Charge transfer and formation of reduced Ce3+ upon adsorption of metal atoms at the ceria (110) surface.

PubMed

Nolan, Michael

2012-04-07

The modification of cerium dioxide with nanoscale metal clusters is intensely researched for catalysis applications, with gold, silver, and copper having been particularly well studied. The interaction of the metal cluster with ceria is driven principally by a localised interaction between a small number of metal atoms (as small as one) and the surface and understanding the fundamentals of the interaction of metal atoms with ceria surfaces is therefore of great interest. Much attention has been focused on the interaction of metals with the (111) surface of ceria, since this is the most stable surface and can be grown as films, which are probed experimentally. However, nanostructures exposing other surfaces such as (110) show high activity for reactions including CO oxidation and require further study; these nanostructures could be modified by deposition of metal atoms or small clusters, but there is no information to date on the atomic level details of metal-ceria interactions involving the (110) surface. This paper presents the results of density functional theory (DFT) corrected for on-site Coulomb interactions (DFT+U) calculations of the adsorption of a number of different metal atoms at an extended ceria (110) surface; the metals are Au, Ag, Cu, Al, Ga, In, La, Ce, V, Cr, and Fe. Upon adsorption all metals are oxidised, transferring electron(s) to the surface, resulting in localised surface distortions. The precise details depend on the identity of the metal atom. Au, Ag, Cu each transfer one electron to the surface, reducing one Ce ion to Ce(3+), while of the trivalent metals, Al and La are fully oxidised, but Ga and In are only partially oxidised. Ce and the transition metals are also partially oxidised, with the number of reduced Ce ions possible in this surface no more than three per adsorbed metal atom. The predicted oxidation states of the adsorbed metal atoms should be testable in experiments on ceria nanostructures modified with metal atoms.

Energetics of charged metal clusters containing vacancies

NASA Astrophysics Data System (ADS)

Pogosov, Valentin V.; Reva, Vitalii I.

2018-01-01

We study theoretically large metal clusters containing vacancies. We propose an approach, which combines the Kohn-Sham results for monovacancy in a bulk of metal and analytical expansions in small parameters cv (relative concentration of vacancies) and RN,v -1, RN ,v being cluster radii. We obtain expressions of the ionization potential and electron affinity in the form of corrections to electron work function, which require only the characteristics of 3D defect-free metal. The Kohn-Sham method is used to calculate the electron profiles, ionization potential, electron affinity, electrical capacitance; dissociation, cohesion, and monovacancy-formation energies of the small perfect clusters NaN, MgN, AlN (N ≤ 270) and the clusters containing a monovacancy (N ≥ 12) in the stabilized-jellium model. The quantum-sized dependences for monovacancy-formation energies are calculated for the Schottky scenario and the "bubble blowing" scenario, and their asymptotic behavior is also determined. It is shown that the asymptotical behaviors of size dependences for these two mechanisms differ from each other and weakly depend on the number of atoms in the cluster. The contribution of monovacancy to energetics of charged clusters and the size dependences of their characteristics and asymptotics are discussed. It is shown that the difference between the characteristics for the neutral and charged clusters is entirely determined by size dependences of ionization potential and electron affinity. Obtained analytical dependences may be useful for the analysis of the results of photoionization experiments and for the estimation of the size dependences of the vacancy concentration including the vicinity of the melting point.

Age determination of 15 old to intermediate-age small Magellanic cloud star clusters

DOE Office of Scientific and Technical Information (OSTI.GOV)

Parisi, M. C.; Clariá, J. J.; Piatti, A. E.

2014-04-01

We present color-magnitude diagrams in the V and I bands for 15 star clusters in the Small Magellanic Cloud (SMC) based on data taken with the Very Large Telescope (VLT, Chile). We selected these clusters from our previous work, wherein we derived cluster radial velocities and metallicities from calcium II infrared triplet (CaT) spectra also taken with the VLT. We discovered that the ages of six of our clusters have been appreciably underestimated by previous studies, which used comparatively small telescopes, graphically illustrating the need for large apertures to obtain reliable ages of old and intermediate-age SMC star clusters. Inmore » particular, three of these clusters, L4, L6, and L110, turn out to be among the oldest SMC clusters known, with ages of 7.9 ± 1.1, 8.7 ± 1.2, and 7.6 ± 1.0 Gyr, respectively, helping to fill a possible 'SMC cluster age gap'. Using the current ages and metallicities from Parisi et al., we analyze the age distribution, age gradient, and age-metallicity relation (AMR) of a sample of SMC clusters measured homogeneously. There is a suggestion of bimodality in the age distribution but it does not show a constant slope for the first 4 Gyr, and we find no evidence for an age gradient. Due to the improved ages of our cluster sample, we find that our AMR is now better represented in the intermediate/old period than we had derived in Parisi et al., where we simply took ages available in the literature. Additionally, clusters younger than ∼4 Gyr now show better agreement with the bursting model of Pagel and Tautvaišienė, but we confirm that this model is not a good representation of the AMR during the intermediate/old period. A more complicated model is needed to explain the SMC chemical evolution in that period.« less

Optical properties of hybrid spherical nanoclusters containing quantum emitters and metallic nanoparticles

NASA Astrophysics Data System (ADS)

Yannopapas, V.; Paspalakis, E.

2018-05-01

We study theoretically the optical response of a hybrid spherical cluster containing quantum emitters and metallic nanoparticles. The quantum emitters are modeled as two-level quantum systems whose dielectric function is obtained via a density matrix approach wherein the modified spontaneous emission decay rate at the position of each quantum emitter is calculated via the electromagnetic Green's tensor. The problem of light scattering off the hybrid cluster is solved by employing the coupled-dipole method. We find, in particular, that the presence of the quantum emitters in the cluster, even in small fractions, can significantly alter the absorption and extinction spectra of the sole cluster of the metallic nanoparticles, where the corresponding electromagnetic modes can have a weak plexcitonic character under suitable conditions.

Quantum chemical calculation of the equilibrium structures of small metal atom clusters

NASA Technical Reports Server (NTRS)

Kahn, L. R.

1982-01-01

Metal atom clusters are studied based on the application of ab initio quantum mechanical approaches. Because these large 'molecular' systems pose special practical computational problems in the application of the quantum mechanical methods, there is a special need to find simplifying techniques that do not compromise the reliability of the calculations. Research is therefore directed towards various aspects of the implementation of the effective core potential technique for the removal of the metal atom core electrons from the calculations.

Structure of transition-metal cluster compounds: Use of an additional orbital resulting from the f, g character of spd bond orbitals*

PubMed Central

Pauling, Linus

1977-01-01

A general theory of the structure of complexes of the transition metals is developed on the basis of the enneacovalence of the metals and the requirements of the electroneutrality principle. An extra orbital may be provided through the small but not negligible amount of f and g character of spd bond orbitals, and an extra electron or electron pair may be accepted in this orbital for a single metal or a cluster to neutralize the positive electric charge resulting from the partial ionic character of the bonds with ligands, such as the carbonyl group. Examples of cluster compounds of cobalt, ruthenium, rhodium, osmium, and gold are discussed. PMID:16592470

Structure of transition-metal cluster compounds: Use of an additional orbital resulting from the f, g character of spd bond orbitals.

PubMed

Pauling, L

1977-12-01

A general theory of the structure of complexes of the transition metals is developed on the basis of the enneacovalence of the metals and the requirements of the electroneutrality principle. An extra orbital may be provided through the small but not negligible amount of f and g character of spd bond orbitals, and an extra electron or electron pair may be accepted in this orbital for a single metal or a cluster to neutralize the positive electric charge resulting from the partial ionic character of the bonds with ligands, such as the carbonyl group. Examples of cluster compounds of cobalt, ruthenium, rhodium, osmium, and gold are discussed.

Tuning the Emission and Quantum Yield of Gold and Silver Nanoclusters Through Ligand Design and Doping

NASA Astrophysics Data System (ADS)

Mishra, Dinesh

Nanoparticles have been extensively studied in the past few decades due to the possibilities they offer in applications ranging from medicine to energy generation. A new class of ultra-small noble metal nanoparticles consisting of tens to hundreds of atoms, commonly known as clusters or nanoclusters, have drawn interest of the research community recently due to their unique optical, electronic and structural properties. Over the past few years, advances have been made in the synthesis of atomically precise noble metal clusters (for example, silver and gold) with distinct optical properties. Their ultra-small size distinguishes them from conventional plasmonic nanoparticles and the properties are very sensitive to the slight variation in the compositon of the cluster, i.e. the number of the metal atoms and/or the nature of the ligands. These clusters are interesting because of their potential applications in field such as sensing, imaging, catalysis, clean energy, photonics, etc. as well as they provide fundamental insight into the evolution of the optical and electronic properties of these clusters. In this project, we explored the strategies to synthesize luminescent metallic clusters of gold and silver and to promote their solubility and stability in aqueous and biological medium. We focused particularly on the thiolate protected clusters due to the higher affinity of gold and silver to sulfur. Lipoic acid (Thioctic acid) is a bio-molecule with a cyclic disulfide ring, which also acts as a chelating ligand. Due to the higher binding affinity of the cyclic disulfide ring to nanocrystal surface, lipoic acid and chemically modified lipoic acid molecules have been widely reported for the synthesis and functionalization of inorganic nanocrystals. Here, we describe the use of bidentate lipoic acid ligands in the one phase growth of luminescent gold and silver nanoclusters. In addition, we have synthesized a new set of monothiol ligands containing PEG and zwitterion for the functionalization of fluorescent clusters. Chapter 1 introduces the fundamental properties of metallic clusters and the origin of these properties from electronic and structural point of view. The optical properties of ultra-small nanocrystals (<2 nm) in comparison to the plasmonic particles is described. In addition, the variation of optical and structural properties from one metal to another as well as one ligand to another is also compared. Chapter 2 describes the synthesis of ultra-small size gold clusters with different optical emission (ranging from blue to red) using photo-activated LA-PEG ligands. The influence of various factors on the growth of the clusters is also studied. Optical properties of the clusters were studied by UV-visible absorption, PL emission and excitation and time resolved fluorescence spectroscopy. XPS and DOSY NMR were used to characterize the oxidation states and sizes of these clusters. The photo-chemical transformation of LA-PEG ligands to thiols and the effect of various experimental parameters such as solvent, oxygen, ligand functional group and effect of acid are described in chapter 3. Thiol yield percentage was quantified using ellman assay. Chapter 4 describes the one phase aqueous synthesis of Ag29 clusters capped with bidentate dihydrolipoic acid (DHLA). We also describe the drastic enhancement of the PL intensity upon gold doping of the Ag29 clusters. Optical properties along with the size characterization by electrospray ionization mass spectrometry is also described. We further describe the growth of these clusters using DHLA-PEG molecules. Chapter 5 describes the synthesis of highly fluorescent Au25-xAgx clusters stabilized with two types of ligands (triphenylphosphine and thiols). We designed a set of monothiolate ligands appended with PEG and zwitterionic moieties. This approach allows to prepare water soluble and stable metallic clusters with enhanced photoluminescence and well defined optical properties. Chapter 6 is the overall summary of our findings and prospects and outlook.

Slow Cooling in Low Metallicity Clouds: An Origin of Globular Cluster Bimodality?

NASA Astrophysics Data System (ADS)

Fernandez, Ricardo; Bryan, Greg L.

2018-05-01

We explore the relative role of small-scale fragmentation and global collapse in low-metallicity clouds, pointing out that in such clouds the cooling time may be longer than the dynamical time, allowing the cloud to collapse globally before it can fragment. This, we suggest, may help to explain the formation of the low-metallicity globular cluster population, since such dense stellar systems need a large amount of gas to be collected in a small region (without significant feedback during the collapse). To explore this further, we carry out numerical simulations of low-metallicity Bonner-Ebert stable gas clouds, demonstrating that there exists a critical metallicity (between 0.001 and 0.01 Z⊙) below which the cloud collapses globally without fragmentation. We also run simulations including a background radiative heating source, showing that this can also produce clouds that do not fragment, and that the critical metallicity - which can exceed the no-radiation case - increases with the heating rate.

Processes of conversion of a hot metal particle into aerogel through clusters

NASA Astrophysics Data System (ADS)

Smirnov, B. M.

2015-10-01

Processes are considered for conversion into a fractal structure of a hot metal micron-size particle that is located in a buffer gas or a gas flow and is heated by an external electric or electromagnetic source or by a plasma. The parameter of this heating is the particle temperature, which is the same in the entire particle volume because of its small size and high conductivity. Three processes determine the particle heat balance: particle radiation, evaporation of metal atoms from the particle surface, and heat transport to the surrounding gas due to its thermal conductivity. The particle heat balance is analyzed based on these processes, which are analogous to those for bulk metals with the small particle size, and its high temperature taken into account. Outside the particle, where the gas temperature is lower than on its surface, the formed metal vapor in a buffer gas flow is converted into clusters. Clusters grow as a result of coagulation until they become liquid, and then clusters form fractal aggregates if they are removed form the gas flow. Subsequently, associations of fractal aggregates join into a fractal structure. The rate of this process increases in medium electric fields, and the formed fractal structure has features of aerogels and fractal fibers. As a result of a chain of the above processes, a porous metal film may be manufactured for use as a filter or catalyst for gas flows.

Time-resolved in situ XAS study of the preparation of supported gold clusters.

PubMed

Bus, Eveline; Prins, Roel; van Bokhoven, Jeroen A

2007-07-07

Incipient-wetness impregnation of gamma-Al(2)O(3) with HAuCl(4) and subsequent removal of chlorine with NaOH, and deposition-precipitation of HAuCl(4) on TiO(2) at pH 7 resulted in supported Au(3+) species. Time-resolved in situ XAS at the Au L(3) edge showed that the Al(2)O(3)-supported oxidic or hydroxidic species were reduced in hydrogen at 440 K to yield small metallic gold clusters. The Au(3+) precursor decomposed to metallic gold in inert atmosphere at 573 K and in oxidizing atmosphere above 623 K. In all atmospheres, initially small clusters were formed that gradually grew with increasing temperature. The TiO(2)-supported species were considerably less stable. In hydrogen and carbon monoxide, Au(0) clusters of 1 to 1.5 nm were formed at room temperature, which was the lowest temperature studied. In inert and oxidizing atmosphere, the Au(3+) precursor decomposed fully to metallic gold at 530 K, as shown by XAS and temperature-programmed experiments. Large clusters were obtained already in the initial stage of reduction. Residual chlorine inhibited the reduction and led to sintering of the gold clusters. Exposure of the TiO(2)-supported catalyst precursor to light or the X-ray beam led to partial reduction, and STEM showed that storage of the reduced gold clusters under ambient conditions led to agglomeration and bimodal cluster-size distributions.

Coupled multipolar interactions in small-particle metallic clusters.

PubMed

Pustovit, Vitaly N; Sotelo, Juan A; Niklasson, Gunnar A

2002-03-01

We propose a new formalism for computing the optical properties of small clusters of particles. It is a generalization of the coupled dipole-dipole particle-interaction model and allows one in principle to take into account all multipolar interactions in the long-wavelength limit. The method is illustrated by computations of the optical properties of N = 6 particle clusters for different multipolar approximations. We examine the effect of separation between particles and compare the optical spectra with the discrete-dipole approximation and the generalized Mie theory.

Magnetic nanostructures.

PubMed

Bennemann, K

2010-06-23

Characteristic results of magnetism in small particles, thin films and tunnel junctions are presented. As a consequence of the reduced atomic coordination in small clusters and thin films the electronic states and density of states are modified. Thus, magnetic moments and magnetization are affected. Generally, in clusters and thin films magnetic anisotropy plays a special role. In tunnel junctions the interplay of magnetism, spin currents and superconductivity are of particular interest. In ring-like mesoscopic systems Aharonov-Bohm-induced currents are studied. Results are given for single transition metal clusters, cluster ensembles, thin films, mesoscopic structures and tunnel systems. © 2010 IOP Publishing Ltd

Scattering of ultrashort electromagnetic pulses on metal clusters

DOE Office of Scientific and Technical Information (OSTI.GOV)

Astapenko, V. A., E-mail: astval@mail.ru; Sakhno, S. V.

We have calculated and analyzed the probability of ultrashort electromagnetic pulse (USP) scattering on small metal clusters in the frequency range of plasmon resonances during the field action. The main attention is devoted to dependence of the probability of scattering on the pulse duration for various detunings of the USP carrier frequency from the plasmon resonance frequency. Peculiarities of the USP scattering from plasmon resonances with various figures of merit are revealed.

Scattering of ultrashort electromagnetic pulses on metal clusters

NASA Astrophysics Data System (ADS)

Astapenko, V. A.; Sakhno, S. V.

2016-12-01

We have calculated and analyzed the probability of ultrashort electromagnetic pulse (USP) scattering on small metal clusters in the frequency range of plasmon resonances during the field action. The main attention is devoted to dependence of the probability of scattering on the pulse duration for various detunings of the USP carrier frequency from the plasmon resonance frequency. Peculiarities of the USP scattering from plasmon resonances with various figures of merit are revealed.

Inherent size effects on XANES of nanometer metal clusters: Size-selected platinum clusters on silica

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dai, Yang; Gorey, Timothy J.; Anderson, Scott L.

2016-12-12

X-ray absorption near-edge structure (XANES) is commonly used to probe the oxidation state of metal-containing nanomaterials, however, as the particle size in the material drops below a few nanometers, it becomes important to consider inherent size effects on the electronic structure of the materials. In this paper, we analyze a series of size-selected Pt n/SiO 2 samples, using X-ray photoelectron spectroscopy (XPS), low energy ion scattering, grazing-incidence small angle X-ray scattering, and XANES. The oxidation state and morphology are characterized both as-deposited in UHV, and after air/O 2 exposure and annealing in H 2. Here, the clusters are found tomore » be stable during deposition and upon air exposure, but sinter if heated above ~150 °C. XANES shows shifts in the Pt L 3 edge, relative to bulk Pt, that increase with decreasing cluster size, and the cluster samples show high white line intensity. Reference to bulk standards would suggest that the clusters are oxidized, however, XPS shows that they are not. Instead, the XANES effects are attributable to development of a band gap and localization of empty state wavefunctions in small clusters.« less

Metal-cluster ionization energy: A profile-insensitive exact expression for the size effect

NASA Astrophysics Data System (ADS)

Seidl, Michael; Perdew, John P.; Brajczewska, Marta; Fiolhais, Carlos

1997-05-01

The ionization energy of a large spherical metal cluster of radius R is I(R)=W+(+c)/R, where W is the bulk work function and c~-0.1 is a material-dependent quantum correction to the electrostatic size effect. We present 'Koopmans' and 'displaced-profile change-in-self-consistent-field' expressions for W and c within the ordinary and stabilized-jellium models. These expressions are shown to be exact and equivalent when the exact density profile of a large neutral cluster is employed; these equivalences generalize the Budd-Vannimenus theorem. With an approximate profile obtained from a restricted variational calculation, the 'displaced-profile' expressions are the more accurate ones. This profile insensitivity is important, because it is not practical to extract c from solutions of the Kohn-Sham equations for small metal clusters.

Encapsulating Metal Clusters and Acid Sites within Small Voids: Synthetic Strategies and Catalytic Consequences

NASA Astrophysics Data System (ADS)

Goel, Sarika

The selective encapsulation of metal clusters within zeolites can be used to prepare clusters that are uniform in diameter and to protect them against sintering and contact with feed impurities, while concurrently allowing active sites to select reactants based on their molecular size, thus conferring enzyme-like specificity to chemical catalysis. The apertures in small and medium-pore zeolites preclude the use of post-synthetic protocols to encapsulate the relevant metal precursors because cationic or anionic precursors with their charge-balancing double layer and gaseous complexes cannot diffuse through their windows or channels. We have developed general strategies to encapsulate metal clusters within small-pore zeolites by using metal precursors stabilized by ammonia or organic amine ligands, which stabilize metal precursors against their premature precipitation at the high temperature and pH conditions required for the hydrothermal synthesis of the target zeolite structures and favor interactions between metal precursors and incipient aluminosilicate nuclei during the self-assembly of microporous frameworks. When synthesis temperatures were higher than 400 K, available ligands were unable to prevent the premature precipitation of the metal precursors. In such cases, encapsulation was achieved instead via interzeolite transformations after successfully encapsulating metal precursors or clusters via post-synthesis exchange or ligand protection into parent zeolites and subsequently converting them into the target structures while retaining the encapsulated clusters or precursors. Such strategies led to the successful selective encapsulation of a wide range of metal clusters (Pt, Pd, Ru, Rh, Ir, Re, and Ag) within small-pore (SOD (sodalite), LTA (Linde type A (zeolite A)), GIS (gismondine), and ANA (analcime)) and medium-pore (MFI (ZSM-5)) zeolites. These protocols provide novel and diverse mechanism-based strategies for the design of catalysts with protected active sites. We have demonstrated the selectivity of the encapsulation processes by combining transmission electron microscopy and chemisorptive titrations with rigorous catalytic assessments of the ability of these materials to catalyze reactions of small molecules, which can access the intracrystalline voids, but not of larger molecules that cannot access the metal clusters within such voids. The selective confinement of clusters also prevented their contact with sulfur compounds (e.g., thiophene and H2S), thus allowing reactions to occur at conditions that otherwise render unconfined clusters unreactive. We have also developed synthetic protocols and guiding principles, inspired by mechanistic considerations, for the synthesis of zeolites via interzeolite transformations without the use of organic structure-directing agents (OSDA). More specifically, we have synthesized high-silica MFI (ZSM-5), CHA (chabazite), STF (SSZ-35) and MTW (ZSM-12) zeolites from FAU (faujasite) or BEA (beta) parent materials. Structures with lower framework densities (FAU or BEA) were successfully transformed into thermodynamically-favored, more stable structures with higher framework densities (MFI, CHA, STF, and MTW); to date, target materials with higher Si/Al ratios (Si/Al >10) have not been synthesized via interzeolite transformations without the aid of the OSDA species used to discover these zeolite structures and deemed essential up until now for their successful synthesis. Overcoming kinetic hurdles in such transformations required either the presence of common composite building units (CBU) between parent and target structures or, in their absence, the introduction of small amount of seeds of the daughter structures. The NaOH/SiO2 ratio, H2O/SiO2 ratio and Al content in reagents are used to enforce synchronization between the swelling and local restructuring within parent zeolite domains with the spalling of fragments or building units from seeds of the target structure. The pseudomorphic nature of these seed-mediated transformations, which conserve the volume occupied by the parent crystals and lead to similar size and crystal shape in products, reflect incipient nucleation of target structures occurring at the outer regions of the parent domains and lead to the formation of mesoporosity as a natural consequence of the space-conserving nature of these structural changes and of the higher density of the daughter frameworks. The synthesis mechanism and the guidelines developed enable us to enforce conditions required for the formation of zeolites that previously required OSDA species for their synthesis, thus expanding to a significant extent the diversity of zeolite frameworks that are accessible via these synthesis protocols and providing potential savings in the time and cost involved in the synthesis of some of these zeolite structures.

The formation of the smallest fullerene-like carbon cages on metal surfaces

NASA Astrophysics Data System (ADS)

Ben Romdhane, F.; Rodríguez-Manzo, J. A.; Andrieux-Ledier, A.; Fossard, F.; Hallal, A.; Magaud, L.; Coraux, J.; Loiseau, A.; Banhart, F.

2016-01-01

The nucleation and growth of carbon on catalytically active metal surfaces is one of the most important techniques to produce nanomaterials such as graphene or nanotubes. Here it is shown by in situ electron microscopy that fullerene-like spherical clusters with diameters down to 0.4 nm and thus much smaller than C60 grow in a polymerized state on Co, Fe, or Ru surfaces. The cages appear on the surface of metallic islands in contact with graphene under heating to at least 650 °C and successively cooling to less than 500 °C. The formation of the small cages is explained by the segregation of carbon on a supersaturated metal, driven by kinetics. First principles energy calculations show that the clusters polymerize and can be attached to defects in graphene. Under compression, the polymerized cages appear in a crystalline structure.The nucleation and growth of carbon on catalytically active metal surfaces is one of the most important techniques to produce nanomaterials such as graphene or nanotubes. Here it is shown by in situ electron microscopy that fullerene-like spherical clusters with diameters down to 0.4 nm and thus much smaller than C60 grow in a polymerized state on Co, Fe, or Ru surfaces. The cages appear on the surface of metallic islands in contact with graphene under heating to at least 650 °C and successively cooling to less than 500 °C. The formation of the small cages is explained by the segregation of carbon on a supersaturated metal, driven by kinetics. First principles energy calculations show that the clusters polymerize and can be attached to defects in graphene. Under compression, the polymerized cages appear in a crystalline structure. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr08212a

Ab initio investigation on hydrogen adsorption capability in Zn and Cu-based metal organic frameworks

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tanuwijaya, V. V., E-mail: viny.veronika@gmail.com; Hidayat, N. N., E-mail: avantgarde.vee@gmail.com; Agusta, M. K., E-mail: kemal@fti.itb.ac.id

2015-09-30

One of the biggest challenge in material technology for hydrogen storage application is to increase hydrogen uptake in room temperature and pressure. As a class of highly porous material, Metal-Organic Frameworks (MOF) holds great potential with its tunable structure. However, little is known about the effect of metal cluster to its hydrogen storage capability. Investigation on this matter has been carried out carefully on small cluster of Zn and Cu-based MOF using first principles method. The calculation of two distinct building units of MOFs, namely octahedral and paddle-wheel models, have been done with B3LYP density functional method using 6-31G(d,p) andmore » LANL2DZ basis sets. From geometry optimization of Zn-based MOF linked by benzene-dicarboxylate (MOF-5), it is found that hydrogen tends to keep distance from metal cluster group and stays above benzene ring. In the other hand, hydrogen molecule prefers to stay atop of the exposed Cu atom in Cu-based MOF system linked by the same linker group (Cu-bdc). Calculated hydrogen binding enthalpies for Zn and Cu octahedral cages at ZnO{sub 3} sites are 1.64kJ/mol and 2.73kJ/mol respectively, while hydrogen binding enthalpies for Zn and Cu paddle-wheel cages calculated on top of metal atoms are found to be at 6.05kJ/mol and 6.10kJ/mol respectively. Major difference between Zn-MOF-5 and Cu-bdc hydrogen uptake performance might be caused by unsaturated metal sites present in Cu-bdc system and the influence of their geometric structures, although a small difference on binding energy in the type of transition metal used is also observed. The comparison between Zn and Cu-based MOF may contribute to a comprehensive understanding of metal clusters and the importance of selecting best transition metal for design and synthesis of metal-organic frameworks.« less

Computational evaluation of sub-nanometer cluster activity of singly exposed copper atom with various coordinative environment in catalytic CO2 transformation

NASA Astrophysics Data System (ADS)

Shanmugam, Ramasamy; Thamaraichelvan, Arunachalam; Ganesan, Tharumeya Kuppusamy; Viswanathan, Balasubramanian

2017-02-01

Metal cluster, at sub-nanometer level has a unique property in the activation of small molecules, in contrast to that of bulk surface. In the present work, singly exposed active site of copper metal cluster at sub-nanometer level was designed to arrive at the energy minimised configurations, binding energy, electrostatic potential map, frontier molecular orbitals and partial density of states. The ab initio molecular dynamics was carried out to probe the catalytic nature of the cluster. Further, the stability of the metal cluster and its catalytic activity in the electrochemical reduction of CO2 to CO were evaluated by means of computational hydrogen electrode via calculation of the free energy profile using DFT/B3LYP level of theory in vacuum. The activity of the cluster is ascertained from the fact that the copper atom, present in a two coordinative environment, performs a more selective conversion of CO2 to CO at an applied potential of -0.35 V which is comparatively lower than that of higher coordinative sites. The present study helps to design any sub-nano level metal catalyst for electrochemical reduction of CO2 to various value added chemicals.

Temperature-programmed reduction of Pt-Ir/. gamma. -Al/sub 2/O/sub 3/ catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wagstaff, N.; Prins, R.

1979-10-15

An intriguing feature of the evidence for the existence of Pt-Re clusters in the reduced state of the catalyst, Pt-Re/..gamma..-Al/sub 2/O/sub 3/ was the segregation of Pt and Re oxides observed after oxidation of the bimetallic clusters at temperatures above about 200/sup 0/C. Evidently, the oxide moieties are immiscible on the scale of the small clusters (up to 10 to 15 atoms) in the case of these metals. The present results for Pt-Ir/..gamma..-Al/sub 2/O/sub 3/ represent an example of a supported, highly dispersed system in which the intimacy of the metals remains intact even after fairly severe oxidation treatments. Studymore » of other bimetallic system on alumina by TPR should yield further valuable information on this interesting aspect of metal cluster behavior. 1 figure.« less

Catalysis applications of size-selected cluster deposition

DOE PAGES

Vajda, Stefan; White, Michael G.

2015-10-23

In this Perspective, we review recent studies of size-selected cluster deposition for catalysis applications performed at the U.S. DOE National Laboratories, with emphasis on work at Argonne National Laboratory (ANL) and Brookhaven National Laboratory (BNL). The focus is on the preparation of model supported catalysts in which the number of atoms in the deposited clusters is precisely controlled using a combination of gas-phase cluster ion sources, mass spectrometry, and soft-landing techniques. This approach is particularly effective for investigations of small nanoclusters, 0.5-2 nm (<200 atoms), where the rapid evolution of the atomic and electronic structure makes it essential to havemore » precise control over cluster size. Cluster deposition allows for independent control of cluster size, coverage, and stoichiometry (e.g., the metal-to-oxygen ratio in an oxide cluster) and can be used to deposit on any substrate without constraints of nucleation and growth. Examples are presented for metal, metal oxide, and metal sulfide cluster deposition on a variety of supports (metals, oxides, carbon/diamond) where the reactivity, cluster-support electronic interactions, and cluster stability and morphology are investigated. Both UHV and in situ/operando studies are presented that also make use of surface-sensitive X-ray characterization tools from synchrotron radiation facilities. Novel applications of cluster deposition to electrochemistry and batteries are also presented. This review also highlights the application of modern ab initio electronic structure calculations (density functional theory), which can essentially model the exact experimental system used in the laboratory (i.e., cluster and support) to provide insight on atomic and electronic structure, reaction energetics, and mechanisms. As amply demonstrated in this review, the powerful combination of atomically precise cluster deposition and theory is able to address fundamental aspects of size-effects, cluster-support interactions, and reaction mechanisms of cluster materials that are central to how catalysts function. Lastly, the insight gained from such studies can be used to further the development of novel nanostructured catalysts with high activity and selectivity.« less

Theoretical study of the electronic and optical properties of photochromic dithienylethene derivatives connected to small gold clusters.

PubMed

Perrier, Aurélie; Maurel, François; Aubard, Jean

2007-10-04

In the course of developing electronic devices on a molecular scale, dithienylethenes photochromic molecules constitute promising candidates for optoelectronic applications such as memories and switches. There is thus a great interest to understand and control the switching behavior of photochromic compounds deposited on metallic surfaces or nanoparticles. Within the framework of the density functional theory, we studied the effect of small gold clusters (Au3 and Au9) on the electronic structure and absorption spectrum of a model dithienylethene molecule. The molecular orbital interactions between the photochromic molecule and the gold cluster made it possible to rationalize some experimental findings (Dulic, D.; van der Molen, S. J.; Kudernac, T.; Jonkman, H. T.; de Jong, J. J. D.; Bowden, T. N.; van Esch, J.; Feringa, B. L.; van Wees, B. J. Phys. Rev. Lett. 2003, 91, 207402). For the closed-ring isomer, grafting a photochromic molecule on a small gold cluster does not change the characteristics of the electronic transition involved in the ring-opening reaction. On the opposite, the absorption spectrum of the photochromic open-ring isomer is strongly modified by the inclusion of the metallic cluster. In agreement with experimental results, our study thus showed that the cycloreversion reaction which involves the closed-ring isomer should be still possible, whereas the ring-closure reaction which involves the open-ring isomer should be inhibited. Connecting a dithienylethene molecule to a small gold cluster hence provides a qualitative comprehension of the photochromic activities of dithienylethenes connected to a gold surface.

Photon-Induced Thermal Desorption of CO from Small Metal-Carbonyl Clusters

NASA Astrophysics Data System (ADS)

Lüttgens, G.; Pontius, N.; Bechthold, P. S.; Neeb, M.; Eberhardt, W.

2002-02-01

Thermal CO desorption from photoexcited free metal-carbonyl clusters has been resolved in real time using two-color pump-probe photoelectron spectroscopy. Sequential energy dissipation steps between the initial photoexcitation and the final desorption event, e.g., electron relaxation and thermalization, have been resolved for Au2(CO)- and Pt2(CO)-5. The desorption rates for the two clusters differ considerably due to the different numbers of vibrational degrees of freedom. The unimolecular CO-desorption thresholds of Au2(CO)- and Pt2(CO)-5 have been approximated by means of a statistical Rice-Ramsperger-Kassel calculation using the experimentally derived desorption rate constants.

Formation of fivefold axes in the FCC-metal nanoclusters

NASA Astrophysics Data System (ADS)

Myasnichenko, Vladimir S.; Starostenkov, Mikhail D.

2012-11-01

Formation of atomistic structures of metallic Cu, Au, Ag clusters and bimetallic Cu-Au clusters was studied with the help of molecular dynamics using the many-body tight-binding interatomic potential. The simulation of the crystallization process of clusters with the number of atoms ranging from 300 to 1092 was carried out. The most stable configurations of atoms in the system, corresponding to the minimum of potential energy, was found during super-fast cooling from 1000 K. Atoms corresponding to fcc, hcp, and Ih phases were identified by the method of common neighbor analysis. Incomplete icosahedral core can be discovered at the intersection of one of the Ih axes with the surface of monometallic cluster. The decahedron-shaped structure of bimetallic Cu-Au cluster with seven completed icosahedral cores was obtained. The principles of the construction of small bimetallic clusters with icosahedral symmetry and increased fractal dimensionality were offered.

Electronic structure, stability and magnetic properties of small M1-2Cr (M = Fe, Co, and Ni) alloy encapsulated inside a (BN)48 cage

NASA Astrophysics Data System (ADS)

Liang, Wenjuan; Jia, Jianfeng; Lv, Jin; Wu, Haishun

2015-09-01

The geometrical structure and magnetic properties of M1-2Cr (M = Fe, Co, and Ni) alloy clusters inside a (BN)48 cage were calculated at the BPW91/LANL2DZ level of theory. The doping with Cr significantly changed the magnetic properties of the transition-metal clusters. When M1-2Cr alloys were placed inside a (BN)48 cage, the alloy clusters interacted strongly with the cage, and the M1-2Cr@(BN)48 clusters showed high stability. Moreover, Cr-doped magnetic metal clusters preferably occupied positions off-center and near the hexagonal rings of (BN)48 cages. Thus, the (BN)48 cages can be used to increase the stability of M1-2Cr alloys, and retain their magnetic nature, except for CoCr and Ni2Cr clusters.

Application and Limitations of Nanocasting in Metal–Organic Frameworks

DOE Office of Scientific and Technical Information (OSTI.GOV)

Malonzo, Camille D.; Wang, Zhao; Duan, Jiaxin

Nanocasting can be a useful strategy to transfer the catalytic metal clusters in metal-organic frameworks (MOFs) to an all-inorganic support such as silica. The incorporation of silica in the MOF pores as a secondary support has the potential to extend the application of the highly tunable metal-based active sites in MOFs to high temperature catalysis. Here, we demonstrate the applicability of the nanocasting method to a range of MOFs that incorporate catalytically attractive hexazirconium, hexacerium, or pentanickel oxide-based clusters (UiO-66, (Ce)UiO-66, (Ce)UiO-67, (Ce)MOF-808, DUT-9, and In- and Ni-post-metalated NU-1000). We describe, in tutorial form, the challenges associated with nanocasting ofmore » MOFs that are related to their small pore size and to considerations of chemical and mechanical stability, and we provide approaches to overcome some of these challenges. Some of these nanocast materials feature the site-isolated clusters in a porous, thermally stable silica matrix, suitable for catalysis at high temperatures; in others, structural rearrangement of clusters or partial cluster aggregation occurs, but extensive aggregation can be mitigated by the silica skeleton introduced during nanocasting.« less

The Chemistry of Population III Supernova Ejecta. II. The Nucleation of Molecular Clusters as a Diagnostic for Dust in the Early Universe

NASA Astrophysics Data System (ADS)

Cherchneff, Isabelle; Dwek, Eli

2010-04-01

We study the formation of molecular precursors to dust in the ejecta of Population III supernovae (Pop. III SNe) using a chemical kinetic approach to follow the evolution of small dust cluster abundances from day 100 to day 1000 after explosion. Our work focuses on zero-metallicity 20 M sun and 170 M sun progenitors, and we consider fully macroscopically mixed and unmixed ejecta. The dust precursors comprise molecular chains, rings, and small clusters of chemical composition relevant to the initial elemental composition of the ejecta under study. The nucleation stage for small silica, metal oxides and sulfides, pure metal, and carbon clusters is described with a new chemical reaction network highly relevant to the kinetic description of dust formation in hot circumstellar environments. We consider the effect of the pressure dependence of critical nucleation rates and test the impact of microscopically mixed He+ on carbon dust formation. Two cases of metal depletion on silica clusters (full and no depletion) are considered to derive upper limits to the amounts of dust produced in SN ejecta at 1000 days, while the chemical composition of clusters gives a prescription for the type of dust formed in Pop. III SNe. We show that the cluster mass produced in the fully mixed ejecta of a 170 M sun progenitor is ~ 25 M sun whereas its 20 M sun counterpart forms ~ 0.16 M sun of clusters. The unmixed ejecta of a 170 M sun progenitor SN synthesize ~5.6 M sun of small clusters, while its 20 M sun counterpart produces ~0.103 M sun. Our results point to smaller amounts of dust formed in the ejecta of Pop. III SNe by a factor of ~ 5 compared to values derived by previous studies, and to different dust chemical compositions. Such deviations result from some erroneous assumptions made, the inappropriate use of classical nucleation theory to model dust formation, and the omission of the synthesis of molecules in SN ejecta. We also find that the unmixed ejecta of massive Pop. III SNe chiefly form silica and/or silicates, and pure silicon grains whereas their lower mass counterparts form a dust mixture dominated by silica and/or silicates, pure silicon, and iron sulfides. Amorphous carbon can only condense via the nucleation of carbon chains and rings characteristic of the synthesis of fullerenes when the ejecta carbon-rich zone is deprived of He+. The first dust enrichment to the primordial gas in the early universe from Pop. III massive SN comprises primarily pure silicon, silica, and silicates. If carbon dust is present at redshift z > 6, alternative dust sources must be considered.

The Electronic Structure of Transition Metal Coated Fullerenes

NASA Astrophysics Data System (ADS)

Patton, David C.; Pederson, Mark R.; Kaxiras, Efthimios

1998-03-01

Clusters composed of fullerene molecules with an outer shell of transition metal atoms in the composition C_60M_62 (M being a transition metal) have been produced with laser vaporisation techniques(F. Tast, N. Malinowski, S. Frank, M. Heinebrodt, I.M.L. Billas, and T. P. Martin, Z. Phys D 40), 351 (1997).. We have studied several of these very large systems with a parallel version of the all-electron NRLMOL cluster code. Optimized geometries of the metal encased fullerenes C_60Ti_62 and C_60V_62 are presented along with their HOMO-LUMO gaps, electron affinities, ionization energies, and cohesive energies. We compare the stability of these clusters to relaxed met-car structures (e.g. Ti_8C_12) and to relaxed rocksalt metal-carbide fragments (TiC)n with n=8 and 32. In addition to metal-coated fullerenes we consider the possibility of a trilayered structure consisting of a small shell of metal atoms enclosed by a metal coated fullerene. The nature of bonding in these systems is analyzed by studying the electronic charge distributions.

Effect of Spin Multiplicity in O2 Adsorption and Dissociation on Small Bimetallic AuAg Clusters.

PubMed

García-Cruz, Raúl; Poulain, Enrique; Hernández-Pérez, Isaías; Reyes-Nava, Juan A; González-Torres, Julio C; Rubio-Ponce, A; Olvera-Neria, Oscar

2017-08-17

To dispose of atomic oxygen, it is necessary the O 2 activation; however, an energy barrier must be overcome to break the O-O bond. This work presents theoretical calculations of the O 2 adsorption and dissociation on small pure Au n and Ag m and bimetallic Au n Ag m (n + m ≤ 6) clusters using the density functional theory (DFT) and the zeroth-order regular approximation (ZORA) to explicitly include scalar relativistic effects. The most stable Au n Ag m clusters contain a higher concentration of Au with Ag atoms located in the center of the cluster. The O 2 adsorption energy on pure and bimetallic clusters and the ensuing geometries depend on the spin multiplicity of the system. For a doublet multiplicity, O 2 is adsorbed in a bridge configuration, whereas for a triplet only one O-metal bond is formed. The charge transfer from metal toward O 2 occupies the σ* O-O antibonding natural bond orbital, which weakens the oxygen bond. The Au 3 ( 2 A) cluster presents the lowest activation energy to dissociate O 2 , whereas the opposite applies to the AuAg ( 3 A) system. In the O 2 activation, bimetallic clusters are not as active as pure Au n clusters due to the charge donated by Ag atoms being shared between O 2 and Au atoms.

Photo-induced transformation process at gold clusters-semiconductor interface: Implications for the complexity of gold clusters-based photocatalysis

NASA Astrophysics Data System (ADS)

Liu, Siqi; Xu, Yi-Jun

2016-03-01

The recent thrust in utilizing atomically precise organic ligands protected gold clusters (Au clusters) as photosensitizer coupled with semiconductors for nano-catalysts has led to the claims of improved efficiency in photocatalysis. Nonetheless, the influence of photo-stability of organic ligands protected-Au clusters at the Au/semiconductor interface on the photocatalytic properties remains rather elusive. Taking Au clusters-TiO2 composites as a prototype, we for the first time demonstrate the photo-induced transformation of small molecular-like Au clusters to larger metallic Au nanoparticles under different illumination conditions, which leads to the diverse photocatalytic reaction mechanism. This transformation process undergoes a diffusion/aggregation mechanism accompanied with the onslaught of Au clusters by active oxygen species and holes resulting from photo-excited TiO2 and Au clusters. However, such Au clusters aggregation can be efficiently inhibited by tuning reaction conditions. This work would trigger rational structural design and fine condition control of organic ligands protected-metal clusters-semiconductor composites for diverse photocatalytic applications with long-term photo-stability.

COMPARING MID-INFRARED GLOBULAR CLUSTER COLORS WITH POPULATION SYNTHESIS MODELS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Barmby, P.; Jalilian, F. F.

2012-04-15

Several population synthesis models now predict integrated colors of simple stellar populations in the mid-infrared bands. To date, the models have not been extensively tested in this wavelength range. In a comparison of the predictions of several recent population synthesis models, the integrated colors are found to cover approximately the same range but to disagree in detail, for example, on the effects of metallicity. To test against observational data, globular clusters (GCs) are used as the closest objects to idealized groups of stars with a single age and single metallicity. Using recent mass estimates, we have compiled a sample ofmore » massive, old GCs in M31 which contain enough stars to guard against the stochastic effects of small-number statistics, and measured their integrated colors in the Spitzer/IRAC bands. Comparison of the cluster photometry in the IRAC bands with the model predictions shows that the models reproduce the cluster colors reasonably well, except for a small (not statistically significant) offset in [4.5] - [5.8]. In this color, models without circumstellar dust emission predict bluer values than are observed. Model predictions of colors formed from the V band and the IRAC 3.6 and 4.5 {mu}m bands are redder than the observed data at high metallicities and we discuss several possible explanations. In agreement with model predictions, V - [3.6] and V - [4.5] colors are found to have metallicity sensitivity similar to or slightly better than V - K{sub s}.« less

Probing the Adsorption of Carbon Monoxide on Transition Metal Clusters Using IR Action Spectroscopy

NASA Astrophysics Data System (ADS)

Lapoutre, Vivike J. F.; Oomens, Jos; Bakker, Joost M.

