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At least 1,603 records · Page 89
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DOE OSTI2016

Reduction-Triggered Self-Assembly of Nanoscale Molybdenum Oxide Molecular Clusters

A 2.9 nm molybdenum oxide cluster {Mo 132 } (Formula: [Mo VI 72 Mo V 60 O 372 (CH 3 COO) 30 (H 2 O) 72 ] 42- ) can be obtained by reducing ammonium molybdate with hydrazine sulfate in weakly acidic CH 3 COOH/CH 3 COO- buffers. This reaction has been monitored by time-resolved UV-Vis, 1H-NMR, small angle X-ray/neutron scattering, and X-ray absorption near edge structure spectroscopy. The growth of {Mo 132 } cluster shows a typical sigmoid curve, suggesting a multi-step assembly mechanism for this reaction. The reaction starts with a lag phase period when partial MoVI centers of molybdate precursors are reduced to form {MoV2(acetate)} structures under the coordination effect of the acetate groups. Once the concentration of {Mo V 2 (acetate)} reaches a critical value, it triggers the assembly of Mo V and Mo VI species into {Mo 132 } clusters. Parameters such as the type and amount of reducing agent, the pH, the type of cation, and the type of organic ligand in the reaction buffer, have been studied for the roles they play in the formation of the target clusters.Understanding the formation mechanism of giant molecular clusters is essential for rational design and synthesis of cluster-based nanomaterials with required morphologies and functionalities. Here, typical synthetic reactions of a 2.9 nm spherical molybdenum oxide cluster, {Mo 132 } (formula: [Mo VI 72 Mo V 60 O 372 (CH 3 COO) 30 (H 2 O) 72 ] 42 ), with systematically varied reaction parameters have been fully explored to determine the morphologies and concentration of products, reduction of metal centers, and chemical environments of the organic ligands. The growth of these clusters shows a typical sigmoid curve, suggesting a general multistep self-assembly mechanism for the formation of giant molecular clusters. The reaction starts with a lag phase period when partial MoVI centers of molybdate precursors are reduced to form {Mo V 2 (acetate)} structures under the coordination effect of the acetate groups. Once the concentration of {MoV2(acetate)} reaches a critical value, it triggers the co-assembly of Mo V and Mo VI species into the giant clusters.

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

GLOBULAR CLUSTERS AND SPUR CLUSTERS IN NGC 4921, THE BRIGHTEST SPIRAL GALAXY IN THE COMA CLUSTER

We resolve a significant fraction of globular clusters (GCs) in NGC 4921, the brightest spiral galaxy in the Coma cluster. We also find a number of extended bright star clusters (star complexes) in the spur region of the arms. The latter are much brighter and bluer than those in the normal star-forming region, being as massive as 3 × 10{sup 5} M{sub ⊙}. The color distribution of the GCs in this galaxy is found to be bimodal. The turnover magnitudes of the luminosity functions of the blue (metal-poor) GCs (0.70 < (V − I) ≤ 1.05) in the halo are estimated V(max) = 27.11 ± 0.09 mag and I(max) = 26.21 ± 0.11 mag. We obtain similar values for NGC 4923, a companion S0 galaxy, and two Coma cD galaxies (NGC 4874 and NGC 4889). The mean value for the turnover magnitudes of these four galaxies is I(max) = 26.25 ± 0.03 mag. Adopting M{sub I} (max) = −8.56 ± 0.09 mag for the metal-poor GCs, we determine the mean distance to the four Coma galaxies to be 91 ± 4 Mpc. Combining this with the Coma radial velocity, we derive a value of the Hubble constant, H{sub 0} = 77.9 ± 3.6 km s{sup −1} Mpc{sup −1}. We estimate the GC specific frequency of NGC 4921 to be S{sub N} = 1.29 ± 0.25, close to the values for early-type galaxies. This indicates that NGC 4921 is in the transition phase to S0s.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2023

Bismuth-Polyoxocation Coordination Networks: Controlling Nuclearity and Dimension-Dependent Photocatalysis

