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At least 1,585 records · Page 88

Dynamic Atom Clusters on AuCu Nanoparticle Surface During CO Oxidation

Supported alloy nanoparticles are prevailing alternative low-cost catalysts for both heterogeneous and electrochemical catalytic processes. Selective interaction of an alloy component with a specific reactant induces a dynamic structural change of alloy nanoparticles under reaction conditions and largely controls their catalytic properties. However, such a multi-component dynamic-interaction-controlled evolution, both structural and chemical, remains far from clear. Herein, by using state-of-the-art environmental TEM, we directly visualize, in-situ at the atomic scale, the evolution of an AuCu alloy nanoparticle supported on CeO2 during CO oxidation. We find that gas molecules can “free” metal atoms on the {001} surface and form highly mobile atom clusters. Remarkably, we discover that CO exposure induces Au segregation and activation on nanoparticle surface, while O2 exposure leads to the segregation and oxidation of Cu on the particle surface. The as-formed Cu2O/AuCu interface may facilitate CO-O interaction corroborated by DFT calculations. These findings provide insights into the atomistic mechanisms on alloy nanoparticles during catalytic CO oxidation reaction, and to a broad scope of rational design of alloy nanoparticle catalysts.

Luo, Langli↗

Porphyrins as Templates for Site-Selective Atomic Layer Deposition: Vapor Metalation and in Situ Monitoring of Island Growth

Examinations of enzymatic catalysts suggest one key to efficient catalytic activity is discrete size metallo clusters. Mimicking enzymatic cluster systems is synthetically challenging because conventional solution methods are prone to aggregation or require capping of the cluster, thereby limiting its catalytic activity. We introduce site-selective atomic layer deposition (ALD) on porphyrins as an alternative approach to grow isolated metal oxide islands that are spatially separated. Surface-bound tetra-acid free base porphyrins (H2TCPP) may be metalated with Mn using conventional ALD precursor exposure to induce homogeneous hydroxide synthetic handles which acts as a nucleation point for subsequent ALD MnO island growth. Analytical fitting of in situ QCM mass uptake reveals island growth to be hemispherical with a convergence radius of 1.74 nm. This growth mode is confirmed with synchrotron grazing-incidence small-angle X-ray scattering (GISAXS) measurements. Finally, we extend this approach to other ALD chemistries to demonstrate the generality of this route to discrete metallo island materials.

atomic layer deposition↗

Synthetic horizontal branch models for globular clusters - The luminosity of the horizontal branch and the Oosterhoff effect

The variation of horizontal-branch (HB) luminosities with metal abundances is analyzed on the basis of HB models synthesized from theoretical HB evolutionary tracks. The focus is on the Oosterhoff effect, as related to period shifts in globular-cluster RR Lyr variables. The construction of the models and the Oosterhoff period groups is explained in detail, and the implications for globular-cluster ages are considered. The ratio of Delta M(bol) (RR) to Delta Fe/H for the HB is calculated as 0.24, slightly steeper than that found by Sandage (1981 and 1982).

Lee, Young-Wook↗

Mean-field model for the Curie-Weiss temperature dependence of coherence length in metallic liquids

The coherence length of the medium-range order (MRO) in metallic liquids is known to display a Curie-Weiss temperature dependence; its inverse is linearly related to temperature, and when extrapolated from temperatures above the glass transition, the coherence length diverges at a negative temperature with a critical exponent of unity. We propose a mean-field pseudospin model that explains this behavior. Specifically, we model the atoms and their local environment as Ising spins with antiferromagnetic exchange interactions. We further superimpose an exchange interaction between dynamical heterogeneities, or clusters of atoms undergoing cooperative motion. The coherence length in the metallic liquid is thus the correlation length between dynamical heterogeneities. Overall, our results reaffirm the idea that the MRO coherence length is a measure of point-to-set correlations, and that local frustrations in the interatomic interactions are prominent in metallic liquids.