2012-06-01

The discovery of enhanced catalytic activity of small gold clusters has led to a great interest in size-dependent catalytic properties of metal clusters. To obtain a better understanding of the catalytic mechanisms it is essential to know the structures of these clusters and the nature of their interaction with reactant molecules. We have studied the structure of gas-phase niobium clusters with a carbon monoxide adsorbed using IR action spectroscopy. We present size-selective IR spectra obtained via IR multiple photon spectroscopy monitoring either photodetachment or photodissociation depending on the charge state. The combination of these spectra with DFT calculations allows for the structural determination of the adsorption product. M. Haruta et al., Journal of Catalysis 115 301-309 (1989). M. Haertelt et al., The Journal of Physical Chemistry Letters 2 1720-1724 (2011)

Photo-induced transformation process at gold clusters-semiconductor interface: Implications for the complexity of gold clusters-based photocatalysis

PubMed Central

Liu, Siqi; Xu, Yi-Jun

2016-01-01

The recent thrust in utilizing atomically precise organic ligands protected gold clusters (Au clusters) as photosensitizer coupled with semiconductors for nano-catalysts has led to the claims of improved efficiency in photocatalysis. Nonetheless, the influence of photo-stability of organic ligands protected-Au clusters at the Au/semiconductor interface on the photocatalytic properties remains rather elusive. Taking Au clusters–TiO2 composites as a prototype, we for the first time demonstrate the photo-induced transformation of small molecular-like Au clusters to larger metallic Au nanoparticles under different illumination conditions, which leads to the diverse photocatalytic reaction mechanism. This transformation process undergoes a diffusion/aggregation mechanism accompanied with the onslaught of Au clusters by active oxygen species and holes resulting from photo-excited TiO2 and Au clusters. However, such Au clusters aggregation can be efficiently inhibited by tuning reaction conditions. This work would trigger rational structural design and fine condition control of organic ligands protected-metal clusters-semiconductor composites for diverse photocatalytic applications with long-term photo-stability. PMID:26947754

Control of wavepacket dynamics in mixed alkali metal clusters by optimally shaped fs pulses

NASA Astrophysics Data System (ADS)

Bartelt, A.; Minemoto, S.; Lupulescu, C.; Vajda, Š.; Wöste, L.

We have performed adaptive feedback optimization of phase-shaped femtosecond laser pulses to control the wavepacket dynamics of small mixed alkali-metal clusters. An optimization algorithm based on Evolutionary Strategies was used to maximize the ion intensities. The optimized pulses for NaK and Na2K converged to pulse trains consisting of numerous peaks. The timing of the elements of the pulse trains corresponds to integer and half integer numbers of the vibrational periods of the molecules, reflecting the wavepacket dynamics in their excited states.

Stabilization of Small Boron Cage by Transition Metal Encapsulation

NASA Astrophysics Data System (ADS)

Zhang, Lijun; Lv, Jian; Wang, Yanchao; Ma, Yanming

2015-03-01

The discovery of chemically stable fullerene-like structures formed by elements other than carbon has been long-standing desired. On this aspect significant efforts have centered around boron, only one electron deficient compared with carbon. However, during the past decade a large number of experimental and theoretical studies have established that small boron clusters are either planar/quasi-planar or forming double-ring tubular structures. Until recently, two all-boron fullerenes have been independently discovered: B38 proposed by our structure searching calculations and B40 observed in a joint experimental and theoretical study. Here we extend our work to the even smaller boron clusters and propose an effective routine to stabilize them by transition metal encapsulation. By combining swarm-intelligence structure searching and first-principles calculations, we have systematically investigated the energy landscapes of transition-metal-doped MB24 clusters (M = Ti, Zr, Hf, Cr, Mo, W, Fe, Ru and Os). Two stable symmetric endohedral boron cages, MoB24 and WB24 are identified. The stability of them can be rationalized in terms of their unique 18-electron closed-shell electronic structures. Funded by Recruitment Program of Global Experts of China and China Postdoctoral Science Foundation.

New mechanisms of cluster diffusion on metal fcc(100) surfaces

NASA Astrophysics Data System (ADS)

Trushin, Oleg; Salo, Petri; Alatalo, Matti; Ala-Nissila, Tapio

2001-03-01

We have studied atomic mechanisms of the diffusion of small clusters on the fcc(100) metal surfaces using semi-empirical and ab-initio molecular static calculations. Primary goal of these studies was to investigate possible many-body mechanisms of cluster motion which can contribute to low temperature crystal growth. We used embedded atom and Glue potentials in semi-empirical simulations of Cu and Al. Combination of the Nudged Elastic Band and Eigenvector Following methods allowed us to find all the possible transition paths for cluster movements on flat terrace. In case of Cu(001) we have found several new mechanisms for diffusion of clusters, including mechanisms called row-shearing and dimer-rotating in which a whole row inside an island moves according to a concerted jump and a dimer rotates at the periphery of an island, respectively. In some cases these mechanisms yield a lower energy barrier than the standard mechanisms.

Keeping the ball rolling: fullerene-like molecular clusters.

PubMed

Kong, Xiang-Jian; Long, La-Sheng; Zheng, Zhiping; Huang, Rong-Bin; Zheng, Lan-Sun

2010-02-16

The discovery of fullerenes in 1985 opened a new chapter in the chemistry of highly symmetric molecules. Fullerene-like metal clusters, characterized by (multi)shell-like structures, are one rapidly developing class of molecules that share this shape. In addition to creating aesthetically pleasing molecular structures, the ordered arrangement of metal atoms within such frameworks provides the opportunity to develop materials with properties not readily achieved in corresponding mononuclear or lower-nuclearity complexes. In this Account, we survey the great variety of fullerene-like metal-containing clusters with an emphasis on their synthetic and structural chemistry, a first step in the discussion of this fascinating field of cluster chemistry. We group the compounds of interest into three categories based on the atomic composition of the cluster core: those with formal metal-metal bonding, those characterized by ligand participation, and those supported by polyoxometalate building blocks. The number of clusters in the first group, containing metal-metal bonds, is relatively small. However, because of the unique and complex bonding scenarios observed for some of these species, these metalloid clusters present a number of research questions with significant ramifications. Because these cores contain molecular clusters of precious metals at the nanoscale, they offer an opportunity to study chemical properties at size ranges from the molecular to nanoscale and to gain insights into the electronic structures and properties of nanomaterials of similar chemical compositions. Clusters of the second type, whose core structures are facilitated by ligand participation, could aid in the development of functional materials. Of particular interest are the magnetic clusters containing both transition and lanthanide elements. A series of such heterometallic clusters that we prepared demonstrates diverse magnetic properties including antiferromagnetism, ferrimagnetism, and ferromagnetism. Considering the diversity of their composition, their distinct electronic structures, and the disparate coordination behaviors of the different metal elements, these materials suggest abundant opportunities for designing multifunctional materials with varied structures. The third type of clusters that we discuss are based on polyoxometalates, in particular those containing pentagonal units. However, unlike in fullerene chemistry, which does not allow the use of discrete pentagonal building blocks, the metal oxide-based pentagonal units can be used as fundamental building blocks for constructing various Keplerate structures. These structures also have a variety of functions, including intriguing magnetic properties in some cases. Coupled with different linking groups, such pentagonal units can be used for the assembly of a large number of spherical molecules whose properties can be tuned and optimized. Although this Account focuses on the topological aspects of fullerene-like metal clusters, we hope that this topical review will stimulate more efforts in the exploratory synthesis of new fullerene-like clusters. More importantly, we hope that further study of the bonding interactions and properties of these molecules will lead to the development of new functional materials.

Polymorphism in magic-sized Au144(SR)60 clusters

NASA Astrophysics Data System (ADS)

Jensen, Kirsten M. Ø.; Juhas, Pavol; Tofanelli, Marcus A.; Heinecke, Christine L.; Vaughan, Gavin; Ackerson, Christopher J.; Billinge, Simon J. L.

2016-06-01

Ultra-small, magic-sized metal nanoclusters represent an important new class of materials with properties between molecules and particles. However, their small size challenges the conventional methods for structure characterization. Here we present the structure of ultra-stable Au144(SR)60 magic-sized nanoclusters obtained from atomic pair distribution function analysis of X-ray powder diffraction data. The study reveals structural polymorphism in these archetypal nanoclusters. In addition to confirming the theoretically predicted icosahedral-cored cluster, we also find samples with a truncated decahedral core structure, with some samples exhibiting a coexistence of both cluster structures. Although the clusters are monodisperse in size, structural diversity is apparent. The discovery of polymorphism may open up a new dimension in nanoscale engineering.

The linkage between ribosomal crystallography, metal ions, heteropolytungstates and functional flexibility

PubMed Central

Bashan, Anat; Yonath, Ada

2009-01-01

Crystallography of ribosomes, the universal cell nucleoprotein assemblies facilitating the translation of the genetic-code into proteins, met with severe problems owing to their large size, complex structure, inherent flexibility and high conformational variability. For the case of the small ribosomal subunit, which caused extreme difficulties, post crystallization treatment by minute amounts of a heteropolytungstate cluster allowed structure determination at atomic resolution. This cluster played a dual role in ribosomal crystallography: providing anomalous phasing power and dramatically increased the resolution, by stabilization of a selected functional conformation. Thus, four out of the fourteen clusters that bind to each of the crystallized small subunits are attached to a specific ribosomal protein in a fashion that may control a significant component of the subunit internal flexibility, by “gluing” symmetrical related subunits. Here we highlight basic issues in the relationship between metal ions and macromolecules and present common traits controlling in the interactions between polymetalates and various macromolecules, which may be extended towards the exploitation of polymetalates for therapeutical treatment. PMID:19915655

Cadmium, lead, and mercury levels in feathers of small passerine birds: noninvasive sampling strategy.

PubMed

Bianchi, Nicola; Ancora, Stefania; di Fazio, Noemi; Leonzio, Claudio

2008-10-01

Bird feathers have been widely used as a nondestructive biological material for monitoring heavy metals. Sources of metals taken up by feathers include diet (metals are incorporated during feather formation), preening, and direct contact with metals in water, air, dust, and plants. In the literature, data regarding the origin of trace elements in feathers are not univocal. Only in the vast literature concerning mercury (as methyl mercury) has endogenous origin been determined. In the present study, we investigate cadmium, lead, and mercury levels in feathers of prey of Falco eleonorae in relation to the ecological characteristics (molt, habitat, and contamination by soil) of the different species. Cluster analysis identified two main groups of species. Differences and correlations within and between groups identified by cluster analysis were then checked by nonparametric statistical analysis. The results showed that mercury levels had a pattern significantly different from those of cadmium and lead, which in turn showed a significant positive correlation, suggesting different origins. Nests of F. eleonorae proved to be a good source for feathers of small trans-Saharan passerines collected by a noninvasive method. They provided abundant feathers of the various species in a relatively small area--in this case, the falcon colony on the Isle of San Pietro, Sardinia, Italy.

Kinetics of copper growth on graphene revealed by time-resolved small-angle x-ray scattering

NASA Astrophysics Data System (ADS)

Hodas, M.; Siffalovic, P.; Jergel, M.; Pelletta, M.; Halahovets, Y.; Vegso, K.; Kotlar, M.; Majkova, E.

2017-01-01

Metal growth on graphene has many applications. Transition metals are known to favor three-dimensional (3D) cluster growth on graphene. Copper is of particular interest for cost-effective surface-supported catalysis applications and as a contact material in electronics. This paper presents an in situ real-time study of Cu growth kinetics on graphene covering all stages preceding formation of a continuous film performed by laboratory-based grazing-incidence small-angle x-ray scattering (GISAXS) technique. In particular, nucleation and 3D cluster growth, coalescence, and percolation stages were identified. The cluster nucleation saturates after reaching a density of 1012c m-2 at ≈1 monolayer thickness. A Kratky plot and a paracrystal model with cumulative structural disorder were necessary to evaluate properly cluster growth and coalescence, respectively. The power law scaling constants 0.27 ±0.05 and 0.81 ±0.02 of the temporal evolution of Cu cluster size suggest the growth of isolated clusters and dynamic cluster coalescence keeping the cluster shape, respectively. Coalescence and percolation thresholds occur at Cu thicknesses of 2 ±0.4 and 8.8 ±0.7 nm , respectively. This paper demonstrates the potential of laboratory-based in situ GISAXS as a vital diagnostic tool for tailoring a large variety of Cu nanostructures on graphene based on an in situ Cu growth monitoring which is applicable in a broad range of deposition times.

SODIUM AND OXYGEN ABUNDANCES IN THE OPEN CLUSTER NGC 6791 FROM APOGEE H-BAND SPECTROSCOPY

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cunha, Katia; Souto, Diogo; Smith, Verne V.

2015-01-10

The open cluster NGC 6791 is among the oldest, most massive, and metal-rich open clusters in the Galaxy. High-resolution H-band spectra from the Apache Point Observatory Galactic Evolution Experiment (APOGEE) of 11 red giants in NGC 6791 are analyzed for their chemical abundances of iron, oxygen, and sodium. The abundances of these three elements are found to be homogeneous (with abundance dispersions at the level of ∼0.05-0.07 dex) in these cluster red giants, which span much of the red-giant branch (T {sub eff} ∼ 3500-4600 K), and include two red clump giants. From the infrared spectra, this cluster is confirmed to be amongmore » the most metal-rich clusters in the Galaxy (([Fe/H]) = 0.34 ± 0.06) and is found to have a roughly solar value of [O/Fe] and slightly enhanced [Na/Fe]. Our non-LTE calculations for the studied Na I lines in the APOGEE spectral region (16373.86 Å and 16388.85 Å) indicate only small departures from LTE (≤0.04 dex) for the parameter range and metallicity of the studied stars. The previously reported double population of cluster members with different Na abundances is not found among the studied sample.« less

Luminescence properties of femtosecond-laser-activated silver oxide nanoparticles embedded in a biopolymer matrix

NASA Astrophysics Data System (ADS)

Gleitsmann, T.; Bernhardt, T. M.; Wöste, L.

2006-01-01

Strong visible luminescence is observed from silver clusters generated by femtosecond-laser-induced reduction of silver oxide nanoparticles embedded in a polymeric gelatin matrix. Light emission from the femtosecond-laser-activated matrix areas considerably exceeds the luminescence intensity of similarly activated bare silver oxide nanoparticle films. Optical spectroscopy of the activated polymer films supports the assignment of the emissive properties to the formation of small silver clusters under focused femtosecond-laser irradiation. The size of the photogenerated clusters is found to sensitively depend on the laser exposure time, eventually leading to the formation of areas of metallic silver in the biopolymer matrix. In this case, luminescence can still be observed in the periphery of the metallic silver structures, emphasizing the importance of the organic matrix for the stabilization of the luminescent nanocluster structures at the metal matrix interface.

Tantalum induced butterfly-like clusters on Si (111)-7 × 7 surface: STM/STS study at low coverage

NASA Astrophysics Data System (ADS)

Shukrynau, Pavel; Mutombo, Pingo; Švec, Martin; Hietschold, Michael; Cháb, Vladimír

2012-02-01

The adsorption of the small amounts of tantalum on Si (111)-7 × 7 reconstructed surface is investigated systematically using scanning tunneling microscopy and tunneling spectroscopy combined with first-principles density functional theory calculations. We find out that the moderate annealing of the Ta covered surface results in the formation of clusters of the butterfly-like shape. The clusters are sporadically distributed over the surface and their density is metal coverage dependent. Filled and empty state STM images of the clusters differ strongly suggesting the existence of covalent bonds within the cluster. Tunneling spectroscopy measurements reveal small energy gap, showing semiconductor-like behavior of the constituent atoms. The cluster model based on experimental images and theoretical calculations has been proposed and discussed. Presented results show that Ta joins the family of adsorbates, that are known to form magic clusters on Si (111)-7 × 7, but its magic cluster has the structural and electronic properties that are different from those reported before.

Nano-confinement inside molecular metal oxide clusters: Dynamics and modified encapsulation behavior

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Zhe; Daemen, Luke L.; Cheng, Yongqiang

Encapsulation behavior, as well as the presence of internal catalytically-active sites, has been spurring the applications of a 3 nm hollow spherical metal oxide cluster {Mo 132} as an encapsulation host and a nano-reactor. Due to its well-defined and tunable cluster structures, and nano-scaled internal void space comparable to the volumes of small molecules, this cluster provides a good model to study the dynamics of materials under ultra-confinement. Neutron scattering studies suggest that bulky internal ligands inside the cluster show slower and limited dynamics compared to their counterparts in the bulk state, revealing the rigid nature of the skeleton ofmore » the internal ligands. Furthermore, NMR studies indicate that the rigid internal ligands that partially cover the interfacial pore on the molybdenum oxide shells are able to block some large guest molecules from going inside the capsule cluster, which provides a convincing protocol for size-selective encapsulation and separation.« less

Nano-confinement inside molecular metal oxide clusters: Dynamics and modified encapsulation behavior

DOE PAGES

Wang, Zhe; Daemen, Luke L.; Cheng, Yongqiang; ...

2016-08-19

Encapsulation behavior, as well as the presence of internal catalytically-active sites, has been spurring the applications of a 3 nm hollow spherical metal oxide cluster {Mo 132} as an encapsulation host and a nano-reactor. Due to its well-defined and tunable cluster structures, and nano-scaled internal void space comparable to the volumes of small molecules, this cluster provides a good model to study the dynamics of materials under ultra-confinement. Neutron scattering studies suggest that bulky internal ligands inside the cluster show slower and limited dynamics compared to their counterparts in the bulk state, revealing the rigid nature of the skeleton ofmore » the internal ligands. Furthermore, NMR studies indicate that the rigid internal ligands that partially cover the interfacial pore on the molybdenum oxide shells are able to block some large guest molecules from going inside the capsule cluster, which provides a convincing protocol for size-selective encapsulation and separation.« less

Estudio de cúmulos estelares de la Nube Menor de Magallanes: fotometría de Washington de 14 cúmulos de edad intermedia

NASA Astrophysics Data System (ADS)

Piatti, A. E.; Clariá, J. J.; Bica, E.; Geisler, D.; Ahumada, A. V.; Girardi, L.

We present CCD photometry in the Washington system C and T1 bands of 14 star clusters of the Small Magellanic Cloud (SMC). We determine ages and metallicities using theoretical isochrones, the T1 parameter and the Red Giant Standard method. Excepting IC 1708, all the observed clusters are aged between 1 and 6.3 Gyr, while their metallicities ([Fe/H]) range be- tween -0.7 and -1.4. Two important cluster formation episodes in the SMC, dated at 2 Gyr and 5 Gyr ago, were detected. During approximately the first 4 Gyr in the SMC lifetime, the cluster formation rate turned out to be constant. A detailed version of this work can be seen in Piatti et al. (2011, MNRAS, 417, 1559). FULL TEXT IN SPANISH

Energy Characteristics of Small Metal Clusters Containing Vacancies

NASA Astrophysics Data System (ADS)

Reva, V. I.; Pogosov, V. V.

2018-02-01

Self-consistent calculations of spatial distributions of electrons, potentials, and energies of dissociation, cohesion, vacancy formation, and electron attachment, as well as the ionization potential of solid Al N , Na N clusters ( N ≥ 254), and clusters containing a vacancy ( N ≥ 12) have been performed using a model of stable jellium. The contribution of a monovacancy to the energy of the cluster, the size dependences of the characteristics, and their asymptotic forms have been considered. The calculations have been performed on the SKIT-3 cluster at the Glushkov Institute of Cybernetics, National Academy of Sciences of Ukraine (Rpeak = 7.4 Tflops).

Iridium clusters in KLTL zeolite: Structure and catalytic selectivity for n-hexane aromatization

DOE Office of Scientific and Technical Information (OSTI.GOV)

Triantafillou, N.D.; Miller, J.T.; Gates, B.C.

Catalysts consisting of Ir clusters in zeolite KLTL were prepared by reduction of [Ir(NH{sub 3}){sub 5}Cl]Cl{sub 2} in the zeolite with H{sub 2} at temperatures 300 or 500{degrees}C. The catalysts were tested for reactions of n-hexane and H{sub 2} at 400, 440 and 480{degrees}C and were characterized by temperature-programmed reduction, hydrogen chemisorption, transmission electron microscopy, infrared spectroscopy of adsorbed CO, and extended X-ray absorption fine structure spectroscopy. The clusters consist of 4 to 6 Ir atoms on average and are sufficiently small to reside within the pores of the zeolite. The infrared spectra characteristic of terminal CO suggest that themore » support environment is slightly basic and that the Ir clusters are electron rich relative to the bulk metal. Notwithstanding the small cluster size, the support basicity, and the confining geometry of the LTL zeolite pore structure, the catalytic performance is similar to those of other Ir catalysts, with a poor selectivity for aromatization and a high selectivity for hydrogenolysis. These results are consistent with the inference that the principal requirements for selective naphtha aromatization catalysts are both a nonacidic support and a metal with a low hydrogenolsis activity, i.e., Pt. 47 refs., 6 figs., 3 tabs.« less

Equilibrium structure and atomic vibrations of Nin clusters

NASA Astrophysics Data System (ADS)

Borisova, Svetlana D.; Rusina, Galina G.

2017-12-01

The equilibrium bond lengths and binding energy, second differences in energy and vibrational frequencies of free clusters Nin (2 ≤ n ≤ 20) were calculated with the use of the interaction potential obtained in the tight-binding approximation (TBA). The results show that the minimum vibration frequency plays a significant role in the evaluation of the dynamic stability of the clusters. A nonmonotonic dependence of the minimum vibration frequency of clusters on their size and the extreme values for the number of atoms in a cluster n = 4, 6, 13, and 19 are demonstrated. This result agrees with the theoretical and experimental data on stable structures of small metallic clusters.

Composite Reinforcement using Boron Nitride Nanotubes

DTIC Science & Technology

2014-05-09

while retaining the nanotube structure. This project involves the use of computational quantum chemistry to study interactions of aluminium (Al...small clusters of 1–4 metal atoms. The effect of varying the radius of the nanotubes and the size of aluminium and titanium clusters was considered...15. SUBJECT TERMS Boron Nitride Nanotubes, composite materials, Aluminum Alloys , Titanium Alloy , Theoretical Chemistry 16. SECURITY

Polymorphism in magic-sized Au144(SR)60 clusters

DOE PAGES

Jensen, Kirsten M. O.; Juhas, Pavol; Tofanelli, Marcus A.; ...

2016-06-14

Ultra-small, magic-sized metal nanoclusters represent an important new class of materials with properties between molecules and particles. However, their small size challenges the conventional methods for structure characterization. We present the structure of ultra-stable Au144(SR)60 magic-sized nanoclusters obtained from atomic pair distribution function analysis of X-ray powder diffraction data. Our study reveals structural polymorphism in these archetypal nanoclusters. Additionally, in order to confirm the theoretically predicted icosahedral-cored cluster, we also find samples with a truncated decahedral core structure, with some samples exhibiting a coexistence of both cluster structures. Although the clusters are monodisperse in size, structural diversity is apparent. Finally,more » the discovery of polymorphism may open up a new dimension in nanoscale engineering.« less

Self-Learning Off-Lattice Kinetic Monte Carlo method as applied to growth on metal surfaces

NASA Astrophysics Data System (ADS)

Trushin, Oleg; Kara, Abdelkader; Rahman, Talat

2007-03-01

We propose a new development in the Self-Learning Kinetic Monte Carlo (SLKMC) method with the goal of improving the accuracy with which atomic mechanisms controlling diffusive processes on metal surfaces may be identified. This is important for diffusion of small clusters (2 - 20 atoms) in which atoms may occupy Off-Lattice positions. Such a procedure is also necessary for consideration of heteroepitaxial growth. The new technique combines an earlier version of SLKMC [1] with the inclusion of off-lattice occupancy. This allows us to include arbitrary positions of adatoms in the modeling and makes the simulations more realistic and reliable. We have tested this new approach for the case of the diffusion of small 2D Cu clusters diffusion on Cu(111) and found good performance and satisfactory agreement with results obtained from previous version of SLKMC. The new method also helped reveal a novel atomic mechanism contributing to cluster migration. We have also applied this method to study the diffusion of Cu clusters on Ag(111), and find that Cu atoms generally prefer to occupy off-lattice sites. [1] O. Trushin, A. Kara, A. Karim, T.S. Rahman Phys. Rev B 2005

Advanced Electrochemistry of Individual Metal Clusters Electrodeposited Atom by Atom to Nanometer by Nanometer.

PubMed

Kim, Jiyeon; Dick, Jeffrey E; Bard, Allen J

2016-11-15

Metal clusters are very important as building blocks for nanoparticles (NPs) for electrocatalysis and electroanalysis in both fundamental and applied electrochemistry. Attention has been given to understanding of traditional nucleation and growth of metal clusters and to their catalytic activities for various electrochemical applications in energy harvesting as well as analytical sensing. Importantly, understanding the properties of these clusters, primarily the relationship between catalysis and morphology, is required to optimize catalytic function. This has been difficult due to the heterogeneities in the size, shape, and surface properties. Thus, methods that address these issues are necessary to begin understanding the reactivity of individual catalytic centers as opposed to ensemble measurements, where the effect of size and morphology on the catalysis is averaged out in the measurement. This Account introduces our advanced electrochemical approaches to focus on each isolated metal cluster, where we electrochemically fabricated clusters or NPs atom by atom to nanometer by nanometer and explored their electrochemistry for their kinetic and catalytic behavior. Such approaches expand the dimensions of analysis, to include the electrochemistry of (1) a discrete atomic cluster, (2) solely a single NP, or (3) individual NPs in the ensemble sample. Specifically, we studied the electrocatalysis of atomic metal clusters as a nascent electrocatalyst via direct electrodeposition on carbon ultramicroelectrode (C UME) in a femtomolar metal ion precursor. In addition, we developed tunneling ultramicroelectrodes (TUMEs) to study electron transfer (ET) kinetics of a redox probe at a single metal NP electrodeposited on this TUME. Owing to the small dimension of a NP as an active area of a TUME, extremely high mass transfer conditions yielded a remarkably high standard ET rate constant, k 0 , of 36 cm/s for outer-sphere ET reaction. Most recently, we advanced nanoscale scanning electrochemical microscopy (SECM) imaging to resolve the electrocatalytic activity of individual electrodeposited NPs within an ensemble sample yielding consistent high k 0 values of ≥2 cm/s for the hydrogen oxidation reaction (HOR) at different NPs. We envision that our advanced electrochemical approaches will enable us to systematically address structure effects on the catalytic activity, thus providing a quantitative guideline for electrocatalysts in energy-related applications.

Supported cluster catalysts synthesized to be small, simple, selective, and stable

DOE PAGES

Guan, Erjia; Fang, Chia-Yu; Yang, Dong; ...

2018-01-01

Molecular metal complexes on supports have drawn wide attention as catalysts offering new properties and opportunities for precise synthesis to make uniform catalytic species that can be understood in depth.

Delayed Ionization in Transition Metal Carbon Clusters

NASA Astrophysics Data System (ADS)

Kooi, S. E.; Castleman, A. W., Jr.

1997-03-01

Mass spectrometric studies of several single and binary transition metal carbon cluster systems, produced in a laser vaporization source, reveal several species that undergo delayed ionization. Pulsed extraction and blocking electric fields, in a time-of-flight mass spectrometer, allow the study of delayed ionization over a time window after excitation with a pulsed laser. In systems where metallocarbohedrenes (Met-Cars) are produced, the Met-Cars are the dominate delayed species. Delayed ionization of binary metal Met-Cars Ti_xM_yC_12 (M=Zr,Nb,Y; x+y=8) is dependent on the ratio of the two metals. Delayed behavior is investigated over a range of photoionization wavelengths and fluences. In order to determine the degree to which the delayed ionization is thermionic in character, the experimental data have been compared to Klots's model for thermionic emission from small particles.

An optical/NIR survey of globular clusters in early-type galaxies. III. On the colour bimodality of globular cluster systems

NASA Astrophysics Data System (ADS)

Chies-Santos, A. L.; Larsen, S. S.; Cantiello, M.; Strader, J.; Kuntschner, H.; Wehner, E. M.; Brodie, J. P.

2012-03-01

Context. The interpretation that bimodal colour distributions of globular clusters (GCs) reflect bimodal metallicity distributions has been challenged. Non-linearities in the colour to metallicity conversions caused for example by the horizontal branch (HB) stars may be responsible for transforming a unimodal metallicity distribution into a bimodal (optical) colour distribution. Aims: We study optical/near-infrared (NIR) colour distributions of the GC systems in 14 E/S0 galaxies. Methods: We test whether the bimodal feature, generally present in optical colour distributions, remains in the optical/NIR ones. The latter colour combination is a better metallicity proxy than the former. We use KMM and GMM tests to quantify the probability that different colour distributions are better described by a bimodal, as opposed to a unimodal distribution. Results: We find that double-peaked colour distributions are more commonly seen in optical than in optical/NIR colours. For some of the galaxies where the optical (g - z) distribution is clearly bimodal, a bimodal distribution is not preferred over a unimodal one at a statistically significant level for the (g - K) and (z - K) distributions. The two most cluster-rich galaxies in our sample, NGC 4486 and NGC 4649, show some interesting differences. The (g - K) distribution of NGC 4649 is better described by a bimodal distribution, while this is true for the (g - K) distribution of NGC 4486 GCs only if restricted to a brighter sub-sample with small K-band errors (<0.05 mag). Formally, the K-band photometric errors cannot be responsible for blurring bimodal metallicity distributions to unimodal (g - K) colour distributions. However, simulations including the extra scatter in the colour-colour diagrams (not fully accounted for in the photometric errors) show that such scatter may contribute to the disappearance of bimodality in (g - K) for the full NGC 4486 sample. For the less cluster-rich galaxies results are inconclusive due to poorer statistics. Conclusions: A bimodal optical colour distribution is not necessarily an indication of an underlying bimodal metallicity distribution. Horizontal branch morphology may play an important role in shaping some of the optical GC colour distributions. However, we find tentative evidence that the (g - K) colour distributions remain bimodal in the two cluster-rich galaxies in our sample (NGC 4486 and NGC 4649) when restricted to clusters with small K-band photometric errors. This bimodality becomes less pronounced when including objects with larger errors, or for the (z - K) colour distributions. Deeper observations of large numbers of GCs will be required to reach more secure conclusions.

Effects of carbonyl bond, metal cluster dissociation, and evaporation rates on predictions of nanotube production in high-pressure carbon monoxide

NASA Technical Reports Server (NTRS)

Scott, Carl D.; Smalley, Richard E.

2003-01-01

The high-pressure carbon monoxide (HiPco) process for producing single-wall carbon nanotubes (SWNTs) uses iron pentacarbonyl as the source of iron for catalyzing the Boudouard reaction. Attempts using nickel tetracarbonyl led to no production of SWNTs. This paper discusses simulations at a constant condition of 1300 K and 30 atm in which the chemical rate equations are solved for different reaction schemes. A lumped cluster model is developed to limit the number of species in the models, yet it includes fairly large clusters. Reaction rate coefficients in these schemes are based on bond energies of iron and nickel species and on estimates of chemical rates for formation of SWNTs. SWNT growth is measured by the conformation of CO2. It is shown that the production of CO2 is significantly greater for FeCO because of its lower bond energy as compared with that of NiCO. It is also shown that the dissociation and evaporation rates of atoms from small metal clusters have a significant effect on CO2 production. A high rate of evaporation leads to a smaller number of metal clusters available to catalyze the Boudouard reaction. This suggests that if CO reacts with metal clusters and removes atoms from them by forming MeCO, this has the effect of enhancing the evaporation rate and reducing SWNT production. The study also investigates some other reactions in the model that have a less dramatic influence.

Effects of Carbonyl Bond and Metal Cluster Dissociation and Evaporation Rates on Predictions of Nanotube Production in HiPco

NASA Technical Reports Server (NTRS)

Scott, Carl D.; Smalley, Richard E.

2002-01-01

The high-pressure carbon monoxide (HiPco) process for producing single-wall carbon nanotubes (SWNT) uses iron pentacarbonyl as the source of iron for catalyzing the Boudouard reaction. Attempts using nickel tetracarbonyl led to no production of SWNTs. This paper discusses simulations at a constant condition of 1300 K and 30 atm in which the chemical rate equations are solved for different reaction schemes. A lumped cluster model is developed to limit the number of species in the models, yet it includes fairly large clusters. Reaction rate coefficients in these schemes are based on bond energies of iron and nickel species and on estimates of chemical rates for formation of SWNTs. SWNT growth is measured by the co-formation of CO2. It is shown that the production of CO2 is significantly greater for FeCO due to its lower bond energy as compared with that ofNiCO. It is also shown that the dissociation and evaporation rates of atoms from small metal clusters have a significant effect on CO2 production. A high rate of evaporation leads to a smaller number of metal clusters available to catalyze the Boudouard reaction. This suggests that if CO reacts with metal clusters and removes atoms from them by forming MeCO, this has the effect of enhancing the evaporation rate and reducing SWNT production. The study also investigates some other reactions in the model that have a less dramatic influence.

Chemical Complexity in the Eu-enhanced Monometallic Globular NGC 5986

NASA Astrophysics Data System (ADS)

Johnson, Christian I.; Caldwell, Nelson; Rich, R. Michael; Mateo, Mario; Bailey, John I., III; Olszewski, Edward W.; Walker, Matthew G.

2017-06-01

NGC 5986 is a poorly studied but relatively massive Galactic globular cluster that shares several physical and morphological characteristics with “iron-complex” clusters known to exhibit significant metallicity and heavy-element dispersions. In order to determine whether NGC 5986 joins the iron-complex cluster class, we investigated the chemical composition of 25 red giant branch and asymptotic giant branch cluster stars using high-resolution spectra obtained with the Magellan-M2FS instrument. Cluster membership was verified using a combination of radial velocity and [Fe/H] measurements, and we found the cluster to have a mean heliocentric radial velocity of +99.76 km s-1 (σ = 7.44 km s-1). We derived a mean metallicity of [Fe/H] = -1.54 dex (σ = 0.08 dex), but the cluster’s small dispersion in [Fe/H] and low [La/Eu] abundance preclude it from being an iron-complex cluster. NGC 5986 has < [{Eu}/{Fe}]> =+0.76 {dex} (σ = 0.08 dex), which is among the highest ratios detected in a Galactic cluster, but the small [Eu/Fe] dispersion is puzzling because such high values near [Fe/H] ˜ -1.5 are typically only found in dwarf galaxies exhibiting large [Eu/Fe] variations. NGC 5986 exhibits classical globular cluster characteristics, such as uniformly enhanced [α/Fe] ratios, a small dispersion in Fe-peak abundances, and (anti)correlated light-element variations. Similar to NGC 2808, we find evidence that NGC 5986 may host at least four to five populations with distinct light-element compositions, and the presence of a clear Mg-Al anticorrelation along with an Al-Si correlation suggests that the cluster gas experienced processing at temperatures ≳65-70 MK. However, the current data do not support burning temperatures exceeding ˜100 MK. We find some evidence that the first- and second-generation stars in NGC 5986 may be fully spatially mixed, which could indicate that the cluster has lost a significant fraction of its original mass. This paper includes data gathered with the 6.5 m Magellan Telescopes located at Las Campanas Observatory, Chile.

Stellar abundances and ages for metal-rich Milky Way globular clusters. Stellar parameters and elemental abundances for 9 HB stars in NGC 6352

NASA Astrophysics Data System (ADS)

Feltzing, S.; Primas, F.; Johnson, R. A.

2009-01-01

Context: Metal-rich globular clusters provide important tracers of the formation of our Galaxy. Moreover, and not less important, they are very important calibrators for the derivation of properties of extra-galactic metal-rich stellar populations. Nonetheless, only a few of the metal-rich globular clusters in the Milky Way have been studied using high-resolution stellar spectra to derive elemental abundances. Additionally, Rosenberg et al. identified a small group of metal-rich globular clusters that appeared to be about 2 billion years younger than the bulk of the Milky Way globular clusters. However, it is unclear if like is compared with like in this dataset as we do not know the enhancement of α-elements in the clusters and the amount of α-elements is well known to influence the derivation of ages for globular clusters. Aims: We derive elemental abundances for the metal-rich globular cluster NGC 6352 and we present our methods to be used in up-coming studies of other metal-rich globular clusters. Methods: We present a study of elemental abundances for α- and iron-peak elements for nine HB stars in the metal-rich globular cluster NGC 6352. The elemental abundances are based on high-resolution, high signal-to-noise spectra obtained with the UVES spectrograph on VLT. The elemental abundances have been derived using standard LTE calculations and stellar parameters have been derived from the spectra themselves by requiring ionizational as well as excitational equilibrium. Results: We find that NGC 6352 has [Fe/H] = -0.55, is enhanced in the α-elements to about +0.2 dex for Ca, Si, and Ti relative to Fe. For the iron-peak elements we find solar values. Based on the spectroscopically derived stellar parameters we find that an E(B-V) = 0.24 and (m-M) ≃ 14.05 better fits the data than the nominal values. An investigation of log gf-values for suitable Fe i lines lead us to the conclusion that the commonly used correction to the May et al. (1974) data should not be employed. Full Table [see full text] are also only available in electronic form at the CDS via anonymous ftp to cdsarc.u-strasbg.fr (130.79.128.5) or via http://cdsweb.u-strasbg.fr/cgi-bin/qcat?J/A+A/493/913 Based on observations collected at the European Southern Observatory, Chile, ESO No. 69.B-0467.

EXPLORING ANTICORRELATIONS AND LIGHT ELEMENT VARIATIONS IN NORTHERN GLOBULAR CLUSTERS OBSERVED BY THE APOGEE SURVEY

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mészáros, Szabolcs; Martell, Sarah L.; Shetrone, Matthew

We investigate the light-element behavior of red giant stars in northern globular clusters (GCs) observed by the SDSS-III Apache Point Observatory Galactic Evolution Experiment. We derive abundances of 9 elements (Fe, C, N, O, Mg, Al, Si, Ca, and Ti) for 428 red giant stars in 10 GCs. The intrinsic abundance range relative to measurement errors is examined, and the well-known C–N and Mg–Al anticorrelations are explored using an extreme-deconvolution code for the first time in a consistent way. We find that Mg and Al drive the population membership in most clusters, except in M107 and M71, the two mostmore » metal-rich clusters in our study, where the grouping is most sensitive to N. We also find a diversity in the abundance distributions, with some clusters exhibiting clear abundance bimodalities (for example M3 and M53) while others show extended distributions. The spread of Al abundances increases significantly as cluster average metallicity decreases as previously found by other works, which we take as evidence that low metallicity, intermediate mass AGB polluters were more common in the more metal-poor clusters. The statistically significant correlation of [Al/Fe] with [Si/Fe] in M15 suggests that {sup 28}Si leakage has occurred in this cluster. We also present C, N, and O abundances for stars cooler than 4500 K and examine the behavior of A(C+N+O) in each cluster as a function of temperature and [Al/Fe]. The scatter of A(C+N+O) is close to its estimated uncertainty in all clusters and independent of stellar temperature. A(C+N+O) exhibits small correlations and anticorrelations with [Al/Fe] in M3 and M13, but we cannot be certain about these relations given the size of our abundance uncertainties. Star-to-star variations of α-element (Si, Ca, Ti) abundances are comparable to our estimated errors in all clusters.« less

Exploring Anticorrelations and Light Element Variations in Northern Globular Clusters Observed by the APOGEE Survey

NASA Astrophysics Data System (ADS)

Mészáros, Szabolcs; Martell, Sarah L.; Shetrone, Matthew; Lucatello, Sara; Troup, Nicholas W.; Bovy, Jo; Cunha, Katia; García-Hernández, Domingo A.; Overbeek, Jamie C.; Allende Prieto, Carlos; Beers, Timothy C.; Frinchaboy, Peter M.; García Pérez, Ana E.; Hearty, Fred R.; Holtzman, Jon; Majewski, Steven R.; Nidever, David L.; Schiavon, Ricardo P.; Schneider, Donald P.; Sobeck, Jennifer S.; Smith, Verne V.; Zamora, Olga; Zasowski, Gail

2015-05-01

We investigate the light-element behavior of red giant stars in northern globular clusters (GCs) observed by the SDSS-III Apache Point Observatory Galactic Evolution Experiment. We derive abundances of 9 elements (Fe, C, N, O, Mg, Al, Si, Ca, and Ti) for 428 red giant stars in 10 GCs. The intrinsic abundance range relative to measurement errors is examined, and the well-known C-N and Mg-Al anticorrelations are explored using an extreme-deconvolution code for the first time in a consistent way. We find that Mg and Al drive the population membership in most clusters, except in M107 and M71, the two most metal-rich clusters in our study, where the grouping is most sensitive to N. We also find a diversity in the abundance distributions, with some clusters exhibiting clear abundance bimodalities (for example M3 and M53) while others show extended distributions. The spread of Al abundances increases significantly as cluster average metallicity decreases as previously found by other works, which we take as evidence that low metallicity, intermediate mass AGB polluters were more common in the more metal-poor clusters. The statistically significant correlation of [Al/Fe] with [Si/Fe] in M15 suggests that 28Si leakage has occurred in this cluster. We also present C, N, and O abundances for stars cooler than 4500 K and examine the behavior of A(C+N+O) in each cluster as a function of temperature and [Al/Fe]. The scatter of A(C+N+O) is close to its estimated uncertainty in all clusters and independent of stellar temperature. A(C+N+O) exhibits small correlations and anticorrelations with [Al/Fe] in M3 and M13, but we cannot be certain about these relations given the size of our abundance uncertainties. Star-to-star variations of α-element (Si, Ca, Ti) abundances are comparable to our estimated errors in all clusters.

Hogg 12 and NGC 3590: A New Open Cluster Binary System Candidate

NASA Astrophysics Data System (ADS)

Piatti, Andrés E.; Clariá, Juan J.; Ahumada, Andrea V.

2010-05-01

We have obtained CCD UBVIKC photometry down to V ˜ 22.0 for the open clusters Hogg 12 and NGC 3590 and the fields surrounding them. Based on photometric and morphological criteria, as well as on the stellar density in the region, our evidence is sufficient to confirm that Hogg 12 is a genuine open cluster. NGC 3590 was used as a control cluster. The color-magnitude diagrams of Hogg 12, cleaned from field star contamination, reveal that this is a solar metal content cluster, affected by E(B - V) = 0.40 ± 0.05, located at a heliocentric distance d = 2.0 ± 0.5 kpc, and of an age similar to that of NGC 3590 (t = 30 Myr). Both clusters are surprisingly small objects whose radii are barely ˜1 pc, andthey are separated in the sky by scarcely 3.6 pc. These facts, added to their similar ages, reddenings, and metallicities, allow us to consider them a new open cluster binary system candidate. Of the ˜180 open cluster binary systems estimated to exist in the Galaxy, of which 27 are actually well known, Hogg 12 and NGC 3590 appear to be one of the two closest pairs.

The formation of the smallest fullerene-like carbon cages on metal surfaces.

PubMed

Ben Romdhane, F; Rodríguez-Manzo, J A; Andrieux-Ledier, A; Fossard, F; Hallal, A; Magaud, L; Coraux, J; Loiseau, A; Banhart, F

2016-02-07

The nucleation and growth of carbon on catalytically active metal surfaces is one of the most important techniques to produce nanomaterials such as graphene or nanotubes. Here it is shown by in situ electron microscopy that fullerene-like spherical clusters with diameters down to 0.4 nm and thus much smaller than C60 grow in a polymerized state on Co, Fe, or Ru surfaces. The cages appear on the surface of metallic islands in contact with graphene under heating to at least 650 °C and successively cooling to less than 500 °C. The formation of the small cages is explained by the segregation of carbon on a supersaturated metal, driven by kinetics. First principles energy calculations show that the clusters polymerize and can be attached to defects in graphene. Under compression, the polymerized cages appear in a crystalline structure.