Bismuth-oxocluster nodes for metal–organic frameworks (MOFs) and coordination networks/polymers are less prolific than other families featuring zinc, zirconium, titanium, lanthanides, etc. However, Bi 3+ is non-toxic, it readily forms polyoxocations, and its oxides are exploited in photocatalysis. This family of compounds provides opportunity in medicinal and energy applications. Here, we show that Bi node nuclearity depends on solvent polarity, leading to a family of Bi x -sulfonate/carboxylate coordination networks with x = 1–38. Larger nuclearity-node networks were obtained from polar and strongly coordinating solvents, and we attribute the solvent’s ability to stabilize larger species in solution. Here, the strong role of the solvent and the lesser role of the linker in defining node topologies differ from other MOF syntheses, and this is due to the Bi 3+ intrinsic lone pair that leads to weak node–linker interactions. We describe this family by single-crystal X-ray diffraction (eleven structures), obtained in pure forms and high yields. Ditopic linkers include NDS (1,5-naphthalenedisulfonate), DDBS (2,2'-[biphenyl-4,4'-diylchethane-2,1-diyl] dibenzenesulphonate), and NH 2 -benzendicarboxylate (BDC). While the BDC and NDS linkers yield more open-framework topologies that resemble those obtained by carboxylate linkers, topologies with DDBS linkers appear to be in part driven by association between DDBS molecules. An in situ small-angle X-ray scattering study of Bi 38 -DDBS reveals stepwise formation, including Bi 38 -assembly, pre-organization in solution, followed by crystallization, confirming the less important role of the linker. We demonstrate photocatalytic hydrogen (H 2 ) generation with select members of the synthesized materials without the benefit of a co-catalyst. Band gap determination from X-ray photoelectron spectroscopy (XPS) and UV–vis data suggest the DDBS linker effectively absorbs in the visible range with ligand-to-Bi-node charge transfer. In addition, materials containing more Bi (larger Bi 38 -nodes or Bi 6 inorganic chains) exhibit strong UV absorption, also contributing to effective photocatalysis by a different mechanism. All tested materials became black with extensive UV–vis exposure, and XPS, transmission electron microscopy, and X-ray scattering of the black Bi 38 -framework suggest that Bi o is formed in situ, without phase segregation. This evolution leads to enhanced photocatalytic performance, perhaps due to increased light absorption.

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

Investigation of finite-size effects in chemical bonding of AuPd nanoalloys

In this paper, the size-dependent changes in energetic, vibrational, and electronic properties of C–O gas molecule interacting with surface Pd atom of a variety of AuPd nanoalloy structures are investigated by means of first principles calculations. The variation in C–O adsorption energies, C–O vibration frequencies (ν{sub C−O}), and Pd d-bond centers (ε{sub d}) on a series of non-supported Au{sub n−1}–Pd{sub 1} nanoparticles (with n varying from 13 to 147) and on two semi-finite surfaces are inspected with cluster size. We demonstrate for the first time that, with small AuPd bimetallic three-dimensional clusters as TOh{sub 38}, one can reach cluster size convergence even for such a sensitive observable as the adsorption energy on a metal surface. Indeed, the results show that the adsorbate-induced perturbation is extremely local and it only concerns the isolated Pd interacting with the reactive gas molecule. Except for 13 atom clusters, in which molecular behaviour is predominant, no finite-size effects are observed for surface Pd atom substituted in AuPd free nanoclusters above 38 atoms.

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

WIYN open cluster study. LIX. Radial velocity membership of the evolved population of the old open cluster NGC 6791