36 MATERIALS SCIENCE↗

A Transferable Force Field for Predicting Adsorption and Diffusion of Water in Cationic Zeolites with Coupled Cluster Accuracy

We present a transferable force field for water in proton-exchanged, alkali (Li, Na, K, Rb, and Cs) metal-exchanged, and alkaline-earth (Mg, Ca, Sr, and Ba) metal-exchanged zeolites. The fitting methodology is based on adsorbate–adsorbent interaction energies obtained from periodic density functional theory calculations and corrected using the coupled-cluster method applied to small model clusters. To ensure an accurate prediction of both adsorption and diffusion properties of water, sets of configurations that sample both adsorption sites and intracrystalline hopping transition states were used in the fitting. The quality of the force field is assessed for a wide range of zeolites with different topologies and chemical compositions, demonstrating good agreement between theoretical predictions and experimental measurements of water adsorption and diffusion.

Adsorption↗

Rediscovery of the Sixth Star Cluster in the Fornax Dwarf Spheroidal Galaxy

Since first noticed by Shapley in 1939, a faint object coincident with the Fornax dwarf spheroidal has long been discussed as a possible sixth globular cluster (GC) system. However, debate has continued over whether this overdensity is a statistical artifact or a blended galaxy group. In this Letter we demonstrate, using deep DECam imaging data, that this object is well resolved into stars and is a bona fide star cluster. The stellar overdensity of this cluster is statistically significant at the level of ~6–6.7σ in several different photometric catalogs including $Gaia$. Therefore, it is highly unlikely to be caused by random fluctuation. We show that Fornax 6 is a star cluster with a peculiarly low surface brightness and irregular shape, which may indicate a strong tidal influence from its host galaxy. The Hess diagram of Fornax 6 is largely consistent with that of Fornax field stars, but it appears to be slightly bluer. However, it is still likely more metal-rich than most of the GCs in the system. Finally, faint clusters like Fornax 6 that orbit and potentially get disrupted in the centers of dwarf galaxies can prove crucial for constraining the dark matter distribution in Milky Way satellites.

79 ASTRONOMY AND ASTROPHYSICS↗

Heat Emission and Temperature Non-uniformity in Rod Bundles with Different Spacing, Cooled by Heavy Liquid-Metal Coolant

Heat emission and temperature non-uniformity along the perimeter of rods in free lattices of fuel elements with heavy liquid-metal coolant are studied. The experimental data for an assembly of smooth rods, assemblies of fuel elements with spiral ribbing, and transverse lattices are analyzed. The studies show that there is almost no temperature non-uniformity in a lattice of smooth fuel elements along its perimeter, which is in contrast to the high general azimuthal temperature non-uniformity in an assembly with spacing by spiral coils. Rib spacing resulted in significant reduction of heat emission. In an assembly with transverse spacer lattices, the heat emission increases only in the region containing the lattices; in the spaces between lattices, it is approximately equal to the heat emission in a bundle with smooth fuel elements. Inside a spacer lattice, periodic temperature non-uniformities appear along the perimeter of the fuel elements; these non-uniformities are due to the fuel elements touching the elements of the lattice. A relation is recommended for calculating heat emission (Nusselt numbers) and temperature non-uniformity along the perimeter of the fuel elements for the studied methods of spacing the fuel elements.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

Overall Performance Losses and Activated Mechanisms in Double Glass and Glass-backsheet Photovoltaic Modules with Monofacial and Bifacial PERC Cells, under Accelerated Exposures

Commercial PV modules have various packaging choices nowadays, which influence their long-term reliability. This study compared the degradation behaviors of sixteen module variants from two brands with varying encapsulant materials (EVA or POE), encapsulant types, module architectures (GB or DG), and cell types (monofacial or bifacial) using null hypothesis testing to determine statistical significant findings. The modules were exposed for 2,520 hours under two accelerated exposures: modified damp heat (mDH) and modified damp heat with full-spectrum light (mDH+FSL). For both brands, two DG module variants with UV-Cutoff rear encapsulant are found to have significantly lower average power loss than the module variants of EVA+GB with opaque rear encapsulant after each accelerated exposure. Metallization interconnect corrosion is identified as the primary degradation mechanism. Furthermore, unsupervised hierarchical clustering finds that the degradation behaviors of modules from one brand with a more strict manufacturing quality control depends on module architectures only.