Direct observation of small cluster mobility and ripening. [during annealing of metal films on amorphous substrates

NASA Technical Reports Server (NTRS)

Heinemann, K.; Poppa, H.

1975-01-01

Direct evidence is reported for the simultaneous occurrence of Ostwald ripening and short-distance cluster mobility during annealing of discontinuous metal films on clean amorphous substrates. The annealing characteristics of very thin particulate deposits of silver on amorphized clean surfaces of single crystalline thin graphite substrates were studied by in-situ transmission electron microscopy (TEM) under controlled environmental conditions (residual gas pressure of 10 to the minus 9th power torr) in the temperature range from 25 to 450 C. Sputter cleaning of the substrate surface, metal deposition, and annealing were monitored by TEM observation. Pseudostereographic presentation of micrographs in different annealing stages, the observation of the annealing behavior at cast shadow edges, and measurements with an electronic image analyzing system were employed to aid the visual perception and the analysis of changes in deposit structure recorded during annealing. Slow Ostwald ripening was found to occur in the entire temperature range, but the overriding surface transport mechanism was short-distance cluster mobility.

Analysis of the heat capacity of nanoclusters of FCC metals on the example of Al, Ni, Cu, Pd, and Au

NASA Astrophysics Data System (ADS)

Gafner, Yu. Ya.; Gafner, S. L.; Zamulin, I. S.; Redel, L. V.; Baidyshev, V. S.

2015-06-01

The heat capacity of ideal nickel, copper, gold, aluminum, and palladium fcc clusters with diameter of up to 6 nm has been studied in the temperature range of 150-800 K in terms of the molecular-dynamics theory using a tight-binding potential. The heat capacity of individual metallic nanoclusters has been found to exceed that characteristic of the bulk state, but by no more than 16-20%, even in the case of very small clusters. To explain the discrepancy between the simulated data and the experimental results on the compacted metals, aluminum and palladium samples with 80% theoretical density have also been investigated. Based on the simulation results and analysis of the experimental data, it has been established that the increased heat capacity of the compacted nanomaterials does not depend on the enhanced heat capacity of the individual clusters but rather, can be due to either the disordered state of the nanomaterial or a significant content of impurities (mainly, hydrogen).

Allosteric control in a metalloprotein dramatically alters function

PubMed Central

Baxter, Elizabeth Leigh; Zuris, John A.; Wang, Charles; Vo, Phu Luong T.; Axelrod, Herbert L.; Cohen, Aina E.; Paddock, Mark L.; Nechushtai, Rachel; Onuchic, Jose N.; Jennings, Patricia A.

2013-01-01

Metalloproteins (MPs) comprise one-third of all known protein structures. This diverse set of proteins contain a plethora of unique inorganic moieties capable of performing chemistry that would otherwise be impossible using only the amino acids found in nature. Most of the well-studied MPs are generally viewed as being very rigid in structure, and it is widely thought that the properties of the metal centers are primarily determined by the small fraction of amino acids that make up the local environment. Here we examine both theoretically and experimentally whether distal regions can influence the metal center in the diabetes drug target mitoNEET. We demonstrate that a loop (L2) 20 Å away from the metal center exerts allosteric control over the cluster binding domain and regulates multiple properties of the metal center. Mutagenesis of L2 results in significant shifts in the redox potential of the [2Fe-2S] cluster and orders of magnitude effects on the rate of [2Fe-2S] cluster transfer to an apo-acceptor protein. These surprising effects occur in the absence of any structural changes. An examination of the native basin dynamics of the protein using all-atom simulations shows that twisting in L2 controls scissoring in the cluster binding domain and results in perturbations to one of the cluster-coordinating histidines. These allosteric effects are in agreement with previous folding simulations that predicted L2 could communicate with residues surrounding the metal center. Our findings suggest that long-range dynamical changes in the protein backbone can have a significant effect on the functional properties of MPs. PMID:23271805

Formation of small gold clusters in solution by laser excitation of interband transition

NASA Astrophysics Data System (ADS)

Mafuné, Fumitaka; Kondow, Tamotsu

2003-04-01

Gold nanoparticles with ˜10 nm in average diameter were prepared by laser ablation of a gold metal plate in an aqueous solution of sodium dodecyl sulfate (SDS) and were fragmented by excitation of an interband transition of gold nanoparticles under irradiation of an intense 355-nm pulsed laser. Fragmentation dynamics was investigated by comparing the fragmentation by excitation of a surface plasmon band of gold nanoparticles by a 532-nm laser. It is found that gold nanoparticles with 1.5-nm average diameter are produced together with small gold clusters by properly optimizing the surfactant concentration.

Dating star clusters in the Small Magellanic Cloud by means of integrated spectra

NASA Astrophysics Data System (ADS)

Ahumada, A. V.; Clariá, J. J.; Bica, E.; Dutra, C. M.

2002-10-01

In this study flux-calibrated integrated spectra in the range (3600-6800) Å are presented for 16 concentrated star clusters in the Small Magellanic Cloud (SMC), approximately half of which constitute unstudied objects. We have estimated ages and foreground interstellar reddening values from the comparison of the line strengths and continuum distribution of the cluster spectra with those of template cluster spectra with known parameters. Most of the sample clusters are young blue clusters (6-50 Myr), while L 28, NGC 643 and L 114 are found to be intermediate-age clusters (1-6 Gyr). One well known SMC cluster (NGC 416) was observed for comparison purposes. The sample includes clusters in the surroundings and main body of the SMC, and the derived foreground reddening values are in the range 0.00 <= E(B-V) <= 0.15. The present data also make up a cluster spectral library at SMC metallicity. Based on observations made at Complejo Astronómico El Leoncito, which is operated under agreement between the Consejo Nacional de Investigaciones Científicas y Técnicas de la República Argentina and the National Universities of La Plata, Córdoba and San Juan, Argentina.

Kinetic Assembly of Near-IR Active Gold Nanoclusters using Weakly Adsorbing Polymers to Control Size

PubMed Central

Tam, Jasmine M.; Murthy, Avinash K.; Ingram, Davis R.; Nguyen, Robin; Sokolov, Konstantin V.; Johnston, Keith P.

2013-01-01

Clusters of metal nanoparticles with an overall size less than 100 nm and high metal loadings for strong optical functionality, are of interest in various fields including microelectronics, sensors, optoelectronics and biomedical imaging and therapeutics. Herein we assemble ~5 nm gold particles into clusters with controlled size, as small as 30 nm and up to 100 nm, which contain only small amounts of polymeric stabilizers. The assembly is kinetically controlled with weakly adsorbing polymers, PLA(2K)-b-PEG(10K)-b-PLA(2K) or PEG (MW = 3350), by manipulating electrostatic, van der Waals (VDW), steric, and depletion forces. The cluster size and optical properties are tuned as a function of particle volume fractions and polymer/gold ratios to modulate the interparticle interactions. The close spacing between the constituent gold nanoparticles and high gold loadings (80–85% w/w gold) produce a strong absorbance cross section of ~9×10−15 m2 in the NIR at 700 nm. This morphology results from VDW and depletion attractive interactions that exclude the weakly adsorbed polymeric stabilizer from the cluster interior. The generality of this kinetic assembly platform is demonstrated for gold nanoparticles with a range of surface charges from highly negative to neutral, with the two different polymers. PMID:20361735

Insight from first principles into the stability and magnetism of alkali-metal superoxide nanoclusters

NASA Astrophysics Data System (ADS)

Arcelus, Oier; Suaud, Nicolas; Katcho, Nebil A.; Carrasco, Javier

2017-05-01

Alkali-metal superoxides are gaining increasing interest as 2p magnetic materials for information and energy storage. Despite significant research efforts on bulk materials, gaps in our knowledge of the electronic and magnetic properties at the nanoscale still remain. Here, we focused on the role that structural details play in determining stability, electronic structure, and magnetic couplings of (MO2)n (M = Li, Na, and K, with n = 2-8) clusters. Using first-principles density functional theory based on the Perdew-Burke-Ernzerhof and Heyd-Scuseria-Ernzerhof functionals, we examined the effect of atomic structure on the relative stability of different polymorphs within each investigated cluster size. We found that small clusters prefer to form planar-ring structures, whereas non-planar geometries become more stable when increasing the cluster size. However, the crossover point depends on the nature of the alkali metal. Our analysis revealed that electrostatic interactions govern the highly ionic M-O2 bonding and ultimately control the relative stability between 2-D and 3-D geometries. In addition, we analyzed the weak magnetic couplings between superoxide molecules in (NaO2)4 clusters comparing model Hamiltonian methods based on Wannier function projections onto πg states with wave function-based multi-reference calculations.

Light and Heavy Element Abundance Variations in the Outer Halo Globular Cluster NGC 6229

NASA Astrophysics Data System (ADS)

Johnson, Christian I.; Caldwell, Nelson; Rich, R. Michael; Walker, Matthew G.

2017-10-01

NGC 6229 is a relatively massive outer halo globular cluster that is primarily known for exhibiting a peculiar bimodal horizontal branch morphology. Given the paucity of spectroscopic data on this cluster, we present a detailed chemical composition analysis of 11 red giant branch members based on high resolution (R ≈ 38,000), high S/N (>100) spectra obtained with the MMT-Hectochelle instrument. We find the cluster to have a mean heliocentric radial velocity of -{138.1}-1.0+1.0 {km} {{{s}}}-1, a small dispersion of {3.8}-0.7+1.0 {km} {{{s}}}-1, and a relatively low {(M/{L}{{V}})}⊙ ={0.82}-0.28+0.49. The cluster is moderately metal-poor with < [{Fe}/{{H}}]> =-1.13 dex and a modest dispersion of 0.06 dex. However, 18% (2/11) of the stars in our sample have strongly enhanced [La, Nd/Fe] ratios that are correlated with a small (˜0.05 dex) increase in [Fe/H]. NGC 6229 shares several chemical signatures with M75, NGC 1851, and the intermediate metallicity populations of ω Cen, which lead us to conclude that NGC 6229 is a lower mass iron-complex cluster. The light elements exhibit the classical (anti-)correlations that extend up to Si, but the cluster possesses a large gap in the O-Na plane that separates first and second generation stars. NGC 6229 also has unusually low [Na, Al/Fe] abundances that are consistent with an accretion origin. A comparison with M54 and other Sagittarius clusters suggests that NGC 6229 could also be the remnant core of a former dwarf spheroidal galaxy.

Standard Giant Branches in the Washington Photometric System

NASA Technical Reports Server (NTRS)

Geisler, Doug; Sarajedini, Ata

1998-01-01

We have obtained CCD photometry in the Washington system C, T(sub 1) filters for some 850,000 objects associated with 10 Galactic globular clusters and 2 old open clusters. These clusters have well-known metal abundances, spanning a metallicity range of 2.5 dex from [Fe/H] approx -2.25 to +0.25 at a spacing of approx. 0.2 dex. Two independent observations were obtained for each cluster and internal checks, as well as external comparisons with existing photoelectric photometry, indicate that the final colors and magnitudes have overall uncertainties of 0.03 mag. Analogous to the method employed by Da Costa and Armandroff for V, I photometry , we then proceed to construct standard ((M(sub T),(C - T(sub 1))(sub 0)) giant branches for these clusters adopting the Lee et distance scale, using some 350 stars per globular cluster to define the giant branch. We then determine the metallicity sensitivity of the ((C - T(sub 1))(sub 0) color at a given M((sub T)(sub 1)) value. The Washington system technique is found to have three times the metallicity sensitivity of the V, I technique. At M((sub T)(sub 1)) = -2 (about a magnitude below the tip of the giant branch, roughly equivalent to M(sub I) = -3), the giant branches of 47 Tuc and M15 are separated by 1.16 magnitudes in (V - l)(sub 0) and only 0.38 magnitudes in (V - I)(sub 0). Thus, for a given photometric accuracy, metallicities can be determined three times more precisely with the Washington technique. We find a linear relationship between (C - T(sub l)(sub 0) (at M(sub T)(sub 1) = -2) and metallicity exists over the full metallicity range, with an rms of only 0.04 dex. We also derive metallicity calibrations for M(sub T)(sub 1) = -2.5 and -1.5, as well as for two other metallicity scales. The Washington technique retains almost the same metallicity sensitivity at faint magnitudes , and indeed the standard giant branches are still well separated even below the horizontal branch. The photometry is used to set upper limits in the range 0.03 - 0.09 dex for any intrinsic metallicity dispersion in the calibrating clusters. The calibrations are applicable to objects with ages approx. greater than 5 Gyr - any age effects are small or negligible for such objects. This new technique is found to have many advantages over the old two-color diagram technique for deriving metallicities from Washington photometry. In addition to only requiring 2 filters instead of 3 or 4, the new technique is generally much less sensitive to reddening and photometric errors, and the metallicity sensitivity is many times higher. The new technique is especially advantageous for metal-poor objects. The five metal-poor clusters determined by Geisler et al., using the old technique, to be much more metal-poor than previous indications, yield metallicities using the new technique which are in excellent agreement with the Zinn scale.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yasui, Chikako; Kobayashi, Naoto; Izumi, Natsuko

To study star formation in low-metallicity environments ([M/H] ∼ −1 dex), we obtained deep near-infrared (NIR) images of Sh 2-207 (S207), which is an H ii region in the outer Galaxy with a spectroscopically determined metallicity of [O/H] ≃ −0.8 dex. We identified a young cluster in the western region of S207 with a limiting magnitude of K{sub S} = 19.0 mag (10σ) that corresponds to a mass detection limit of ≲0.1 M{sub ⊙} and enables the comparison of star-forming properties under low metallicity with those of the solar neighborhood. From the fitting of the K-band luminosity function (KLF), the age and distance of the S207more » cluster are estimated at 2–3 Myr and ∼4 kpc, respectively. The estimated age is consistent with the suggestion of small extinctions of stars in the cluster (A{sub V} ∼ 3 mag) and the non-detection of molecular clouds. The reasonably good fit between the observed KLF and the model KLF suggests that the underlying initial mass function (IMF) of the cluster down to the detection limit is not significantly different from the typical IMFs in the solar metallicity. From the fraction of stars with NIR excesses, a low disk fraction (<10%) in the cluster with a relatively young age is suggested, as we had previously proposed.« less

Gemini Spectra of Star Clusters in the Spiral Galaxy M101

NASA Astrophysics Data System (ADS)

Simanton-Coogan, Lesley A.; Chandar, Rupali; Miller, Bryan; Whitmore, Bradley C.

2017-12-01

We present low resolution, visible light spectra of 41 star clusters in the spiral galaxy M101, taken with the Gemini/GMOS instrument. We measure Lick indices for each cluster and compare with BaSTI models to estimate their ages and metallicities. We also measure the line-of-sight velocities. We find that 25 of the clusters are fairly young massive clusters (YMCs) with ages of hundreds of millions of years, and 16 appear to be older, globular clusters (GCs). There are at least four GCs with best-fit ages of ≈1–3 Gyr and eight with best-fit ages of ≈5–10 Gyr. The mean metallicity of the YMCs is [Fe/H] ≈ ‑0.1 and for the GCs is [Fe/H] ≈ ‑0.9. We find a near-continuous spread in both age and metallicity for our sample, which may indicate that M101 had a more-or-less continuous history of cluster and star formation. From the kinematics, we find that the YMCs rotate with the H I gas fairly well, while the GCs do not. We cannot definitively say whether the GCs sampled here lie in an inner halo, thick disk, or bulge/psuedobulge component, although given the very small bulge in M101, the last seems unlikely. The kinematics and ages of the YMCs suggest that M101 may have undergone heating of its disk or possibly a continuous merger/accretion history for the galaxy.

Washington photometry of 14 intermediate-age to old star clusters in the Small Magellanic Cloud

NASA Astrophysics Data System (ADS)

Piatti, Andrés E.; Clariá, Juan J.; Bica, Eduardo; Geisler, Doug; Ahumada, Andrea V.; Girardi, Léo

2011-10-01

We present CCD photometry in the Washington system C, T1 and T2 passbands down to T1˜ 23 in the fields of L3, L28, HW 66, L100, HW 79, IC 1708, L106, L108, L109, NGC 643, L112, HW 84, HW 85 and HW 86, 14 Small Magellanic Cloud (SMC) clusters, most of them poorly studied objects. We measured T1 magnitudes and C-T1 and T1-T2 colours for a total of 213 516 stars spread throughout cluster areas of 14.7 × 14.7 arcmin2 each. We carried out an in-depth analysis of the field star contamination of the colour-magnitude diagrams (CMDs) and statistically cleaned the cluster CMDs. Based on the best fits of isochrones computed by the Padova group to the (T1, C-T1) CMDs, as well as from the δ(T1) index and the standard giant branch procedure, we derived ages and metallicities for the cluster sample. With the exception of IC 1708, a relatively metal-poor Hyades-age cluster, the remaining 13 objects are between intermediate and old age (from 1.0 to 6.3 Gyr), their [Fe/H] values ranging from -1.4 to -0.7 dex. By combining these results with others available in the literature, we compiled a sample of 43 well-known SMC clusters older than 1 Gyr, with which we produced a revised age distribution. We found that the present clusters' age distribution reveals two primary excesses of clusters at t˜ 2 and 5 Gyr, which engraves the SMC with clear signs of enhanced formation episodes at both ages. In addition, we found that from the birth of the SMC cluster system until approximately the first 4 Gyr of its lifetime, the cluster formation resembles that of a constant formation rate scenario.

On the calculation of the energies of dissociation, cohesion, vacancy formation, electron attachment, and the ionization potential of small metallic clusters containing a monovacancy

NASA Astrophysics Data System (ADS)

Pogosov, V. V.; Reva, V. I.

2017-09-01

In terms of the model of stable jellium, self-consistent calculations of spatial distributions of electrons and potentials, as well as of energies of dissociation, cohesion, vacancy formation, electron attachment, and ionization potentials of solid clusters of Mg N , Li N (with N ≤ 254 ) and of clusters containing a vacancy ( N ≥ 12) have been performed. The contribution of a monovacancy to the energy of the cluster and size dependences of its characteristics and of asymptotics have been discussed. Calculations have been performed using a SKIT-3 cluster at Glushkov Institute of Cybernetics, National Academy of Sciences, Ukraine (Rpeak = 7.4 Tflops).

Force Field Development and Molecular Dynamics of [NiFe] Hydrogenase

DOE Office of Scientific and Technical Information (OSTI.GOV)

Smith, Dayle MA; Xiong, Yijia; Straatsma, TP

2012-05-09

Classical molecular force-field parameters describing the structure and motion of metal clusters in [NiFe] hydrogenase enzymes can be used to compare the dynamics and thermodynamics of [NiFe] under different oxidation, protonation, and ligation circumstances. Using density functional theory (DFT) calculations of small model clusters representative of the active site and the proximal, medial, and distal Fe/S metal centers and their attached protein side chains, we have calculated classical force-field parameters for [NiFe] in reduced and oxidized states, including internal coordinates, force constants, and atom-centered charges. Derived force constants revealed that cysteinate ligands bound to the metal ions are more flexiblemore » in the Ni-B active site, which has a bridging hydroxide ligand, than in the Ni-C active site, which has a bridging hydride. Ten nanosecond all-atom, explicit-solvent MD simulations of [NiFe] hydrogenase in oxidized and reduced catalytic states established the stability of the derived force-field parameters in terms of C{alpha} and metal cluster fluctuations. Average active site structures from the protein MD simulations are consistent with [NiFe] structures from the Protein Data Bank, suggesting that the derived force-field parameters are transferrable to other hydrogenases beyond the structure used for testing. A comparison of experimental H{sub 2}-production rates demonstrated a relationship between cysteinate side chain rotation and activity, justifying the use of a fully dynamic model of [NiFe] metal cluster motion.« less

From astrophysics to mesoscopic physics: a sightseeing tour in the world of clusters and fullerenes

NASA Astrophysics Data System (ADS)

Rosen, Arne; Ostling, Daniel; Apell, P.; Tomanek, D.

1996-12-01

The discovery of the fullerenes in 1985 by Kroto, Heath, O'Brien, Curl and Smalley and the development of a method for production of macroscopic amounts in 1990 by Kraetschmer, Lamb, Fostiropoulos and Huffman opened a new area of carbon research with possible production of new materials with unique properties. The field has developed further later on with discoveries of nanotubes, metal filled nanotubes, carbon onions and more recently metal covered fullerenes. All these new discoveries show how cluster science opens approaches to the area of meososcopic physics. The general trend is here in the direction from small to large contrary to the general trend of modern meososcopic physics or micro-electronics where the movement is from large to small. It is especially fascinating how the whole area of fullerene research was initiated by problems in astrophysics. Originally Kraetschmer and Huffman had the intention to explain an observed strong extinction form interstellar dust and produced in experiments special carbon soot with a characteristics optical absorption known as 'the camel hump smoke'. This paper gives a short overview of some of our more recent theoretical work of the electronic properties of C60, metal covered C60 and nanotubes. In addition some results are also presented of optical properties of metal covered C60 as a function of metal coverage.

ECOLOGIC STUDY OF MESOSCALE ENVIRONMENTS WITH EXCESS DISEASE PREVALENCE

EPA Science Inventory

This work employs an ecologic epidemiological approach to assess the relationship between environmental stressors and excess disease prevalence in small communities. Specifically, the childhood leukemia cluster in Fallon Nevada is used as an example; heavy metals (tungsten and c...

Quantum-Size Dependence of the Energy for Vacancy Formation in Charged Small Metal Clusters. Drop Model

NASA Astrophysics Data System (ADS)

Pogosov, V. V.; Reva, V. I.

2018-04-01

Self-consistent computations of the monovacancy formation energy are performed for Na N , Mg N , and Al N (12 < N ≤ 168) spherical clusters in the drop model for stable jelly. Scenarios of the Schottky vacancy formation and "bubble vacancy blowing" are considered. It is shown that the asymptotic behavior of the size dependences of the energy for the vacancy formation by these two mechanisms is different and the difference between the characteristics of a charged and neutral cluster is entirely determined by the difference between the ionization potentials of clusters and the energies of electron attachment to them.

The Gaia-ESO Survey: Probes of the inner disk abundance gradient

NASA Astrophysics Data System (ADS)

Jacobson, H. R.; Friel, E. D.; Jílková, L.; Magrini, L.; Bragaglia, A.; Vallenari, A.; Tosi, M.; Randich, S.; Donati, P.; Cantat-Gaudin, T.; Sordo, R.; Smiljanic, R.; Overbeek, J. C.; Carraro, G.; Tautvaišienė, G.; San Roman, I.; Villanova, S.; Geisler, D.; Muñoz, C.; Jiménez-Esteban, F.; Tang, B.; Gilmore, G.; Alfaro, E. J.; Bensby, T.; Flaccomio, E.; Koposov, S. E.; Korn, A. J.; Pancino, E.; Recio-Blanco, A.; Casey, A. R.; Costado, M. T.; Franciosini, E.; Heiter, U.; Hill, V.; Hourihane, A.; Lardo, C.; de Laverny, P.; Lewis, J.; Monaco, L.; Morbidelli, L.; Sacco, G. G.; Sousa, S. G.; Worley, C. C.; Zaggia, S.

2016-06-01

Context. The nature of the metallicity gradient inside the solar circle (RGC < 8 kpc) is poorly understood, but studies of Cepheids and a small sample of open clusters suggest that it steepens in the inner disk. Aims: We investigate the metallicity gradient of the inner disk using a sample of inner disk open clusters that is three times larger than has previously been studied in the literature to better characterize the gradient in this part of the disk. Methods: We used the Gaia-ESO Survey (GES) [Fe/H] values and stellar parameters for stars in 12 open clusters in the inner disk from GES-UVES data. Cluster mean [Fe/H] values were determined based on a membership analysis for each cluster. Where necessary, distances and ages to clusters were determined via comparison to theoretical isochrones. Results: The GES open clusters exhibit a radial metallicity gradient of -0.10 ± 0.02 dex kpc-1, consistent with the gradient measured by other literature studies of field red giant stars and open clusters in the range RGC ~ 6-12 kpc. We also measure a trend of increasing [Fe/H] with increasing cluster age, as has also been found in the literature. Conclusions: We find no evidence for a steepening of the inner disk metallicity gradient inside the solar circle as earlier studies indicated. The age-metallicity relation shown by the clusters is consistent with that predicted by chemical evolution models that include the effects of radial migration, but a more detailed comparison between cluster observations and models would be premature. Based on data products from observations made with ESO Telescopes at the La Silla Paranal Observatory under programme ID 188.B-3002 and 193.B-0936. These data products have been processed by the Cambridge Astronomy Survey Unit (CASU) at the Institute of Astronomy, University of Cambridge, and by the FLAMES/UVES reduction team at INAF/Osservatorio Astrofisico di Arcetri. These data have been obtained from the Gaia-ESO Survey Data Archive, prepared and hosted by the Wide Field Astronomy Unit, Institute for Astronomy, University of Edinburgh, which is funded by the UK Science and Technology Facilities Council.Full Table 2 is only available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (http://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/591/A37

High-resolution Spectroscopic Abundances of Red Giant Branch Stars in NGC 6584 and NGC 7099

NASA Astrophysics Data System (ADS)

O’Malley, Erin M.; Chaboyer, Brian

2018-04-01

We obtain high-resolution spectra of red giant branch stars in NGC 6584 and NGC 7099 to perform a detailed abundance analysis. We confirm cluster membership for these stars based on consistent radial velocities measured in this study and small pixel offsets between the observations of Sarajedini et al. and Piotto et al. We find mean metallicities of [Fe/H] = ‑1.53 ± 0.08 dex and [Fe/H] = ‑2.29 ± 0.07 dex for NGC 6584 and NGC 7099, respectively. We also find these clusters to be enhanced in their [α/Fe] ratios, consistent with what is expected for metal-poor globular clusters. Additionally, we find evidence of a statistically significant Na–O anti-correlation in both clusters. Finally, with the use of HST photometry, we compare the location of the enhanced and pristine populations in chromosome maps of the clusters to confirm previous photometric evidence of multiple stellar populations. Although we cannot confirm the nature of the polluter stars responsible for the abundance differences, our results can be used to constrain pollution models.

Fourier transform infrared isotopic studies on novel metal-carbon clusters trapped in argon matrix environments

NASA Astrophysics Data System (ADS)

Bates, Sarah Anne

The characterization of the vibrational spectra and structures of small metal-carbon (MnCm) clusters is important to the detection of astrophysical species and may elucidate the bonding and growth mechanisms of metallocarbohedrenes, or metcars. Additionally, transition metal-carbon clusters have applications in modern materials science as catalysts for nanomaterial formation. A new experimental apparatus for the preparation of MnC m clusters has been designed and constructed, incorporating a new closed cycle refrigeration system, a chamber for the deposition of samples, associated vacuum system, and a fully automated mechanism to simultaneously translate and rotate carbon and metal rods during laser ablation. A new technique for fabricating carbon rods has been developed to expedite carbon rod production and to facilitate the formation of the MnC m clusters studied. Fourier transform infrared (FTIR) investigations have been done for the first time on transition metal-carbon clusters. The molecular clusters were formed by trapping the products from dual laser ablation of metal and carbon rods in solid Ar at ˜10 K. Comparing FTIR measurements of vibrational fundamentals and 13C isotopic shifts with the predictions of density functional theory (DFT) calculations has enabled the identification of five novel metal-carbon molecules, establishing their ground state geometries and permitting the assignment of vibrational fundamentals, including the nu 1(sigma) modes of (5pi) linear CrC3, ( 2Delta) linear CoC3, and (2pi) linear CuC3 at 1789.5, 1918.2, and 1830.0 cm-1, respectively, the nu3(sigmau)=1624.0 and nu 4(sigmau)=528.3 cm-1 modes of (1Sigmag+) linear AlC3Al, and the nu2(sigma)=1210.9 cm -1 mode of linear AlC3. Evidence for the tentative identification of the nu1(a1)=1554.3 cm-1 mode of (3B1) fanlike CrC4 and the nu4(sigmau)=1987.3 cm-1 mode of (1Sigmag +) linear AlC4Al is also presented. All FTIR measurements of vibrational frequencies and 13C shifts are in very good agreement with DFT predictions, resulting in the first identification of vibrational fundamentals and the characterization of molecular geometries for these species specifically and for transition metal-carbon clusters in general. A catalog of potential VnCm absorptions has also been developed to aid in future vanadium-carbon studies.

Edades y metalicidades de cinco cúmulos estelares proyectados en dirección a la Nube Menor de Magallanes: implicaciones sobre los procesos de formación y evolución de estos sistemas

NASA Astrophysics Data System (ADS)

Piatti, A. E.; Santos, J. F. C.; Clariá, J. J.; Bica, E.; Sarajedini, A.; Geisler, D.

Washington photometry of the 5 star clusters Lindsay 32, Lindsay 38, Kron 28, Kron 44 and Lindsay 116 and their surrounding fields located towards the Small Magellanic Cloud (SMC) is presented for the first time. From the color-magnitude diagrams, cleaned from field stars contamination, the cluster and SMC field reddenings, ages and metallicities are determined. The ages - derived from the difference in the T1 magnitude betweem the giant clump and the Main Sequence turnoff point - vary between 2 and 6 Gyr, and the metallicities ([Fe/H]) between -1.65 and -1.10. Lindsay 116 is located closer to the Large Magellanic Cloud (LMC) than to the SMC and its fundamental parameters suggests a higher probability of belonging to the LMC. The results obtained in this work, combined with previous estimates of age and metallicity for other seven clusters, allow us to draw the following conclusions: (1) There does not exist an age-position relation in the SMC, but a age-metallicity one. (2) The chemical enrichment in the SMC has been very efficient during the last 5 Gyr. (3) The SMC clusters formation and evolution can be better represented by a bursting star formation process than by a continuum star formation mechanism.

Molecular dynamics simulation of metal nanoislands growth

NASA Astrophysics Data System (ADS)

Kapralov, N. V.; Babich, E. S.; Redkov, A. V.

2017-11-01

We present the atomistic model and the simulation of a self-assembled growth of a silver nanoisland film and small groups of nanoislands on a glass substrate after thermal poling of the glass with a profiled electrode. The calculations were performed in molecular dynamics simulator LAMMPS taking into account the diffusion of the metal atoms towards and along the glass surface and their clustering. Lennard-Jones potential was used to describe metal-metal and metal-glass interaction. The potential parameters were determined to provide qualitative coincidence of the simulated configurations of the metal nanostructures and the experimental ones, such as an isolated nanoisland, a pair and a set of three nanoislands and a “plasmonic molecule”.

Extending the Compositional Range of Nanocasting in the Oxozirconium Cluster-Based Metal–Organic Framework NU-1000—A Comparative Structural Analysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhao, Wenyang; Wang, Zhao; Malonzo, Camille D.

The process of nanocasting in metal-organic frameworks (MOFs) is a versatile approach to modify these porous materials by introducing supporting scaffolds. The nanocast scaffolds can stabilize metal-oxo clusters in MOFs at high temperatures and modulate their chemical environments. Here we demonstrate a range of nanocasting approaches in the MOF NU-1000, which contains hexanuclear oxozirconium clusters (denoted as Zr6 clusters) that are suitable for modification with other metals. We developed methods for introducing SiO2, TiO2, polymeric, and carbon scaffolds into the NU-1000 structure. The responses of NU-1000 towards different scaffold precursors were studied, including the effects on morphology, precursor distribution, andmore » porosity after nanocasting. Upon removal of organic linkers in the MOF by calcination/pyrolysis at 500 °C or above, the Zr6 clusters remained accessible and maintained their Lewis acidity in SiO2 nanocast samples, whereas additional treatment was necessary for Zr6 clusters to become accessible in carbon nanocast samples. Aggregation of Zr6 clusters was largely prevented with SiO2 or carbon scaffolds even after thermal treatment at 500 °C or above. In the case of titania nanocasting, NU- 1000 crystals underwent a pseudomorphic transformation, in which Zr6 clusters reacted with titania to form small oxaggregates of a Zr/Ti mixed oxide with a local structure resembling that of ZrTi2O6. The ability to maintain high densities of discrete Lewis acidic Zr6 clusters on SiO2 or carbon supports at high temperatures provides a starting point for designing new thermally stable catalysts.« less

First-principles investigation of the dissociation and coupling of methane on small copper clusters: Interplay of collision dynamics and geometric and electronic effects

DOE Office of Scientific and Technical Information (OSTI.GOV)

Varghese, Jithin J.; Mushrif, Samir H., E-mail: shmushrif@ntu.edu.sg

Small metal clusters exhibit unique size and morphology dependent catalytic activity. The search for alternate minimum energy pathways and catalysts to transform methane to more useful chemicals and carbon nanomaterials led us to investigate collision induced dissociation of methane on small Cu clusters. We report here for the first time, the free energy barriers for the collision induced activation, dissociation, and coupling of methane on small Cu clusters (Cu{sub n} where n = 2–12) using ab initio molecular dynamics and metadynamics simulations. The collision induced activation of the stretching and bending vibrations of methane significantly reduces the free energy barriermore » for its dissociation. Increase in the cluster size reduces the barrier for dissociation of methane due to the corresponding increase in delocalisation of electron density within the cluster, as demonstrated using the electron localisation function topology analysis. This enables higher probability of favourable alignment of the C–H stretching vibration of methane towards regions of high electron density within the cluster and makes higher number of sites available for the chemisorption of CH{sub 3} and H upon dissociation. These characteristics contribute in lowering the barrier for dissociation of methane. Distortion and reorganisation of cluster geometry due to high temperature collision dynamics disturb electron delocalisation within them and increase the barrier for dissociation. Coupling reactions of CH{sub x} (x = 1–3) species and recombination of H with CH{sub x} have free energy barriers significantly lower than complete dehydrogenation of methane to carbon. Thus, competition favours the former reactions at high hydrogen saturation on the clusters.« less

Self-consistent physical parameters for five intermediate-age SMC stellar clusters from CMD modelling

NASA Astrophysics Data System (ADS)

Dias, B.; Kerber, L. O.; Barbuy, B.; Santiago, B.; Ortolani, S.; Balbinot, E.

2014-01-01

Context. Stellar clusters in the Small Magellanic Cloud (SMC) are useful probes for studying the chemical and dynamical evolution of this neighbouring dwarf galaxy, enabling inspection of a large period covering over 10 Gyr. Aims: The main goals of this work are the derivation of age, metallicity, distance modulus, reddening, core radius, and central density profiles for six sample clusters, in order to place them in the context of the Small Cloud evolution. The studied clusters are AM 3, HW 1, HW 34, HW 40, Lindsay 2, and Lindsay 3; HW 1, HW 34, and Lindsay 2 are studied for the first time. Methods: Optical colour-magnitude diagrams (V,B - V CMDs) and radial density profiles were built from images obtained with the 4.1 m Southern Astrophysical Research (SOAR) telescope, reaching V ~ 23. The determination of structural parameters were carried out by applying King profile fitting. The other parameters were derived in a self-consistent way by means of isochrone fitting, which uses likelihood statistics to identify the synthetic CMDs that best reproduce the observed ones. Membership probabilities were determined comparing the cluster and control field CMDs. Completeness and photometric uncertainties were obtained by performing artificial star tests. Results: The results confirm that these clusters (except HW 34, identified as a field fluctuation) are intermediate-age clusters, with ages between 1.2 Gyr (Lindsay 3) and ~5.0 Gyr (HW 1). In particular HW 1, Lindsay 2 and Lindsay 3 are located in a region that we called West Halo, where studies of ages and metallicity gradients are still lacking. Moreover, Lindsay 2 was identified as a moderately metal-poor cluster with [Fe/H] = -1.4 ± 0.2 dex, lower than expected from the age-metallicity relation by Pagel & Tautvaisiene (1998). We also found distances varying from ~53 kpc to 66 kpc, compatible with the large depth of the SMC. Based on observations obtained at the Southern Astrophysical Research (SOAR) telescope, which is a joint project of the Ministério da Ciência, Tecnologia, e Inovação (MCTI) da República Federativa do Brasil, the US National Optical Astronomy Observatory (NOAO), the University of North Carolina at Chapel Hill (UNC), and Michigan State University (MSU).Appendix A is available in electronic form at http://www.aanda.orgThe tables of photometry are only available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (ftp://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/561/A106

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Avila, Jason R.; Emery, Jonathan D.; Pellin, Michael J.

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. Analyticalmore » 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.« less

Detailed chemical composition of classical Cepheids in the LMC cluster NGC 1866 and in the field of the SMC

NASA Astrophysics Data System (ADS)

Lemasle, B.; Groenewegen, M. A. T.; Grebel, E. K.; Bono, G.; Fiorentino, G.; François, P.; Inno, L.; Kovtyukh, V. V.; Matsunaga, N.; Pedicelli, S.; Primas, F.; Pritchard, J.; Romaniello, M.; da Silva, R.

2017-12-01

Context. Cepheids are excellent tracers of young stellar populations. They play a crucial role in astrophysics as standard candles. The chemistry of classical Cepheids in the Milky Way is now quite well-known, however despite a much larger sample, the chemical composition of Magellanic Cepheids has been only scarcely investigated. Aims: For the first time, we study the chemical composition of several Cepheids located in the same populous cluster: NGC 1866, in the Large Magellanic Cloud (LMC). To also investigate the chemical composition of Cepheids at lower metallicity, we look at four targets located in the Small Magellanic Cloud (SMC). Our sample allows us to increase the number of Cepheids with known metallicities in the LMC/SMC by 20%/25% and the number of Cepheids with detailed chemical composition in the LMC/SMC by 46%/50%. Methods: We use canonical spectroscopic analysis to determine the chemical composition of Cepheids and provide abundances for a good number of α, iron-peak, and neutron-capture elements. Results: We find that six Cepheids in the LMC cluster NGC 1866 have a very homogeneous chemical composition, also consistent with red giant branch (RGB) stars in the cluster. Period-age relations that include no or average rotation indicate that all the Cepheids in NGC 1866 have a similar age and therefore belong to the same stellar population. Our results are in good agreement with theoretical models accounting for luminosity and radial velocity variations. Using distances based on period-luminosity relations in the near- or mid-infrared, we investigate for the first time the metallicity distribution of the young population in the SMC in the depth direction. Preliminary results show no metallicity gradient along the SMC main body, but our sample is small and does not contain Cepheids in the inner few degrees of the SMC. Based on observations collected at the European Organisation for Astronomical Research in the Southern Hemisphere under ESO programme 082.D-0792(B).

In-Plane Multimagnetron Approach

DOE Office of Scientific and Technical Information (OSTI.GOV)

Johnson, Grant E.; Laskin, Julia

2017-04-01

Nanoparticles (NPs) and sub-nanometer clusters containing controlled amounts of different atoms are of interest for a variety of potential applications including catalysis,1, 2 optics,3, 4 magnetics,5-7 sensors,8, 9 and biotheraputics.10, 11 Alloy NPs may possess enhanced physical and chemical properties compared to single metal species due to the additional interplay between their different elemental components. By reducing the quantity of expensive precious metals in alloy NPs by substituting cheaper base metals, it may also be possible to achieve equivalent or even superior performance to pure noble metal NPs for applications such as heterogeneous catalysis at substantially reduced material costs.12 Inmore » addition, alloying of elements that are immiscible in bulk form is possible in NPs because the enthalpy of mixing decreases and becomes negative at small particle sizes.13, 14 As a result, a substantially broader array of alloy species may be generated in the form of NPs and sub-nanometer clusters.« less

Computational chemistry of modified [MFe3S4] and [M2Fe2S4] clusters: assessment of trends in electronic structure and properties.

PubMed

Jensen, Kasper P; Ooi, Bee-Lean; Christensen, Hans E M

2008-12-18

The aim of this work is to understand the molecular evolution of iron-sulfur clusters in terms of electronic structure and function. Metal-substituted models of biological [Fe(4)S(4)] clusters in oxidation states [M(x)Fe(4-x)S(4)](3+/2+/1+) have been studied by density functional theory (M = Cr, Mn, Fe, Co, Ni, Cu, Zn, and Pd, with x = 1 or 2). Most of these clusters have not been characterized before. For those that have been characterized experimentally, very good agreement is obtained, implying that also the predicted structures and properties of new clusters are accurate. Mean absolute errors are 0.024 A for bond lengths ([Fe(4)S(4)], [NiFe(3)S(4)], [CoFe(3)S(4)]) and 0.09 V for shifts in reduction potentials relative to the [Fe(4)S(4)] cluster. All structures form cuboidal geometries similar to the all-iron clusters, except the Pd-substituted clusters, which instead form highly distorted trigonal and tetragonal local sites in compromised, pseudocuboidal geometries. In contrast to other electron-transfer sites, cytochromes, blue copper proteins, and smaller iron-sulfur clusters, we find that the [Fe(4)S(4)] clusters are very insensitive to metal substitution, displaying quite small changes in reorganization energies and reduction potentials upon substitution. Thus, the [Fe(4)S(4)] clusters have an evolutionary advantage in being robust to pollution from other metals, still retaining function. We analyze in detail the electronic structure of individual clusters and rationalize spin couplings and redox activity. Often, several configurations are very close in energy, implying possible use as spin-crossover systems, and spin states are predicted accurately in all but one case ([CuFe(3)S(4)]). The results are anticipated to be helpful in defining new molecular systems with catalytic and magnetic properties.

Astrophysical properties of star clusters in the Magellanic Clouds homogeneously estimated by ASteCA

NASA Astrophysics Data System (ADS)

Perren, G. I.; Piatti, A. E.; Vázquez, R. A.

2017-06-01

Aims: We seek to produce a homogeneous catalog of astrophysical parameters of 239 resolved star clusters, located in the Small and Large Magellanic Clouds, observed in the Washington photometric system. Methods: The cluster sample was processed with the recently introduced Automated Stellar Cluster Analysis (ASteCA) package, which ensures both an automatized and a fully reproducible treatment, together with a statistically based analysis of their fundamental parameters and associated uncertainties. The fundamental parameters determined for each cluster with this tool, via a color-magnitude diagram (CMD) analysis, are metallicity, age, reddening, distance modulus, and total mass. Results: We generated a homogeneous catalog of structural and fundamental parameters for the studied cluster sample and performed a detailed internal error analysis along with a thorough comparison with values taken from 26 published articles. We studied the distribution of cluster fundamental parameters in both Clouds and obtained their age-metallicity relationships. Conclusions: The ASteCA package can be applied to an unsupervised determination of fundamental cluster parameters, which is a task of increasing relevance as more data becomes available through upcoming surveys. A table with the estimated fundamental parameters for the 239 clusters analyzed is only available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (http://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/602/A89

The extended stellar substructures of four metal-poor globular clusters in the galactic bulge

NASA Astrophysics Data System (ADS)

Chun, Sang-Hyun; Sohn, Young-Jong

2015-08-01

We investigated stellar spatial density distribution around four metal-poor globular clusters (NGC 6266, NGC 6626, NGC 6642 and NGC 6723) in order to find extended stellar substructures. Wide-field deep J, H, and K imaging data were taken using the WFCAM near-infrared array on United Kingdom Infrared Telescope (UKIRT). The contamination of field stars around clusters was minimised by applying a statistical weighted filtering algorithm for the stars on the color-magnitude diagram. In two-dimensional isodensity contour map, we find that all four of the globular clusters shows tidal stripping stellar features in the form of tidal tails (NGC 6266 and NGC 6723) or small density lobes/chunk (NGC 6642 and NGC 6723). The stellar substructures extend toward the Galactic centre or anticancer, and the proper motion direction of the clusters. The radial density profiles of the clusters also depart from theoretical King and Wilson models and show overdensity feature with a break in a slope of profile at the outer region of clusters. The observed results indicate that four globular clusters in the Galactic bulge have experienced strong tidal force or bulge/disk shock effect of the Galaxy. These observational results provide us further constraints to understand the evolution of clusters in the Galactic bulge region as well as the formation of the Galaxy.