The open cluster NGC 6791 has been the focus of much recent study due to its intriguing combination of old age and high metallicity (∼8 Gyr, [Fe/H] = +0.30), as well as its location within the Kepler field. As part of the WIYN Open Cluster Study, we present precise (σ = 0.38 km s{sup –1}) radial velocities for proper motion candidate members of NGC 6791 from Platais et al. Our survey, extending down to g' ∼ 16.8, is comprised of the evolved cluster population, including blue stragglers, giants, and horizontal branch stars. Of the 280 proper-motion-selected stars above our magnitude limit, 93% have at least one radial velocity measurement and 79% have three measurements over the course of at least 200 days, sufficient for secure radial-velocity-determined membership of non-velocity-variable stars. The Platais et al. proper motion catalog includes 12 anomalous horizontal branch candidates blueward of the red clump, of which we find only 4 to be cluster members. Three fall slightly blueward of the red clump and the fourth is consistent with being a blue straggler. The cleaned color-magnitude diagram shows a richly populated red giant branch and a blue straggler population. Half of the blue stragglers are in binaries. From our radial velocity measurement distribution, we find the cluster's radial velocity dispersion to be σ {sub c} = 0.62 ± 0.10 km s{sup –1}. This corresponds to a dynamical mass of ∼4600 M {sub ☉}.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2015

Bayesian investigation of isochrone consistency using the old open cluster NGC 188

This paper provides a detailed comparison of the differences in parameters derived for a star cluster from its color–magnitude diagrams (CMDs) depending on the filters and models used. We examine the consistency and reliability of fitting three widely used stellar evolution models to 15 combinations of optical and near-IR photometry for the old open cluster NGC 188. The optical filter response curves match those of theoretical systems and are thus not the source of fit inconsistencies. NGC 188 is ideally suited to this study thanks to a wide variety of high-quality photometry and available proper motions and radial velocities that enable us to remove non-cluster members and many binaries. Our Bayesian fitting technique yields inferred values of age, metallicity, distance modulus, and absorption as a function of the photometric band combinations and stellar models. We show that the historically favored three-band combinations of UBV and VRI can be meaningfully inconsistent with each other and with longer baseline data sets such as UBVRIJHK{sub S}. Differences among model sets can also be substantial. For instance, fitting Yi et al. (2001) and Dotter et al. (2008) models to UBVRIJHK{sub S} photometry for NGC 188 yields the following cluster parameters: age = (5.78 ± 0.03, 6.45 ± 0.04) Gyr, [Fe/H] = (+0.125 ± 0.003, −0.077 ± 0.003) dex, (m−M){sub V} = (11.441 ± 0.007, 11.525 ± 0.005) mag, and A{sub V} = (0.162 ± 0.003, 0.236 ± 0.003) mag, respectively. Within the formal fitting errors, these two fits are substantially and statistically different. Such differences among fits using different filters and models are a cautionary tale regarding our current ability to fit star cluster CMDs. Additional modeling of this kind, with more models and star clusters, and future Gaia parallaxes are critical for isolating and quantifying the most relevant uncertainties in stellar evolutionary models.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2026

The Kinematically Hot, Extremely Metal-poor C-19 Stellar Stream in DESI DR2

Stellar streams are the result of a host galaxy’s gravitational potential tidally disrupting satellite dwarf galaxies and globular clusters (GCs), causing them to grow leading and trailing tidal tails. The C-19 stellar stream is an extremely metal-poor stellar population, showing chemical abundance patterns characteristic of a GC. However, its large velocity dispersion is difficult to reconcile with a conventional, purely baryonic, disrupting-GC progenitor. Current techniques for stream characterization are primarily applied to Gaia DR3, relying heavily on proper-motion measurements. Using the Dark Energy Spectroscopic Instrument (DESI), which provides radial velocities and metallicities for over 10 million stars and reaches significantly fainter magnitudes than comparable surveys, we employ a mixture model approach to jointly characterize stream populations in proper motions, radial velocities, and metallicities against a Milky Way halo background. By applying this framework to the C-19 stellar stream, we identify a total of 47 spectroscopically confirmed member stars, of which 41 are newly identified and only 6 were previously reported in the literature. In this work, we measure a velocity dispersion of $7.8^{+1.5}_{-1.3}$km s −1 and a mean metallicity of [Fe/H] = $-3.36^{+0.12}_{-0.10}$. We further identify a novel “spur” feature within the stream. We conclude that our measurements are in line with previous works identifying C-19 as a “hot,” metal-poor stream. In forthcoming work, we will apply this approach to many more streams in the DESI footprint, enabling population-level comparisons with predictions from simulations.