14 SOLAR ENERGY↗

Enhancing T c in a composite superconductor/metal bilayer system: A dynamical cluster approximation study

It has been proposed that the superconducting transition temperature T c of an unconventional superconductor with a large pairing scale but strong phase fluctuations can be enhanced by coupling it to a metal. However, the general efficacy of this approach across different parameter regimes remains an open question. Using the dynamical cluster approximation, we study this question in a system composed of an attractive Hubbard layer in the intermediate coupling regime, where the magnitude of the attractive Coulomb interaction |U| is slightly larger than the bandwidth W, hybridized with a noninteracting metallic layer. We find that while the superconducting transition becomes more mean-field-like with increasing interlayer hopping, the superconducting transition temperature T c exhibits a nonmonotonic dependence on the strength of the hybridization t ⊥ . Furthermore, this behavior arises from a reduction of the effective pairing interaction in the correlated layer that outcompetes the growth in the intrinsic pair-field susceptibility induced by the coupling to the metallic layer. We find that the largest T c inferred here for the composite system is comparable to the maximum value currently estimated for the isolated negative-U Hubbard model.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Quantitative spectroscopic J-band study of red supergiants in Perseus OB-1

We demonstrate how the metallicities of red supergiant (RSG) stars can be measured from quantitative spectroscopy down to resolutions of ≈3000 in the J-band. We have obtained high resolution spectra on a sample of the RSG population of h and χ Persei, a double cluster in the solar neighborhood. We show that careful application of the MARCS model atmospheres returns measurements of Z consistent with solar metallicity. Using two grids of synthetic spectra–one in pure LTE and one with non-LTE (NLTE) calculations for the most important diagnostic lines–we measure Z = +0.04 ± 0.10 (LTE) and Z = –0.04 ± 0.08 (NLTE) for the sample of eleven RSGs in the cluster. We degrade the spectral resolution of our observations and find that those values remain consistent down to resolutions of less than λ/δλ of 3000. Using measurements of effective temperatures we compare our results with stellar evolution theory and find good agreement. We construct a synthetic cluster spectrum and find that analyzing this composite spectrum with single-star RSG models returns an accurate metallicity. We conclude that the RSGs make ideal targets in the near infrared for measuring the metallicities of star forming galaxies out to 7-10 Mpc and up to 10 times farther by observing the integrated light of unresolved super star clusters.

79 ASTRONOMY AND ASTROPHYSICS↗

Molecular Rhodium Complexes Supported on the Metal-Oxide-Like Nodes of Metal Organic Frameworks and on Zeolite HY: Catalysts for Ethylene Hydrogenation and Dimerization

Metal–organic frameworks (MOFs) with nodes consisting of zirconium oxide clusters (Zr 6 ) offer new opportunities as supports for catalysts with well-defined, essentially molecular, structures. We used the precursor Rh(C 2 H 4 ) 2 (acac) (acac is acetylacetonate) to anchor Rh(I) complexes to the nodes of the MOF UiO-67 and, for comparison, to the zeolite dealuminated HY (DAY). These were characterized experimentally by measurement of catalytic activities and selectivities for ethylene hydrogenation and dimerization in a once-through flow reactor at 298 K and 1 bar. The catalyst performance data are complemented with structural information determined by infrared and extended X-ray absorption fine structure spectroscopies and by calculations at the level of density functional theory, the latter carried out also to extend the investigation to a related MOF, NU-1000. The agreement between the experimental and calculated structural metrics is good, and the calculations have led to predictions of reaction mechanisms and associated energetics. Finally, the data demonstrate a correlation between the catalytic activity and selectivity and the electron-donor tendency of the supported rhodium (as measured by the frequencies of CO ligands bonded as probes to the Rh(I) centers), which is itself a measure of the electron-donor tendency of the support.