Kinetic Monte Carlo Simulation of the Growth of Various Nanostructures through Atomic and Cluster Deposition: Application to Gold Nanostructure Growth on Graphite

NASA Astrophysics Data System (ADS)

Claassens, C. H.; Hoffman, M. J. H.; Terblans, J. J.; Swart, H. C.

2006-01-01

A Kinetic Monte Carlo (KMC) method is presented to describe the growth of metallic nanostructures through atomic and cluster deposition in the mono -and multilayer regime. The model makes provision for homo- and heteroepitaxial systems with small lattice mismatch. The accuracy of the model is tested with simulations of the growth of gold nanostructures on HOPG and comparisons are made with existing experimental data.

The history of chemical enrichment in the intracluster medium from cosmological simulations

NASA Astrophysics Data System (ADS)

Biffi, V.; Planelles, S.; Borgani, S.; Fabjan, D.; Rasia, E.; Murante, G.; Tornatore, L.; Dolag, K.; Granato, G. L.; Gaspari, M.; Beck, A. M.

2017-06-01

The distribution of metals in the intracluster medium (ICM) of galaxy clusters provides valuable information on their formation and evolution, on the connection with the cosmic star formation and on the effects of different gas processes. By analysing a sample of simulated galaxy clusters, we study the chemical enrichment of the ICM, its evolution, and its relation with the physical processes included in the simulation and with the thermal properties of the core. These simulations, consisting of re-simulations of 29 Lagrangian regions performed with an upgraded version of the smoothed particle hydrodynamics (SPH) gadget-3 code, have been run including two different sets of baryonic physics: one accounts for radiative cooling, star formation, metal enrichment and supernova (SN) feedback, and the other one further includes the effects of feedback from active galactic nuclei (AGN). In agreement with observations, we find an anti-correlation between entropy and metallicity in cluster cores, and similar radial distributions of heavy-element abundances and abundance ratios out to large cluster-centric distances (˜R180). In the outskirts, namely outside of ˜0.2 R180, we find a remarkably homogeneous metallicity distribution, with almost flat profiles of the elements produced by either SNIa or SNII. We investigated the origin of this phenomenon and discovered that it is due to the widespread displacement of metal-rich gas by early (z > 2-3) AGN powerful bursts, acting on small high-redshift haloes. Our results also indicate that the intrinsic metallicity of the hot gas for this sample is on average consistent with no evolution between z = 2 and z = 0, across the entire radial range.

Embedded cluster metal-polymeric micro interface and process for producing the same

DOEpatents

Menezes, Marlon E.; Birnbaum, Howard K.; Robertson, Ian M.

2002-01-29

A micro interface between a polymeric layer and a metal layer includes isolated clusters of metal partially embedded in the polymeric layer. The exposed portion of the clusters is smaller than embedded portions, so that a cross section, taken parallel to the interface, of an exposed portion of an individual cluster is smaller than a cross section, taken parallel to the interface, of an embedded portion of the individual cluster. At least half, but not all of the height of a preferred spherical cluster is embedded. The metal layer is completed by a continuous layer of metal bonded to the exposed portions of the discontinuous clusters. The micro interface is formed by heating a polymeric layer to a temperature, near its glass transition temperature, sufficient to allow penetration of the layer by metal clusters, after isolated clusters have been deposited on the layer at lower temperatures. The layer is recooled after embedding, and a continuous metal layer is deposited upon the polymeric layer to bond with the discontinuous metal clusters.

Ultra-small Ag clusters in zeolite A4: Antibacterial and thermochromic applications

NASA Astrophysics Data System (ADS)

Horta-Fraijo, P.; Cortez-Valadez, M.; Flores-Lopez, N. S.; Britto Hurtado, R.; Vargas-Ortiz, R. A.; Perez-Rodriguez, A.; Flores-Acosta, M.

2018-03-01

The physical and chemical properties of metal clusters depend on their atomic structure, therefore, it is important to determine the lowest-energy structures of the clusters in order to understand and utilize their properties. In this work, we use the Density Functional Theory (DFT) at the generalized gradient approximation level Becke's three-parameter and the gradient corrected functional of Lee, Yang and Puar (B3LYP) in combination with the basis set LANL2DZ (the effective core potentials and associated double-zeta valence) to determine some of the structural, electronic and vibrational properties of the planar silver clusters (Agn clusters n = 2-24). Additionally, the study reports the experimental synthesis of small silver clusters in synthetic zeolite A4. The synthesis was possible using the ion exchange method with some precursors like silver nitrate (AgNO3) and synthetic zeolite A4. The silver clusters in zeolite powder underwent thermal treatment at 450 °C to release the remaining water or humidity on it. The morphology of the particles was determined by Transmission Electron microscopy. The nanomaterials obtained show thermochromic properties. The structural parameters were correlated theoretically and experimentally.

Alloy formation and metal oxide segregation on Pt-Re/. gamma. -Al/sub 2/O/sub 3/ catalysts as investigated by temperature-programmed reduction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wagstaff, N.; Prins, R.

1979-10-15

Catalysts resembling reforming catalysts were prepared to contain finely dispersed 0.75% Pt, 0.7% Re, or 0.35% Pt plus 0.1-2% Re on chlorided ..gamma..-alumina. The catalysts were dried in an oxidizing atmosphere and studied by temperature-programed reduction. Up to a Re/Pt ratio of 0.6:1 the metals were completely reduced in hydrogen below 255/sup 0/C, i.e., the platinum catalyzed rhenium reduction. A small amount of added water (< 50 ppm) also promoted rhenium reduction. Segregation of the metals occurred in oxygen above 200/sup 0/C, but at 100/sup 0/C, the rate of segregation was slow. These results suggested that under reforming conditions, Pt-Remore » catalysts are completely reduced bimetallic clusters. The mechanisms of reduction, cluster formation, and oxidative segregation are discussed.« less

The effect of metal cluster deposition route on structure and photocatalytic activity of mono- and bimetallic nanoparticles supported on TiO2 by radiolytic method

NASA Astrophysics Data System (ADS)

Klein, Marek; Nadolna, Joanna; Gołąbiewska, Anna; Mazierski, Paweł; Klimczuk, Tomasz; Remita, Hynd; Zaleska-Medynska, Adriana

2016-08-01

TiO2 (P25) was modified with small and relatively monodisperse mono- and bimetallic clusters (Ag, Pd, Pt, Ag/Pd, Ag/Pt and Pd/Pt) induced by radiolysis to improve its photocatalytic activity. The as-prepared samples were characterized by X-ray fluorescence spectrometry (XRF), photoluminescence spectrometry (PL), diffuse reflectance spectroscopy (DRS), X-ray powder diffractometry (XRD), scanning transition electron microscopy (STEM) and BET surface area analysis. The effect of metal type (mono- and bimetallic modification) as well as deposition method (simultaneous or subsequent deposition of two metals) on the photocatalytic activity in toluene removal in gas phase under UV-vis irradiation (light-emitting diodes- LEDs) and phenol degradation in liquid phase under visible light irradiation (λ > 420 nm) were investigated. The highest photoactivity under Vis light was observed for TiO2 co-loaded with platinum (0.1%) and palladium (0.1%) clusters. Simultaneous addition of metal precursors results in formation of larger metal nanoparticles (15-30 nm) on TiO2 surface and enhances the Vis-induced activity of Ag/Pd-TiO2 up to four times, while the subsequent metal ions addition results in formation of metal particle size ranging from 4 to 20 nm. Subsequent addition of metal precursors results in formation of BNPs (bimetallic nanoparticle) composites showing higher stability in four cycles of toluene degradation under UV-vis. Obtained results indicated that direct electron transfer from the BNPs to the conduction band of the semiconductor is responsible for visible light photoactivity, whereas superoxide radicals (such as O2rad- and rad OOH) are responsible for pollutants degradation over metal-TiO2 composites.

Molecular metal catalysts on supports: organometallic chemistry meets surface science.

PubMed

Serna, Pedro; Gates, Bruce C

2014-08-19

Recent advances in the synthesis and characterization of small, essentially molecular metal complexes and metal clusters on support surfaces have brought new insights to catalysis and point the way to systematic catalyst design. We summarize recent work unraveling effects of key design variables of site-isolated catalysts: the metal, metal nuclearity, support, and other ligands on the metals, also considering catalysts with separate, complementary functions on supports. The catalysts were synthesized with the goal of structural simplicity and uniformity to facilitate incisive characterization. Thus, they are essentially molecular species bonded to porous supports chosen for their high degree of uniformity; the supports are crystalline aluminosilicates (zeolites) and MgO. The catalytic species are synthesized in reactions of organometallic precursors with the support surfaces; the precursors include M(L)2(acetylacetonate)1-2, with M = Ru, Rh, Ir, or Au and the ligands L = C2H4, CO, or CH3. Os3(CO)12 and Ir4(CO)12 are used as precursors of supported metal clusters, and some such catalysts are made by ship-in-a-bottle syntheses to trap the clusters in zeolite cages. The simplicity and uniformity of the supported catalysts facilitate precise structure determinations, even in reactive atmospheres and during catalysis. The methods of characterizing catalysts in reactive atmospheres include infrared (IR), extended X-ray absorption fine structure (EXAFS), X-ray absorption near edge structure (XANES), and nuclear magnetic resonance (NMR) spectroscopies, and complementary methods include density functional theory and atomic-resolution aberration-corrected scanning transmission electron microscopy for imaging of individual metal atoms. IR, NMR, XANES, and microscopy data demonstrate the high degrees of uniformity of well-prepared supported species. The characterizations determine the compositions of surface metal complexes and clusters, including the ligands and the metal-support bonding and structure, which identify the supports as ligands with electron-donor properties that influence reactivity and catalysis. Each of the catalyst design variables has been varied independently, illustrated by mononuclear and tetranuclear iridium on zeolite HY and on MgO and by isostructural rhodium and iridium (diethylene or dicarbonyl) complexes on these supports. The data provide examples resolving the roles of the catalyst design variables and place the catalysis science on a firm foundation of organometallic chemistry linked with surface science. Supported molecular catalysts offer the advantages of characterization in the absence of solvents and with surface-science methods that do not require ultrahigh vacuum. Families of supported metal complexes have been made by replacement of ligands with others from the gas phase. Spectroscopically identified catalytic reaction intermediates help to elucidate catalyst performance and guide design. The methods are illustrated for supported complexes and clusters of rhodium, iridium, osmium, and gold used to catalyze reactions of small molecules that facilitate identification of the ligands present during catalysis: alkene dimerization and hydrogenation, H-D exchange in the reaction of H2 with D2, and CO oxidation. The approach is illustrated with the discovery of a highly active and selective MgO-supported rhodium carbonyl dimer catalyst for hydrogenation of 1,3-butadiene to give butenes.

CHEMICAL ABUNDANCES IN A SAMPLE OF RED GIANTS IN THE OPEN CLUSTER NGC 2420 FROM APOGEE

DOE Office of Scientific and Technical Information (OSTI.GOV)

Souto, Diogo; Cunha, K.; Smith, V.

NGC 2420 is a ∼2 Gyr old well-populated open cluster that lies about 2 kpc beyond the solar circle, in the general direction of the Galactic anti-center. Most previous abundance studies have found this cluster to be mildly metal-poor, but with a large scatter in the obtained metallicities. Detailed chemical abundance distributions are derived for 12 red-giant members of NGC 2420 via a manual abundance analysis of high-resolution ( R = 22,500) near-infrared ( λ 1.5–1.7 μ m) spectra obtained from the Apache Point Observatory Galactic Evolution Experiment (APOGEE) survey. The sample analyzed contains six stars that are identified asmore » members of the first-ascent red giant branch (RGB), as well as six members of the red clump (RC). We find small scatter in the star-to-star abundances in NGC 2420, with a mean cluster abundance of [Fe/H] = −0.16 ± 0.04 for the 12 red giants. The internal abundance dispersion for all elements (C, N, O, Na, Mg, Al, Si, K, Ca, Ti, V, Cr, Mn, Co and Ni) is also very small (∼0.03–0.06 dex), indicating a uniform cluster abundance distribution within the uncertainties. NGC 2420 is one of the clusters used to calibrate the APOGEE Stellar Parameter and Chemical Abundance Pipeline (ASPCAP). The results from this manual analysis compare well with ASPCAP abundances for most of the elements studied, although for Na, Al, and V there are more significant offsets. No evidence of extra-mixing at the RGB luminosity bump is found in the {sup 12}C and {sup 14}N abundances from the pre-luminosity-bump RGB stars in comparison to the post-He core-flash RC stars.« less

Superplasticity - A Fundamental Investigation on Deformation Mechanism and Cavitation Phenomena.

DTIC Science & Technology

1988-02-15

NI-MODIFIED SUPERPLASTIC Ti- 6Al - 4V ALLOY, B. Hidalgo-Prada and A.K. Mukherjee, Proc. of Intnl. Conf. of Strength of Metals and AlloyS-7, Montreal...features, e.g., initial porosity (15 to 500 pm diam.), stringers (of Fe-rich particles, 5-30 pm diam.), and small (0.3-3 pm) copper- rich particles...500% or greater, porosity between grains was observed. Some grains as well as grain clusters are visible in Fig. 6. The grain clusters are believed to

Fullerene-like boron clusters stabilized by an endohedrally doped iron atom: B(n)Fe with n = 14, 16, 18 and 20.

PubMed

Tam, Nguyen Minh; Pham, Hung Tan; Duong, Long Van; Pham-Ho, My Phuong; Nguyen, Minh Tho

2015-02-07

Stabilized fullerene and tubular forms can be produced in boron clusters Bn in small sizes from n∼ 14 to 20 upon doping by transition metal atoms. B14Fe and B16Fe are stable tubes whereas B18Fe and B20Fe are stable fullerenes. Their formation and stability suggest the use of dopants to induce different growth paths leading to larger cages, fullerenes and tubes of boron.

Stabilization of fullerene-like boron cages by transition metal encapsulation

NASA Astrophysics Data System (ADS)

Lv, Jian; Wang, Yanchao; Zhang, Lijun; Lin, Haiqing; Zhao, Jijun; Ma, Yanming

2015-06-01

The stabilization of fullerene-like boron (B) cages in the free-standing form has been long sought after and a challenging problem. Studies that have been carried out for more than a decade have confirmed that the planar or quasi-planar polymorphs are energetically favored ground states over a wide range of small and medium-sized B clusters. Recently, the breakthroughs represented by Nat. Chem., 2014, 6, 727 established that the transition from planar/quasi-planar to cage-like Bn clusters occurs around n = ~38-40, paving the way for understanding the intriguing chemistry of B-fullerene. We herein demonstrate that the transition demarcation, n, can be significantly reduced with the help of transition metal encapsulation. We explore via extensive first-principles swarm-intelligence based structure searches the free energy landscapes of B24 clusters doped by a series of transition metals and find that the low-lying energy regime is generally dominated by cage-like isomers. This is in sharp contrast to that of bare B24 clusters, where the quasi-planar and rather irregular polyhedrons are prevalent. Most strikingly, a highly symmetric B cage with D3h symmetry is discovered in the case of Mo or W encapsulation. The endohedral D3h cages exhibit robust thermodynamic, dynamic and chemical stabilities, which can be rationalized in terms of their unique electronic structure of an 18-electron closed-shell configuration. Our results indicate that transition metal encapsulation is a feasible route for stabilizing medium-sized B cages, offering a useful roadmap for the discovery of more B fullerene analogues as building blocks of nanomaterials.The stabilization of fullerene-like boron (B) cages in the free-standing form has been long sought after and a challenging problem. Studies that have been carried out for more than a decade have confirmed that the planar or quasi-planar polymorphs are energetically favored ground states over a wide range of small and medium-sized B clusters. Recently, the breakthroughs represented by Nat. Chem., 2014, 6, 727 established that the transition from planar/quasi-planar to cage-like Bn clusters occurs around n = ~38-40, paving the way for understanding the intriguing chemistry of B-fullerene. We herein demonstrate that the transition demarcation, n, can be significantly reduced with the help of transition metal encapsulation. We explore via extensive first-principles swarm-intelligence based structure searches the free energy landscapes of B24 clusters doped by a series of transition metals and find that the low-lying energy regime is generally dominated by cage-like isomers. This is in sharp contrast to that of bare B24 clusters, where the quasi-planar and rather irregular polyhedrons are prevalent. Most strikingly, a highly symmetric B cage with D3h symmetry is discovered in the case of Mo or W encapsulation. The endohedral D3h cages exhibit robust thermodynamic, dynamic and chemical stabilities, which can be rationalized in terms of their unique electronic structure of an 18-electron closed-shell configuration. Our results indicate that transition metal encapsulation is a feasible route for stabilizing medium-sized B cages, offering a useful roadmap for the discovery of more B fullerene analogues as building blocks of nanomaterials. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr01659b

Direct observation of small cluster mobility and ripening

NASA Technical Reports Server (NTRS)

Heinemann, K.; Poppa, H.

1976-01-01

Direct evidence is reported for the simultaneous occurrence of Ostwald ripening and short-distance cluster mobility during annealing of discontinuous metal films on clean amorphous substrates. The annealing characteristics of very thin particulate deposits of silver on amorphized clean surfaces of single-crystalline thin graphite substrates have been studied by in situ transmission electron microscopy (TEM) under controlled environmental conditions in the temperature range from 25 to 450 C. It was possible to monitor all stages of the experiments by TEM observation of the same specimen area. Slow Ostwald ripening was found to occur over the entire temperature range, but the overriding surface transport mechanism was short-distance cluster mobility. This was concluded from in situ observations of individual particles during annealing and from measurements of cluster size distributions, cluster number densities, area coverages, and mean cluster diameters.

Low-temperature cluster catalysis.

PubMed

Judai, Ken; Abbet, Stéphane; Wörz, Anke S; Heiz, Ulrich; Henry, Claude R

2004-03-10

Free and supported metal clusters reveal unique chemical and physical properties, which vary as a function of size as each cluster possesses a characteristic electron confinement. Several previous experimental results showed that the outcome of a given chemical reaction can be controlled by tuning the cluster size. However, none of the examples indicate that clusters prepared in the gas phase and then deposited on a support material are indeed catalytically active over several reaction cycles nor that their catalytic properties remain constant during such a catalytic process. In this work we report turn-over frequencies (TOF) for Pd(n) (n = 4, 8, 30) clusters using pulsed molecular beam experiments. The obtained results illustrate that the catalytic reactivity for the NO reduction by CO (CO + NO --> 1/2N(2) + CO(2)) is indeed a function of cluster size and that the measured TOF remain constant at a given temperature. More interestingly, the temperature of maximal reactivity is at least 100 K lower than observed for palladium nanoparticles or single crystals. One reason for this surprising observation is the character of the binding sites of these small clusters: N(2) forms already at relatively low temperatures (400 and 450 K) and therefore poisoning by adsorbed nitrogen adatoms is prevented. Thus, small clusters not only open the possibility of tuning a catalytic process by changing cluster size, but also of catalyzing chemical reactions at low temperatures.

Phase transition temperatures of 405-725 K in superfluid ultra-dense hydrogen clusters on metal surfaces

DOE Office of Scientific and Technical Information (OSTI.GOV)

Holmlid, Leif, E-mail: holmlid@chem.gu.se; Kotzias, Bernhard

Ultra-dense hydrogen H(0) with its typical H-H bond distance of 2.3 pm is superfluid at room temperature as expected for quantum fluids. It also shows a Meissner effect at room temperature, which indicates that a transition point to a non-superfluid state should exist above room temperature. This transition point is given by a disappearance of the superfluid long-chain clusters H{sub 2N}(0). This transition point is now measured for several metal carrier surfaces at 405 - 725 K, using both ultra-dense protium p(0) and deuterium D(0). Clusters of ordinary Rydberg matter H(l) as well as small symmetric clusters H{sub 4}(0) andmore » H{sub 3}(0) (which do not give a superfluid or superconductive phase) all still exist on the surface at high temperature. This shows directly that desorption or diffusion processes do not remove the long superfluid H{sub 2N}(0) clusters. The two ultra-dense forms p(0) and D(0) have different transition temperatures under otherwise identical conditions. The transition point for p(0) is higher in temperature, which is unexpected.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Merchant Boesgaard, Ann; Lum, Michael G.; Deliyannis, Constantine P., E-mail: boes@ifa.hawaii.edu, E-mail: mikelum@ifa.hawaii.edu, E-mail: cdeliyan@indiana.edu

The study of star clusters has advanced our understanding of stellar evolution, Galactic chemical evolution, and nucleosynthesis. Here we investigate the composition of turn-off stars in the intriguing open cluster, NGC 6791, which is old, but super-metal-rich with high-resolution (R = 46,000) Keck/HIRES spectra. We find [Fe/H] = +0.30 ± 0.02 from measurements of some 40 unblended, unsaturated lines of both Fe I and Fe II in eight turn-off stars. Our O abundances come from the O I triplet near 7774 Å and we perform a differential analysis relative to the Sun from our Lunar spectrum also obtained with Keck/HIRES. The O results aremore » corrected for small nLTE effects. We find consistent ratios of [O/Fe]{sub n} with a mean of –0.06 ± 0.02. This is low with respect to field stars that are also both old and metal-rich and continue the trend of decreasing [O/Fe] with increasing [Fe/H]. The small range in our oxygen abundances is consistent with a single population of stars. Our results for the alpha elements [Mg/Fe], [Si/Fe], [Ca/Fe], and [Ti/Fe] are near solar and compare well with those of the old, metal-rich field stars. The two Fe-peak elements, Cr and Ni, are consistent with Fe. These turn-off-star abundances provide benchmark abundances to investigate whether there are any observable abundance differences with the giants that might arise from nuclear-burning and dredge-up processes. Determinations of upper limits were found for Li by spectrum synthesis and are consistent with the upper limits in similar stars in the relatively old, super-metal-rich cluster NGC 6253. Our results support the prediction from standard theory that higher-metallicity stars deplete more Li. Probably no stars in NGC 6791 have retained their initial Li.« less

Exploring the Chemical Composition and Double Horizontal Branch of the Bulge Globular Cluster NGC 6569

NASA Astrophysics Data System (ADS)

Johnson, Christian I.; Rich, R. Michael; Caldwell, Nelson; Mateo, Mario; Bailey, John I., III; Olszewski, Edward W.; Walker, Matthew G.

2018-02-01

Photometric and spectroscopic analyses have shown that the Galactic bulge cluster Terzan 5 hosts several populations with different metallicities and ages that manifest as a double red horizontal branch (HB). A recent investigation of the massive bulge cluster NGC 6569 revealed a similar, though less extended, HB luminosity split, but little is known about the cluster’s detailed chemical composition. Therefore, we have used high-resolution spectra from the Magellan–M2FS and VLT–FLAMES spectrographs to investigate the chemical compositions and radial velocity distributions of red giant branch and HB stars in NGC 6569. We found the cluster to have a mean heliocentric radial velocity of ‑48.8 km s‑1 (σ = 5.3 km s‑1 148 stars) and < [{Fe}/{{H}}]> =-0.87 dex (19 stars), but the cluster’s 0.05 dex [Fe/H] dispersion precludes a significant metallicity spread. NGC 6569 exhibits light- and heavy-element distributions that are common among old bulge/inner Galaxy globular clusters, including clear (anti)correlations between [O/Fe], [Na/Fe], and [Al/Fe]. The light-element data suggest that NGC 6569 may be composed of at least two distinct populations, and the cluster’s low < [{La}/{Eu}]> =-0.11 dex indicates significant pollution with r-process material. We confirm that both HBs contain cluster members, but metallicity and light-element variations are largely ruled out as sources for the luminosity difference. However, He mass fraction differences as small as ΔY ∼ 0.02 cannot be ruled out and may be sufficient to reproduce the double HB.

Supersonic Bare Metal Cluster Beams. Technical Progress Report, March 16, 1984 - April 1, 1985

DOE R&D Accomplishments Database

Smalley, R. E.

1985-01-01

There have been four major areas of concentration for the study of bare metal cluster beams: neutral cluster, chemical reactivity, cold cluster ion source development (both positive and negative), bare cluster ion ICR (ion cyclotron resonance) development, and photofragmentation studies of bare metal cluster ions.

Adsorption of Bromine on Gold Nanoclusters

NASA Astrophysics Data System (ADS)

Salvo, Christopher; Keagy, Josiah; Yarmoff, Jory

Small metal nanoclusters are extremely effective as catalysts, with rates that rival those of enzymes in biological systems. The first step in a catalytic reaction is the adsorption of a precursor molecule. The neutralization of alkali projectiles during low energy ion scattering (LEIS), which is acutely sensitive to the local electrostatic potential a few Å's above the surface, is used here to probe Au nanoclusters grown on SiO2 as they are reacted with Br2. Previous work had demonstrated very efficient neutralization in scattering from small catalytically active Au clusters, which was interpreted as an indication that the bare clusters are negatively charged. X-ray photoelectron spectroscopy and LEIS show little or no Br signal after exposing SiO2 and Au foil to Br2, suggesting that adsorption does not occur because the Br-Br bond does not break. Dissociative adsorption occurs rapidly, however, when small Au nanoclusters are reacted with Br2. 1.5 keV Na+ ions scattered from the Au clusters show a decrease in the neutralization probability as Br is reacted, indicating that adsorption results in charge being transferred from the cluster to the Br adatom. This material is based upon work supported by the National Science Foundation under CHE - 1611563.

Effects of manganese doping on the structure evolution of small-sized boron clusters

NASA Astrophysics Data System (ADS)

Zhao, Lingquan; Qu, Xin; Wang, Yanchao; Lv, Jian; Zhang, Lijun; Hu, Ziyu; Gu, Guangrui; Ma, Yanming

2017-07-01

Atomic doping of clusters is known as an effective approach to stabilize or modify the structures and properties of resulting doped clusters. We herein report the effect of manganese (Mn) doping on the structure evolution of small-sized boron (B) clusters. The global minimum structures of both neutral and charged Mn doped B cluster \\text{MnB}nQ (n  =  10-20 and Q  =  0, ±1) have been proposed through extensive first-principles swarm-intelligence based structure searches. It is found that Mn doping has significantly modified the grow behaviors of B clusters, leading to two novel structural transitions from planar to tubular and then to cage-like B structures in both neutral and charged species. Half-sandwich-type structures are most favorable for small \\text{MnB}n-/0/+ (n  ⩽  13) clusters and gradually transform to Mn-centered double-ring tubular structures at \\text{MnB}16-/0/+ clusters with superior thermodynamic stabilities compared with their neighbors. Most strikingly, endohedral cages become the ground-state structures for larger \\text{MnB}n-/0/+ (n  ⩾  19) clusters, among which \\text{MnB}20+ adopts a highly symmetric structure with superior thermodynamic stability and a large HOMO-LUMO gap of 4.53 eV. The unique stability of the endohedral \\text{MnB}\\text{20}+ cage is attributed to the geometric fit and formation of 18-electron closed-shell configuration. The results significantly advance our understanding about the structure and bonding of B-based clusters and strongly suggest transition-metal doping as a viable route to synthesize intriguing B-based nanomaterials.

Internal gettering by metal alloy clusters

DOEpatents

Buonassisi, Anthony; Heuer, Matthias; Istratov, Andrei A.; Pickett, Matthew D.; Marcus, Mathew A.; Weber, Eicke R.

2010-07-27

The present invention relates to the internal gettering of impurities in semiconductors by metal alloy clusters. In particular, intermetallic clusters are formed within silicon, such clusters containing two or more transition metal species. Such clusters have melting temperatures below that of the host material and are shown to be particularly effective in gettering impurities within the silicon and collecting them into isolated, less harmful locations. Novel compositions for some of the metal alloy clusters are also described.

The merger remnant NGC 3610 and its globular cluster system: a large-scale study

NASA Astrophysics Data System (ADS)

Bassino, Lilia P.; Caso, Juan P.

2017-04-01

We present a photometric study of the prototype merger remnant NGC 3610 and its globular cluster (GC) system, based on new Gemini/GMOS and Advanced Camera for Surveys/Hubble Space Telescope archival images. Thanks to the large field of view of our GMOS data, larger than previous studies, we are able to detect a 'classical' bimodal GC colour distribution, corresponding to metal-poor and metal-rich GCs, at intermediate radii and a small subsample of likely young clusters of intermediate colours, mainly located in the outskirts. The extent of the whole GC system is settled as about 40 kpc. The GC population is quite poor, about 500 ± 110 members that corresponds to a low total specific frequency SN ˜ 0.8. The effective radii of a cluster sample are determined, including those of two spectroscopically confirmed young and metal-rich clusters, that are in the limit between GC and UCD sizes and brightness. The large-scale galaxy surface-brightness profile can be decomposed as an inner embedded disc and an outer spheroid, determining for both larger extents than earlier research (10 and 30 kpc, respectively). We detect boxy isophotes, expected in merger remnants, and show a wealth of fine-structure in the surface-brightness distribution with unprecedented detail, coincident with the outer spheroid. The lack of symmetry in the galaxy colour map adds a new piece of evidence to the recent merger scenario of NGC 3610.

Tidal stripping stellar substructures around four metal-poor globular clusters in the galactic bulge

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chun, Sang-Hyun; Kang, Minhee; Jung, DooSeok

2015-01-01

We investigate the spatial density configuration of stars around four metal-poor globular clusters (NGC 6266, NGC 6626, NGC 6642, and NGC 6723) in the Galactic bulge region using wide-field deep J, H, and K imaging data obtained with the Wide Field Camera near-infrared array on the United Kingdom Infrared Telescope. A statistical weighted filtering algorithm for the stars on the color–magnitude diagram is applied in order to sort cluster member candidates from the field star contamination. In two-dimensional isodensity contour maps of the clusters, we find that all four of the globular clusters exhibit strong evidence of tidally stripped stellarmore » features beyond the tidal radius in the form of tidal tails or small density lobes/chunks. The orientations of the extended stellar substructures are likely to be associated with the effect of dynamic interaction with the Galaxy and the cluster's space motion. The observed radial density profiles of the four globular clusters also describe the extended substructures; they depart from theoretical King and Wilson models and have an overdensity feature with a break in the slope of the profile at the outer region of clusters. The observed results could imply that four globular clusters in the Galactic bulge region have experienced strong environmental effects such as tidal forces or bulge/disk shocks of the Galaxy during the dynamical evolution of globular clusters. These observational results provide further details which add to our understanding of the evolution of clusters in the Galactic bulge region as well as the formation of the Galaxy.« less

The metallicity of the intracluster medium over cosmic time: further evidence for early enrichment

NASA Astrophysics Data System (ADS)

Mantz, Adam B.; Allen, Steven W.; Morris, R. Glenn; Simionescu, Aurora; Urban, Ondrej; Werner, Norbert; Zhuravleva, Irina

2017-12-01

We use Chandra X-ray data to measure the metallicity of the intracluster medium (ICM) in 245 massive galaxy clusters selected from X-ray and Sunyaev-Zel'dovich (SZ) effect surveys, spanning redshifts 0 < z < 1.2. Metallicities were measured in three different radial ranges, spanning cluster cores through their outskirts. We explore trends in these measurements as a function of cluster redshift, temperature and surface brightness 'peakiness' (a proxy for gas cooling efficiency in cluster centres). The data at large radii (0.5-1 r500) are consistent with a constant metallicity, while at intermediate radii (0.1-0.5 r500) we see a late-time increase in enrichment, consistent with the expected production and mixing of metals in cluster cores. In cluster centres, there are strong trends of metallicity with temperature and peakiness, reflecting enhanced metal production in the lowest entropy gas. Within the cool-core/sharply peaked cluster population, there is a large intrinsic scatter in central metallicity and no overall evolution, indicating significant astrophysical variations in the efficiency of enrichment. The central metallicity in clusters with flat surface brightness profiles is lower, with a smaller intrinsic scatter, but increases towards lower redshifts. Our results are consistent with other recent measurements of ICM metallicity as a function of redshift. They reinforce the picture implied by observations of uniform metal distributions in the outskirts of nearby clusters, in which most of the enrichment of the ICM takes place before cluster formation, with significant later enrichment taking place only in cluster centres, as the stellar populations of the central galaxies evolve.

The low-metallicity starburst NGC346: massive-star population and feedback

NASA Astrophysics Data System (ADS)

Oskinova, Lida

2017-08-01

The Small Magellanic Cloud (SMC) is ideal to study young, massive stars at low metallicity. The compact cluster NGC346 contains about half of all O-type stars in the entire SMC. The massive-star population of this cluster powers N66, the brightest and largest HII region in the SMC. We propose to use HST-STIS to slice NGC346 with 20 long-slit exposures, in order to obtain the UV spectra of most of the massive early-type stars of this cluster. Archival data of 13 exposures that cover already a minor part of this cluster will be included in our analyses. Our aim is to quantitatively analyze virtually the whole massive-star population of NGC346. We have already secured the optical spectra of all massive stars in the field with the integral-field spectrograph MUSE at the ESO-VLT. However, for the determination of the stellar-wind parameters, i.e. the mass-loss rates and the wind velocities, ultraviolet spectra are indispensable. Our advanced Potsdam Wolf-Rayet (PoWR) code will be used for modeling the stellar and wind spectra in the course of the analysis. Finally, we will obtain:(a) the fundamental stellar and wind parameters of all stars brighter than spectral type B2V in the field, which, e,g,, will constrain the initial mass function in this young low-metallicity starburst;(b) mass-loss rates of many more OB-type stars at SMC metallicity than hitherto known, allowing to better constrain their metallicity dependence;(c) the integrated feedback by ionizing radiation and stellar winds of the whole massive-star population of NGC346, which will be used as input to model the ecology of the giant HII region N66.These HST UV data will be of high legacy value.

Probing the History of Galaxy Clusters with Metallicity and Entropy Measurements

NASA Astrophysics Data System (ADS)

Elkholy, Tamer Yohanna

Galaxy clusters are the largest gravitationally bound objects found today in our Universe. The gas they contain, the intra-cluster medium (ICM), is heated to temperatures in the approximate range of 1 to 10 keV, and thus emits X-ray radiation. Studying the ICM through the spatial and spectral analysis of its emission returns the richest information about both the overall cosmological context which governs the formation of clusters, as well as the physical processes occurring within. The aim of this thesis is to learn about the history of the physical processes that drive the evolution of galaxy clusters, through careful, spatially resolved measurements of their metallicity and entropy content. A sample of 45 nearby clusters observed with Chandra is analyzed to produce radial density, temperature, entropy and metallicity profiles. The entropy profiles are computed to larger radial extents than in previous Chandra analyses. The results of this analysis are made available to the scientific community in an electronic database. Comparing metallicity and entropy in the outskirts of clusters, we find no signature on the entropy profiles of the ensemble of supernovae that produced the observed metals. In the centers of clusters, we find that the metallicities of high-mass clusters are much less dispersed than those of low-mass clusters. A comparison of metallicity with the regularity of the X-ray emission morphology suggests that metallicities in low-mass clusters are more susceptible to increase from violent events such as mergers. We also find that the variation in the stellar-to-gas mass ratio as a function of cluster mass can explain the variation of central metallicity with cluster mass, only if we assume that there is a constant level of metallicity for clusters of all masses, above which the observed galaxies add more metals in proportion to their mass. (Copies available exclusively from MIT Libraries, libraries.mit.edu/docs - docs mit.edu)

First estimates of the fundamental parameters of the relatively bright Galactic open cluster NGC 5288

NASA Astrophysics Data System (ADS)

Piatti, Andrés E.; Clariá, Juan J.; Ahumada, Andrea V.

2006-04-01

In this paper we present charge-coupled device (CCD) images in the Johnson B and V and Kron-Cousins I passbands for the previously unstudied open cluster NGC 5288. The sample consists of 15688 stars reaching down to V~ 20.5. The cluster appears to have a relatively small but conspicuous nucleus and a low-density extended coronal region. Star counts carried out in 25 × 25 pixel2 boxes distributed throughout the whole observed field allowed us to estimate the angular core and corona radii as ~1.3 and 6.3arcmin, respectively. Our analysis suggests that NGC 5288 is moderately young and probably more metal-rich than the Sun. Adopting the theoretical metal content Z= 0.040, which provides the best global fit, we derive an age of 130+40-30Myr. Simultaneously, we have obtained colour excesses E(B-V) = 0.75 and E(V-I) = 0.95 and an apparent distance modulus V-MV= 14.00. The law of interstellar extinction in the cluster direction is found to be normal. NGC 5288 is located at 2.1 +/- 0.3kpc from the Sun beyond the Carina spiral feature and ~7.4kpc from the Galactic Centre. The cluster metallicity seems to be compatible with the cluster position in the Galaxy, given the recognized radial abundance gradient in the disc. For the first time, in this paper we determine the basic parameters for the open cluster NGC 5381, situated in the same direction as NGC 5288. This determination was reached by using CCD VI data published almost a decade ago by Pietrzyński et al. (1997) for NGC 5381. The properties of some open clusters aligned along the line of sight of NGC 5288 are examined. The properties of clusters of similar ages to NGC 5288 are also looked into. Evidence is presented that these did not form mainly along the spiral arms but rather in the thin Galactic disc (Z~+/-100pc).

Multiple populations in more metal-rich galactic globular clusters

NASA Astrophysics Data System (ADS)

Cordero, Maria J.

In this thesis we present chemical abundances for bright stars in the intermediate metallicity globular cluster (GC) M5, and the relatively metal-rich GCs M71 and 47 Tuc with the goal of improving the understanding of chemical evolution in the metallicity regime sampled by these three GCs. The first chapter presents a brief historical overview in light element abundance variations in globular clusters. In the second chapter we present the results obtained for 47 Tuc, the most-metal rich cluster of my sample. 47 Tuc is an ideal target to study chemical evolution and GC formation in massive more metal-rich GCs since it is the closest massive GC. Chemical abundances for O, Na, Al, Si, Ca, Ti, Fe, Ni, La, and Eu were determined for 164 red giant branch (RGB) stars in 47 Tuc using spectra obtained with both the Hydra multi-fiber spectrograph at the Blanco 4-m telescope and the FLAMES multi-object spectrograph at the ESO Very Large Telescope. The average [Fe/H]= --0.79+/-0.09 dex is consistent with literature values, as well as over-abundances of alpha-elements ([alpha/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 anti-correlation, 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 KS-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 AGB nucleosynthesis yields. Aluminum is the heaviest light element displaying large star-to-star variations in Galactic GCs. This element may provide additional insight into the origin of the multiple populations and the nature of the first-generation stars responsible for chemical inhomogeneities. We found that, unlike more metal-poor GCs, 47 Tuc did not exhibit a strong Na-Al correlation, which motivates a careful study of the similar metallicity but less massive GC M71. In chapter 3, we present chemical abundances of O, Na, Al, and Fe for 33 giants in M71 using spectra obtained with the WIYN-Hydra spectrograph. Our spectroscopic analysis finds that, similar to 47 Tuc and in contrast with more metal-poor GCs, M71 stars do not exhibit a strong Na-Al correlation and span a relatively narrow range in [Al/Fe]. Furthermore, these data suggest that only a small fraction of stars (29%) have an [Na/Fe] ratio similar to halo stars at this metallicity, which is a characteristic reproduced by GC formation and evolution models. In the fourth chapter we present chemical abundances for a sample of 61 red giants in the intermediate-metallicity GC M5. The data were obtained using the Hydra multi-fiber positioner and bench spectrograph on the WIYN telescope. We find that our abundance ratios for Na, Al, Si, Ca, Ti, Fe, Ni, La, and Eu agree with published values for this cluster. The scatter seen in Fe-peak, alpha, and neutron-capture elements is consistent with typical spectroscopic errors. However, we identified a star modestly enhanced in La by performing a careful comparison of stellar spectra with similar atmospheric parameters. La-enhanced stars are rare in GCs. For instance, we have found only one such star in each of M5 and 47 Tuc. M5 red giants exhibit a strong Na-Al correlation, which is absent in M71 and 47 Tuc. Furthermore, M5 is at the metallicity regime where GCs seem to transition from small to large [Al/Fe] scatter. Interestingly, this metallicity regime also separates metal-poor from metal-rich Galactic GCs. In the fifth chapter we present radial distributions, population fractions, detailed examination of behavior of Al in more metal-rich GCs in the context of cluster chemical evolution, and, finally, a kinematical study of the GC M13 using spectra acquired with the WIYN-Hydra spectrograph. We find a rotational signal and a kinematical difference between the intermediate and extreme generations. Specifically, we find that the extreme O-depleted population, which is also more centrally concentrated than the primordial and intermediate populations, has the highest rotational amplitude. (Abstract shortened by UMI.)

Reduction of N2 by supported tungsten clusters gives a model of the process by nitrogenase

PubMed Central

Murakami, Junichi; Yamaguchi, Wataru

2012-01-01

Metalloenzymes catalyze difficult chemical reactions under mild conditions. Mimicking their functions is a challenging task and it has been investigated using homogeneous systems containing metal complexes. The nitrogenase that converts N2 to NH3 under mild conditions is one of such enzymes. Efforts to realize the biological function have continued for more than four decades, which has resulted in several reports of reduction of N2, ligated to metal complexes in solutions, to NH3 by protonation under mild conditions. Here, we show that seemingly distinct supported small tungsten clusters in a dry environment reduce N2 under mild conditions like the nitrogenase. N2 is reduced to NH3 via N2H4 by addition of neutral H atoms, which agrees with the mechanism recently proposed for the N2 reduction on the active site of nitrogenase. The process on the supported clusters gives a model of the biological N2 reduction. PMID:22586517

Generation of subnanometric platinum with high stability during transformation of a 2D zeolite into 3D.

PubMed

Liu, Lichen; Díaz, Urbano; Arenal, Raul; Agostini, Giovanni; Concepción, Patricia; Corma, Avelino

2017-01-01

Single metal atoms and metal clusters have attracted much attention thanks to their advantageous capabilities as heterogeneous catalysts. However, the generation of stable single atoms and clusters on a solid support is still challenging. Herein, we report a new strategy for the generation of single Pt atoms and Pt clusters with exceptionally high thermal stability, formed within purely siliceous MCM-22 during the growth of a two-dimensional zeolite into three dimensions. These subnanometric Pt species are stabilized by MCM-22, even after treatment in air up to 540 °C. Furthermore, these stable Pt species confined within internal framework cavities show size-selective catalysis for the hydrogenation of alkenes. High-temperature oxidation-reduction treatments result in the growth of encapsulated Pt species to small nanoparticles in the approximate size range of 1 to 2 nm. The stability and catalytic activity of encapsulated Pt species is also reflected in the dehydrogenation of propane to propylene.

