on the IIE parent body. Instead the results of this study are fully consistent with a single partial metal-silicate differentiation event driven by endogenic heating at ~4–5 Ma, followed by one or multiple impact events causing mixing and re-equilibration of metal and silicates at a later stage. As a result, the exact timing of these impact event(s) remains poorly constrained, but they most likely occurred in the first few tens of Ma of Solar System history.

58 GEOSCIENCES↗
DOE OSTI2025

Side-On N 2 Binding and Reduction by a Heterotetrametallic Zr 2 Co 2 Cluster

In multimetallic compounds, N 2 typically bridges late transition metals in an end-on (η 1 :η 1 ) fashion while early transition metals often bind N 2 side-on (η 2 ), with the latter resulting in more significant N–N bond elongation. In this work, N 2 fixation is accomplished by using a well-defined scaffold featuring a heterobimetallic combination of Zr and Co. We report a heterotetrametallic Zr 2 Co 2 cluster in which N 2 is bound side-on to the two Co centers and end-on to Zr in a μ 3 -η 1 :η 2 :η 2 binding mode that defies established paradigms for N 2 binding. The heterometallic approach is shown to facilitate catalytic reductive silylation of N 2 with turnover numbers far exceeding those of reported cobalt catalysts.

catalysts↗