36 MATERIALS SCIENCE↗

IUE observations of the clusters of the Magellanic Clouds

IUE observations of 17 clusters in the Large Magellanic Cloud are presented. The derived ultraviolet colors become progressively redder as the cluster's classification in the scheme of Searle, Wilkinson, and Bagnuolo increases. With the aid of theoretical models of the integrated light of coeval clusters of varying ages, it is shown that the SWB classification is one of increasing age accompanied by decreasing metallicity toward later SWB classes. The behavior of the UV absorption line features in the integrated light of the LMC clusters supports the contention.

Cohen, J. G.↗

Hybrid Quantum Mechanics/Molecular Mechanics Solvation Scheme for Computing Free Energies of Reactions at Metal–Water Interfaces

We report the development of a quantum mechanics/molecular mechanics free energy perturbation (QM/MM-FEP) method for modeling chemical reactions at metal-water interfaces. This novel solvation scheme combines planewave density function theory (DFT), periodic electrostatic embedded cluster method (PEECM) calculations using Gaussian-type orbitals, and classical molecular dynamics (MD) simulations to obtain a free energy description of a complex metal-water system. We derive a potential of mean force (PMF) of the reaction system within the QM/MM framework. A fixed-size, finite ensemble of MM conformations is used to permit precise evaluation of the PMF of QM coordinates and its gradient defined within this ensemble. Local conformations of adsorbed reaction moieties are optimized using sequential MD-sampling and QM-optimization steps. An approximate reaction coordinate is constructed using a number of interpolated states and the free energy difference between adjacent states is calculated using the QM/MM-FEP method. By avoiding on-the-fly QM calculations and by circumventing the challenges associated with statistical averaging during MD sampling, a computational speedup of multiple orders of magnitude is realized. The method is systematically validated against the results of ab initio QM calculations and demonstrated for C–C cleavage in double-dehydrogenated ethylene glycol on a Pt (111) model surface.

Chemical calculations↗

Addressing the characterisation challenge to understand catalysis in MOFs: the case of nanoscale Cu supported in NU-1000

Here, we explore the dynamic structure and reactivity of Cu species supported on NU-1000. By combining pair distribution function (PDF) analysis and difference envelope density (DED) analysis of in situ synchrotron-based X-ray scattering data, we simultaneously probe the local structure of supported Cu-species, their distribution within NU-1000 and distortions of the NU-1000 lattice under conditions relevant to catalysis and catalyst activation. Our analyses show that atomic layer deposition (ALD) of Cu in NU-1000 (Cu-AIM) leads to the formation of Cu-oxo clusters within the small pores that connect the triangular and hexagonal channels. Exposure of Cu-AIM to a reducing atmosphere at 200 °C produces metallic Cu 0 of two distinct particle sizes: ~4 nm nanoparticles and small sub-nanometer clusters. The size of these nanoparticles appears to be constrained by NU-1000 pore dimensions, with evidence of the sub-nanometer clusters being bound within the triangular channels flanked by pyrene rings. This supported Cu 0 –NU-1000 system is catalytically active for gas-phase ethylene hydrogenation. Exposure of the catalyst to oxidative atmosphere re-oxidises the Cu species to a Cu 2 O cuprite phase. The dynamic restructuring of the system in different chemical environments underscores the importance of probing these systems in situ .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DETECTION OF A NEARBY HALO DEBRIS STREAM IN THE WISE AND 2MASS SURVEYS

Combining the Wide-Field Infrared Survey Explorer All-Sky Release with the Two Micron All Sky Survey Point Source Catalog, we detect a nearby, moderately metal-poor stellar debris stream spanning 24° across the southern sky. The stream, which we designate Alpheus, is at an estimated distance of ∼1.9 kpc. Its position, orientation, width, estimated metallicity, and, to some extent, its distance, are in approximate agreement with what one might expect of the leading tidal tail of the southern globular cluster NGC 288.