Infrared Spectroscopy of Metal Ion Complexes: Models for Metal Ligand Interactions and Solvation

NASA Astrophysics Data System (ADS)

Duncan, Michael

2006-03-01

Weakly bound complexes of the form M^+-Lx (M=Fe, Ni, Co, etc.; L=CO2, C2H2, H2O, benzene, N2) are prepared in supersonic molecular beams by laser vaporization in a pulsed-nozzle cluster source. These species are mass analyzed and size-selected in a reflectron time-of-flight mass spectrometer. Clusters are photodissociated at infrared wavelengths with a Nd:YAG pumped infrared optical parametric oscillator/amplifier (OPO/OPA) laser or with a tunable infrared free-electron laser. M^+-(CO2)x complexes absorb near the free CO2 asymmetric stretch near 2349 cm-1 but with an interesting size dependent variation in the resonances. Small clusters have blue-shifted resonances, while larger complexes have additional bands due to surface CO2 molecules not attached to the metal. M^+(C2H2)n complexes absorb near the C-H stretches in acetylene, but resonances in metal complexes are red-shifted with repect to the isolated molecule. Ni^+ and Co^+ complexes with acetylene undergo intracluster cyclization reactions to form cyclobutadiene. Transition metal water complexes are studied in the O-H stretch region, and partial rotational structure can be measured. M^+(benzene) and M^+(benzene)2 ions (M=V, Ti, Al) represent half-sandwich and sandwich species, whose spectra are measured near the free benzene modes. These new IR spectra and their assignments will be discussed as well as other new IR spectra for similar complexes.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mantz, Adam B.; Allen, Steven W.; Morris, R. Glenn

Here, we use Chandra X-ray data to measure the metallicity of the intracluster medium (ICM) in 245 massive galaxy clusters selected from X-ray and Sunyaev–Zel'dovich (SZ) effect surveys, spanning redshifts 0 < z < 1.2. Metallicities were measured in three different radial ranges, spanning cluster cores through their outskirts. We explore trends in these measurements as a function of cluster redshift, temperature and surface brightness ‘peakiness’ (a proxy for gas cooling efficiency in cluster centres). The data at large radii (0.5–1 r500) are consistent with a constant metallicity, while at intermediate radii (0.1–0.5 r500) we see a late-time increase inmore » enrichment, consistent with the expected production and mixing of metals in cluster cores. In cluster centres, there are strong trends of metallicity with temperature and peakiness, reflecting enhanced metal production in the lowest entropy gas. Within the cool-core/sharply peaked cluster population, there is a large intrinsic scatter in central metallicity and no overall evolution, indicating significant astrophysical variations in the efficiency of enrichment. The central metallicity in clusters with flat surface brightness profiles is lower, with a smaller intrinsic scatter, but increases towards lower redshifts. Our results are consistent with other recent measurements of ICM metallicity as a function of redshift. They reinforce the picture implied by observations of uniform metal distributions in the outskirts of nearby clusters, in which most of the enrichment of the ICM takes place before cluster formation, with significant later enrichment taking place only in cluster centres, as the stellar populations of the central galaxies evolve.« less

Cluster-assembled metallic glasses

PubMed Central

2013-01-01

A bottom-up approach to nanofabricate metallic glasses from metal clusters as building blocks is presented. Considering metallic glasses as a subclass of cluster-assembled materials, the relation between the two lively fields of metal clusters and metallic glasses is pointed out. Deposition of selected clusters or collections of them, generated by state-of-the-art cluster beam sources, could lead to the production of a well-defined amorphous material. In contrast to rapidly quenched glasses where only the composition of the glass can be controlled, in cluster-assembled glasses, one can precisely control the structural building blocks. Comparing properties of glasses with similar compositions but differing in building blocks and therefore different in structure will facilitate the study of structure–property correlation in metallic glasses. This bottom-up method provides a novel alternative path to the synthesis of glassy alloys and will contribute to improving fundamental understanding in the field of metallic glasses. It may even permit the production of glassy materials for alloys that cannot be quenched rapidly enough to circumvent crystallization. Additionally, gaining deeper insight into the parameters governing the structure–property relation in metallic glasses can have a great impact on understanding and design of other cluster-assembled materials. PMID:23899019

DOE Office of Scientific and Technical Information (OSTI.GOV)

Not Available

The following are reported: theoretical calculations (configuration interaction, relativistic effective core potentials, polyatomics, CASSCF); proposed theoretical studies (clusters of Cu, Ag, Au, Ni, Pt, Pd, Rh, Ir, Os, Ru; transition metal cluster ions; transition metal carbide clusters; bimetallic mixed transition metal clusters); reactivity studies on transition metal clusters (reactivity with H{sub 2}, C{sub 2}H{sub 4}, hydrocarbons; NO and CO chemisorption on surfaces). Computer facilities and codes to be used, are described. 192 refs, 13 figs.

The metallicity of the intracluster medium over cosmic time: further evidence for early enrichment

DOE PAGES

Mantz, Adam B.; Allen, Steven W.; Morris, R. Glenn; ...

2017-08-26

Here, we use Chandra X-ray data to measure the metallicity of the intracluster medium (ICM) in 245 massive galaxy clusters selected from X-ray and Sunyaev–Zel'dovich (SZ) effect surveys, spanning redshifts 0 < z < 1.2. Metallicities were measured in three different radial ranges, spanning cluster cores through their outskirts. We explore trends in these measurements as a function of cluster redshift, temperature and surface brightness ‘peakiness’ (a proxy for gas cooling efficiency in cluster centres). The data at large radii (0.5–1 r500) are consistent with a constant metallicity, while at intermediate radii (0.1–0.5 r500) we see a late-time increase inmore » enrichment, consistent with the expected production and mixing of metals in cluster cores. In cluster centres, there are strong trends of metallicity with temperature and peakiness, reflecting enhanced metal production in the lowest entropy gas. Within the cool-core/sharply peaked cluster population, there is a large intrinsic scatter in central metallicity and no overall evolution, indicating significant astrophysical variations in the efficiency of enrichment. The central metallicity in clusters with flat surface brightness profiles is lower, with a smaller intrinsic scatter, but increases towards lower redshifts. Our results are consistent with other recent measurements of ICM metallicity as a function of redshift. They reinforce the picture implied by observations of uniform metal distributions in the outskirts of nearby clusters, in which most of the enrichment of the ICM takes place before cluster formation, with significant later enrichment taking place only in cluster centres, as the stellar populations of the central galaxies evolve.« less

Correspondence between ion-cluster and bulk thermodynamics: on the validity of the cluster pair approximation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vlcek, Lukas; Chialvo, Ariel; Simonson, J Michael

2013-01-01

Molecular models and experimental estimates based on the cluster pair approximation (CPA) provide inconsistent predictions of absolute single-ion hydration properties. To understand the origin of this discrepancy we used molecular simulations to study the transition between hydration of alkali metal and halide ions in small aqueous clusters and bulk water. The results demonstrate that the assumptions underlying the CPA are not generally valid as a result of a significant shift in the ion hydration free energies (~15 kJ/mol) and enthalpies (~47 kJ/mol) in the intermediate range of cluster sizes. When this effect is accounted for, the systematic differences between modelsmore » and experimental predictions disappear, and the value of absolute proton hydration enthalpy based on the CPA gets in closer agreement with other estimates.« less

Multicolor CCD photometry of the open cluster NGC 752

NASA Astrophysics Data System (ADS)

Bartašiūtė, Stanislava; Janusz, Robert; Boyle, Richard P.; Philip, A. G. Davis; Deveikis, Viktoras

2010-01-01

We obtained CCD observations of the open cluster NGC 752 with the 1.8m Vatican Advanced Technology Telescope (Mt. Graham, Arizona) with a 4K CCD camera and eight intermediate-band filters of the Stromvil (Strömgren + Vilnius) system. Four 12‧ × 12‧ fields were observed, covering the central part of the cluster. The good-quality multicolor data made it possible to obtain precise estimates of distance moduli, metallicity and foreground reddening for individual stars down to the limiting magnitude, V = 17.5, enabling photometric identification of faint cluster members. The new observations provide an extension of the lower main sequence to three magnitudes beyond the previous (photographic) limit. A relatively small number of photometric members identified at fainter magnitudes seems to be indicative of actual dissolution of the cluster from the low-mass end.

Stabilization of fullerene-like boron cages by transition metal encapsulation.

PubMed

Lv, Jian; Wang, Yanchao; Zhang, Lijun; Lin, Haiqing; Zhao, Jijun; Ma, Yanming

2015-06-21

The stabilization of fullerene-like boron (B) cages in the free-standing form has been long sought after and a challenging problem. Studies that have been carried out for more than a decade have confirmed that the planar or quasi-planar polymorphs are energetically favored ground states over a wide range of small and medium-sized B clusters. Recently, the breakthroughs represented by Nat. Chem., 2014, 6, 727 established that the transition from planar/quasi-planar to cage-like Bn clusters occurs around n = ∼38-40, paving the way for understanding the intriguing chemistry of B-fullerene. We herein demonstrate that the transition demarcation, n, can be significantly reduced with the help of transition metal encapsulation. We explore via extensive first-principles swarm-intelligence based structure searches the free energy landscapes of B24 clusters doped by a series of transition metals and find that the low-lying energy regime is generally dominated by cage-like isomers. This is in sharp contrast to that of bare B24 clusters, where the quasi-planar and rather irregular polyhedrons are prevalent. Most strikingly, a highly symmetric B cage with D3h symmetry is discovered in the case of Mo or W encapsulation. The endohedral D3h cages exhibit robust thermodynamic, dynamic and chemical stabilities, which can be rationalized in terms of their unique electronic structure of an 18-electron closed-shell configuration. Our results indicate that transition metal encapsulation is a feasible route for stabilizing medium-sized B cages, offering a useful roadmap for the discovery of more B fullerene analogues as building blocks of nanomaterials.

Formation of globular cluster candidates in merging proto-galaxies at high redshift: a view from the FIRE cosmological simulations

DOE PAGES

Kim, Ji-hoon; Ma, Xiangcheng; Grudić, Michael Y.; ...

2017-11-23

Using a state-of-the-art cosmological simulation of merging proto-galaxies at high redshift from the FIRE project, with explicit treatments of star formation and stellar feedback in the interstellar medium, we investigate the formation of star clusters and examine one of the formation hypotheses of present-day metal-poor globular clusters. Here, we find that frequent mergers in high-redshift proto-galaxies could provide a fertile environment to produce long-lasting bound star clusters. The violent merger event disturbs the gravitational potential and pushes a large gas mass of ≳ 10 5–6 M ⊙ collectively to high density, at which point it rapidly turns into stars beforemore » stellar feedback can stop star formation. The high dynamic range of the reported simulation is critical in realizing such dense star-forming clouds with a small dynamical time-scale, tff ≲ 3 Myr, shorter than most stellar feedback time-scales. Our simulation then allows us to trace how clusters could become virialized and tightly bound to survive for up to ~420 Myr till the end of the simulation. Finally, because the cluster's tightly bound core was formed in one short burst, and the nearby older stars originally grouped with the cluster tend to be preferentially removed, at the end of the simulation the cluster has a small age spread.« less

Formation of globular cluster candidates in merging proto-galaxies at high redshift: a view from the FIRE cosmological simulations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, Ji-hoon; Ma, Xiangcheng; Grudić, Michael Y.

Using a state-of-the-art cosmological simulation of merging proto-galaxies at high redshift from the FIRE project, with explicit treatments of star formation and stellar feedback in the interstellar medium, we investigate the formation of star clusters and examine one of the formation hypotheses of present-day metal-poor globular clusters. Here, we find that frequent mergers in high-redshift proto-galaxies could provide a fertile environment to produce long-lasting bound star clusters. The violent merger event disturbs the gravitational potential and pushes a large gas mass of ≳ 10 5–6 M ⊙ collectively to high density, at which point it rapidly turns into stars beforemore » stellar feedback can stop star formation. The high dynamic range of the reported simulation is critical in realizing such dense star-forming clouds with a small dynamical time-scale, tff ≲ 3 Myr, shorter than most stellar feedback time-scales. Our simulation then allows us to trace how clusters could become virialized and tightly bound to survive for up to ~420 Myr till the end of the simulation. Finally, because the cluster's tightly bound core was formed in one short burst, and the nearby older stars originally grouped with the cluster tend to be preferentially removed, at the end of the simulation the cluster has a small age spread.« less

Formation of globular cluster candidates in merging proto-galaxies at high redshift: a view from the FIRE cosmological simulations

NASA Astrophysics Data System (ADS)

Kim, Ji-hoon; Ma, Xiangcheng; Grudić, Michael Y.; Hopkins, Philip F.; Hayward, Christopher C.; Wetzel, Andrew; Faucher-Giguère, Claude-André; Kereš, Dušan; Garrison-Kimmel, Shea; Murray, Norman

2018-03-01

Using a state-of-the-art cosmological simulation of merging proto-galaxies at high redshift from the FIRE project, with explicit treatments of star formation and stellar feedback in the interstellar medium, we investigate the formation of star clusters and examine one of the formation hypotheses of present-day metal-poor globular clusters. We find that frequent mergers in high-redshift proto-galaxies could provide a fertile environment to produce long-lasting bound star clusters. The violent merger event disturbs the gravitational potential and pushes a large gas mass of ≳ 105-6 M⊙ collectively to high density, at which point it rapidly turns into stars before stellar feedback can stop star formation. The high dynamic range of the reported simulation is critical in realizing such dense star-forming clouds with a small dynamical time-scale, tff ≲ 3 Myr, shorter than most stellar feedback time-scales. Our simulation then allows us to trace how clusters could become virialized and tightly bound to survive for up to ˜420 Myr till the end of the simulation. Because the cluster's tightly bound core was formed in one short burst, and the nearby older stars originally grouped with the cluster tend to be preferentially removed, at the end of the simulation the cluster has a small age spread.

Bonding and vibrations of CO molecules adsorbed at transition metal impurity sites on the MgO (001) surface. A density functional model cluster study

NASA Astrophysics Data System (ADS)

Neyman, K. M.; Rösch, N.

1993-11-01

First principles density functional cluster investigations of adsorption at the (001) surface of pure and doped magnesium oxide are carried out to characterize and compare the interaction of CO molecules with main group (Mg 2+) and d metal (Co 2+, Ni 2+, Cu 2+) surface cationic centers of the ionic substrate. The geometry of the adsorption complexes, the binding mechanism and spectroscopic manifestations of the surface species are analyzed. Special attention is payed to vibrational frequencies and intensities. The calculations qualitatively reproduce observed trends in the adsorption-induced frequency shifts for the series of the surface aggregates Mg 5cCO→Ni 5cCO→CO 5cCO and the corresponding change of the infrared intensities of the CO vibrational mode. For the transition metal impurity sites these results are rationalized in terms of a small, but notable Md πCOπ interaction.

Blood trace metals in a sporadic amyotrophic lateral sclerosis geographical cluster.

PubMed

De Benedetti, Stefano; Lucchini, Giorgio; Del Bò, Cristian; Deon, Valeria; Marocchi, Alessandro; Penco, Silvana; Lunetta, Christian; Gianazza, Elisabetta; Bonomi, Francesco; Iametti, Stefania

2017-06-01

Amyotrophic lateral sclerosis (ALS) is a fatal disorder with unknown etiology, in which genetic and environmental factors interplay to determine the onset and the course of the disease. Exposure to toxic metals has been proposed to be involved in the etiology of the disease either through a direct damage or by promoting oxidative stress. In this study we evaluated the concentration of a panel of metals in serum and whole blood of a small group of sporadic patients, all living in a defined geographical area, for which acid mine drainage has been reported. ALS prevalence in this area is higher than in the rest of Italy. Results were analyzed with software based on artificial neural networks. High concentrations of metals (in particular Se, Mn and Al) were associated with the disease group. Arsenic serum concentration resulted lower in ALS patients, but it positively correlated with disease duration. Comet assay was performed to evaluate endogenous DNA damage that resulted not different between patients and controls. Up to now only few studies considered geographically well-defined clusters of ALS patients. Common geographical origin among patients and controls gave us the chance to perform metallomic investigations under comparable conditions of environmental exposure. Elaboration of these data with software based on machine learning processes has the potential to be extremely useful to gain a comprehensive view of the complex interactions eventually leading to disease, even in a small number of subjects.

From linking of metal-oxide building blocks in a dynamic library to giant clusters with unique properties and towards adaptive chemistry.

PubMed

Müller, Achim; Gouzerh, Pierre

2012-11-21

Following Nature's lessons, today chemists can cross the boundary of the small molecule world to construct multifunctional and highly complex molecular nano-objects up to protein size and even cell-like nanosystems showing responsive sensing. Impressive examples emerge from studies of the solutions of some oxoanions of the early transition metals especially under reducing conditions which enable the controlled linking of metal-oxide building blocks. The latter are available from constitutional dynamic libraries, thus providing the option to generate multifunctional unique nanoscale molecular systems with exquisite architectures, which even opens the way towards adaptive and evolutive (Darwinian) chemistry. The present review presents the first comprehensive report of current knowledge (including synthesis aspects not discussed before) regarding the related giant metal-oxide clusters mainly of the type {Mo(57)M'(6)} (M' = Fe(III), V(IV)) (torus structure), {M(72)M'(30)} (M = Mo, M' = V(IV), Cr(III), Fe(III), Mo(V)), {M(72)Mo(60)} (M = Mo, W) (Keplerates), {Mo(154)}, {Mo(176)}, {Mo(248)} ("big wheels"), and {Mo(368)} ("blue lemon") - all having the important transferable pentagonal {(M)M(5)} groups in common. These discoveries expanded the frontiers of inorganic chemistry to the mesoscopic world, while there is probably no collection of discrete inorganic compounds which offers such a versatile chemistry and the option to study new phenomena of interdisciplinary interest. The variety of different properties of the sphere- and wheel-type metal-oxide-based clusters can directly be related to their unique architectures: The spherical Keplerate-type capsules having 20 crown-ether-type pores and tunable internal functionalities allow the investigation of confined matter as well as that of sphere-surface-supramolecular and encapsulation chemistry - including related new aspects of the biologically important hydrophobic effects - but also of nanoscale ion transport and separation. The wheel-type molybdenum-oxide clusters exhibiting complex landscapes do not only have well-defined reaction sites but also show unprecedented adaptability regarding the integration of various kinds of matter. Applications in different fields, e.g. in materials science and catalysis including those in small spaces, investigated by several groups, are discussed while possible directions for future work are outlined.

From atoms to layers: in situ gold cluster growth kinetics during sputter deposition

NASA Astrophysics Data System (ADS)

Schwartzkopf, Matthias; Buffet, Adeline; Körstgens, Volker; Metwalli, Ezzeldin; Schlage, Kai; Benecke, Gunthard; Perlich, Jan; Rawolle, Monika; Rothkirch, André; Heidmann, Berit; Herzog, Gerd; Müller-Buschbaum, Peter; Röhlsberger, Ralf; Gehrke, Rainer; Stribeck, Norbert; Roth, Stephan V.

2013-05-01

The adjustment of size-dependent catalytic, electrical and optical properties of gold cluster assemblies is a very significant issue in modern applied nanotechnology. We present a real-time investigation of the growth kinetics of gold nanostructures from small nuclei to a complete gold layer during magnetron sputter deposition with high time resolution by means of in situ microbeam grazing incidence small-angle X-ray scattering (μGISAXS). We specify the four-stage growth including their thresholds with sub-monolayer resolution and identify phase transitions monitored in Yoneda intensity as a material-specific characteristic. An innovative and flexible geometrical model enables the extraction of morphological real space parameters, such as cluster size and shape, correlation distance, layer porosity and surface coverage, directly from reciprocal space scattering data. This approach enables a large variety of future investigations of the influence of different process parameters on the thin metal film morphology. Furthermore, our study allows for deducing the wetting behavior of gold cluster films on solid substrates and provides a better understanding of the growth kinetics in general, which is essential for optimization of manufacturing parameters, saving energy and resources.The adjustment of size-dependent catalytic, electrical and optical properties of gold cluster assemblies is a very significant issue in modern applied nanotechnology. We present a real-time investigation of the growth kinetics of gold nanostructures from small nuclei to a complete gold layer during magnetron sputter deposition with high time resolution by means of in situ microbeam grazing incidence small-angle X-ray scattering (μGISAXS). We specify the four-stage growth including their thresholds with sub-monolayer resolution and identify phase transitions monitored in Yoneda intensity as a material-specific characteristic. An innovative and flexible geometrical model enables the extraction of morphological real space parameters, such as cluster size and shape, correlation distance, layer porosity and surface coverage, directly from reciprocal space scattering data. This approach enables a large variety of future investigations of the influence of different process parameters on the thin metal film morphology. Furthermore, our study allows for deducing the wetting behavior of gold cluster films on solid substrates and provides a better understanding of the growth kinetics in general, which is essential for optimization of manufacturing parameters, saving energy and resources. Electronic supplementary information (ESI) available: The full GISAXS image sequence of the experiment, the model-based IsGISAXS-simulation sequence as movie files for comparison and detailed information about sample cleaning, XRR, FESEM, IsGISAXS, comparison μGIWAXS/μGISAXS, and sampling statistics. See DOI: 10.1039/c3nr34216f

The Gaia-ESO Survey. Mg-Al anti-correlation in iDR4 globular clusters

NASA Astrophysics Data System (ADS)

Pancino, E.; Romano, D.; Tang, B.; Tautvaišienė, G.; Casey, A. R.; Gruyters, P.; Geisler, D.; San Roman, I.; Randich, S.; Alfaro, E. J.; Bragaglia, A.; Flaccomio, E.; Korn, A. J.; Recio-Blanco, A.; Smiljanic, R.; Carraro, G.; Bayo, A.; Costado, M. T.; Damiani, F.; Jofré, P.; Lardo, C.; de Laverny, P.; Monaco, L.; Morbidelli, L.; Sbordone, L.; Sousa, S. G.; Villanova, S.

2017-05-01

We use Gaia-ESO (GES) Survey iDR4 data to explore the Mg-Al anti-correlation in globular clusters that were observed as calibrators, as a demonstration of the quality of Gaia-ESO Survey data and analysis. The results compare well with the available literature, within 0.1 dex or less, after a small (compared to the internal spreads) offset between the UVES and GIRAFFE data of 0.10-0.15 dex was taken into account. In particular, for the first time we present data for NGC 5927, which is one of the most metal-rich globular clusters studied in the literature so far with [ Fe / H ] = - 0.39 ± 0.04 dex; this cluster was included to connect with the open cluster regime in the Gaia-ESO Survey internal calibration. The extent and shape of the Mg-Al anti-correlation provide strong constraints on the multiple population phenomenon in globular clusters. In particular, we studied the dependency of the Mg-Al anti-correlation extension with metallicity, present-day mass,and age of the clusters, using GES data in combination with a large set of homogenized literature measurements.We find a dependency with both metallicity and mass, which is evident when fitting for the two parameters simultaneously, but we do not find significant dependency with age. We confirm that the Mg-Al anti-correlation is not seen in all clusters, but disappears for the less massive or most metal-rich clusters. We also use our data set to see whether a normal anti-correlation would explain the low [Mg/α] observed in some extragalactic globular clusters, but find that none of the clusters in our sample can reproduce it; a more extreme chemical composition, such as that of NGC 2419, would be required. We conclude that GES iDR4 data already meet the requirements set by the main survey goals and can be used to study globular clusters in detail, even if the analysis procedures were not specifically designed for them. Based on data products from observations made with ESO Telescopes at the La Silla Paranal Observatory under programme ID 188.B-3002.Full Table 2 is only available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (http://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/601/A112

Understanding and Practical Use of Ligand and Metal Exchange Reactions in Thiolate-Protected Metal Clusters to Synthesize Controlled Metal Clusters.

PubMed

Niihori, Yoshiki; Hossain, Sakiat; Sharma, Sachil; Kumar, Bharat; Kurashige, Wataru; Negishi, Yuichi

2017-05-01

It is now possible to accurately synthesize thiolate (SR)-protected gold clusters (Au n (SR) m ) with various chemical compositions with atomic precision. The geometric structure, electronic structure, physical properties, and functions of these clusters are well known. In contrast, the ligand or metal atom exchange reactions between these clusters and other substances have not been studied extensively until recently, even though these phenomena were observed during early studies. Understanding the mechanisms of these reactions could allow desired functional metal clusters to be produced via exchange reactions. Therefore, we have studied the exchange reactions between Au n (SR) m and analogous clusters and other substances for the past four years. The results have enabled us to gain deep understanding of ligand exchange with respect to preferential exchange sites, acceleration means, effect on electronic structure, and intercluster exchange. We have also synthesized several new metal clusters using ligand and metal exchange reactions. In this account, we summarize our research on ligand and metal exchange reactions. © 2017 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of functionalization of boron nitride flakes by main group metal clusters on their optoelectronic properties

NASA Astrophysics Data System (ADS)

Chakraborty, Debdutta; Chattaraj, Pratim Kumar

2017-10-01

The possibility of functionalizing boron nitride flakes (BNFs) with some selected main group metal clusters, viz. OLi4, NLi5, CLi6, BLI7 and Al12Be, has been analyzed with the aid of density functional theory (DFT) based computations. Thermochemical as well as energetic considerations suggest that all the metal clusters interact with the BNF moiety in a favorable fashion. As a result of functionalization, the static (first) hyperpolarizability (β ) values of the metal cluster supported BNF moieties increase quite significantly as compared to that in the case of pristine BNF. Time dependent DFT analysis reveals that the metal clusters can lower the transition energies associated with the dominant electronic transitions quite significantly thereby enabling the metal cluster supported BNF moieties to exhibit significant non-linear optical activity. Moreover, the studied systems demonstrate broad band absorption capability spanning the UV-visible as well as infra-red domains. Energy decomposition analysis reveals that the electrostatic interactions principally stabilize the metal cluster supported BNF moieties.

Effect of functionalization of boron nitride flakes by main group metal clusters on their optoelectronic properties.

PubMed

Chakraborty, Debdutta; Chattaraj, Pratim Kumar

2017-10-25

The possibility of functionalizing boron nitride flakes (BNFs) with some selected main group metal clusters, viz. OLi 4 , NLi 5 , CLi 6 , BLI 7 and Al 12 Be, has been analyzed with the aid of density functional theory (DFT) based computations. Thermochemical as well as energetic considerations suggest that all the metal clusters interact with the BNF moiety in a favorable fashion. As a result of functionalization, the static (first) hyperpolarizability ([Formula: see text]) values of the metal cluster supported BNF moieties increase quite significantly as compared to that in the case of pristine BNF. Time dependent DFT analysis reveals that the metal clusters can lower the transition energies associated with the dominant electronic transitions quite significantly thereby enabling the metal cluster supported BNF moieties to exhibit significant non-linear optical activity. Moreover, the studied systems demonstrate broad band absorption capability spanning the UV-visible as well as infra-red domains. Energy decomposition analysis reveals that the electrostatic interactions principally stabilize the metal cluster supported BNF moieties.

Electronic levels and charge distribution near the interface of nickel

NASA Technical Reports Server (NTRS)

Waber, J. T.

1982-01-01

The energy levels in clusters of nickel atoms were investigated by means of a series of cluster calculations using both the multiple scattering and computational techniques (designated SSO) which avoids the muffin-tin approximation. The point group symmetry of the cluster has significant effect on the energy of levels nominally not occupied. This influences the electron transfer process during chemisorption. The SSO technique permits the approaching atom or molecule plus a small number of nickel atoms to be treated as a cluster. Specifically, molecular levels become more negative in the O atom, as well as in a CO molecule, as the metal atoms are approached. Thus, electron transfer from the nickel and bond formation is facilitated. This result is of importance in understanding chemisorption and catalytic processes.

Production of metal particles and clusters

NASA Technical Reports Server (NTRS)

Mcmanus, S. P.

1982-01-01

The feasibility of producing novel metals or metal clusters in a low gravity environment was studied. The production of coordinately unsaturated metal carbonyls by thermolysis or photolysis of stable metal carbonyls has the potential to generate novel catalysts by this technique. Laser irradiation of available metal carbonyls was investigated. It is found that laser induced decomposition of metal carbonyls is feasible for producing a variety of coordinately unsaturated species. Formation of clustered species does occur but is hampered by weak metal-metal bonds.

Dynamics of stellar black holes in young star clusters with different metallicities - II. Black hole-black hole binaries

NASA Astrophysics Data System (ADS)

Ziosi, Brunetto Marco; Mapelli, Michela; Branchesi, Marica; Tormen, Giuseppe

2014-07-01

In this paper, we study the formation and dynamical evolution of black hole-black hole (BH-BH) binaries in young star clusters (YSCs), by means of N-body simulations. The simulations include metallicity-dependent recipes for stellar evolution and stellar winds, and have been run for three different metallicities (Z = 0.01, 0.1 and 1 Z⊙). Following recent theoretical models of wind mass-loss and core-collapse supernovae, we assume that the mass of the stellar remnants depends on the metallicity of the progenitor stars. We find that BH-BH binaries form efficiently because of dynamical exchanges: in our simulations, we find about 10 times more BH-BH binaries than double neutron star binaries. The simulated BH-BH binaries form earlier in metal-poor YSCs, which host more massive black holes (BHs) than in metal-rich YSCs. The simulated BH-BH binaries have very large chirp masses (up to 80 M⊙), because the BH mass is assumed to depend on metallicity, and because BHs can grow in mass due to the merger with stars. The simulated BH-BH binaries span a wide range of orbital periods (10-3-107 yr), and only a small fraction of them (0.3 per cent) is expected to merge within a Hubble time. We discuss the estimated merger rate from our simulations and the implications for Advanced VIRGO and LIGO.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Akter, Nusnin; Wang, Mengen; Zhong, Jian-Qiang

Copper is an important industrial catalyst. The ability to manipulate the oxidation state of copper clusters in a controlled way is critical to understanding structure–reactivity relations of copper catalysts at the molecular level. Experimentally, cupric oxide surfaces or even small domains can only be stabilized at elevated temperatures and in the presence of oxygen, as copper can be easily reduced under reaction conditions. Herein bilayer silica films grown on a metallic substrate are used to trap diluted copper oxide clusters. By combining in situ experiments with first principles calculations, it is found that the confined space created by the silicamore » film leads to an increase in the energy barrier for Cu diffusion. Dispersed copper atoms trapped by the silica film can be easily oxidized by surface oxygen chemisorbed on the metallic substrate, which results in the formation and stabilization of Cu 2+ cations.« less

The uniformity and time-invariance of the intra-cluster metal distribution in galaxy clusters from the IllustrisTNG simulations

NASA Astrophysics Data System (ADS)

Vogelsberger, Mark; Marinacci, Federico; Torrey, Paul; Genel, Shy; Springel, Volker; Weinberger, Rainer; Pakmor, Rüdiger; Hernquist, Lars; Naiman, Jill; Pillepich, Annalisa; Nelson, Dylan

2018-02-01

The distribution of metals in the intra-cluster medium (ICM) encodes important information about the enrichment history and formation of galaxy clusters. Here, we explore the metal content of clusters in IllustrisTNG - a new suite of galaxy formation simulations building on the Illustris project. Our cluster sample contains 20 objects in TNG100 - a ˜(100 Mpc)3 volume simulation with 2 × 18203 resolution elements, and 370 objects in TNG300 - a ˜(300 Mpc)3 volume simulation with 2 × 25003 resolution elements. The z = 0 metallicity profiles agree with observations, and the enrichment history is consistent with observational data going beyond z ˜ 1, showing nearly no metallicity evolution. The abundance profiles vary only minimally within the cluster samples, especially in the outskirts with a relative scatter of ˜ 15 per cent. The average metallicity profile flattens towards the centre, where we find a logarithmic slope of -0.1 compared to -0.5 in the outskirts. Cool core clusters have more centrally peaked metallicity profiles (˜0.8 solar) compared to non-cool core systems (˜0.5 solar), similar to observational trends. Si/Fe and O/Fe radial profiles follow positive gradients. The outer abundance profiles do not evolve below z ˜ 2, whereas the inner profiles flatten towards z = 0. More than ˜ 80 per cent of the metals in the ICM have been accreted from the proto-cluster environment, which has been enriched to ˜0.1 solar already at z ˜ 2. We conclude that the intra-cluster metal distribution is uniform among our cluster sample, nearly time-invariant in the outskirts for more than 10 Gyr, and forms through a universal enrichment history.

MURI Center for Multidimensional Surface-Enhanced Sensing and Spectroscopy

DTIC Science & Technology

2007-06-30

and detection using SERS; new understanding of the electromagnetic enhancement properties of nanohole arrays; new first principles theoretical Page 2...support for the experimental program: 1. Studies of the electrodynamics of molecules adsorbed on anisotropic nanoparticles and nanoholes to determine...nanoparticles. George C. Schatz Electrodynamics of metal nanoparticles, small clusters of nanoparticles and nanoholes . We have performed extensive

Lithium-air batteries, method for making lithium-air batteries

DOEpatents

Vajda, Stefan; Curtiss, Larry A.; Lu, Jun; Amine, Khalil; Tyo, Eric C.

2016-11-15

The invention provides a method for generating Li.sub.2O.sub.2 or composites of it, the method uses mixing lithium ions with oxygen ions in the presence of a catalyst. The catalyst comprises a plurality of metal clusters, their alloys and mixtures, each cluster consisting of between 3 and 18 metal atoms. The invention also describes a lithium-air battery which uses a lithium metal anode, and a cathode opposing the anode. The cathode supports metal clusters, each cluster consisting of size selected clusters, taken from a range of between approximately 3 and approximately 18 metal atoms, and an electrolyte positioned between the anode and the cathode.

Nitrogen vacancy complexes in nitrogen irradiated metals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Veen, A. van; Westerduin, K.T.; Schut, H.

1996-12-31

Gas desorption and positron annihilation techniques have been employed to study the evolution of nitrogen associated defects in nitrogen irradiated metals: Fe, Ni, Mo and W. Nitrogen in these metals has a rather high affinity to vacancy type defects. The results obtained for low irradiation dose show that substitutional nitrogen (NV; with V = vacancy) is formed. The nitrogen vacancy complex dissociates at temperatures ranging from 350 K for Ni to 900 K for Mo and 1,100 K for W. At high doses defects are formed which can be characterized as nitrogen saturated vacancy clusters. These defect, as observed bymore » helium probing, disappear during annealing for nickel at 800 K, and for Mo at 1,100 K. The direct observation of the desorbing nitrogen for nickel and molybdenum reveals a very fast desorption transient at the dissociation temperature of the clusters. This is the characteristic desorption transient of a small nitride cluster, e.g., by shrinkage with constant rate. For iron the nitrogen desorption is more complicated because of a general background that continuously rises with temperature. With the positron beam technique depth information was obtained for defects in iron and the defect character could be established with the help of the information provided on annihilation with conduction and core electrons of the defect trapped positrons.« less

Metal oxide-polymer composites

NASA Technical Reports Server (NTRS)

Wellinghoff, Stephen T. (Inventor)

1997-01-01

A method of making metal oxide clusters in a single stage by reacting a metal oxide with a substoichiometric amount of an acid in the presence of an oxide particle growth terminator and solubilizer. A method of making a ceramer is also disclosed in which the metal oxide clusters are reacted with a functionalized polymer. The resultant metal oxide clusters and ceramers are also disclosed.

Metal oxide-polymer composites

NASA Technical Reports Server (NTRS)

Wellinghoff, Stephen T. (Inventor)

1994-01-01

A method of making metal oxide clusters in a single stage by reacting a metal oxide with a substoichiometric amount of an acid in the presence of an oxide particle growth terminator and solubilizer. A method of making a ceramer is also disclosed in which the metal oxide clusters are reacted with a functionalized polymer. The resultant metal oxide clusters and ceramers are also disclosed.

The Chemical Composition of NGC 5824, a Globular Cluster without Iron Spread but with an Extreme Mg–Al Anticorrelation

NASA Astrophysics Data System (ADS)

Mucciarelli, Alessio; Lapenna, Emilio; Ferraro, Francesco R.; Lanzoni, Barbara

2018-05-01

NGC 5824 is a massive Galactic globular cluster suspected to have an intrinsic spread in its iron content, according to the strength of the calcium triplet lines. We present chemical abundances of 117 cluster giant stars using high-resolution spectra acquired with the multi-object spectrograph FLAMES. The metallicity distribution of 87 red giant branch stars is peaked at [Fe/H] = ‑2.11 ± 0.01 dex, while that derived from 30 asymptotic giant branch stars is peaked at [Fe/H] = ‑2.20 ± 0.01 dex. Both the distributions are compatible with a null spread, indicating that this cluster did not retain the ejecta of supernovae. The small iron abundance offset between the two groups of stars is similar to the abundances already observed among red and asymptotic giant branch stars in other clusters. The lack of intrinsic iron spread rules out the possibility that NGC 5824 is the remnant of a disrupted dwarf galaxy, as previously suggested. We also find evidence of the chemical anomalies usually observed in globular clusters, namely the Na–O and the Mg–Al anticorrelations. In particular, NGC 5824 exhibits a huge range of [Mg/Fe] abundance, observed in only a few metal-poor and/or massive clusters. We conclude that NGC 5824 is a normal globular cluster, without spread in [Fe/H] but with an unusually large spread in [Mg/Fe], possibly due to an efficient self-enrichment driven by massive asymptotic giant branch stars. Based on observations collected at the ESO-VLT under the program 095.D-0290.

Generic features of the primary relaxation in glass-forming materials (Review Article)

NASA Astrophysics Data System (ADS)

Kokshenev, Valery B.

2017-08-01

We discuss structural relaxation in molecular and polymeric supercooled liquids, metallic alloys and orientational glass crystals. The study stresses especially the relationships between observables raised from underlying constraints imposed on degrees of freedom of vitrification systems. A self-consistent parametrization of the α-timescale on macroscopic level results in the material-and-model independent universal equation, relating three fundamental temperatures, characteristic of the primary relaxation, that is numerically proven in all studied glass formers. During the primary relaxation, the corresponding small and large mesoscopic clusters modify their size and structure in a self-similar way, regardless of underlying microscopic realizations. We show that cluster-shape similarity, instead of cluster-size fictive divergence, gives rise to universal features observed in primary relaxation. In all glass formers with structural disorder, including orientational-glass materials (with the exception of plastic crystals), structural relaxation is shown to be driven by local random fields. Within the dynamic stochastic approach, the universal subdiffusive dynamics corresponds to random walks on small and large fractals.

Structures and stability of metal-doped Ge nM (n = 9, 10) clusters

DOE Office of Scientific and Technical Information (OSTI.GOV)

Qin, Wei; Lu, Wen-Cai; Xia, Lin-Hua

The lowest-energy structures of neutral and cationic Ge nM (n = 9, 10; M = Si, Li, Mg, Al, Fe, Mn, Pb, Au, Ag, Yb, Pm and Dy) clusters were studied by genetic algorithm (GA) and first-principles calculations. The calculation results show that doping of the metal atoms and Si into Ge 9 and Ge 10 clusters is energetically favorable. Most of the metal-doped Ge cluster structures can be viewed as adding or substituting metal atom on the surface of the corresponding ground-state Ge n clusters. However, the neutral and cationic FeGe 9,10,MnGe 9,10 and Ge 10Al are cage-like withmore » the metal atom encapsulated inside. Such cage-like transition metal doped Ge n clusters are shown to have higher adsorption energy and thermal stability. Our calculation results suggest that Ge 9,10Fe and Ge 9Si would be used as building blocks in cluster-assembled nanomaterials because of their high stabilities.« less

Structures and stability of metal-doped Ge nM (n = 9, 10) clusters

DOE PAGES

Qin, Wei; Lu, Wen-Cai; Xia, Lin-Hua; ...

2015-06-26

The lowest-energy structures of neutral and cationic Ge nM (n = 9, 10; M = Si, Li, Mg, Al, Fe, Mn, Pb, Au, Ag, Yb, Pm and Dy) clusters were studied by genetic algorithm (GA) and first-principles calculations. The calculation results show that doping of the metal atoms and Si into Ge 9 and Ge 10 clusters is energetically favorable. Most of the metal-doped Ge cluster structures can be viewed as adding or substituting metal atom on the surface of the corresponding ground-state Ge n clusters. However, the neutral and cationic FeGe 9,10,MnGe 9,10 and Ge 10Al are cage-like withmore » the metal atom encapsulated inside. Such cage-like transition metal doped Ge n clusters are shown to have higher adsorption energy and thermal stability. Our calculation results suggest that Ge 9,10Fe and Ge 9Si would be used as building blocks in cluster-assembled nanomaterials because of their high stabilities.« less

Structures and stability of metal-doped GenM (n = 9, 10) clusters

NASA Astrophysics Data System (ADS)

Qin, Wei; Lu, Wen-Cai; Xia, Lin-Hua; Zhao, Li-Zhen; Zang, Qing-Jun; Wang, C. Z.; Ho, K. M.

2015-06-01

The lowest-energy structures of neutral and cationic GenM (n = 9, 10; M = Si, Li, Mg, Al, Fe, Mn, Pb, Au, Ag, Yb, Pm and Dy) clusters were studied by genetic algorithm (GA) and first-principles calculations. The calculation results show that doping of the metal atoms and Si into Ge9 and Ge10 clusters is energetically favorable. Most of the metal-doped Ge cluster structures can be viewed as adding or substituting metal atom on the surface of the corresponding ground-state Gen clusters. However, the neutral and cationic FeGe9,10,MnGe9,10 and Ge10Al are cage-like with the metal atom encapsulated inside. Such cage-like transition metal doped Gen clusters are shown to have higher adsorption energy and thermal stability. Our calculation results suggest that Ge9,10Fe and Ge9Si would be used as building blocks in cluster-assembled nanomaterials because of their high stabilities.

The role of electronegativity on the extent of nitridation of group 5 metals as revealed by reactions of tantalum cluster cations with ammonia molecules.

PubMed

Arakawa, Masashi; Ando, Kota; Fujimoto, Shuhei; Mishra, Saurabh; Patwari, G Naresh; Terasaki, Akira

2018-05-10

Reactions of the free tantalum cation, Ta+, and tantalum cluster cations, Tan+ (n = 2-10), with ammonia are presented. The reaction of the monomer cation, Ta+, with two molecules of NH3 leads to the formation of TaN2H2+ along with release of two H2 molecules. The dehydrogenation occurs until the formal oxidation number of the tantalum atom reaches +5. On the other hand, all the tantalum cluster cations, Tan+, react with two molecules of NH3 and form TanN2+ with the release of three H2 molecules. Further exposure to ammonia showed that TanNmH+ and TanNm+ are produced through successive reactions; a pure nitride and three H2 molecules are formed for every other NH3 molecule. The nitridation occurred until the formal oxidation number of the tantalum atoms reaches +5 as in the case of TaN2H2+ in contrast to other group 5 elements, i.e., vanadium and niobium, which have been reported to produce nitrides with lower oxidation states. The present results on small gas-phase metal-nitride clusters show correlation with their bulk properties: tantalum is known to form bulk nitrides in the oxidation states of either +5 (Ta3N5) or +3 (TaN), whereas vanadium and niobium form nitrides in the oxidation state of +3 (VN and NbN). Along with DFT calculations, these findings reveal that nitridation is driven by the electron-donating ability of group 5 elements, i.e., electronegativity of the metal plays a key role in determining the composition of the metal nitrides.

THE OPTICAL COLORS OF GIANT ELLIPTICAL GALAXIES AND THEIR METAL-RICH GLOBULAR CLUSTERS INDICATE A BOTTOM-HEAVY INITIAL MASS FUNCTION

DOE Office of Scientific and Technical Information (OSTI.GOV)

Goudfrooij, Paul; Diederik Kruijssen, J. M., E-mail: goudfroo@stsci.edu, E-mail: kruijssen@mpa-garching.mpg.de

2013-01-10

We report a systematic and statistically significant offset between the optical (g - z or B - I) colors of seven massive elliptical galaxies and the mean colors of their associated massive metal-rich globular clusters (GCs) in the sense that the parent galaxies are redder by {approx}0.12-0.20 mag at a given galactocentric distance. However, spectroscopic indices in the blue indicate that the luminosity-weighted ages and metallicities of such galaxies are equal to that of their averaged massive metal-rich GCs at a given galactocentric distance, to within small uncertainties. The observed color differences between the red GC systems and their parentmore » galaxies cannot be explained by the presence of multiple stellar generations in massive metal-rich GCs, as the impact of the latter to the populations' integrated g - z or B - I colors is found to be negligible. However, we show that this paradox can be explained if the stellar initial mass function (IMF) in these massive elliptical galaxies was significantly steeper at subsolar masses than canonical IMFs derived from star counts in the solar neighborhood, with the GC colors having become bluer due to dynamical evolution, causing a significant flattening of the stellar MF of the average surviving GC.« less

The most metal-poor Galactic globular cluster: the first spectroscopic observations of ESO280-SC06

NASA Astrophysics Data System (ADS)

Simpson, Jeffrey D.