Mohammed, Nasser [University of Toronto; Dunlap In↗
DOE OSTI2016

Activation of Cu(111) surface by decomposition into nanoclusters driven by CO adsorption

The (111) surface of copper (Cu), its most compact and lowest energy surface, became unstable when exposed to carbon monoxide (CO) gas. Scanning tunneling microscopy revealed that at room temperature in the pressure range 0.1 to 100 Torr, the surface decomposed into clusters decorated by CO molecules attached to edge atoms. Between 0.2 and a few Torr CO, the clusters became mobile in the scale of minutes. Density functional theory showed that the energy gain from CO binding to low-coordinated Cu atoms and the weakening of binding of Cu to neighboring atoms help drive this process. Particularly for softer metals, the optimal balance of these two effects occurs near reaction conditions. Finally, cluster formation activated the surface for water dissociation, an important step in the water-gas shift reaction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

A PECULIAR FAINT SATELLITE IN THE REMOTE OUTER HALO OF M31

We present Hubble Space Telescope imaging of a newly discovered faint stellar system, PAndAS-48, in the outskirts of the M31 halo. Our photometry reveals this object to be comprised of an ancient and very metal-poor stellar population with age {approx}> 10 Gyr and [Fe/H] {approx}< -2.3. Our inferred distance modulus (m - M){sub 0} = 24.57 {+-} 0.11 confirms that PAndAS-48 is most likely a remote M31 satellite with a three-dimensional galactocentric radius of 149{sup +19}{sub -8} kpc. We observe an apparent spread in color on the upper red giant branch that is larger than the photometric uncertainties should allow, and briefly explore the implications of this. Structurally, PAndAS-48 is diffuse, faint, and moderately flattened, with a half-light radius r{sub h}=26{sup +4}{sub -3} pc, integrated luminosity M{sub V} = -4.8 {+-} 0.5, and ellipticity {epsilon}=0.30{sup +0.08}{sub -0.15}. On the size-luminosity plane it falls between the extended globular clusters seen in several nearby galaxies and the recently discovered faint dwarf satellites of the Milky Way; however, its characteristics do not allow us to unambiguously classify it as either type of system. If PAndAS-48 is a globular cluster then it is among the most elliptical, isolated, and metal-poor of any seen in the Local Group, extended or otherwise. Conversely, while its properties are generally consistent with those observed for the faint Milky Way dwarfs, it would be a factor of {approx}2-3 smaller in spatial extent than any known counterpart of comparable luminosity.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2012

DISCOVERY OF THE MOST ISOLATED GLOBULAR CLUSTER IN THE LOCAL UNIVERSE

We report the discovery of two new globular clusters in the remote halos of M81 and M82 in the M81 Group based on Hubble Space Telescope archive images. They are brighter than typical globular clusters (M{sub V} = -9.34 mag for GC-1 and M{sub V} = -10.51 mag for GC-2), and much larger than known globular clusters with similar luminosity in the Milky Way Galaxy and M81. Radial surface brightness profiles for GC-1 and GC-2 do not show any features of tidal truncation in the outer part. They are located much farther from both M81 and M82 in the sky, compared with previously known star clusters in these galaxies. Color-magnitude diagrams of resolved stars in each cluster show a well-defined red giant branch (RGB), indicating that they are metal-poor and old. We derive a low metallicity with [Fe/H] Almost-Equal-To -2.3 and an old age {approx}14 Gyr for GC-2 from the analysis of the absorption lines in its spectrum in the Sloan Digital Sky Survey in comparison with the simple stellar population models. The I-band magnitude of the tip of the RGB for GC-2 is 0.26 mag fainter than that for the halo stars in the same field, showing that GC-2 is {approx}400 kpc behind the M81 halo along our line of sight. The deprojected distance to GC-2 from M81 is much larger than any other known globular clusters in the local universe. This shows that GC-2 is the most isolated globular cluster in the local universe.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2012