79 ASTRONOMY AND ASTROPHYSICS↗

The sluggs survey: HST/ACS mosaic imaging of the NGC 3115 globular cluster system

We present Hubble Space Telescope/Advanced Camera for Surveys (HST/ACS) g and z photometry and half-light radii R {sub h} measurements of 360 globular cluster (GC) candidates around the nearby S0 galaxy NGC 3115. We also include Subaru/Suprime-Cam g, r, and i photometry of 421 additional candidates. The well-established color bimodality of the GC system is obvious in the HST/ACS photometry. We find evidence for a 'blue tilt' in the blue GC subpopulation, wherein the GCs in the blue subpopulation get redder as luminosity increases, indicative of a mass-metallicity relationship. We find a color gradient in both the red and blue subpopulations, with each group of clusters becoming bluer at larger distances from NGC 3115. The gradient is of similar strength in both subpopulations, but is monotonic and more significant for the blue clusters. On average, the blue clusters have ∼10% larger R {sub h} than the red clusters. This average difference is less than is typically observed for early-type galaxies but does match that measured in the literature for the Sombrero Galaxy (M104), suggesting that morphology and inclination may affect the measured size difference between the red and blue clusters. However, the scatter on the R {sub h} measurements is large. We also identify 31 clusters more extended than typical GCs, which we term ultra-compact dwarf (UCD) candidates. Many of these objects are actually considerably fainter than typical UCDs. While it is likely that a significant number will be background contaminants, six of these UCD candidates are spectroscopically confirmed as NGC 3115 members. To explore the prevalence of low-mass X-ray binaries in the GC system, we match our ACS and Suprime-Cam detections to corresponding Chandra X-ray sources. We identify 45 X-ray-GC matches: 16 among the blue subpopulation and 29 among the red subpopulation. These X-ray/GC coincidence fractions are larger than is typical for most GC systems, probably due to the increased depth of the X-ray data compared to previous studies of GC systems.

79 ASTRONOMY AND ASTROPHYSICS↗

Josephson behavior in a metal-decorated topological-insulator Bi 0.91 Sb 0.09

We have fabricated W nanoscale clusters on a topological insulator Bi 0.91 Sb 0.09 . The W island arrays effectively induce two-dimensional superconductivity at the surface of Bi 0.91 Sb 0.09 via the superconducting proximity effect. We find that this heterostructure behaves as a dynamic Josephson junction, which shows a Fraunhofer-like pattern of the critical current versus the applied magnetic field. Microwave irradiation experiments reveal the existence of a 4π-periodic supercurrent carried by the topological surface state. Our results open up a route to induce topological superconductivity in a topological insulator.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Exciton Migration and Amplified Quenching on Two-Dimensional Metal–Organic Layers

The dimensionality dependency of resonance energy transfer is of great interest due to its importance in understanding energy transfer on cell membranes and in low-dimension nanostructures. Light harvesting two-dimensional metal–organic layers (2D-MOLs) and three-dimensional metal–organic frameworks (3D-MOFs) provide comparative models to study such dimensionality dependence with molecular accuracy. Here we report the construction of 2D-MOLs and 3D-MOFs from a donor ligand 4,4',4''-(benzene-1,3,5-triyl-tris(ethyne-2,1-diyl))tribenzoate (BTE) and a doped acceptor ligand 3,3',3''-nitro-4,4',4''-(benzene-1,3,5-triyl-tris(ethyne-2,1-diyl))tribenzoate (BTE-NO2). These 2D-MOLs and 3D-MOFs are connected by similar hafnium clusters, with key differences in the topology and dimensionality of the metal–ligand connection. Energy transfer from donors to acceptors through the 2D-MOL or 3D-MOF skeletons is revealed by measuring and modeling the fluorescence quenching of the donors. We found that energy transfer in 3D-MOFs is more efficient than that in 2D-MOLs, but excitons on 2D-MOLs are more accessible to external quenchers as compared with those in 3D-MOFs. These results not only provide support to theoretical analysis of energy transfer in low dimensions, but also present opportunities to use efficient exciton migration in 2D materials for light-harvesting and fluorescence sensing.

36 MATERIALS SCIENCE↗