2018-07-01

We present the first spectroscopic observations of the very metal-poor Milky Way globular cluster ESO280-SC06. Using spectra acquired with the 2dF/AAOmega spectrograph on the Anglo-Australian Telescope, we have identified 13 members of the cluster, and estimate from their infrared calcium triplet lines that the cluster has a metallicity of [Fe/H]=-2.48^{+0.06 }_{ -0.11}. This would make it the most metal-poor globular cluster known in the Milky Way. This result was verified with comparisons to three other metal-poor globular clusters that had been observed and analysed in the same manner. We also present new photometry of the cluster from EFOSC2 and SkyMapper and confirm that the cluster is located 22.9 ± 2.1 kpc from the Sun and 15.2 ± 2.1 kpc from the Galactic Centre, and has a radial velocity of 92.5^{+2.4 }_{ -1.6} km s-1. These new data finds the cluster to have a radius about half that previously estimated, and we find that the cluster has a dynamical mass of the cluster of (12 ± 2) × 103 M⊙. Unfortunately, we lack reliable proper motions to fully characterize its orbit about the Galaxy. Intriguingly, the photometry suggests that the cluster lacks a well-populated horizontal branch, something that has not been observed in a cluster so ancient or metal poor.

The most metal-poor Galactic globular cluster: the first spectroscopic observations of ESO280-SC06

NASA Astrophysics Data System (ADS)

Simpson, Jeffrey D.

2018-04-01

We present the first spectroscopic observations of the very metal-poor Milky Way globular cluster ESO280-SC06. Using spectra acquired with the 2dF/AAOmega spectrograph on the Anglo-Australian Telescope, we have identified 13 members of the cluster, and estimate from their infrared calcium triplet lines that the cluster has a metallicity of [Fe/H]={-2.48}^{+0.06}_{-0.11}. This would make it the most metal-poor globular cluster known in the Milky Way. This result was verified with comparisons to three other metal-poor globular clusters that had been observed and analyzed in the same manner. We also present new photometry of the cluster from EFOSC2 and SkyMapper and confirm that the cluster is located 22.9 ± 2.1 kpc from the Sun and 15.2 ± 2.1 kpc from the Galactic centre, and has a radial velocity of 92.5 + 2.4-1.6 km s-1. These new data finds the cluster to have a radius about half that previously estimated, and we find that the cluster has a dynamical mass of the cluster of (12 ± 2) × 103 M⊙. Unfortunately, we lack reliable proper motions to fully characterize its orbit about the Galaxy. Intriguingly, the photometry suggests that the cluster lacks a well-populated horizontal branch, something that has not been observed in a cluster so ancient or metal-poor.

Early Transition Metal Oxides as Catalysts: Crossing Scales from Clusters to Single Crystals to Functioning Materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lai-Sheng Wang

2009-07-07

The overall goal of this program is to investigate the electronic structure and chemical bonding of early transition metal oxide clusters and use them as well-defined molecular models to obtain insight into properties and mechanisms of oxide catalysts, as well as to provide accurate spectroscopic and molecular information to verify theoretical methods used to predict materials properties. A laser vaporization cluster source is used to produce metal oxide clusters with different sizes, structures, and compositions. Well-defined inorganic polyoxometalate clusters in solution are transported in the gas phase using electrospray. Two state-of-the-art photoelectron spectroscopy apparatuses are used to interrogate the oxidemore » clusters and polyoxometalate anions in the gas phase to obtain spectroscopic and electronic structure information. The experimental effort is assisted by theoretical calculations to understanding the structures, chemical bonding, and catalytical properties of the transition metal oxide clusters. The research approach combines novel and flexible experimental techniques and advanced theoretical/computational methodologies and seeks molecular-level information to aiding the design of new catalysts, as well as mechanistic understanding. We have focused on the investigation of tungsten oxide clusters containing three W atoms: W{sub 3}O{sub x}{sup -} (x = 7-11). A number of interesting findings have been made. We observed that the oxygen-poor W{sub 3}O8 cluster contains a localized W{sup 4+} center, which can be used as a molecular model for O-deficient defect sites. A chemisorption energy was obtained through density functional calculations for W{sub 3}O8 + O{sub 2} {yields} W{sub 3}O{sub 10} as -78 kcal/mol. We further found that the neutral stoichiometric W{sub 2}O{sub 6} and W{sub 3}O{sub 9} clusters do not react with O{sub 2} and they only form physi-sorbed complexes, W{sub 2}O{sub 6}(O{sub 2}) and W{sub 3}O{sub 9}(O{sub 2}). However, the negatively charged W{sub 2}O{sub 6}{sup -} and W{sub 3}O{sub 9}{sup -} clusters are found to form chemisorbed complexes due to the presence of the extra electron. Thus, the W{sub 2}O{sub 6}{sup -} and W{sub 3}O{sub 9}{sup -} negative clusters can be viewed as models for O{sub 2} interaction with a reduced W site (W{sup 5+}) on the oxide surface. These studies also led to the surprising observation of the first d-orbital aromatic clusters in W{sub 3}O{sub 9}{sup 2-} and Mo{sub 3}O{sub 9}{sup 2-}, which each contains a completely delocalized three-center two-electron bond made entirely made of the metal d orbitals. This last result was highlighted in both Chem & Eng. News and Nature. We further studied a series of small metalate anions using electrospray, including the hydroxo and methoxo oxometalate MO{sub 3}(OH){sup -} and MO{sub 3}(OCH{sub 3}){sup -}, and the dimetalates: M{sub 2}O{sub 7}{sup 2-}, MM{prime}O{sub 7}{sup 2-}, and M{sub 2}O{sub 7}{sup -} (M, M{prime} = Cr, Mo, and W).« less

Structure of mono- and bimetallic heterogeneous catalysts based on noble metals obtained by means of fluid technology and metal-vapor synthesis

NASA Astrophysics Data System (ADS)

Said-Galiev, E. E.; Vasil'kov, A. Yu.; Nikolaev, A. Yu.; Lisitsyn, A. I.; Naumkin, A. V.; Volkov, I. O.; Abramchuk, S. S.; Lependina, O. L.; Khokhlov, A. R.; Shtykova, E. V.; Dembo, K. A.; Erkey, C.

2012-10-01

Monometallic nanocomposites are obtained with the use of supercritical carbon dioxide (fluid technique) and metal-vapor synthesis (MVS), while bimetallic nanocomposites of Pt and Au noble metals and γ-Al2O3 oxide matrix are synthesized by a combination of these two methods. The structures, concentrations, and chemical states of metal atoms in composites are studied by means of small-angle X-ray scattering (SAXS), transparent electron microscopy (TEM), X-ray fluorescent analysis (XFA), and X-ray photoelectron spectroscopy (XPS). The neutral state of metal atoms in clusters is shown by XPS and their size distribution is found according to SAXS; as is shown, it is determined by the pore sizes of the oxide matrices and lies in the range of 1 to 50 nm. The obtained composites manifest themselves as effective catalysts in the oxidation of CO to CO2.

Color-magnitude diagrams for six metal-rich, low-latitude globular clusters

NASA Technical Reports Server (NTRS)

Armandroff, Taft E.

1988-01-01

Colors and magnitudes for stars on CCD frames for six metal-rich, low-latitude, previously unstudied globular clusters and one well-studied, metal-rich cluster (47 Tuc) have been derived and color-magnitude diagrams have been constructed. The photometry for stars in 47 Tuc are in good agreement with previous studies, while the V magnitudes of the horizontal-branch stars in the six program clusters do not agree with estimates based on secondary methods. The distances to these clusters are different from prior estimates. Redding values are derived for each program cluster. The horizontal branches of the program clusters all appear to lie entirely redwards of the red edge of the instability strip, as is normal for their metallicities.

Carbon nitride supported Fe2 cluster catalysts with superior performance for alkene epoxidation.

PubMed

Tian, Shubo; Fu, Qiang; Chen, Wenxing; Feng, Quanchen; Chen, Zheng; Zhang, Jian; Cheong, Weng-Chon; Yu, Rong; Gu, Lin; Dong, Juncai; Luo, Jun; Chen, Chen; Peng, Qing; Draxl, Claudia; Wang, Dingsheng; Li, Yadong

2018-06-15

Sub-nano metal clusters often exhibit unique and unexpected properties, which make them particularly attractive as catalysts. Herein, we report a "precursor-preselected" wet-chemistry strategy to synthesize highly dispersed Fe 2 clusters that are supported on mesoporous carbon nitride (mpg-C 3 N 4 ). The obtained Fe 2 /mpg-C 3 N 4 sample exhibits superior catalytic performance for the epoxidation of trans-stilbene to trans-stilbene oxide, showing outstanding selectivity of 93% at high conversion of 91%. Molecular oxygen is the only oxidant and no aldehyde is used as co-reagent. Under the same condition, by contrast, iron porphyrin, single-atom Fe, and small Fe nanoparticles (ca. 3 nm) are nearly reactively inert. First-principles calculations reveal that the unique reactivity of the Fe 2 clusters originates from the formation of active oxygen species. The general applicability of the synthesis approach is further demonstrated by producing other diatomic clusters like Pd 2 and Ir 2 , which lays the foundation for discovering diatomic cluster catalysts.

Subnanometer to nanometer transition metal CO oxidation catalysts

DOEpatents

Vajda, Stefan; Fortunelli, Alessandro; Yasumatsu, Hisato

2017-12-26

The present invention provides a catalyst defined in part by a conductive substrate; a film overlaying a surface of the substrate; and a plurality of metal clusters supported by the layer, wherein each cluster comprises between 8 and 11 atoms. Further provided is a catalyst defined in part by a conductive substrate; a layer overlaying a surface of the substrate; and a plurality of metal clusters supported by the layer, wherein each cluster comprises at least two metals.

An efficient laser vaporization source for chemically modified metal clusters characterized by thermodynamics and kinetics

NASA Astrophysics Data System (ADS)

Masubuchi, Tsugunosuke; Eckhard, Jan F.; Lange, Kathrin; Visser, Bradley; Tschurl, Martin; Heiz, Ulrich

2018-02-01

A laser vaporization cluster source that has a room for cluster aggregation and a reactor volume, each equipped with a pulsed valve, is presented for the efficient gas-phase production of chemically modified metal clusters. The performance of the cluster source is evaluated through the production of Ta and Ta oxide cluster cations, TaxOy+ (y ≥ 0). It is demonstrated that the cluster source produces TaxOy+ over a wide mass range, the metal-to-oxygen ratio of which can easily be controlled by changing the pulse duration that influences the amount of reactant O2 introduced into the cluster source. Reaction kinetic modeling shows that the generation of the oxides takes place under thermalized conditions at less than 300 K, whereas metal cluster cores are presumably created with excess heat. These characteristics are also advantageous to yield "reaction intermediates" of interest via reactions between clusters and reactive molecules in the cluster source, which may subsequently be mass selected for their reactivity measurements.

The structure of deposited metal clusters generated by laser evaporation

NASA Astrophysics Data System (ADS)

Faust, P.; Brandstättner, M.; Ding, A.

1991-09-01

Metal clusters have been produced using a laser evaporation source. A Nd-YAG laser beam focused onto a solid silver rod was used to evaporate the material, which was then cooled to form clusters with the help of a pulsed high pressure He beam. TOF mass spectra of these clusters reveal a strong occurrence of small and medium sized clusters ( n<100). Clusters were also deposited onto grid supported thin layers of carbon-films which were investigated by transmission electron microscopy. Very high resolution pictures of these grids were used to analyze the size distribution and the structure of the deposited clusters. The diffraction pattern caused by crystalline structure of the clusters reveals 3-and 5-fold symmetries as well as fcc bulk structure. This can be explained in terms of icosahedron and cuboctahedron type clusters deposited on the surface of the carbon layer. There is strong evidence that part of these cluster geometries had already been formed before the depostion process. The non-linear dependence of the cluster size and the cluster density on the generating conditions is discussed. Therefore the samples were observed in HREM in the stable DEEKO 100 microscope of the Fritz-Haber-Institut operating at 100 KV with the spherical aberration c S =0.5 mm. The quality of the pictures was improved by using the conditions of minimum phase contrast hollow cone illumination. This procedure led to a minimum of phase contrast artefacts. Among the well-crystallized particles were a great amount of five- and three-fold symmetries, icosahedra and cuboctahedra respectively. The largest clusters with five- and three-fold symmetries have been found with diameters of 7 nm; the smallest particles displaying the same undistorted symmetries were of about 2 mm. Even smaller ones with strong distortions could be observed although their classification is difficult. The quality of the images was improved by applying Fourier filtering techniques.

Metal Sulfide Cluster Complexes and their Biogeochemical Importance in the Environment

NASA Astrophysics Data System (ADS)

Luther, George W.; Rickard, David T.

2005-10-01

Aqueous clusters of FeS, ZnS and CuS constitute a major fraction of the dissolved metal load in anoxic oceanic, sedimentary, freshwater and deep ocean vent environments. Their ubiquity explains how metals are transported in anoxic environmental systems. Thermodynamic and kinetic considerations show that they have high stability in oxic aqueous environments, and are also a significant fraction of the total metal load in oxic river waters. Molecular modeling indicates that the clusters are very similar to the basic structural elements of the first condensed phase forming from aqueous solutions in the Fe-S, Zn-S and Cu-S systems. The structure of the first condensed phase is determined by the structure of the cluster in solution. This provides an alternative explanation of Ostwald's Rule, where the most soluble, metastable phases form before the stable phases. For example, in the case of FeS, we showed that the first condensed phase is nanoparticulate, metastable mackinawite with a particle size of 2 nm consisting of about 150 FeS subunits, representing the end of a continuum between aqueous FeS clusters and condensed material. These metal sulfide clusters and nanoparticles are significant in biogeochemistry. Metal sulfide clusters reduce sulfide and metal toxicity and help drive ecology. FeS cluster formation drives vent ecology and AgS cluster formation detoxifies Ag in Daphnia magna neonates. We also note a new reaction between FeS and DNA and discuss the potential role of FeS clusters in denaturing DNA.

Slow Photoelectron Velocity-Map Imaging of Cryogenically Cooled Anions

NASA Astrophysics Data System (ADS)

Weichman, Marissa L.; Neumark, Daniel M.

2018-04-01

Slow photoelectron velocity-map imaging spectroscopy of cryogenically cooled anions (cryo-SEVI) is a powerful technique for elucidating the vibrational and electronic structure of neutral radicals, clusters, and reaction transition states. SEVI is a high-resolution variant of anion photoelectron spectroscopy based on photoelectron imaging that yields spectra with energy resolution as high as 1-2 cm‑1. The preparation of cryogenically cold anions largely eliminates hot bands and dramatically narrows the rotational envelopes of spectral features, enabling the acquisition of well-resolved photoelectron spectra for complex and spectroscopically challenging species. We review the basis and history of the SEVI method, including recent experimental developments that have improved its resolution and versatility. We then survey recent SEVI studies to demonstrate the utility of this technique in the spectroscopy of aromatic radicals, metal and metal oxide clusters, nonadiabatic interactions between excited states of small molecules, and transition states of benchmark bimolecular reactions.

Mechanism of Mo-Dependent Nitrogenase

PubMed Central

Seefeldt, Lance C.; Hoffman, Brian M.; Dean, Dennis R.

2010-01-01

Nitrogen-fixing bacteria catalyze the reduction of dinitrogen (N2) to two ammonia molecules (NH3), the major contribution of fixed nitrogen into the biogeochemical nitrogen cycle. The most widely studied nitrogenase is the Mo-dependent enzyme. The reduction of N2 by this enzyme involves the transient interaction of two component proteins, designated the Fe protein and the MoFe protein, and minimally requires sixteen MgATP, eight protons, and eight electrons. The current state of knowledge on how these proteins and small molecules together effect the reduction of N2 to ammonia is reviewed. Included is a summary of the roles of the Fe protein and MgATP hydrolysis, information on the roles of the two metal clusters contained in the MoFe protein in catalysis, insights gained from recent success in trapping substrates and inhibitors at the active site metal cluster FeMo-cofactor, and finally, considerations of the mechanism of N2 reduction catalyzed by nitrogenase. PMID:19489731

Stabilization of Oxidized Copper Nanoclusters in Confined Spaces

DOE PAGES

Akter, Nusnin; Wang, Mengen; Zhong, Jian-Qiang; ...

2018-01-04

Copper is an important industrial catalyst. The ability to manipulate the oxidation state of copper clusters in a controlled way is critical to understanding structure–reactivity relations of copper catalysts at the molecular level. Experimentally, cupric oxide surfaces or even small domains can only be stabilized at elevated temperatures and in the presence of oxygen, as copper can be easily reduced under reaction conditions. Herein bilayer silica films grown on a metallic substrate are used to trap diluted copper oxide clusters. By combining in situ experiments with first principles calculations, it is found that the confined space created by the silicamore » film leads to an increase in the energy barrier for Cu diffusion. Dispersed copper atoms trapped by the silica film can be easily oxidized by surface oxygen chemisorbed on the metallic substrate, which results in the formation and stabilization of Cu 2+ cations.« less

Heteronuclear Metal Cluster Compounds Synthesis and Reactivity

DTIC Science & Technology

1990-08-10

important role in the formation of complexes with heteronuclear metal - metal bonds. Since this is our Final Report recent results are reported and...DTe FL’ Copy AFOSR-86-0125 Lfl X’ HETERONUCLEAR METAL CLUSTER COMPOUNDS00 SYNTHESIS AND REACTIVITY F. Gordon A. Stone, IDepartment of Inorganic...Security Classification) HETERONUCLEAR METAL CLUSTER COMPOUNDS: SYNTHESIS AND REACTIVITY 12. PERSONAL AUTHOR(S) F. GORDON A. STONE 13a. TYPE OF REPORT

Role of Anions Associated with the Formation and Properties of Silver Clusters.

PubMed

Wang, Quan-Ming; Lin, Yu-Mei; Liu, Kuan-Guan

2015-06-16

Metal clusters have been very attractive due to their aesthetic structures and fascinating properties. Different from nanoparticles, each cluster of a macroscopic sample has a well-defined structure with identical composition, size, and shape. As the disadvantages of polydispersity are ruled out, informative structure-property relationships of metal clusters can be established. The formation of a high-nuclearity metal cluster involves the organization of metal ions into a complex entity in an ordered way. To achieve controllable preparation of metal clusters, it is helpful to introduce a directing agent in the formation process of a cluster. To this end, anion templates have been used to direct the formation of high nuclearity clusters. In this Account, the role of anions played in the formation of a variety of silver clusters has been reviewed. Silver ions are positively charged, so anionic species could be utilized to control the formation of silver clusters on the basis of electrostatic interactions, and the size and shape of the resulted clusters can be dictated by the templating anions. In addition, since the anion is an integral component in the silver clusters described, the physical properties of the clusters can be modulated by functional anions. The templating effects of simple inorganic anions and polyoxometales are shown in silver alkynyl clusters and silver thiolate clusters. Intercluster compounds are also described regarding the importance of anions in determining the packing of the ion pairs and making contribution to electron communications between the positive and negative counterparts. The role of the anions is threefold: (a) an anion is advantageous in stabilizing a cluster via balancing local positive charges of the metal cations; (b) an anion template could help control the size and shape of a cluster product; (c) an anion can be a key factor in influencing the function of a cluster through bringing in its intrinsic properties. Properties including electron communication, luminescent thermochromism, single-molecule magnet, and intercluster charge transfer associated with anion-directed silver clusters have been discussed. We intend to attract chemists' attention to the role that anions could play in determining the structures and properties of metal complexes, especially clusters. We hope that this Account will stimulate more efforts in exploiting new role of anions in various metal cluster systems. Anions can do much more than counterions for charge balance, and they should be considered in the design and synthesis of cluster-based functional materials.

Integrated-light spectroscopy of globular clusters at the infrared Ca II lines

NASA Technical Reports Server (NTRS)

Armandroff, Taft E.; Zinn, Robert

1988-01-01

Integrated-light spectroscopy has been obtained for 27 globular clusters at the Ca II IR triplet. Line strengths and radial velocities have been measured from the spectra. For the well-studied clusters in the sample, the strength of the Ca II lines is very well correlated with previous metallicity estimates. Thus, the triplet is useful as a metallicity indicator in globular cluster integrated-light spectra. The greatly reduced effect of interstellar extinction at these wavelengths (compared to the blue region of the spectrum) has permitted observations of some of the most heavily reddened clusters in the Galaxy. For several such clusters, the Ca II triplet metallicities are in poor agreement with metallicity estimates from IR photometry by Malkan (1981). The strength of an interstellar band at 8621A has been used to estimate the amount of extinction towards these clusters. Using the new metallicity and radial-velocity data, the metallicity distribution, kinematics, and spatial distribution of the disk globular cluster system have been analyzed. Results very similar to those of Zinn (1985) have been found. The relation of the disk globulars to the stellar thick disk is discussed.

NOEMA Observations of a Molecular Cloud in the Low-metallicity Galaxy Kiso 5639

NASA Astrophysics Data System (ADS)

Elmegreen, Bruce G.; Herrera, Cinthya; Rubio, Monica; Elmegreen, Debra Meloy; Sánchez Almeida, Jorge; Muñoz-Tuñón, Casiana; Olmo-García, Amanda

2018-06-01

A giant star-forming region in a metal-poor dwarf galaxy has been observed in optical lines with the 10 m Gran Telescopio Canarias (GTC) and in the emission line of CO(1–0) with the Northern Extended Millimeter Array (NOEMA) mm-wave interferometer. The metallicity was determined to be 12+{log}({{O}}/{{H}})=7.83+/- 0.09, from which we estimate a conversion factor of α CO ∼ 100 M ⊙ pc‑2(K km s‑1)‑1 and a molecular cloud mass of ∼2.9 × 107 M ⊙. This is an enormous concentration of molecular mass at one end of a small galaxy, suggesting a recent accretion. The molecular cloud properties seem normal: the surface density, 120 M ⊙ pc‑2, is comparable to that of a standard giant molecular cloud; the cloud’s virial ratio of ∼1.8 is in the star formation range; and the gas consumption time, 0.5 Gyr, at the present star formation rate is typical for molecular regions. The low metallicity implies that the cloud has an average visual extinction of only 0.8 mag, which is close to the threshold for molecule formation. With such an extinction threshold, molecular clouds in metal-poor regions should have high surface densities and high internal pressures. If high pressure is associated with the formation of massive clusters, then metal-poor galaxies such as dwarfs in the early universe could have been the hosts of metal-poor globular clusters.

Structures and stability of metal-doped Ge{sub n}M (n = 9, 10) clusters

DOE Office of Scientific and Technical Information (OSTI.GOV)

Qin, Wei, E-mail: qinw@qdu.edu.cn; Xia, Lin-Hua; Zhao, Li-Zhen

The lowest-energy structures of neutral and cationic Ge{sub n}M (n = 9, 10; M = Si, Li, Mg, Al, Fe, Mn, Pb, Au, Ag, Yb, Pm and Dy) clusters were studied by genetic algorithm (GA) and first-principles calculations. The calculation results show that doping of the metal atoms and Si into Ge{sub 9} and Ge{sub 10} clusters is energetically favorable. Most of the metal-doped Ge cluster structures can be viewed as adding or substituting metal atom on the surface of the corresponding ground-state Ge{sub n} clusters. However, the neutral and cationic FeGe{sub 9,10},MnGe{sub 9,10} and Ge{sub 10}Al are cage-like withmore » the metal atom encapsulated inside. Such cage-like transition metal doped Ge{sub n} clusters are shown to have higher adsorption energy and thermal stability. Our calculation results suggest that Ge{sub 9,10}Fe and Ge{sub 9}Si would be used as building blocks in cluster-assembled nanomaterials because of their high stabilities.« less

The Connection Between Local Icosahedral Order in Metallic Liquids and the Nucleation Behavior of Ordered Phases

NASA Technical Reports Server (NTRS)

Kelton, K. F.; Gangopadhyay, A. K.; Lee, G. W.; Hyers, R. W.; Rathz, T. J.; Rogers, J. R.; Robinson, M. B.; Schenk, T.; Simonet, V.

2003-01-01

Over fifty years ago, David Turnbull showed that the temperature of many metallic liquids could be decreased far below their equilibrium melting temperature before crystallization occurred. To explain those surprising results, Charles Frank hypothesized that the local structures of undercooled metallic liquids are different from those of crystal phases, containing a significant degree of icosahedral order that is incompatible with extended periodicity. Such structural differences must create a barrier to the formation crystal phases, explaining the observed undercooling behavior. If true, the nucleation from the liquid of phases with extended icosahedral order should be easier. Icosahedral order is often favored in small clusters, as observed recently in liquid-like clusters of pure Pb on the (111) surface of Si[3], for example. However, it has never been shown that an increasing preference for icosahedral phase formation can be directly linked with the development of icosahedral order in the undercooled liquid. Owing to the combination of very recent advances in levitation techniques and the availability of synchrotron x-ray and high flux neutron facilities, this is shown here.

The Connection Between Local Icosahedral Order in Metallic Liquids and the Nucleation of Ordered Phases

NASA Technical Reports Server (NTRS)

Curreri, Peter A. (Technical Monitor); Kelton, K. F.; Gangopadhyay, A.; Lee, G. W.; Hyers, R. W.; Rathz, R. J.; Rogers, J.; Schenk, T.; Simonet, V.; Holland-Moritz, D.

2003-01-01

Over fifty years ago, David Turnbull showed that the temperature of many metallic liquids could be decreased far below their equilibrium melting temperature before crystallization occurred. To explain those surprising results, Charles Frank hypothesized that the local structures of undercooled metallic liquids are different from those of crystal phases, containing a significant degree of icosahedral order that is incompatible with extended periodicity. Such structural differences must create a barrier to the formation crystal phases, explaining the observed undercooling behavior. If true, the nucleation from the liquid of phases with extended icosahedral order should be easier. Icosahedral order is often favored in small clusters, as observed recently in liquid-like clusters of pure Pb on the (111) surface of Si, for example. However, it has never been shown that an increasing preference for icosahedral phase formation can be directly linked with the development of icosahedral order in the undercooled liquid. Owing to the combination of very recent advances in levitation techniques and the availability of synchrotron x-ray and high flux neutron facilities, this is shown here.

The Connection Between Local Icosahedral Order in Metallic Liquids and the Nucleation of Ordered Phases

NASA Technical Reports Server (NTRS)

Kelton, K. F.; Gangopadhyay, A. K.; Lee, G. W.; Hyers, R. W.; Rathz, T. J.; Rogers, J. R.; Robinson, M. B.; Schenk, T.; Simonet, V.; Holland-Moritz, D.;

The Design, Synthesis, and Characterization of Open Sites on Metal Clusters

NASA Astrophysics Data System (ADS)

Nigra, Michael Mark

Coordinatively unsaturated corner and edge atoms have been hypothesized to have the highest activity of sites responsible for many catalytic reactions on a metal surface. Recent studies have validated this hypothesis in varied reaction systems. However, quantification of different types of coordinatively unsaturated sites, and elucidation of their individual catalytic rates has remained a largely unresolved challenge when understanding catalysis on metal surfaces. Yet such structure-function knowledge would be invaluable to the design of more active and selective metal-surface catalysts in the future. I investigated the catalytic contributions of undercoordinated sites such as corner and edge atoms are investigated in a model reaction system using organic ligands bound to the gold nanoparticle surface. The catalyst consisted of 4 nm gold nanoparticles on a metal oxide support, using resazurin to resorufin as a model reaction system. My results demonstrate that in this system, corner atom sites are the most undercoordinated sites, and are over an order of magnitude more active when compared to undercoordinated edge atom sites, while terrace sites remain catalytically inactive for the reduction reaction of resazurin to resorufin. Catalytic activity has been also demonstrated for calixarene-bound gold nanoparticles using the reduction of 4-nitrophenol. With the 4-nitrophenol reduction reaction, a comparative study was undertaken to compare calixarene phosphine and calixarene thiol bound 4 nm gold particles. The results of the study suggested that a leached site was responsible for catalysis and not sites on the original gold nanoparticles. Future experiments with calixarene bound gold clusters could investigate ligand effects in reactions where the active site is not a leached or aggregated gold species, possibly in oxidation reactions, where electron-rich gold is hypothesized to be a good catalyst. The results that emphasize the enhanced catalytic activity of undercoordinated sites led me to synthesize small gold clusters consisting of a high fraction of coordinatively unsaturated open sites. This was enabled through an approach that utilized bulky calix[4]arene ligands that are bound to a gold core. Since the size of the calix[4]arene ligand is commensurate with the size of the gold cluster core, the calix[4]arene ligand does not pack closely together on the gold cluster surface. This in turn results in areas of accessible gold atom sites between ligands. Additionally, these calix[4]arene ligands prevent cluster aggregation and electronically tune the gold core in a manner conceptually similar to enzymes affecting reactivity through organic side-chains acting as ligands. I quantified the number of open sites that result from this packing problem on the gold cluster surface, using fluorescence probe chemisorption experiments. The results of these chemisorption measurements support the mechanical model of accessibility whereby accessibility is not dependent on the identity of the functional group, whether it be calixarene phosphines or N-heterocyclic carbenes, bound to the gold surface, but rather to the relative radii of curvature of bound ligands and the gold cluster core. Additional materials characterization was completed with transmission electron microscopy in both bright-field imaging of zeolites, in MCM-22 and delaminated ITQ-2 and UCB-1 materials, and in dark field imaging of glucan coatings on oxide particles. These materials could prove to be interesting materials as to use as supports for the calixarene-bound metal clusters described above or for other metal clusters.

Chandra observations of dying radio sources in galaxy clusters

NASA Astrophysics Data System (ADS)

Murgia, M.; Markevitch, M.; Govoni, F.; Parma, P.; Fanti, R.; de Ruiter, H. R.; Mack, K.-H.

2012-12-01

Context. The dying radio sources represent a very interesting and largely unexplored stage of the active galactic nucleus (AGN) evolution. They are considered to be very rare, and almost all of the few known ones were found in galaxy clusters. However, considering the small number detected so far, it has not been possible to draw any firm conclusions about their X-ray environment. Aims: We present X-ray observations performed with the Chandra satellite of the three galaxy clusters Abell 2276, ZwCl 1829.3+6912, and RX J1852.1+5711, which harbor at their center a dying radio source with an ultra-steep spectrum that we recently discovered. Methods: We analyzed the physical properties of the X-ray emitting gas surrounding these elusive radio sources. We determined the global X-ray properties of the clusters, derived the azimuthally averaged profiles of metal abundance, gas temperature, density, and pressure. Furthermore, we estimated the total mass profiles. Results: The large-scale X-ray emission is regular and spherical, suggesting a relaxed state for these systems. Indeed, we found that the three clusters are also characterized by significant enhancements in the metal abundance and declining temperature profiles toward the central region. For all these reasons, we classified RX J1852.1+5711, Abell 2276, and ZwCl 1829.3+6912 as cool-core galaxy clusters. Conclusions: We calculated the non-thermal pressure of the radio lobes assuming that the radio sources are in the minimum energy condition. For all dying sources we found that this is on average about one to two orders of magnitude lower than that of the external gas, as found for many other radio sources at the center of galaxy groups and clusters. We found marginal evidence for the presence of X-ray surface brightness depressions coincident with the fossil radio lobes of the dying sources in A2276 and ZwCl 1829.3+691. We estimated the outburst age and energy output for these two dying sources. The energy power from the AGN outburst is significantly higher than the X-ray luminosity in both clusters. Indeed, it is sufficient that a small fraction of this power is dissipated in the intra-cluster medium to reheat the cool cores. Appendix is available in electronic form at http://www.aanda.org

Chandra Observations of Dying Radio Sources in Galaxy Clusters

NASA Technical Reports Server (NTRS)

Murgia, M.; Markevitch, M.; Govoni, F.; Parma, P.; Fanti, R.; de Ruiter, H. R.; Mack, K.-H.

2012-01-01

Context. The dying radio sources represent a very interesting and largely unexplored stage of the active galactic nucleus (AGN) evolution. They are considered to be very rare, and almost all of the few known ones were found in galaxy clusters. However, considering the small number detected so far, it has not been possible to draw any firm conclusions about their X-ray environment. Aims. We present X-ray observations performed with the Chandra satellite of the three galaxy clusters Abell 2276, ZwCl 1829.3+6912, and RX J1852.1+5711, which harbor at their center a dying radio source with an ultra-steep spectrum that we recently discovered. Methods. We analyzed the physical properties of the X-ray emitting gas surrounding these elusive radio sources. We determined the global X-ray properties of the clusters, derived the azimuthally averaged profiles of metal abundance, gas temperature, density, and pressure. Furthermore, we estimated the total mass profiles. Results. The large-scale X-ray emission is regular and spherical, suggesting a relaxed state for these systems. Indeed, we found that the three clusters are also characterized by significant enhancements in the metal abundance and declining temperature profiles toward the central region. For all these reasons, we classified RX J1852.1+5711, Abell 2276, and ZwCl 1829.3+6912 as cool-core galaxy clusters. Conclusions. We calculated the non-thermal pressure of the radio lobes assuming that the radio sources are in the minimum energy condition. For all dying sources we found that this is on average about one to two orders of magnitude lower than that of the external gas, as found for many other radio sources at the center of galaxy groups and clusters. We found marginal evidence for the presence of X-ray surface brightness depressions coincident with the fossil radio lobes of the dying sources in A2276 and ZwCl 1829.3+691. We estimated the outburst age and energy output for these two dying sources. The energy power from the AGN outburst is significantly higher than the X-ray luminosity in both clusters. Indeed, it is sufficient that a small fraction of this power is dissipated in the intra-cluster medium to reheat the cool cores.

Development of Wien filter for small ion gun of surface analysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bahng, Jungbae; Busan Center, Korea Basic Science Institute, Busan 609-735; Hong, Jonggi

The gas cluster ion beam (GCIB) and liquid metal ion beam have been studied in the context of ion beam usage for analytical equipment in applications such as X-ray photoelectron spectroscopy and secondary ion mass spectroscopy (SIMS). In particular, small ion sources are used for the secondary ion generation and ion etching. To set the context to this study, the SIMS project has been launched to develop ion-gun based analytical equipment for the Korea Basic Science Institute. The objective of the first stage of the project is the generation of argon beams with a GCIB system [A. Kirkpatrick, Nucl. Instrum.more » Methods Phys. Res., Sect. B 206, 830–837 (2003)] that consists of a nozzle, skimmer, ionizer, acceleration tube, separation system, transport system, and target. The Wien filter directs the selected cluster beam to the target system by exploiting the velocity difference of the generated particles from GCIB. In this paper, we present the theoretical modeling and three-dimensional electromagnetic analysis of the Wien filter, which can separate Ar{sup +}{sub 2500} clusters from Ar{sup +}{sub 2400} to Ar{sup +}{sub 2600} clusters with a 1-mm collimator.« less

Detailed Abundances in a Metal-Poor Stellar Stream

NASA Astrophysics Data System (ADS)

Roederer, I. U.; Sneden, C.; Thompson, I. B.; Preston, G. W.; Shectman, S. A.

2010-10-01

We present the results of a detailed abundance analysis of one of the confirmed building blocks of the Milky Way stellar halo, a kinematically-coherent metal-poor stellar stream. We have obtained high resolution and high S/N spectra of 8 confirmed and 4 rejected stream members using the MIKE spectrograph on the Magellan-Clay Telescope at Las Campanas Observatory and the 2dCoude spectrograph on the Smith Telescope at McDonald Observatory. We have derived abundances or upper limits for nearly 50 species of more than 40 elements in each of these stars. The stream members show a range of metallicity (-2.5 < [Fe/H] < -1.5) but are otherwise chemically homogeneous, with the same star-to-star chemical dispersion in [X/Fe] as halo stars. They show no evolution in the α or Fe-group elements over the range of metallicity. The stream does not resemble a globular cluster in that its members show a range of metallicities, and the small chemical dispersion and lack of chemical evolution demonstrate that it is also unlike the classical Milky Way dwarf spheroidal galaxies. Our results support the notion that a significant fraction of the Milky Way stellar halo was formed from accreted systems, and these systems likely did not resemble the present-day globular clusters or luminous dwarf galaxies. This stream is mildly enriched (in, e.g., [Eu/Fe]) by material produced by the main and weak components of the rapid neutron-capture process and shows no evidence for enrichment by the slow neutron-capture process. Except for the observed metallicity range of the stream stars, the enrichment pattern of the stream is nearly identical to that of the massive metal-poor globular cluster M15. The kinematics of M15 and the stream are also similar. It is possible that both systems may have originated from a common progenitor but not likely that the stream originated from M15.

Probing C-O bond activation on gas-phase transition metal clusters: Infrared multiple photon dissociation spectroscopy of Fe, Ru, Re, and W cluster CO complexes

NASA Astrophysics Data System (ADS)

Lyon, Jonathan T.; Gruene, Philipp; Fielicke, André; Meijer, Gerard; Rayner, David M.

2009-11-01

The binding of carbon monoxide to iron, ruthenium, rhenium, and tungsten clusters is studied by means of infrared multiple photon dissociation spectroscopy. The CO stretching mode is used to probe the interaction of the CO molecule with the metal clusters and thereby the activation of the C-O bond. CO is found to adsorb molecularly to atop positions on iron clusters. On ruthenium and rhenium clusters it also binds molecularly. In the case of ruthenium, binding is predominantly to atop sites, however higher coordinated CO binding is also observed for both metals and becomes prevalent for rhenium clusters containing more than nine atoms. Tungsten clusters exhibit a clear size dependence for molecular versus dissociative CO binding. This behavior denotes the crossover to the purely dissociative CO binding on the earlier transition metals such as tantalum.

Chronology of the halo globular cluster system formation.

NASA Astrophysics Data System (ADS)

Salaris, M.; Weiss, A.

1997-11-01

Using up-to-date stellar models and isochrones we determine the age of 25 galactic halo clusters. The clusters are distributed into four groups according to metallicity. We measure the absolute age of a reference cluster in each group, and then find the relative ages of the other clusters relative to this one. This combination yields the most reliable results. We find that the oldest cluster group on average is 11.8+/-0.9Gyr or 12.3+/-0.3Gyr old, depending on whether we include Arp 2 and Rup 106. The average age of all clusters is about 10.5Gyr. Questions concerning a common age for all clusters and a relation between metallicity and age are addressed. The groups of lower metallicity appear to be coeval, but our results indicate that globally the sample has an age spread, and age and metallicity are correlated but not with a simple linear relation.

Thermally stable solids based on endohedrally doped ZnS clusters.

PubMed

Matxain, Jon M; Piris, Mario; Lopez, Xabier; Ugalde, Jesus M

2009-01-01

The existence of inorganic, hollow, fullerene-like ZnS clusters has been theoretically predicted and then recently confirmed experimentally. These clusters were observed to trap alkali metals and halogens because the ionization energies (IE) of alkali metals are very similar to the electron affinities (EA) of halogens. This opens the possibility of forming molecular solids composed of these fullerene building blocks because the energy released due to the difference between the IE and EA would be very small. Herein we have focused on assembling bare Zn(12)S(12) and endohedral X@Zn(12)S(12)-Y@Zn(12)S(12) dimers (X = Na, K; Y = Cl, Br) by considering the square-faces-square orientation of every two adjacent clusters, which leads to a fcc cubic crystal structure in the solid. The structures were fully optimized in all cases, and their thermal stability was confirmed by ab initio thermal molecular dynamics calculations. The optimum lattice parameter of the solids was found to be around 13.8 A, which corresponds to distances of about 2.5 A between monomers, which is typical of covalent Zn-S bonds. The resulting solids are nanoporous materials similar to B(12)N(12). Due to their nanoporous structure, these zeolite-shaped solids could be used in heterogeneous catalysis and as storage materials and molecular sieves.

Dinámica de cúmulos estelares en la Nube Menor de Magallanes

NASA Astrophysics Data System (ADS)

Mondino-Llermanos, A. E.; Piatti, A. E.; Carpintero, D. D.

2016-08-01

The dynamical evolution of star clusters in the Small Magellanic Cloud is nowadays a conundrum which deserves particular attention. In this work, we address such an issue by performing numerical simulations of their orbital motions. In order to do that, we adopted a gravitational potential for the galaxy and the presently known spatial-age-metallicity distribution, and attained their birthplaces by computing their orbital motions backwards for an interval equals to their ages. We aim at investigating the impact on the metal abundance spatial distribution by considering their original positions instead of the present ones.

Mass functions for globular cluster main sequences based on CCD photometry and stellar models

NASA Astrophysics Data System (ADS)

McClure, Robert D.; Vandenberg, Don A.; Smith, Graeme H.; Fahlman, Gregory G.; Richer, Harvey B.; Hesser, James E.; Harris, William E.; Stetson, Peter B.; Bell, R. A.

1986-08-01

Main-sequence luminosity functions constructed from CCD observations of globular clusters reveal a strong trend in slope with metal abundance. Theoretical luminosity functions constructed from VandenBerg and Bell's (1985) isochrones have been fitted to the observations and reveal a trend between x, the power-law index of the mass function, and metal abundance. The most metal-poor clusters require an index of about x = 2.5, whereas the most metal-rich clusters exhibit an index of x of roughly -0.5. The luminosity functions for two sparse clusters, E3 and Pal 5, are distinct from those of the more massive clusters, in that they show a turndown which is possibly a result of mass loss or tidal disruption.

Post-Hartree-Fock studies of the He/Mg(0001) interaction: Anti-corrugation, screening, and pairwise additivity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lara-Castells, María Pilar de, E-mail: Pilar.deLara.Castells@csic.es; Fernández-Perea, Ricardo; Madzharova, Fani

2016-06-28

The adsorption of noble gases on metallic surfaces represents a paradigmatic case of van-der-Waals (vdW) interaction due to the role of screening effects on the corrugation of the interaction potential [J. L. F. Da Silva et al., Phys. Rev. Lett. 90, 066104 (2003)]. The extremely small adsorption energy of He atoms on the Mg(0001) surface (below 3 meV) and the delocalized nature and mobility of the surface electrons make the He/Mg(0001) system particularly challenging, even for state-of-the-art vdW-corrected density functional-based (vdW-DFT) approaches [M. P. de Lara-Castells et al., J. Chem. Phys. 143, 194701 (2015)]. In this work, we meet thismore » challenge by applying two different procedures. First, the dispersion-corrected second-order Möller-Plesset perturbation theory (MP2C) approach is adopted, using bare metal clusters of increasing size. Second, the method of increments [H. Stoll, J. Chem. Phys. 97, 8449 (1992)] is applied at coupled cluster singles and doubles and perturbative triples level, using embedded cluster models of the metal surface. Both approaches provide clear evidences of the anti-corrugation of the interaction potential: the He atom prefers on-top sites, instead of the expected hollow sites. This is interpreted as a signature of the screening of the He atom by the metal for the on-top configuration. The strong screening in the metal is clearly reflected in the relative contribution of successively deeper surface layers to the main dispersion contribution. Aimed to assist future dynamical simulations, a pairwise potential model for the He/surface interaction as a sum of effective He–Mg pair potentials is also presented, as an improvement of the approximation using isolated He–Mg pairs.« less

Enhanced photochemical hydrogen evolution from Fe4S4-based biomimetic chalcogels containing M2+ (M = Pt, Zn, Co, Ni, Sn) centers.

PubMed

Shim, Yurina; Young, Ryan M; Douvalis, Alexios P; Dyar, Scott M; Yuhas, Benjamin D; Bakas, Thomas; Wasielewski, Michael R; Kanatzidis, Mercouri G

2014-09-24

Naturally abundant enzymes often feature active sites comprising transition metal cluster units that catalyze chemical processes and reduce small molecules as well as protons. We introduce a family of new chalcogenide aerogels (chalcogels), aiming to model the function of active sites and the structural features of a larger protective framework. New metal incorporated iron sulfur tin sulfide chalcogels referred to as ternary chalcogels and specifically the chalcogels M-ITS-cg3, fully integrate biological redox-active Fe4S4 clusters into a semiconducting porous framework by bridging them with Sn4S10 linking units. In the M-ITS-cg3 system we can tailor the electro- and photocatalytic properties of chalcogels through the control of spatial distance of redox-active Fe4S4 centers using additional linking metal ions, M(2+) (Pt, Zn, Co, Ni, Sn). The presence of a third metal does not change the structural properties of the biomimetic chalcogels but modifies and even enhances their functional performance. M-ITS-cg3s exhibit electrocatalytic activity in proton reduction that arises from the Fe4S4 clusters but is tuned inductively by M(2+). The metal ions alter the reduction potential of Fe4S4 in a favorable manner for photochemical hydrogen production. The Pt incorporated ITS-cg3 shows the greatest improvement in the overall hydrogen yield compared to the binary ITS-cg3. The ability to manipulate the properties of biomimetic chalcogels through synthetic control of the composition, while retaining both structural and functional properties, illustrates the chalcogels' flexibility and potential in carrying out useful electrochemical and photochemical reactions.