Insights into the Temperature-Dependent “Breathing” of a Flexible Fluorinated Metal-Organic Framework

The framework expansion and contraction upon carbon dioxide uptake was studied in a partially fluorinated metal-organic framework, FMOF-2. The results show framework expansion and contraction (breathing) as a function of pressure and temperature. Even at temperatures as low as -30 ºC, two phase transitions seem to take place with a pressure step (corresponding to the second transition) that is greatly dependent on temperature. This behavior is described by the model proposed by Coudert and co-workers showing that the material seems to undergo two phase transitions that are temperature dependent. The isosteric heats of adsorption at high pressures show a minimum that is concurrent with the region of CO2 loadings where the second pressure step occurs. It was deduced that these lower enthalpy values are a consequence of the energy cost related to the expansion or reopening of the framework. Lastly, the large and reversible breathing behavior may be a product of the combination of the high elasticity of zinc (II) coordination and the apparent high flexibility of the V-shaped organic building block.

carbon dioxide↗
DOE OSTI2023

Exploring NaCl-PuCl 3 molten salts with machine learning interatomic potentials and graph theory

Actinide molten salts are the basis of the liquid fuels used in molten salt reactors. Due to the inherent difficulties associated with high temperature and hazardous conditions, experimental investigations of fundamental properties of these materials are usually challenging. In this work, we describe the structure and transport of NaCl-PuCl 3 mixtures using computational techniques. Three compositions were considered (16, 25, and 36 mol% PuCl 3 ) over a temperature range (730 – 1257K) using ab initio molecular dynamics, which provided the necessary data sets for training machine learned interatomic potentials. Further, molecular dynamics simulations based on these potentials were then used to determine structure and transport properties. A substantial change was noted in the structure factor when increasing the PuCl 3 content from 25 to 36 mol%. This change is linked to the aggregation of larger Pu 3+ clusters. In addition, the similarity of the atomic environments of metal cations in molten salt systems to their solid states counterparts was investigated using an unsupervised learning technique. Finally, graph theory was employed to explore the structure and size of actinide networks. Consistent with the structure factor, a dense Pu 3+ intermolecular structure is observed within the 36 mol% PuCl 3 mixture. The structure of cation-cation inter-junctions is also discussed. In all cases, the diffusion of Pu 3+ is significantly lower than that of Na + and Cl - .

36 MATERIALS SCIENCE↗
DOE OSTI2016

Core–Shell to Doped Quantum Dots: Evolution of the Local Environment Using XAFS

Internal structure study at an atomic level is a challenging task with far reaching consequences to its material properties, specifically in the field of transition metal doping in quantum dots. Diffusion of transition metal ions in and out of quantum dots forming magnetic clusters has been a major bottleneck in this class of materials. Diffusion of the magnetic ions from the core into the nonmagnetic shell in a core/shell heterostructure architecture to attain uniform doping has been recently introduced and yet to be understood. In this work, we have studied the local structure variation of Fe as a function of CdS matrix thickness and annealing time during the overcoating of Fe 3 O 4 core with CdS using X-ray absorption spectroscopy. The data reveals that Fe 3 O 4 core initially forms a core/shell structure with CdS followed by alloying at the interface eventually completely diffusing all the way through the CdS matrix to form homogeneously Fe-doped CdS QDs with excellent control over size and size distribution. Study of Fe K-edge shows a complete change of Fe local environment from Fe–O to FeS.

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

Catalytic, Spectroscopic, and Theoretical Studies of Fe 4 S 4 -Based Coordination Polymers as Heterogenous Coupled Proton–Electron Transfer Mediators for Electrocatalysis