Post-Hartree-Fock studies of the He/Mg(0001) interaction: Anti-corrugation, screening, and pairwise additivity

NASA Astrophysics Data System (ADS)

de Lara-Castells, María Pilar; Fernández-Perea, Ricardo; Madzharova, Fani; Voloshina, Elena

2016-06-01

The adsorption of noble gases on metallic surfaces represents a paradigmatic case of van-der-Waals (vdW) interaction due to the role of screening effects on the corrugation of the interaction potential [J. L. F. Da Silva et al., Phys. Rev. Lett. 90, 066104 (2003)]. The extremely small adsorption energy of He atoms on the Mg(0001) surface (below 3 meV) and the delocalized nature and mobility of the surface electrons make the He/Mg(0001) system particularly challenging, even for state-of-the-art vdW-corrected density functional-based (vdW-DFT) approaches [M. P. de Lara-Castells et al., J. Chem. Phys. 143, 194701 (2015)]. In this work, we meet this challenge by applying two different procedures. First, the dispersion-corrected second-order Möller-Plesset perturbation theory (MP2C) approach is adopted, using bare metal clusters of increasing size. Second, the method of increments [H. Stoll, J. Chem. Phys. 97, 8449 (1992)] is applied at coupled cluster singles and doubles and perturbative triples level, using embedded cluster models of the metal surface. Both approaches provide clear evidences of the anti-corrugation of the interaction potential: the He atom prefers on-top sites, instead of the expected hollow sites. This is interpreted as a signature of the screening of the He atom by the metal for the on-top configuration. The strong screening in the metal is clearly reflected in the relative contribution of successively deeper surface layers to the main dispersion contribution. Aimed to assist future dynamical simulations, a pairwise potential model for the He/surface interaction as a sum of effective He-Mg pair potentials is also presented, as an improvement of the approximation using isolated He-Mg pairs.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Laskin, Julia; Johnson, Grant E.; Prabhakaran, Venkateshkumar

Immobilization of complex molecules and clusters on supports plays an important role in a variety of disciplines including materials science, catalysis and biochemistry. In particular, deposition of clusters on surfaces has attracted considerable attention due to their non-scalable, highly size-dependent properties. The ability to precisely control the composition and morphology of clusters and small nanoparticles on surfaces is crucial for the development of next generation materials with rationally tailored properties. Soft- and reactive landing of ions onto solid or liquid surfaces introduces unprecedented selectivity into surface modification by completely eliminating the effect of solvent and sample contamination on the qualitymore » of the film. The ability to select the mass-to-charge ratio of the precursor ion, its kinetic energy and charge state along with precise control of the size, shape and position of the ion beam on the deposition target makes soft-landing an attractive approach for surface modification. High-purity uniform thin films on surfaces generated using mass-selected ion deposition facilitate understanding of critical interfacial phenomena relevant to catalysis, energy generation and storage, and materials science. Our efforts have been directed toward understanding charge retention by soft-landed metal and metal-oxide cluster ions, which may affect both their structure and reactivity. Specifically, we have examined the effect of the surface on charge retention by both positively and negatively charged cluster ions. We found that the electronic properties of the surface play an important role in charge retention by cluster cations. Meanwhile, the electron binding energy is a key factor determining charge retention by cluster anions. These findings provide the scientific foundation for the rational design of interfaces for advanced catalysts and energy storage devices. Further optimization of electrode-electrolyte interfaces for applications in energy storage and electrocatalysis may be achieved by understanding and controlling the properties of soft-landed cluster ions.« less

SMC west halo: a slice of the galaxy that is being tidally stripped?. Star clusters trace age and metallicity gradients

NASA Astrophysics Data System (ADS)

Dias, B.; Kerber, L.; Barbuy, B.; Bica, E.; Ortolani, S.

2016-06-01

Context. The evolution and structure of the Magellanic Clouds is currently under debate. The classical scenario in which both the Large and Small Magellanic Clouds (LMC, SMC) are orbiting the Milky Way has been challenged by an alternative in which the LMC and SMC are in their first close passage to our Galaxy. The clouds are close enough to us to allow spatially resolved observation of their stars, and detailed studies of stellar populations in the galaxies are expected to be able to constrain the proposed scenarios. In particular, the west halo (WH) of the SMC was recently characterized with radial trends in age and metallicity that indicate tidal disruption. Aims: We intend to increase the sample of star clusters in the west halo of the SMC with homogeneous age, metallicity, and distance derivations to allow a better determination of age and metallicity gradients in this region. Positions are compared with the orbital plane of the SMC from models. Methods: Comparisons of observed and synthetic V(B-V) colour-magnitude diagrams were used to derive age, metallicity, distance, and reddening for star clusters in the SMC west halo. Observations were carried out using the 4.1 m SOAR telescope. Photometric completeness was determined through artificial star tests, and the members were selected by statistical comparison with a control field. Results: We derived an age of 1.23 ± 0.07 Gyr and [Fe/H] = -0.87 ± 0.07 for the reference cluster NGC 152, compatible with literature parameters. Age and metallicity gradients are confirmed in the WH: 2.6 ± 0.6 Gyr/° and -0.19 ± 0.09 dex/°, respectively. The age-metallicity relation for the WH has a low dispersion in metallicity and is compatible with a burst model of chemical enrichment. All WH clusters seem to follow the same stellar distribution predicted by dynamical models, with the exception of AM-3, which should belong to the counter-bridge. Brück 6 is the youngest cluster in our sample. It is only 130 ± 40 Myr old and may have been formed during the tidal interaction of SMC-LMC that created the WH and the Magellanic bridge. Conclusions: We suggest that it is crucial to split the SMC cluster population into groups: main body, wing and bridge, counter-bridge, and WH. This is the way to analyse the complex star formation and dynamical history of our neighbour. In particular, we show that the WH has clear age and metallicity gradients and an age-metallicity relation that is also compatible with the dynamical model that claims a tidal influence of the LMC on the SMC. Based on observations obtained at the Southern Astrophysical Research (SOAR) telescope, which is a joint project of the Ministério da Ciência, Tecnologia, e Inovação (MCTI) da República Federativa do Brasil, the US National Optical Astronomy Observatory (NOAO), the University of North Carolina at Chapel Hill (UNC), and Michigan State University (MSU).Tables of photometry are only available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (http://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/591/A11

Enhanced magnetic properties in ZnCoAlO caused by exchange-coupling to Co nanoparticles

NASA Astrophysics Data System (ADS)

Feng, Qi; Dizayee, Wala; Li, Xiaoli; Score, David S.; Neal, James R.; Behan, Anthony J.; Mokhtari, Abbas; Alshammari, Marzook S.; Al-Qahtani, Mohammed S.; Blythe, Harry J.; Chantrell, Roy W.; Heald, Steve M.; Xu, Xiao-Hong; Fox, A. Mark; Gehring, Gillian A.

2016-11-01

We report the results of a sequence of magnetisation and magneto-optical studies on laser ablated thin films of ZnCoAlO and ZnCoO that contain a small amount of metallic cobalt. The results are compared to those expected when all the magnetization is due to isolated metallic clusters of cobalt and with an oxide sample that is almost free from metallic inclusions. Using a variety of direct magnetic measurements and also magnetic circular dichroism we find that there is ferromagnetism within both the oxide and the metallic inclusions, and furthermore that these magnetic components are exchange-coupled when aluminium is included. This enhances both the coercive field and the remanence. Hence the presence of a controlled quantity of metallic nanoparticles in ZnAlO can improve the magnetic response of the oxide, thus giving great advantages for applications in spintronics.

Enhanced magnetic properties in ZnCoAlO caused by exchange-coupling to Co nanoparticles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Feng, Qi; Dizayee, Wala; Li, Xiaoli

2016-11-01

We report the results of a sequence of magnetisation and magneto-optical studies on laser ablated thin films of ZnCoAlO and ZnCoO that contain a small amount of metallic cobalt. The results are compared to those expected when all the magnetization is due to isolated metallic clusters of cobalt and with an oxide sample that is almost free from metallic inclusions. Using a variety of direct magnetic measurements and also magnetic circular dichroism we find that there is ferromagnetism within both the oxide and the metallic inclusions, and furthermore that these magnetic components are exchange-coupled when aluminium is included. This enhancesmore » both the coercive field and the remanence. Hence the presence of a controlled quantity of metallic nanoparticles in ZnAlO can improve the magnetic response of the oxide, thus giving great advantages for applications in spintronics.« less

Small angle neutron and X-ray studies of carbon structures with metal atoms

NASA Astrophysics Data System (ADS)

Lebedev, V. T.; Szhogina, A. A.; Bairamukov, V. Yu

2017-05-01

Encapsulation of metal atoms inside carbon single-wall cages or within multi-layer cells has been realized using molecular precursors and high temperature processes transforming them into desirable structures. Endohedral fullerenols Fe@C60(OH)X with 3d-metal (iron) have been studied by SANS in aqueous solutions where they form stable globular clusters with radii R C ∼ 10-12 nm and aggregation numbers N C ∼ 104. This self-assembly is a crucial feature of paramagnetic fullerenols as perspective contrast agents for Magneto-Resonance Imaging in medicine. Cellular carbon-metal structures have been created by the pyrolysis of diphthalocyanines of lanthanides and actinides. It was established that these ultra porous matrices consist of globular cells of molecular precursor size (∼ 1 nm) which are aggregated into superstructures. This provides retain of metal atoms inside matrices which may serve for safety storage of spent fuel of nuclear power plants.

Anion photoelectron spectroscopy of germanium and tin clusters containing a transition- or lanthanide-metal atom; MGe(n)- (n = 8-20) and MSn(n)- (n = 15-17) (M = Sc-V, Y-Nb, and Lu-Ta).

PubMed

Atobe, Junko; Koyasu, Kiichirou; Furuse, Shunsuke; Nakajima, Atsushi

2012-07-14

The electronic properties of germanium and tin clusters containing a transition- or lanthanide-metal atom from group 3, 4, or 5, MGe(n) (M = Sc, Ti, V, Y, Zr, Nb, Lu, Hf, and Ta) and MSn(n) (M = Sc, Ti, Y. Zr, and Hf), were investigated by anion photoelectron spectroscopy at 213 nm. In the case of the group 3 elements Sc, Y, and Lu, the threshold energy of electron detachment of MGe(n)(-) exhibits local maxima at n = 10 and 16, while in the case of the group 4 elements Ti, Zr, and Hf, it exhibits a local minimum only at n = 16, associated with the presence of a small bump in the spectrum. A similar behavior is observed for MSn(n)(-) around n = 16, and these electronic characteristics of MGe(n) and MSn(n) are closely related to those of MSi(n). Compared to MSi(n), however, the larger cavity size of a Ge(n) cage allows metal atom encapsulation at a smaller size n. A cooperative effect between the electronic and geometric structures of clusters with a large cavity of Ge(16) or Sn(16) is discussed together with the results of experiments that probe their geometric stability via their reactivity to H(2)O adsorption.

Diffusion of two-dimensional epitaxial clusters on metal (100) surfaces: Facile versus nucleation-mediated behavior and their merging for larger sizes

NASA Astrophysics Data System (ADS)

Lai, King C.; Liu, Da-Jiang; Evans, James W.

2017-12-01

For diffusion of two-dimensional homoepitaxial clusters of N atoms on metal (100) surfaces mediated by edge atom hopping, macroscale continuum theory suggests that the diffusion coefficient scales like DN˜ N-β with β =3 /2 . However, we find quite different and diverse behavior in multiple size regimes. These include: (i) facile diffusion for small sizes N <9 ; (ii) slow nucleation-mediated diffusion with small β <1 for "perfect" sizes N = Np= L2 or L (L +1 ) , for L =3 ,4 , ... having unique ground-state shapes, for moderate sizes 9 ≤N ≤O (102) ; the same also applies for N =Np+3 , Np+ 4 , ... (iii) facile diffusion but with large β >2 for N =Np+1 and Np+2 also for moderate sizes 9 ≤N ≤O (102) ; (iv) merging of the above distinct branches and subsequent anomalous scaling with 1 ≲β <3 /2 , reflecting the quasifacetted structure of clusters, for larger N =O (102) to N =O (103) ; (v) classic scaling with β =3 /2 for very large N =O (103) and above. The specified size ranges apply for typical model parameters. We focus on the moderate size regime where we show that diffusivity cycles quasiperiodically from the slowest branch for Np+3 (not Np) to the fastest branch for Np+1 . Behavior is quantified by kinetic Monte Carlo simulation of an appropriate stochastic lattice-gas model. However, precise analysis must account for a strong enhancement of diffusivity for short time increments due to back correlation in the cluster motion. Further understanding of this enhancement, of anomalous size scaling behavior, and of the merging of various branches, is facilitated by combinatorial analysis of the number of the ground-state and low-lying excited state cluster configurations, and also of kink populations.

Diffusion of two-dimensional epitaxial clusters on metal (100) surfaces: Facile versus nucleation-mediated behavior and their merging for larger sizes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lai, King C.; Liu, Da -Jiang; Evans, James W.

For diffusion of two-dimensional homoepitaxial clusters of N atoms on metal(100) surfaces mediated by edge atom hopping, macroscale continuum theory suggests that the diffusion coefficient scales like DN ~ N -β with β = 3/2. However, we find quite different and diverse behavior in multiple size regimes. These include: (i) facile diffusion for small sizes N < 9; (ii) slow nucleation-mediated diffusion with small β < 1 for “perfect” sizes N = N p = L 2 or L(L+1), for L = 3, 4,… having unique ground state shapes, for moderate sizes 9 ≤ N ≤ O(10 2); the samemore » also applies for N = N p +3, N p + 4,… (iii) facile diffusion but with large β > 2 for N = Np + 1 and N p + 2 also for moderate sizes 9 ≤ N ≤ O(10 2); (iv) merging of the above distinct branches and subsequent anomalous scaling with 1 ≲ β < 3/2, reflecting the quasi-facetted structure of clusters, for larger N = O(10 2) to N = O(10 3); and (v) classic scaling with β = 3/2 for very large N = O(103) and above. The specified size ranges apply for typical model parameters. We focus on the moderate size regime where show that diffusivity cycles quasi-periodically from the slowest branch for N p + 3 (not Np) to the fastest branch for Np + 1. Behavior is quantified by Kinetic Monte Carlo simulation of an appropriate stochastic lattice-gas model. However, precise analysis must account for a strong enhancement of diffusivity for short time increments due to back-correlation in the cluster motion. Further understanding of this enhancement, of anomalous size scaling behavior, and of the merging of various branches, is facilitated by combinatorial analysis of the number of the ground state and low-lying excited state cluster configurations, and also of kink populations.« less

Diffusion of two-dimensional epitaxial clusters on metal (100) surfaces: Facile versus nucleation-mediated behavior and their merging for larger sizes

DOE PAGES

Lai, King C.; Liu, Da -Jiang; Evans, James W.

2017-12-05

For diffusion of two-dimensional homoepitaxial clusters of N atoms on metal(100) surfaces mediated by edge atom hopping, macroscale continuum theory suggests that the diffusion coefficient scales like DN ~ N -β with β = 3/2. However, we find quite different and diverse behavior in multiple size regimes. These include: (i) facile diffusion for small sizes N < 9; (ii) slow nucleation-mediated diffusion with small β < 1 for “perfect” sizes N = N p = L 2 or L(L+1), for L = 3, 4,… having unique ground state shapes, for moderate sizes 9 ≤ N ≤ O(10 2); the samemore » also applies for N = N p +3, N p + 4,… (iii) facile diffusion but with large β > 2 for N = Np + 1 and N p + 2 also for moderate sizes 9 ≤ N ≤ O(10 2); (iv) merging of the above distinct branches and subsequent anomalous scaling with 1 ≲ β < 3/2, reflecting the quasi-facetted structure of clusters, for larger N = O(10 2) to N = O(10 3); and (v) classic scaling with β = 3/2 for very large N = O(103) and above. The specified size ranges apply for typical model parameters. We focus on the moderate size regime where show that diffusivity cycles quasi-periodically from the slowest branch for N p + 3 (not Np) to the fastest branch for Np + 1. Behavior is quantified by Kinetic Monte Carlo simulation of an appropriate stochastic lattice-gas model. However, precise analysis must account for a strong enhancement of diffusivity for short time increments due to back-correlation in the cluster motion. Further understanding of this enhancement, of anomalous size scaling behavior, and of the merging of various branches, is facilitated by combinatorial analysis of the number of the ground state and low-lying excited state cluster configurations, and also of kink populations.« less

Chemical pre-processing of cluster galaxies over the past 10 billion years in the IllustrisTNG simulations

NASA Astrophysics Data System (ADS)

Gupta, Anshu; Yuan, Tiantian; Torrey, Paul; Vogelsberger, Mark; Martizzi, Davide; Tran, Kim-Vy H.; Kewley, Lisa J.; Marinacci, Federico; Nelson, Dylan; Pillepich, Annalisa; Hernquist, Lars; Genel, Shy; Springel, Volker

2018-06-01

We use the IllustrisTNG simulations to investigate the evolution of the mass-metallicity relation (MZR) for star-forming cluster galaxies as a function of the formation history of their cluster host. The simulations predict an enhancement in the gas-phase metallicities of star-forming cluster galaxies (109 < M* < 1010 M⊙ h-1) at z ≤ 1.0 in comparisons to field galaxies. This is qualitatively consistent with observations. We find that the metallicity enhancement of cluster galaxies appears prior to their infall into the central cluster potential, indicating for the first time a systematic `chemical pre-processing' signature for infalling cluster galaxies. Namely, galaxies that will fall into a cluster by z = 0 show a ˜0.05 dex enhancement in the MZR compared to field galaxies at z ≤ 0.5. Based on the inflow rate of gas into cluster galaxies and its metallicity, we identify that the accretion of pre-enriched gas is the key driver of the chemical evolution of such galaxies, particularly in the stellar mass range (109 < M* < 1010 M⊙ h-1). We see signatures of an environmental dependence of the ambient/inflowing gas metallicity that extends well outside the nominal virial radius of clusters. Our results motivate future observations looking for pre-enrichment signatures in dense environments.

Integrated Light Chemical Abundance Analyses of 7 M31 Outer Halo Globular Clusters from the Pan-Andromeda Archaeological Survey

NASA Astrophysics Data System (ADS)

Sakari, Charli; Venn, Kim; Mackey, Dougal; Shetrone, Matthew D.; Dotter, Aaron L.; Wallerstein, George

2015-01-01

Detailed chemical abundances of globular clusters provide insight into the formation and evolution of galaxies and their globular cluster systems. This talk presents detailed chemical abundances for seven M31 outer halo globular clusters (with projected radii greater than 30 kpc), as derived from high resolution integrated light spectra. Five of these clusters were recently discovered in the Pan-Andromeda Archaeological Survey (PAndAS). The integrated abundances show that 4 of these clusters are metal-poor ([Fe/H] < -1.5) while the other 3 are more metal-rich. The most metal-poor globular clusters are α-enhanced, though 3 of the 4 are possibly less α-enhanced than MW stars (at the 1σ level). Other chemical abundance ratios ([Ba/Eu], [Eu/Ca], and [Ni/Fe]) are consistent with origins in low mass dwarf galaxies (similar to Fornax). The most metal-rich cluster ([Fe/H] ~ -1) stands out as being chemically distinct from Milky Way field stars of the same metallicity---its chemical abundance ratios agree best with the stars and clusters in the Large Magellanic Cloud (LMC) and the Sagittarius dwarf spheroidal (Sgr) than with the Milky Way field stars. The other metal-rich clusters, H10 and H23, look similar to the LMC and Milky Way field stars in all abundance ratios. These results indicate that M31's outer halo is being at least partially built up by the accretion of dwarf satellites, in agreement with previous observations.

Deriving physical parameters of unresolved star clusters. V. M 31 PHAT star clusters

NASA Astrophysics Data System (ADS)

de Meulenaer, P.; Stonkutė, R.; Vansevičius, V.

2017-06-01

Context. This study is the fifth of a series that investigates the degeneracy and stochasticity problems present in the determination of physical parameters such as age, mass, extinction, and metallicity of partially resolved or unresolved star cluster populations in external galaxies when using HST broad-band photometry. Aims: In this work we aim to derive parameters of star clusters using models with fixed and free metallicity based on the HST WFC3+ACS photometric system. The method is applied to derive parameters of a subsample of 1363 star clusters in the Andromeda galaxy observed with the HST. Methods: Following Paper III, we derive the star cluster parameters using a large grid of stochastic models that are compared to the six observed integrated broad-band WFC3+ACS magnitudes of star clusters. Results: We show that the age, mass, and extinction of the M 31 star clusters, derived assuming fixed solar metallicity, are in agreement with previous studies. We also demonstrate the ability of the WFC3+ACS photometric system to derive metallicity of star clusters older than 1 Gyr. We show that the metallicity derived using broad-band photometry of 36 massive M 31 star clusters is in good agreement with the metallicity derived using spectroscopy. Table 1 is only available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (http://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/602/A112

A self-consistent density based embedding scheme applied to the adsorption of CO on Pd(111)

NASA Astrophysics Data System (ADS)

Lahav, D.; Klüner, T.

2007-06-01

We derive a variant of a density based embedded cluster approach as an improvement to a recently proposed embedding theory for metallic substrates (Govind et al 1999 J. Chem. Phys. 110 7677; Klüner et al 2001 Phys. Rev. Lett. 86 5954). In this scheme, a local region in space is represented by a small cluster which is treated by accurate quantum chemical methodology. The interaction of the cluster with the infinite solid is taken into account by an effective one-electron embedding operator representing the surrounding region. We propose a self-consistent embedding scheme which resolves intrinsic problems of the former theory, in particular a violation of strict density conservation. The proposed scheme is applied to the well-known benchmark system CO/Pd(111).

Thermodynamics and Charging of Interstellar Iron Nanoparticles

NASA Astrophysics Data System (ADS)

Hensley, Brandon S.; Draine, B. T.

2017-01-01

Interstellar iron in the form of metallic iron nanoparticles may constitute a component of the interstellar dust. We compute the stability of iron nanoparticles to sublimation in the interstellar radiation field, finding that iron clusters can persist down to a radius of ≃4.5 Å, and perhaps smaller. We employ laboratory data on small iron clusters to compute the photoelectric yields as a function of grain size and the resulting grain charge distribution in various interstellar environments, finding that iron nanoparticles can acquire negative charges, particularly in regions with high gas temperatures and ionization fractions. If ≳10% of the interstellar iron is in the form of ultrasmall iron clusters, the photoelectric heating rate from dust may be increased by up to tens of percent relative to dust models with only carbonaceous and silicate grains.

Spectroscopic Assessment of the Reliability of Metal/Metal Oxide Interfaces

DTIC Science & Technology

1994-10-01

vapor deposition(LCVD)1, 2 of thin films, clusters and ultrafine particles offers many unique opportunities in materials synthesis. As precursors for LCVD...films, the chemistry is directly applicable to other oxidizable metals. Puretsky and Demyanenko9 reported that gas phase clusters and ultrafine ... particles can be synthesized using excimer laser dissociation of all group six metal hexacarbonyls. Our earlier work on platinum clusters and our current

Molecular dynamics study of the role of symmetric tilt grain boundaries on the helium distribution in nickel

NASA Astrophysics Data System (ADS)

Torres, E.; Pencer, J.

2018-04-01

Helium impurities, from either direct implantation or transmutation reactions, have been associated with embrittlement in nickel-based alloys. Helium has very low solubility in nickel, and has been found to aggregate at lattice defects such as vacancies, dislocations, and grain boundaries. The retention and precipitation of helium in nickel-based alloys have deleterious effects on the material mechanical properties. However, the underlying mechanisms that lead to helium effects in the host metal are not fully understood. In the present work, we investigate the role of symmetric tilt grain boundary (STGB) structures on the distribution of helium in nickel using molecular dynamics simulations. We investigate the family of STGBs specific to the 〈 110 〉 tilt axis. The present results indicate that accumulation of helium at the grain boundary may be modulated by details of grain boundary geometry. A plausible correlation between the grain boundary energy and misorientation with the accumulation and mobility of helium is proposed. Small clusters with up to 6 helium atoms show significant interstitial mobility in the nickel bulk, but also become sites for nucleation and grow of more stable helium clusters. High-energy GBs are found mainly populated with small helium clusters. The high mobility of small clusters along the GBs indicates the role of these GBs as fast two-dimensional channels for diffusion. In contrast, the accumulation of helium in large helium clusters at low-energy STGB creates a favorable environment for the formation of large helium bubbles, indicating a potential role for low-energy STGB in promoting helium-induced GB embrittlement.

Structural characterization of metal binding to a cold-adapted frataxin.

PubMed

Noguera, Martín E; Roman, Ernesto A; Rigal, Juan B; Cousido-Siah, Alexandra; Mitschler, André; Podjarny, Alberto; Santos, Javier

2015-06-01

Frataxin is an evolutionary conserved protein that participates in iron metabolism. Deficiency of this small protein in humans causes a severe neurodegenerative disease known as Friedreich's ataxia. A number of studies indicate that frataxin binds iron and regulates Fe-S cluster biosynthesis. Previous structural studies showed that metal binding occurs mainly in a region of high density of negative charge. However, a comprehensive characterization of the binding sites is required to gain further insights into the mechanistic details of frataxin function. In this work, we have solved the X-ray crystal structures of a cold-adapted frataxin from a psychrophilic bacterium in the presence of cobalt or europium ions. We have identified a number of metal-binding sites, mainly solvent exposed, several of which had not been observed in previous studies on mesophilic homologues. No major structural changes were detected upon metal binding, although the structures exhibit significant changes in crystallographic B-factors. The analysis of these B-factors, in combination with crystal packing and RMSD among structures, suggests the existence of localized changes in the internal motions. Based on these results, we propose that bacterial frataxins possess binding sites of moderate affinity for a quick capture and transfer of iron to other proteins and for the regulation of Fe-S cluster biosynthesis, modulating interactions with partner proteins.

FAST TRACK COMMUNICATION: Poly(methyl methacrylate)-palladium clusters nanocomposite formation by supersonic cluster beam deposition: a method for microstructured metallization of polymer surfaces

NASA Astrophysics Data System (ADS)

Ravagnan, Luca; Divitini, Giorgio; Rebasti, Sara; Marelli, Mattia; Piseri, Paolo; Milani, Paolo

2009-04-01

Nanocomposite films were fabricated by supersonic cluster beam deposition (SCBD) of palladium clusters on poly(methyl methacrylate) (PMMA) surfaces. The evolution of the electrical conductance with cluster coverage and microscopy analysis show that Pd clusters are implanted in the polymer and form a continuous layer extending for several tens of nanometres beneath the polymer surface. This allows the deposition, using stencil masks, of cluster-assembled Pd microstructures on PMMA showing a remarkably high adhesion compared with metallic films obtained by thermal evaporation. These results suggest that SCBD is a promising tool for the fabrication of metallic microstructures on flexible polymeric substrates.

Integral field spectroscopy with GEMINI: Extragalactic star cluster in NGC1275

NASA Astrophysics Data System (ADS)

Trancho, Gelys; Miller, Bryan; García-Lorenzo, Begoña; Sánchez, Sebastián F.

2006-01-01

Studies of globular cluster systems play a critical role in our understanding of galaxy formation. Imaging with the Hubble Space Telescope has revealed that young star clusters are formed copiously in galaxy mergers, strengthening theories in which giant elliptical galaxies are formed by the merger of spirals [e.g. Whitmore, B.C., Schweizer, F., Leitherer, C., Borne, K., Robert, C., 1993. Astronomical Journal. 106, 1354; Miller, B.W., Whitmore, B.C., Schweizer, F., Fall, S.M., 1997. Astronomical Journal. 114, 2381; Zepf, S.E., Ashman, K.M., English, J., Freeman, K.C., Sharples, R.M., 1999. Astronomical Journal. 118, 752; Ashman, K.M., Zepf, S.E., 1992. Astrophysical Journal. 384, 50]. However, the formation and evolution of globular cluster systems is still not well understood. Ages and metallicities of the clusters are uncertain either because of degeneracy in the broad-band colors or due to variable reddening. Also, the luminosity function of the young clusters, which depends critically on the metallicities and ages of the clusters, appears to be single power-laws while the luminosity function of old clusters has a well-defined break. Either there is significant dynamical evolution of the cluster systems or metallicity affects the mass function of forming clusters. Spectroscopy of these clusters are needed to improve the metallicity and age measurements and to study the kinematics of young cluster systems. Therefore, we have obtained GMOS IFU data of 4 clusters in NGC1275. We will present preliminary results like metallicities, ages, and velocities of the star clusters from IFU spectroscopy.

Growth of polymer-metal nanocomposites by pulsed laser deposition

NASA Astrophysics Data System (ADS)

Röder, Johanna; Faupel, Jörg; Krebs, Hans-Ulrich

2008-12-01

Complex polymer-metal nanocomposites have a wide range of applications, e.g. as flexible displays and packaging materials. Pulsed laser deposition was applied to form nanostructured materials consisting of metal clusters (Ag, Au, Pd and Cu) embedded in a polymer (polycarbonate, PC) matrix. The size and amount of the metal clusters are controlled by the number of laser pulses hitting the respective targets. For Cu and Pd, smaller clusters and higher cluster densities are obtained as in the cases of Ag and Au due to a stronger reactivity with the polymers and thus a lower diffusivity. Implantation effects, differences in metal diffusivity and reactivity on the polymer surfaces, and the coalescence properties are discussed with respect to the observed microstructures on PC and compared to the metal growth on poly (methyl methacrylate), PMMA.

Discovery of a loose star cluster in the Large Magellanic Cloud

NASA Astrophysics Data System (ADS)

Piatti, Andrés E.

2016-06-01

We present results for an up-to-date uncatalogued star cluster projected towards the Eastern side of the Large Magellanic Cloud (LMC) outer disc. The new object was discovered from a search of loose star cluster in the Magellanic Clouds' (MCs) outskirts using kernel density estimators on Washington CT1 deep images. Contrarily to what would be commonly expected, the star cluster resulted to be a young object (log(t yr-1) = 8.45) with a slightly subsolar metal content (Z = 0.013) and a total mass of 650 M⊙. Its core, half-mass and tidal radii also are within the frequent values of LMC star clusters. However, the new star cluster is placed at the Small Magellanic Cloud distance and at 11.3 kpc from the LMC centre. We speculate with the possibility that it was born in the inner body of the LMC and soon after expelled into the intergalactic space during the recent Milky Way/MCs interaction. Nevertheless, radial velocity and chemical abundance measurements are needed to further understand its origin, as well as extensive search for loose star clusters in order to constrain the effectiveness of star cluster scattering during galaxy interactions.

Atomically precise arrays of fluorescent silver clusters: a modular approach for metal cluster photonics on DNA nanostructures.

PubMed

Copp, Stacy M; Schultz, Danielle E; Swasey, Steven; Gwinn, Elisabeth G

2015-03-24

The remarkable precision that DNA scaffolds provide for arraying nanoscale optical elements enables optical phenomena that arise from interactions of metal nanoparticles, dye molecules, and quantum dots placed at nanoscale separations. However, control of ensemble optical properties has been limited by the difficulty of achieving uniform particle sizes and shapes. Ligand-stabilized metal clusters offer a route to atomically precise arrays that combine desirable attributes of both metals and molecules. Exploiting the unique advantages of the cluster regime requires techniques to realize controlled nanoscale placement of select cluster structures. Here we show that atomically monodisperse arrays of fluorescent, DNA-stabilized silver clusters can be realized on a prototypical scaffold, a DNA nanotube, with attachment sites separated by <10 nm. Cluster attachment is mediated by designed DNA linkers that enable isolation of specific clusters prior to assembly on nanotubes and preserve cluster structure and spectral purity after assembly. The modularity of this approach generalizes to silver clusters of diverse sizes and DNA scaffolds of many types. Thus, these silver cluster nano-optical elements, which themselves have colors selected by their particular DNA templating oligomer, bring unique dimensions of control and flexibility to the rapidly expanding field of nano-optics.

Mass Spectroscopy of Neutral Metal Oxide Clusters Using a Desk-Top Soft X-Ray Laser

NASA Astrophysics Data System (ADS)

Dong, F.; Heinbuch, S.; Bernstein, E. R.; Rocca, J. J.

We report the use of a compact 46.9 nm capillary discharge soft x-ray laser in the study of metal-oxide nanoclusters using mass spectroscopy. Transition metal oxides are widely used as heterogeneous catalysts and catalytic supports in industrial processes. There are numerous applications for transition metal oxide catalysts, and although they are widely used, there is a lack of fundamental understanding of the complicated processes that occur on the metal oxide surface during catalysis. Conventional nanocluster spectroscopy techniques have used 193 nm radiation from an ArF excimer laser corresponding to a photon energy of 6.4 eV in order to photoionize a sample. Typical metal oxide nanocluster ionization energies fall into the range of 7-12 eV while some have even higher energies. Therefore a single 6.4 eV photon can not ionize the cluster making multiphoton processes the dominant ionization method. A major problem associated with mass spectroscopy can become evident during the multiphoton ionization of clusters. Specifically, the clusters may fragment during the ionization process and the identification of the neutral parent cluster can become difficult. In the present experiment neutral vanadium, niobium and tantalum oxide clusters are studied by single photon ionization with the 26.5 eV photons produced by a capillary discharge soft x-ray laser.1 During ionization, the metal oxide clusters are observed to be almost free of serious fragmentation. The most stable neutral cluster of vanadium, niobium, and tantalum oxide growth in a saturated oxygen condition are identified as MO2, M2O4/M2O5, M3O7, M4O10, M5O12, M6O15, M7O17, M8O20, and M9O22, which can be represented as a form (MO2)0,1(M2O5)y. M2O5 is identified as a basic unit to build-up the three kinds of metal oxide clusters. In the case of niobium and tantalum oxide clusters, the oxygen-deficient clusters with a structure of (MO2)2(M2O5)y are detected for groups that contain an even number of metal atoms. For vanadium oxide clusters, the oxygen-deficient clusters are detected for every family, indicating a stable structure of (VO2)x(V2O5)y. The stoichiometry of oxygen-rich clusters can be expressed as (MO2)0,1(M2O5)yO1-3 and their structures are consistent with chemically bonded species.

Route to the Smallest Doped Semiconductor: Mn(2+)-Doped (CdSe)13 Clusters.

PubMed

Yang, Jiwoong; Fainblat, Rachel; Kwon, Soon Gu; Muckel, Franziska; Yu, Jung Ho; Terlinden, Hendrik; Kim, Byung Hyo; Iavarone, Dino; Choi, Moon Kee; Kim, In Young; Park, Inchul; Hong, Hyo-Ki; Lee, Jihwa; Son, Jae Sung; Lee, Zonghoon; Kang, Kisuk; Hwang, Seong-Ju; Bacher, Gerd; Hyeon, Taeghwan

2015-10-14

Doping semiconductor nanocrystals with magnetic transition-metal ions has attracted fundamental interest to obtain a nanoscale dilute magnetic semiconductor, which has unique spin exchange interaction between magnetic spin and exciton. So far, the study on the doped semiconductor NCs has usually been conducted with NCs with larger than 2 nm because of synthetic challenges. Herein, we report the synthesis and characterization of Mn(2+)-doped (CdSe)13 clusters, the smallest doped semiconductors. In this study, single-sized doped clusters are produced in large scale. Despite their small size, these clusters have semiconductor band structure instead of that of molecules. Surprisingly, the clusters show multiple excitonic transitions with different magneto-optical activities, which can be attributed to the fine structure splitting. Magneto-optically active states exhibit giant Zeeman splittings up to elevated temperatures (128 K) with large g-factors of 81(±8) at 4 K. Our results present a new synthetic method for doped clusters and facilitate the understanding of doped semiconductor at the boundary of molecules and quantum nanostructure.

Spectroscopic Study of Local Interactions of Platinum in Small [CexOy]Ptx' - Clusters

NASA Astrophysics Data System (ADS)

Ray, Manisha; Kafader, Jared O.; Chick Jarrold, Caroline

2016-06-01

Cerium oxide is a good ionic conductor, and the conductivity can be enhanced with oxygen vacancies and doping. This conductivity may play an important role in the enhancement of noble or coinage metal toward the water-gas shift reaction when supported by cerium oxide. The ceria-supported platinum catalyst in particular has received much attention because of higher activity at lower temperatures (LT) compared to the most common commercial LT-WGS catalyst. We have used a combination of anion photoelectron spectroscopy and density functional theory calculations to study the interesting molecular and electronic structures and properties of cluster models of ceria-supported platinum. [CexOy]Ptx' - (x,x'=1,2 ; y≤2x') clusters exhibit evidence of ionic bonding possible because of the high electron affinity of Pt and the low ionization potential of cerium oxide clusters. In addition, Pt- is a common daughter ion resulting from photodissociation of [CexOy]Ptx' - clusters. Finally, several of the anion and neutral clusters have profoundly different structures. These features may play a role in the enhancement of catalytic activity toward the water-gas shift reaction.

Triosmium Clusters on a Support: Determination of Structure by X-Ray Absorption Spectroscopy and High-Resolution Microscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shareghe, Mehraeen; Chi, Miaofang; Browning, Nigel D.

2011-01-01

The structures of small, robust metal clusters on a solid support were determined by a combination of spectroscopic and microscopic methods: extended X-ray absorption fine structure (EXAFS) spectroscopy, scanning transmission electron microscopy (STEM), and aberration-corrected STEM. The samples were synthesized from [Os{sub 3}(CO){sub 12}] on MgO powder to provide supported clusters intended to be triosmium. The results demonstrate that the supported clusters are robust in the absence of oxidants. Conventional high-angle annular dark-field (HAADF) STEM images demonstrate a high degree of uniformity of the clusters, with root-mean-square (rms) radii of 2.03 {+-} 0.06 {angstrom}. The EXAFS OsOs coordination number ofmore » 2.1 {+-} 0.4 confirms the presence of triosmium clusters on average and correspondingly determines an average rms cluster radius of 2.02 {+-} 0.04 {angstrom}. The high-resolution STEM images show the individual Os atoms in the clusters, confirming the triangular structures of their frames and determining OsOs distances of 2.80 {+-} 0.14 {angstrom}, matching the EXAFS value of 2.89 {+-} 0.06 {angstrom}. IR and EXAFS spectra demonstrate the presence of CO ligands on the clusters. This set of techniques is recommended as optimal for detailed and reliable structural characterization of supported clusters.« less

Composition formulas of Fe-based transition metals-metalloid bulk metallic glasses derived from dual-cluster model of binary eutectics.

PubMed

Naz, Gul Jabeen; Dong, Dandan; Geng, Yaoxiang; Wang, Yingmin; Dong, Chuang

2017-08-22

It is known that bulk metallic glasses follow simple composition formulas [cluster](glue atom) 1 or 3 with 24 valence electrons within the framework of the cluster-plus-glue-atom model. Though the relevant nearest-neighbor cluster can be readily identified from a devitrification phase, the glue atoms remains poorly defined. The present work is devoted to understanding the composition rule of Fe-(B,P,C) based multi-component bulk metallic glasses, by introducing a cluster-based eutectic liquid model. This model regards a eutectic liquid to be composed of two stable liquids formulated respectively by cluster formulas for ideal metallic glasses from the two eutectic phases. The dual cluster formulas are first established for binary Fe-(B,C,P) eutectics: [Fe-Fe 14 ]B 2 Fe + [B-B 2 Fe 8 ]Fe ≈ Fe 83.3 B 16.7 for eutectic Fe 83 B 17 , [P-Fe 14 ]P + [P-Fe 9 ]P 2 Fe≈Fe 82.8 P 17.2 for Fe 83 P 17 , and [C-Fe 6 ]Fe 3  + [C-Fe 9 ]C 2 Fe ≈ Fe 82.6 C 17.4 for Fe 82.7 C 17.3 . The second formulas in these dual-cluster formulas, being respectively relevant to devitrification phases Fe 2 B, Fe 3 P, and Fe 3 C, well explain the compositions of existing Fe-based transition metals-metalloid bulk metallic glasses. These formulas also satisfy the 24-electron rule. The proposition of the composition formulas for good glass formers, directly from known eutectic points, constitutes a new route towards understanding and eventual designing metallic glasses of high glass forming abilities.

The Magellanic Bridge Cluster NGC 796: Deep Optical AO Imaging Reveals the Stellar Content and Initial Mass Function of a Massive Open Cluster

NASA Astrophysics Data System (ADS)

Kalari, Venu M.; Carraro, Giovanni; Evans, Christopher J.; Rubio, Monica

2018-04-01

NGC 796 is a massive young cluster located 59 kpc from us in the diffuse intergalactic medium of the 1/5–1/10 Z⊙ Magellanic Bridge, allowing us to probe variations in star formation and stellar evolution processes as a function of metallicity in a resolved fashion, and providing a link between resolved studies of nearby solar-metallicity and unresolved distant metal-poor clusters located in high-redshift galaxies. In this paper, we present adaptive optics griHα imaging of NGC 796 (at 0.″5, which is ∼0.14 pc at the cluster distance) along with optical spectroscopy of two bright members to quantify the cluster properties. Our aim is to explore whether star formation and stellar evolution vary as a function of metallicity by comparing the properties of NGC 796 to higher-metallicity clusters. We find an age of {20}-5+12 Myr from isochronal fitting of the cluster main sequence in the color–magnitude diagram. Based on the cluster luminosity function, we derive a top-heavy stellar initial mass function (IMF) with a slope α = 1.99 ± 0.2, hinting at a metallicity and/or environmental dependence of the IMF, which may lead to a top-heavy IMF in the early universe. Study of the Hα emission-line stars reveals that classical Be stars constitute a higher fraction of the total B-type stars when compared with similar clusters at greater metallicity, providing some support to the chemically homogeneous theory of stellar evolution. Overall, NGC 796 has a total estimated mass of 990 ± 200 M⊙, and a core radius of 1.4 ± 0.3 pc, which classifies it as a massive young open cluster, unique in the diffuse interstellar medium of the Magellanic Bridge.

Hund’s rule in superatoms with transition metal impurities

PubMed Central

Medel, Victor M.; Reveles, Jose Ulises; Khanna, Shiv N.; Chauhan, Vikas; Sen, Prasenjit; Castleman, A. Welford

2011-01-01

The quantum states in metal clusters bunch into supershells with associated orbitals having shapes resembling those in atoms, giving rise to the concept that selected clusters could mimic the characteristics of atoms and be classified as superatoms. Unlike atoms, the superatom orbitals span over multiple atoms and the filling of orbitals does not usually exhibit Hund’s rule seen in atoms. Here, we demonstrate the possibility of enhancing exchange splitting in superatom shells via a composite cluster of a central transition metal and surrounding nearly free electron metal atoms. The transition metal d states hybridize with superatom D states and result in enhanced splitting between the majority and minority sets where the moment and the splitting can be controlled by the nature of the central atom. We demonstrate these findings through studies on TMMgn clusters where TM is a 3d atom. The clusters exhibit Hund’s filling, opening the pathway to superatoms with magnetic shells. PMID:21646542

Hund's rule in superatoms with transition metal impurities.