Iron–sulfur clusters play essential roles in biological systems, and thus synthetic [Fe 4 S 4 ] clusters have been an area of active research. Recent studies have demonstrated that soluble [Fe 4 S 4 ] clusters can serve as net H atom transfer mediators, improving the activity and selectivity of a homogeneous Mn CO 2 reduction catalyst. Here, in this work, we demonstrate that incorporating these [Fe 4 S 4 ] clusters into a coordination polymer enables heterogeneous H atom transfer from an electrode surface to a Mn complex dissolved in solution. A previously reported solution-processable Fe 4 S 4 -based coordination polymer was successfully deposited on the surfaces of different electrodes. The coated electrodes serve as H atom transfer mediators to a soluble Mn CO 2 reduction catalyst displaying good product selectivity for formic acid. Furthermore, these electrodes are recyclable with a minimal decrease in activity after multiple catalytic cycles. The heterogenization of the mediator also enables the characterization of solution-phase and electrode surface species separately. Surface enhanced infrared absorption spectroscopy (SEIRAS) reveals spectroscopic signatures for an in situ generated active Mn–H species, providing a more complete mechanistic picture for this system. The active species, reaction mechanism, and the protonation sites on the [Fe 4 S 4 ] clusters were further confirmed by density functional theory calculations. The observed H atom transfer reactivity of these coordination polymer-coated electrodes motivates additional applications of this composite material in reductive H atom transfer electrocatalysis.

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

Manganese–Cobalt Oxido Cubanes Relevant to Manganese-Doped Water Oxidation Catalysts

Incorporation of Mn into an established water oxidation catalyst based on a Co(III) 4 O 4 cubane was achieved by a simple and efficient assembly of permanganate, cobalt(II) acetate, and pyridine to form the cubane oxo cluster MnCo 3 O 4 (OAc) 5 py 3 (OAc = acetate, py = pyridine) (1-OAc) in good yield. This allows characterization of electronic and chemical properties for a manganese center in a cobalt oxide environment, and provides a molecular model for Mn-doped cobalt oxides. The electronic properties of the cubane are readily tuned by exchange of the OAc - ligand for Cl - (1-Cl), NO 3 - (1-NO 3 ), and pyridine ([1-py] + ). EPR spectroscopy, SQUID magnetometry, and DFT calculations thoroughly characterized the valence assignment of the cubane as [Mn IV Co III 3 ]. These cubanes are redox-active, and calculations reveal that the Co ions behave as the reservoir for electrons, but their redox potentials are tuned by the choice of ligand at Mn. This MnCo 3 O 4 cubane system represents a new class of easily prepared, versatile, and redox-active oxido clusters that should contribute to an understanding of mixed-metal, Mn-containing oxides.

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

Chemical and kinematical properties of galactic bulge stars surrounding the stellar system Terzan 5

As part of a study aimed at determining the kinematical and chemical properties of Terzan 5, we present the first characterization of the bulge stars surrounding this puzzling stellar system. We observed 615 targets located well beyond the tidal radius of Terzan 5 and found that their radial velocity distribution is well described by a Gaussian function peaked at (v {sub rad}) = +21.0 ± 4.6 km s{sup –1} with dispersion σ {sub v} = 113.0 ± 2.7 km s{sup –1}. This is one of the few high-precision spectroscopic surveys of radial velocities for a large sample of bulge stars in such a low and positive latitude environment (b = +1.°7). We found no evidence of the peak at (v {sub rad}) ∼ +200 km s{sup –1} found in Nidever et al. Strong contamination of many observed spectra by TiO bands prevented us from deriving the iron abundance for the entire spectroscopic sample, introducing a selection bias. The metallicity distribution was finally derived for a subsample of 112 stars in a magnitude range where the effect of the selection bias is negligible. The distribution is quite broad and roughly peaked at solar metallicity ([Fe/H] ≅ +0.05 dex) with a similar number of stars in the super-solar and in the sub-solar ranges. The population number ratios in different metallicity ranges agree well with those observed in other low-latitude bulge fields, suggesting (1) the possible presence of a plateau for |b| < 4° in the ratio between stars in the super-solar (0 < [Fe/H] <0.5 dex) and sub-solar (–0.5 < [Fe/H] <0 dex) metallicity ranges; (2) a severe drop in the metal-poor component ([Fe/H] <–0.5) as a function of Galactic latitude.

79 ASTRONOMY AND ASTROPHYSICS↗