PubMed

Medel, Victor M; Reveles, Jose Ulises; Khanna, Shiv N; Chauhan, Vikas; Sen, Prasenjit; Castleman, A Welford

2011-06-21

The quantum states in metal clusters bunch into supershells with associated orbitals having shapes resembling those in atoms, giving rise to the concept that selected clusters could mimic the characteristics of atoms and be classified as superatoms. Unlike atoms, the superatom orbitals span over multiple atoms and the filling of orbitals does not usually exhibit Hund's rule seen in atoms. Here, we demonstrate the possibility of enhancing exchange splitting in superatom shells via a composite cluster of a central transition metal and surrounding nearly free electron metal atoms. The transition metal d states hybridize with superatom D states and result in enhanced splitting between the majority and minority sets where the moment and the splitting can be controlled by the nature of the central atom. We demonstrate these findings through studies on TMMg(n) clusters where TM is a 3d atom. The clusters exhibit Hund's filling, opening the pathway to superatoms with magnetic shells.

A CONTINUUM OF PLANET FORMATION BETWEEN 1 AND 4 EARTH RADII

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schlaufman, Kevin C., E-mail: kschlauf@mit.edu

2015-02-01

It has long been known that stars with high metallicity are more likely to host giant planets than stars with low metallicity. Yet the connection between host star metallicity and the properties of small planets is only just beginning to be investigated. It has recently been argued that the metallicity distribution of stars with exoplanet candidates identified by Kepler provides evidence for three distinct clusters of exoplanets, distinguished by planet radius boundaries at 1.7 R{sub ⨁} and 3.9 R{sub ⨁}. This would suggest that there are three distinct planet formation pathways for super-Earths, mini-Neptunes, and giant planets. However, as Imore » show through three independent analyses, there is actually no evidence for the proposed radius boundary at 1.7 R{sub ⨁}. On the other hand, a more rigorous calculation demonstrates that a single, continuous relationship between planet radius and metallicity is a better fit to the data. The planet radius and metallicity data therefore provides no evidence for distinct categories of small planets. This suggests that the planet formation process in a typical protoplanetary disk produces a continuum of planet sizes between 1 R{sub ⨁} and 4 R{sub ⨁}. As a result, the currently available planet radius and metallicity data for solar-metallicity F and G stars give no reason to expect that the amount of solid material in a protoplanetary disk determines whether super-Earths or mini-Neptunes are formed.« less

Dispersed metal cluster catalysts by design. Synthesis, characterization, structure, and performance

DOE Office of Scientific and Technical Information (OSTI.GOV)

Arslan, Ilke; Dixon, David A.; Gates, Bruce C.

2015-09-30

To understand the class of metal cluster catalysts better and to lay a foundation for the prediction of properties leading to improved catalysts, we have synthesized metal catalysts with well-defined structures and varied the cluster structures and compositions systematically—including the ligands bonded to the metals. These ligands include supports and bulky organics that are being tuned to control both the electron transfer to or from the metal and the accessibility of reactants to influence catalytic properties. We have developed novel syntheses to prepare these well-defined catalysts with atomic-scale control the environment by choice and placement of ligands and applied state-of-themore » art spectroscopic, microscopic, and computational methods to determine their structures, reactivities, and catalytic properties. The ligands range from nearly flat MgO surfaces to enveloping zeolites to bulky calixarenes to provide controlled coverages of the metal clusters, while also enforcing unprecedented degrees of coordinative unsaturation at the metal site—thereby facilitating bonding and catalysis events at exposed metal atoms. With this wide range of ligand properties and our arsenal of characterization tools, we worked to achieve a deep, fundamental understanding of how to synthesize robust supported and ligand-modified metal clusters with controlled catalytic properties, thereby bridging the gap between active site structure and function in unsupported and supported metal catalysts. We used methods of organometallic and inorganic chemistry combined with surface chemistry for the precise synthesis of metal clusters and nanoparticles, characterizing them at various stages of preparation and under various conditions (including catalytic reaction conditions) and determining their structures and reactivities and how their catalytic properties depend on their compositions and structures. Key characterization methods included IR, NMR, and EXAFS spectroscopies to identify ligands on the metals and their reactions; EXAFS spectroscopy and high-resolution STEM to determine cluster framework structures and changes resulting from reactant treatment and locations of metal atoms on support surfaces; X-ray diffraction crystallography to determine full structures of cluster-ligand combinations in the absence of a support, and TEM with tomographic methods to observe individual metal atoms and determine three-dimensional structures of catalysts. Electronic structure calculations were used to verify and interpret spectra and extend the understanding of reactivity beyond what is measurable experimentally.« less

Topological Aspects of Infinite Metal Clusters and Superconductors.

DTIC Science & Technology

1987-08-11

tetrahedra. T chemical bonding topologies qf discrete octahedral metal clusters can be either edge- localized (e.g., MoX8L 6 4 derivatives), face- localized ...constructed from edge- localized metal polyhedra such as the Mo 6 octahedra in the ternary molybdenum chalcogenides (Chevrel phases) and Rh4 tetrahedra in the...chemical bonding topologies of discrete octahedral metal clusters can be either e4ge- localized (e.g., No X L 4+ derivatives), face- localized (e.g

Open cluster Dolidze 25: Stellar parameters and the metallicity in the Galactic anticentre

NASA Astrophysics Data System (ADS)

Negueruela, I.; Simón-Díaz, S.; Lorenzo, J.; Castro, N.; Herrero, A.

2015-12-01

Context. The young open cluster Dolidze 25, in the direction of the Galactic anticentre, has been attributed a very low metallicity, with typical abundances between -0.5 and -0.7 dex below solar. Aims: We intend to derive accurate cluster parameters and accurate stellar abundances for some of its members. Methods: We have obtained a large sample of intermediate- and high-resolution spectra for stars in and around Dolidze 25. We used the fastwind code to generate stellar atmosphere models to fit the observed spectra. We derive stellar parameters for a large number of OB stars in the area, and abundances of oxygen and silicon for a number of stars with spectral types around B0. Results: We measure low abundances in stars of Dolidze 25. For the three stars with spectral types around B0, we find 0.3 dex (Si) and 0.5 dex (O) below the values typical in the solar neighbourhood. These values, even though not as low as those given previously, confirm Dolidze 25 and the surrounding H ii region Sh2-284 as the most metal-poor star-forming environment known in the Milky Way. We derive a distance 4.5 ± 0.3 kpc to the cluster (rG ≈ 12.3 kpc). The cluster cannot be older than ~3 Myr, and likely is not much younger. One star in its immediate vicinity, sharing the same distance, has Si and O abundances at most 0.15 dex below solar. Conclusions: The low abundances measured in Dolidze 25 are compatible with currently accepted values for the slope of the Galactic metallicity gradient, if we take into account that variations of at least ±0.15 dex are observed at a given radius. The area traditionally identified as Dolidze 25 is only a small part of a much larger star-forming region that comprises the whole dust shell associated with Sh2-284 and very likely several other smaller H ii regions in its vicinity. Based on observations made with the Nordic Optical Telescope, the Mercator Telescope, and the telescopes of the Isaac Newton Group.

Formation of the metal and energy-carrier price clusters on the world market of nonferrous metals in the postcrisis period

NASA Astrophysics Data System (ADS)

Bogdanov, S. V.; Shevelev, I. M.; Chernyi, S. A.

2016-06-01

The laws of formation of price clusters are revealed upon statistical processing of the data on changing the quotation prices of nonferrous and precious metals, oil, black oil, gasoline, and natural gas in the postcrisis period from January 1, 2009 to November 1, 2013. It is found that the metal prices entering in the price cluster of nonferrous metals most strongly affect the formation of the nonferrous metal price and that the prices of precious metals and energy carriers correct the exchange price of the metal to some extent but do not determine its formation. Equations are derived to calculate the prices. The results of calculation by these equations agree well with the real nonferrous metal prices in the near future.

An updated survey of globular clusters in M 31. III. A spectroscopic metallicity scale for the Revised Bologna Catalog

NASA Astrophysics Data System (ADS)

Galleti, S.; Bellazzini, M.; Buzzoni, A.; Federici, L.; Fusi Pecci, F.

2009-12-01

Aims. We present a new homogeneous set of metallicity estimates based on Lick indices for the old globular clusters of the M 31 galaxy. The final aim is to add homogeneous spectroscopic metallicities to as many entries as possible of the Revised Bologna Catalog of M 31 clusters, by reporting Lick index measurements from any source (literature, new observations, etc.) on the same scale. Methods: New empirical relations of [Fe/H] as a function of [MgFe] and Mg2 indices are based on the well-studied galactic globular clusters, complemented with theoretical model predictions for -0.2≤ [Fe/H]≤ +0.5. Lick indices for M 31 clusters from various literature sources (225 clusters) and from new observations by our team (71 clusters) have been transformed into the Trager et al. system, yielding new metallicity estimates for 245 globular clusters of M 31. Results: Our values are in good agreement with recent estimates based on detailed spectral fitting and with those obtained from color magnitude diagrams of clusters imaged with the Hubble Space Telescope. The typical uncertainty on individual estimates is ≃±0.25 dex, as resulted from the comparison with metallicities derived from color magnitude diagrams of individual clusters. Conclusions: The metallicity distribution of M 31 globular cluster is briefly discussed and compared with that of the Milky Way. Simple parametric statistical tests suggest that the distribution is probably not unimodal. The strong correlation between metallicity and kinematics found in previous studies is confirmed. The most metal-rich GCs tend to be packed into the center of the system and to cluster tightly around the galactic rotation curve defined by the HI disk, while the velocity dispersion about the curve increases with decreasing metallicity. However, also the clusters with [Fe/H]<-1.0 display a clear rotation pattern, at odds with their Milky Way counterparts. Based on observations made at La Palma, at the Spanish Observatorio del Roque de los Muchachos of the IAC, with the William Herschel Telescope of the Isaac Newton Group and with the Italian Telescopio Nazionale Galileo (TNG) operated by the Fundación Galileo Galilei of INAF. Also based on observations made with the G.B. Cassini Telescope at Loiano (Italy), operated by the Osservatorio Astronomico di Bologna (INAF). Appendices are only available in electronic form at http://www.aanda.org

CARBON ABUNDANCES FOR RED GIANTS IN THE DRACO DWARF SPHEROIDAL GALAXY

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shetrone, Matthew D.; Stanford, Laura M.; Smith, Graeme H.

2013-05-15

Measurements of [C/Fe], [Ca/H], and [Fe/H] have been derived from Keck I LRISb spectra of 35 giants in the Draco dwarf spheroidal galaxy. The iron abundances are derived by a spectrum synthesis modeling of the wavelength region from 4850 to 5375 A, while calcium and carbon abundances are obtained by fitting the Ca II H and K lines and the CH G band, respectively. A range in metallicity of -2.9 {<=} [Fe/H] {<=} -1.6 is found within the giants sampled, with a good correlation between [Fe/H] and [Ca/H]. The great majority of stars in the sample would be classified asmore » having weak absorption in the {lambda}3883 CN band, with only a small scatter in band strengths at a given luminosity on the red giant branch. In this sense the behavior of CN among the Draco giants is consistent with the predominantly weak CN bands found among red giants in globular clusters of metallicity [Fe/H] < -1.8. Over half of the giants in the Draco sample have [Fe/H] > -2.25, and among these there is a trend for the [C/Fe] abundance to decrease with increasing luminosity on the red giant branch. This is a phenomenon that is also seen among both field and globular cluster giants of the Galactic halo, where it has been interpreted as a consequence of deep mixing of material between the base of the convective envelope and the outer limits of the hydrogen-burning shell. However, among the six Draco giants observed that turn out to have metallicities -2.65 < [Fe/H] < -2.25 there is no such trend seen in the carbon abundance. This may be due to small sample statistics or primordial inhomogeneities in carbon abundance among the most metal-poor Draco stars. We identify a potential carbon-rich extremely metal-poor star in our sample. This candidate will require follow-up observations for confirmation.« less

Pal 12 - A metal-rich globular cluster in the outer halo

NASA Technical Reports Server (NTRS)

Cohen, J. G.; Frogel, J. A.; Persson, S. E.; Zinn, R.

1980-01-01

New optical and infrared observations of several stars in the distant globular cluster Pal 12 show that they have CO strengths and heavy element abundances only slightly less than in M 71, one of the more metal-rich globular clusters. Pal 12 thus has a metal abundance near the high end of the range over which globular clusters exist and lies in the outer galactic halo. Its red horizontal branch is not anomalous in view of the abundance that has been found.

The Gaia-ESO Survey: the present-day radial metallicity distribution of the Galactic disc probed by pre-main-sequence clusters

NASA Astrophysics Data System (ADS)

Spina, L.; Randich, S.; Magrini, L.; Jeffries, R. D.; Friel, E. D.; Sacco, G. G.; Pancino, E.; Bonito, R.; Bravi, L.; Franciosini, E.; Klutsch, A.; Montes, D.; Gilmore, G.; Vallenari, A.; Bensby, T.; Bragaglia, A.; Flaccomio, E.; Koposov, S. E.; Korn, A. J.; Lanzafame, A. C.; Smiljanic, R.; Bayo, A.; Carraro, G.; Casey, A. R.; Costado, M. T.; Damiani, F.; Donati, P.; Frasca, A.; Hourihane, A.; Jofré, P.; Lewis, J.; Lind, K.; Monaco, L.; Morbidelli, L.; Prisinzano, L.; Sousa, S. G.; Worley, C. C.; Zaggia, S.

2017-05-01

Context. The radial metallicity distribution in the Galactic thin disc represents a crucial constraint for modelling disc formation and evolution. Open star clusters allow us to derive both the radial metallicity distribution and its evolution over time. Aims: In this paper we perform the first investigation of the present-day radial metallicity distribution based on [Fe/H] determinations in late type members of pre-main-sequence clusters. Because of their youth, these clusters are therefore essential for tracing the current interstellar medium metallicity. Methods: We used the products of the Gaia-ESO Survey analysis of 12 young regions (age < 100 Myr), covering Galactocentric distances from 6.67 to 8.70 kpc. For the first time, we derived the metal content of star forming regions farther than 500 pc from the Sun. Median metallicities were determined through samples of reliable cluster members. For ten clusters the membership analysis is discussed in the present paper, while for other two clusters (I.e. Chamaeleon I and Gamma Velorum) we adopted the members identified in our previous works. Results: All the pre-main-sequence clusters considered in this paper have close-to-solar or slightly sub-solar metallicities. The radial metallicity distribution traced by these clusters is almost flat, with the innermost star forming regions having [Fe/H] values that are 0.10-0.15 dex lower than the majority of the older clusters located at similar Galactocentric radii. Conclusions: This homogeneous study of the present-day radial metallicity distribution in the Galactic thin disc favours models that predict a flattening of the radial gradient over time. On the other hand, the decrease of the average [Fe/H] at young ages is not easily explained by the models. Our results reveal a complex interplay of several processes (e.g. star formation activity, initial mass function, supernova yields, gas flows) that controlled the recent evolution of the Milky Way. Based on observations made with the ESO/VLT, at Paranal Observatory, under program 188.B-3002 (The Gaia-ESO Public Spectroscopic Survey).Full Table 1 is only available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (http://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/601/A70

The evolution of the intracluster medium metallicity in Sunyaev Zel'dovich-selected galaxy clusters at 0 < z < 1.5

DOE PAGES

McDonald, M.; Bulbul, E.; Haan, T. de; ...

2016-07-27

Here, we present the results of an X-ray spectral analysis of 153 galaxy clusters observed with the Chandra, XMM-Newton, and Suzaku space telescopes. These clusters, which span 0 < z < 1.5, were drawn from a larger, mass-selected sample of galaxy clusters discovered in the 2500 square degree South Pole Telescope Sunyaev Zel'dovich (SPT-SZ) survey. With a total combined exposure time of 9.1 Ms, these data yield the strongest constraints to date on the evolution of the metal content of the intracluster medium (ICM). We find no evidence for strong evolution in the global (r < R 500) ICM metallicity (dZ/dz = –0.06 ± 0.04 Z ⊙), with a mean value at z = 0.6 ofmore » $$\\langle Z\\rangle =0.23\\pm 0.01$$ Z ⊙ and a scatter of σ Z = 0.08 ± 0.01 Z ⊙. These results imply that the emission-weighted metallicity has not changed by more than 40% since z = 1 (at 95% confidence), consistent with the picture of an early (z > 1) enrichment. We find, in agreement with previous works, a significantly higher mean value for the metallicity in the centers of cool core clusters versus non-cool core clusters. We find weak evidence for evolution in the central metallicity of cool core clusters (dZ/dz = –0.21 ± 0.11 Z ⊙), which is sufficient to account for this enhanced central metallicity over the past ~10 Gyr. We find no evidence for metallicity evolution outside of the core (dZ/dz = –0.03 ± 0.06 Z ⊙), and no significant difference in the core-excised metallicity between cool core and non-cool core clusters. This suggests that strong radio-mode active galactic nucleus feedback does not significantly alter the distribution of metals at $$r\\gt 0.15{R}_{500}$$. Given the limitations of current-generation X-ray telescopes in constraining the ICM metallicity at z > 1, significant improvements on this work will likely require next-generation X-ray missions.« less

Preparation and analysis of particulate metal deposits

NASA Technical Reports Server (NTRS)

Poppa, H.; Moorhead, D.; Heinemann, K.

1985-01-01

Small particles and clusters of palladium were grown by deposition from the vapor phase under ultrahigh vacuum conditions. Amorphous and crystalline support films of Al2O3 and ultrathin amorphous carbon films were used as substrate materials. The growth of the metal deposit was monitored in situ by scanning transmission diffraction of energy-filtered 100 kV electrons and high resolution transmission electron microscopy (TEM) analysis was performed in a separate instrument. It was established by in situ TEM, however, that the transfer of specimens in this case did not unduly affect the size and distribution of deposit particles. It was found that the cleanness, stoichiometry, crystallinity and structural perfection of the support surface play an essential role in determining the crystalline perfection and structure of the particles. The smallest palladium clusters reproducibly prepared contained not more than six atoms but size determinations below 1 nm average particle diameter are very problematic with conventional TEM. Palladium particles grown on carbon supports feature an impurity-stabilized mosaic structure.

THERMODYNAMICS AND CHARGING OF INTERSTELLAR IRON NANOPARTICLES

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hensley, Brandon S.; Draine, B. T., E-mail: brandon.s.hensley@jpl.nasa.gov

Interstellar iron in the form of metallic iron nanoparticles may constitute a component of the interstellar dust. We compute the stability of iron nanoparticles to sublimation in the interstellar radiation field, finding that iron clusters can persist down to a radius of ≃4.5 Å, and perhaps smaller. We employ laboratory data on small iron clusters to compute the photoelectric yields as a function of grain size and the resulting grain charge distribution in various interstellar environments, finding that iron nanoparticles can acquire negative charges, particularly in regions with high gas temperatures and ionization fractions. If ≳10% of the interstellar ironmore » is in the form of ultrasmall iron clusters, the photoelectric heating rate from dust may be increased by up to tens of percent relative to dust models with only carbonaceous and silicate grains.« less

Probing Globular Cluster Formation in Low Metallicity Dwarf Galaxies

NASA Astrophysics Data System (ADS)

Johnson, Kelsey E.; Hunt, Leslie K.; Reines, Amy E.

2008-12-01

The ubiquitous presence of globular clusters around massive galaxies today suggests that these extreme star clusters must have been formed prolifically in the earlier universe in low-metallicity galaxies. Numerous adolescent and massive star clusters are already known to be present in a variety of galaxies in the local universe; however most of these systems have metallicities of 12 + log(O/H) > 8, and are thus not representative of the galaxies in which today's ancient globular clusters were formed. In order to better understand the formation and evolution of these massive clusters in environments with few heavy elements, we have targeted several low-metallicity dwarf galaxies with radio observations, searching for newly-formed massive star clusters still embedded in their birth material. The galaxies in this initial study are HS 0822+3542, UGC 4483, Pox 186, and SBS 0335-052, all of which have metallicities of 12 + log(O/H) < 7.75. While no thermal radio sources, indicative of natal massive star clusters, are found in three of the four galaxies, SBS 0335-052 hosts two such objects, which are incredibly luminous. The radio spectral energy distributions of these intense star-forming regions in SBS 0335-052 suggest the presence of ~12,000 equivalent O-type stars, and the implied star formation rate is nearing the maximum starburst intensity limit.

Measuring consistent masses for 25 Milky Way globular clusters

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kimmig, Brian; Seth, Anil; Ivans, Inese I.

2015-02-01

We present central velocity dispersions, masses, mass-to-light ratios (M/Ls ), and rotation strengths for 25 Galactic globular clusters (GCs). We derive radial velocities of 1951 stars in 12 GCs from single order spectra taken with Hectochelle on the MMT telescope. To this sample we add an analysis of available archival data of individual stars. For the full set of data we fit King models to derive consistent dynamical parameters for the clusters. We find good agreement between single-mass King models and the observed radial dispersion profiles. The large, uniform sample of dynamical masses we derive enables us to examine trendsmore » of M/L with cluster mass and metallicity. The overall values of M/L and the trends with mass and metallicity are consistent with existing measurements from a large sample of M31 clusters. This includes a clear trend of increasing M/L with cluster mass and lower than expected M/Ls for the metal-rich clusters. We find no clear trend of increasing rotation with increasing cluster metallicity suggested in previous work.« less

STAR CLUSTERS IN M31. II. OLD CLUSTER METALLICITIES AND AGES FROM HECTOSPEC DATA

DOE Office of Scientific and Technical Information (OSTI.GOV)

Caldwell, Nelson; Schiavon, Ricardo; Morrison, Heather

2011-02-15

We present new high signal-to-noise spectroscopic data on the M31 globular cluster (GC) system, obtained with the Hectospec multifiber spectrograph on the 6.5 m MMT. More than 300 clusters have been observed at a resolution of 5 A and with a median S/N of 75 per A, providing velocities with a median uncertainty of 6 km s{sup -1}. The primary focus of this paper is the determination of mean cluster metallicities, ages, and reddenings. Metallicities were estimated using a calibration of Lick indices with [Fe/H] provided by Galactic GCs. These match well the metallicities of 24 M31 clusters determined frommore » Hubble Space Telescope color-magnitude diagrams, the differences having an rms of 0.2 dex. The metallicity distribution is not generally bimodal, in strong distinction with the bimodal Galactic globular distribution. Rather, the M31 distribution shows a broad peak, centered at [Fe/H] = -1, possibly with minor peaks at [Fe/H] = -1.4, -0.7, and -0.2, suggesting that the cluster systems of M31 and the Milky Way had different formation histories. Ages for clusters with [Fe/H] > - 1 were determined using the automatic stellar population analysis program EZ{sub A}ges. We find no evidence for massive clusters in M31 with intermediate ages, those between 2 and 6 Gyr. Moreover, we find that the mean ages of the old GCs are remarkably constant over about a decade in metallicity (-0.95{approx}< [Fe/H] {approx}<0.0).« less

Dynamical Formation of Low-mass Merging Black Hole Binaries like GW151226

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chatterjee, Sourav; Rodriguez, Carl L.; Kalogera, Vicky

2017-02-20

Using numerical models for star clusters spanning a wide range in ages and metallicities (Z) we study the masses of binary black holes (BBHs) produced dynamically and merging in the local universe ( z ≲ 0.2). After taking into account cosmological constraints on star formation rate and metallicity evolution, which realistically relate merger delay times obtained from models with merger redshifts, we show here for the first time that while old, metal-poor globular clusters can naturally produce merging BBHs with heavier components, as observed in GW150914, lower-mass BBHs like GW151226 are easily formed dynamically in younger, higher-metallicity clusters. More specifically,more » we show that the mass of GW151226 is well within 1 σ of the mass distribution obtained from our models for clusters with Z/Z{sub ⊙} ≳ 0.5. Indeed, dynamical formation of a system like GW151226 likely requires a cluster that is younger and has a higher metallicity than typical Galactic globular clusters. The LVT151012 system, if real, could have been created in any cluster with Z/Z{sub ⊙} ≲ 0.25. On the other hand, GW150914 is more massive (beyond 1 σ ) than typical BBHs from even the lowest-metallicity (Z/Z{sub ⊙} = 0.005) clusters we consider, but is within 2 σ of the intrinsic mass distribution from our cluster models with Z/Z{sub ⊙} ≲ 0.05; of course, detection biases also push the observed distributions toward higher masses.« less

Super-reduced polyoxometalates: excellent molecular cluster battery components and semipermeable molecular capacitors.

PubMed

Nishimoto, Yoshio; Yokogawa, Daisuke; Yoshikawa, Hirofumi; Awaga, Kunio; Irle, Stephan

2014-06-25

Theoretical investigations are presented on the molecular and electronic structure changes that occur as α-Keggin-type polyoxometalate (POM(3-)) clusters [PM12O40](3-) (M = Mo, W) are converted toward their super-reduced POM(27-) state during the discharging process in lithium-based molecular cluster batteries. Density functional theory was employed in geometry optimization, and first-principles molecular dynamics simulations were used to explore local minima on the potential energy surface of neutral POM clusters adorned with randomly placed Li atoms as electron donors around the cluster surface. On the basis of structural, electron density, and molecular orbital studies, we present evidence that the super-reduction is accompanied by metal-metal bond formation, beginning from the 12th to 14th excess electron transferred to the cluster. Afterward, the number of metal-metal bonds increases nearly linearly with the number of additionally transferred excess electrons. In α-Keggin-type POMs, metal triangles are a prominently emerging structural feature. The origin of the metal triangle formation during super-reduction stems from the formation of characteristic three-center two-electron bonds in triangular metal atom sites, created under preservation of the POM skeleton via "squeezing out" of oxygen atoms bridging two metal atoms when the underlying metal atoms form covalent bonds. The driving force for this unusual geometrical and electronic structure change is a local Jahn-Teller distortion at individual transition-metal octahedral sites, where the triply degenerate t2 d orbitals become partially filled during reduction and gain energy by distortion of the octahedron in such a way that metal-metal bonds are formed. The bonding orbitals show strong contributions from mixing with metal-oxygen antibonding orbitals, thereby "shuffling away" excess electrons from the cluster center to the outside of the cage. The high density of negatively charged yet largely separated oxygen atoms on the surface of the super-reduced POM(27-) polyanion allows the huge Coulombic repulsion due to the presence of the excess electrons to be counterbalanced by the presence of Li countercations, which partially penetrate into the outer oxygen shell. This "semiporous molecular capacitor" structure is likely the reason for the effective electron uptake in POMs.

A new family of Ln₇ clusters with an ideal D(3h) metal-centered trigonal prismatic geometry, and SMM and photoluminescence behaviors.

PubMed

Mazarakioti, Eleni C; Poole, Katye M; Cunha-Silva, Luis; Christou, George; Stamatatos, Theocharis C

2014-08-14

The first use of the flexible Schiff base ligand N-salicylidene-2-aminocyclohexanol in metal cluster chemistry has afforded a new family of Ln7 clusters with ideal D(3h) point group symmetry and metal-centered trigonal prismatic topology; solid-state and solution studies revealed SMM and photoluminescence behaviors.

Manipulating Light with Transition Metal Clusters, Organic Dyes, and Metal Organic Frameworks

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ogut, Serdar

The primary goals of our research program is to develop and apply state-of-the-art first-principles methods to predict electronic and optical properties of three systems of significant scientific and technological interest: transition metal clusters, organic dyes, and metal-organic frameworks. These systems offer great opportunities to manipulate light for a wide ranging list of energy-related scientific problems and applications. During this grant period, we focused our investigations on the development, implementation, and benchmarking of many-body Green’s function methods (GW approximation and the Bethe-Salpeter equation) to examine excited-state properties of transition metal/transition-metal-oxide clusters and organic molecules that comprise the building blocks of dyesmore » and metal-organic frameworks.« less

Metal and Metal Oxide Interactions and Their Catalytic Consequences for Oxygen Reduction Reaction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jia, Qingying; Ghoshal, Shraboni; Li, Jingkun

2017-06-01

Many industrial catalysts are composed of metal particles supported on metal oxides (MMO). It is known that the catalytic activity of MMO materials is governed by metal and metal oxide interactions (MMOI), but how to optimize MMO systems via manipulation of MMOI remains unclear, due primarily to the ambiguous nature of MMOI. Herein, we develop a Pt/NbOx/C system with tunable structural and electronic properties via a modified arc plasma deposition method. We unravel the nature of MMOI by characterizing this system under reactive conditions utilizing combined electrochemical, microscopy, and in situ spectroscopy. We show that Pt interacts with the Nbmore » in unsaturated NbOx owing to the oxygen deficiency in the MMO interface, whereas Pt interacts with the O in nearly saturated NbOx, and further interacts with Nb when the oxygen atoms penetrate into the Pt cluster at elevated potentials. While the Pt–Nb interactions do not benefit the inherent activity of Pt toward oxygen reduction reaction (ORR), the Pt–O interactions improve the ORR activity by shortening the Pt–Pt bond distance. Pt donates electrons to NbOx in both Pt–Nb and Pt–O cases. The resultant electron efficiency stabilizes low-coordinated Pt sites, hereby stabilizing small Pt particles. This determines the two characteristic features of MMO systems: dispersion of small metal particles and high catalytic durability. These findings contribute to our understandings of MMO catalytic systems.« less

Models of metal binding structures in fulvic acid from the Suwannee River, Georgia

USGS Publications Warehouse

Leenheer, J.A.; Brown, G.K.; MacCarthy, P.; Cabaniss, S.E.

1998-01-01

Fulvic acid, isolated from the Suwannee River, Georgia, was assessed for its ability to bind Ca2+, Cd2+, Cu2+, Ni2+, and Zn2+ ions at pH 6 before and after extensive fractionation that was designed to reveal the nature of metal binding functional groups. The binding constant for Ca2+ ion had the greatest increase of all the ions in a metal binding fraction that was selected for intensive characterization for the purpose of building quantitative average model structures. The 'metal binding' fraction was characterized by quantitative 13C NMR, 1H NMR, and FT-1R spectrometry and elemental, titrimetric, and molecular weight determinations. The characterization data revealed that carboxyl groups were clustered in short- chain aliphatic dibasic acid structures. The Ca2+ binding data suggested that ether-substituted oxysuccinic acid structures are good models for the metal binding sites at pH 6. Structural models were derived based upon oxidation and photolytic rearrangements of cutin, lignin, and tannin precursors. These structural models rich in substituted dibasic acid structures revealed polydentate binding sites with the potential for both inner-sphere and outer-sphere type binding. The majority of the fulvic acid molecule was involved with metal binding rather than a small substructural unit.Fulvic acid, isolated from the Suwannee River, Georgia, was assessed for its ability to bind Ca2+, Cd2+, Cu2+, Ni2+, and Zn2+ ions at pH 6 before and after extensive fractionation that was designed to reveal the nature of metal binding functional groups. The binding constant for Ca2+ ion had the greatest increase of all the ions in a metal binding fraction that was selected for intensive characterization for the purpose of building quantitative average model structures. The `metal binding' fraction was characterized by quantitative 13C NMR, 1H NMR, and FT-IR spectrometry and elemental, titrimetric, and molecular weight determinations. The characterization data revealed that carboxyl groups were clustered in short-chain aliphatic dibasic acid structures. The Ca2+ binding data suggested that ether-substituted oxysuccinic acid structures are good models for the metal binding sites at pH 6. Structural models were derived based upon oxidation and photolytic rearrangements of cutin, lignin, and tannin precursors. These structural models rich in substituted dibasic acid structures revealed polydentate binding sites with the potential for both inner-sphere and outer-sphere type binding. The majority of the fulvic acid molecule was involved with metal binding rather than a small substructural unit.

Studies of Copper, Silver, and Gold Cluster Anions: Evidence of Electronic Shell Structure.

NASA Astrophysics Data System (ADS)

Pettiette, Claire Lynn

A new Ultraviolet Magnetic Time-of-Flight Photoelectron Spectrometer (MTOFPES) has been developed for the study of the electronic structure of clusters produced in a pulsed supersonic molecular beam. This is the first technique which has been successful in probing the valence electronic states of metal clusters. The ultraviolet photoelectron spectra of negative cluster ions of the noble metals have been taken at several different photon energies. These are presented along with the electron affinity and HOMO-LUMO gap measurements for Cu_6^- to Cu_ {41}^-, using 4.66 eV and 6.42 eV detachment energies; Ag_3^- to Ag_{21}^-, using 6.42 eV detachment energy; and Au_3^ - to Au_{21}^-, using 6.42 eV and 7.89 eV detachment energies. The spectra provide the first detailed probes of the s valence electrons of the noble metal clusters. In addition, the 6.42 eV and 7.89 eV spectra probe the first one to two electron volts of the molecular orbitals of the d valence electrons of copper and gold clusters. The electron affinity and HOMO-LUMO gap measurements of the noble metal clusters agree with the predictions of the ellipsoidal shell model for mono-valent metal clusters. In particular, cluster numbers 8, 20, and 40--which correspond to the spherical shell closings of this model--have low electron affinities and large HOMO-LUMO gaps. The spectra of the gold cluster ions indicate that the molecular orbital energies of the cluster valence electrons are more widely spaced for gold than for copper or silver. This is to be expected for the heavy atom clusters when relativistic effects are taken into account.

Development of Metal Cluster-Based Energetic Materials at NSWC-IHD

DTIC Science & Technology

2011-01-01

reactivity of NixAly + clusters with nitromethane was investigated using a gas-phase molecular beam system. Results indicate that nitromethane is highly...clusters make up the subunit of a molecular metal-based energetic material. The reactivity of NixAly+ clusters with nitromethane was investigated using...a gas-phase molecular beam system. Results indicate that nitromethane is highly reactive toward the NixAly+ clusters and suggests it would not make

Photosensitized Reduction of Carbon Dioxide in Solution Using Noble-Metal Clusters for Electron Transfer

NASA Astrophysics Data System (ADS)

Toshima, Naoki; Yamaji, Yumi; Teranishi, Toshiharu; Yonezawa, Tetsu

1995-03-01

Carbon dioxide was reduced to methane by visible-light irradiation of a solution composed of tris(bipyridine)ruthenium(III) as photosensitizer, ethylenediaminetetraacetic acid disodium salt as sacrificial reagent, methyl viologen as electron relay, and a colloidal dispersion of polymer-protected noble-metal clusters, prepared by alcohol-reduction, as catalyst. Among the noble-metal clusters examined, Pt clusters showed the highest activity for the formation of methane as well as hydrogen. In order to improve the activity, oxidized clusters and bimetallic clusters were also applied. For example, the CH4 yield in 3-h irradiation increased from 51 x 10-3 μmol with unoxidized Pt clusters to 72 x 10-3 μmol with partially oxidized ones. In the case of Pt/Ru bimetalic systems, the improvement of the catalytic activity by air treatment was much greater than in case of monometallic clusters.

Numerical taxonomy of heavy metal tolerant bacteria isolated from the estuarine environment

DOE Office of Scientific and Technical Information (OSTI.GOV)

Allen, D.A.; Austin, B.; Mills, A.L.

1977-01-01

Metal tolerant bacteria, totalling 301 strains, were isolated from water and sediment samples collected from Chesapeake Bay. Growth in the presence of 100 ppm cadmium, chromium, cobalt, lead, mercury and molybdenum was tested. In addition, the strains were examined for 118 biochemical, cultural, morphological, nutritional and physiological, characters and the data were analyzed by computer, using the simple matching and Jaccard coefficients. From sorted similarity matrices, 293 strains, 97% of the total, were removed in 12 clusters defined at the 80 to 85% similarity level. The clusters included Bacillus and Pseudomonas spp. and genera and species of Enterobacteriaceae. Three clusters,more » containing gram negative rods, were not identified. Several of the clusters were composed of strains exhibiting tolerance to a wide range of heavy metals, whereas three of the clusters contained bacteria that were capable of growth in the presence of only a few of the metals examined in this study. Antibiotic resistance of the metal resistant strains has also been examined.« less

Unconventional Current Scaling and Edge Effects for Charge Transport through Molecular Clusters

PubMed Central

2017-01-01

Metal–molecule–metal junctions are the key components of molecular electronics circuits. Gaining a microscopic understanding of their conducting properties is central to advancing the field. In the present contribution, we highlight the fundamental differences between single-molecule and ensemble junctions focusing on the fundamentals of transport through molecular clusters. In this way, we elucidate the collective behavior of parallel molecular wires, bridging the gap between single molecule and large-area monolayer electronics, where even in the latter case transport is usually dominated by finite-size islands. On the basis of first-principles charge-transport simulations, we explain why the scaling of the conductivity of a junction has to be distinctly nonlinear in the number of molecules it contains. Moreover, transport through molecular clusters is found to be highly inhomogeneous with pronounced edge effects determined by molecules in locally different electrostatic environments. These effects are most pronounced for comparably small clusters, but electrostatic considerations show that they prevail also for more extended systems. PMID:29043825

Essential factors for control of the equilibrium in the reversible rearrangement of M₃N@I(h)-C₈₀ fulleropyrrolidines: exohedral functional groups versus endohedral metal clusters.

PubMed

Aroua, Safwan; Garcia-Borràs, Marc; Osuna, Sílvia; Yamakoshi, Yoko

2014-10-20

The effects of exohedral moieties and endohedral metal clusters on the isomerization of M3N@I(h)-C80 products from the Prato reaction through [1,5]-sigmatropic rearrangement were systematically investigated by using three types of fulleropyrrolidine derivatives and four different endohedral metal clusters. As a result, all types of derivatives provided the same ratios of the isomers for a given trimetallic nitride template (TNT) as the thermodynamic products, thus indicating that the size of the endohedral metal clusters inside C80 was the single essential factor in determining the equilibrium between the [6,6]-isomer (kinetic product) and the [5,6]-isomer. In all the derivatives, the [6,6]- and [5,6]-Prato adducts with larger metal clusters, such as Y3N and Gd3N, were equally stable, which is in good agreement with DFT calculations. The reaction rate of the rearrangement was dependent on both the substituent of exohedral functional groups and the endohedral metal-cluster size. Further DFT calculations and (13)C NMR spectroscopic studies were employed to rationalize the equilibrium in the rearrangement between the [6,6]- and [5,6]-fulleropyrrolidines. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Systems and methods for producing metal clusters; functionalized surfaces; and droplets including solvated metal ions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cooks, Robert Graham; Li, Anyin; Luo, Qingjie

The invention generally relates to systems and methods for producing metal clusters; functionalized surfaces; and droplets including solvated metal ions. In certain aspects, the invention provides methods that involve providing a metal and a solvent. The methods additionally involve applying voltage to the solvated metal to thereby produce solvent droplets including ions of the metal containing compound, and directing the solvent droplets including the metal ions to a target. In certain embodiments, once at the target, the metal ions can react directly or catalyze reactions.

Systems and methods for producing metal clusters; functionalized surfaces; and droplets including solvated metal ions

DOEpatents

Cooks, Robert Graham; Li, Anyin; Luo, Qingjie

2017-01-24

The invention generally relates to systems and methods for producing metal clusters; functionalized surfaces; and droplets including solvated metal ions. In certain aspects, the invention provides methods that involve providing a metal and a solvent. The methods additionally involve applying voltage to the solvated metal to thereby produce solvent droplets including ions of the metal containing compound, and directing the solvent droplets including the metal ions to a target. In certain embodiments, once at the target, the metal ions can react directly or catalyze reactions.

The stabilization mechanism of titanium cluster

NASA Astrophysics Data System (ADS)

Sun, Houqian; Ren, Yun; Hao, Yuhua; Wu, Zhaofeng; Xu, Ning

2015-05-01

A systematic and comparative theoretical study on the stabilization mechanism of titanium cluster has been performed by selecting the clusters Tin (n=3, 4, 5, 7, 13, 15 and 19) as representatives in the framework of density-functional theory. For small clusters Tin (n=3, 4 and 5), the binding energy gain due to spin polarization is substantially larger than that due to structural distortion. For medium clusters Ti13 and Ti15, both have about the same contribution. For Tin (n=4, 5, 13 and 15), when the undistorted high symmetric structure with spin-polarization is changed into the lowest energy structure, the energy level spelling due to distortion fails to reverse the level order of occupied and unoccupied molecular orbital (MO) of two type spin states, the spin configuration remains unchanged. In spin restricted and undistorted high symmetric structure, d orbitals participate in the hybridization in MOs, usually by way of a less distorted manner, and weak bonds are formed. In contrast, d orbitals take part in the formation of MOs in the ground state structure, usually in a distorted manner, and strong covalent metallic bonds are formed.

Effects of lateral diffusion on morphology and dynamics of a microscopic lattice-gas model of pulsed electrodeposition.

PubMed

Frank, Stefan; Roberts, Daniel E; Rikvold, Per Arne

2005-02-08

The influence of nearest-neighbor diffusion on the decay of a metastable low-coverage phase (monolayer adsorption) in a square lattice-gas model of electrochemical metal deposition is investigated by kinetic Monte Carlo simulations. The phase-transformation dynamics are compared to the well-established Kolmogorov-Johnson-Mehl-Avrami theory. The phase transformation is accelerated by diffusion, but remains in accord with the theory for continuous nucleation up to moderate diffusion rates. At very high diffusion rates the phase-transformation kinetic shows a crossover to instantaneous nucleation. Then, the probability of medium-sized clusters is reduced in favor of large clusters. Upon reversal of the supersaturation, the adsorbate desorbs, but large clusters still tend to grow during the initial stages of desorption. Calculation of the free energy of subcritical clusters by enumeration of lattice animals yields a quasiequilibrium distribution which is in reasonable agreement with the simulation results. This is an improvement relative to classical droplet theory, which fails to describe the distributions, since the macroscopic surface tension is a bad approximation for small clusters.

The young SMC cluster NGC 330

NASA Technical Reports Server (NTRS)

Carney, B. W.; Janes, K. A.; Flower, P. J.

1985-01-01

A color-magnitude diagram has been obtained for the young SMC cluster NGC 330. The diagram shows a well-defined main sequence, a group of blue supergiants, a group of red supergiants between B-V = 1.2 m and 1.6 m about one magnitude fainter, and an empty Hertzsprung gap. The surrounding field is a composite of a very gold population resembling galactic globular clusters and a very young population. DDO and infrared photometry strongly suggest that the cluster is metal-poor, but a definitive measure could not be made because of calibration difficulties. The cluster's age is estimated at 12 million years, with the surrounding field about 50 percent older. The cluster will prove very useful in testing stellar evolution models for young, metal-poor stars if the cluster's metallicity can be established via high-resolution spectroscopy.

Effect of Graphene with Nanopores on Metal Clusters

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhou, Hu; Chen, Xianlang; Wang, Lei

Porous graphene, which is a novel type of defective graphene, shows excellent potential as a support material for metal clusters. In this work, the stability and electronic structures of metal clusters (Pd, Ir, Rh) supported on pristine graphene and graphene with different sizes of nanopore were investigated by first-principle density functional theory (DFT) calculations. Thereafter, CO adsorption and oxidation reaction on the Pd-graphene system were chosen to evaluate its catalytic performance. Graphene with nanopore can strongly stabilize the metal clusters and cause a substantial downshift of the d-band center of the metal clusters, thus decreasing CO adsorption. All binding energies,more » d-band centers, and adsorption energies show a linear change with the size of the nanopore: a bigger size of nanopore corresponds to a stronger metal clusters bond to the graphene, lower downshift of the d-band center, and weaker CO adsorption. By using a suitable size nanopore, supported Pd clusters on the graphene will have similar CO and O2 adsorption ability, thus leading to superior CO tolerance. The DFT calculated reaction energy barriers show that graphene with nanopore is a superior catalyst for CO oxidation reaction. These properties can play an important role in instructing graphene-supported metal catalyst preparation to prevent the diffusion or agglomeration of metal clusters and enhance catalytic performance. This work was supported by National Basic Research Program of China (973Program) (2013CB733501), the National Natural Science Foundation of China (NSFC-21176221, 21136001, 21101137, 21306169, and 91334013). D. Mei acknowledges the support from the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. Pacific Northwest National Laboratory (PNNL) is a multiprogram national laboratory operated for DOE by Battelle. Computing time was granted by the grand challenge of computational catalysis of the William R. Wiley Environmental Molecular Sciences Laboratory (EMSL) and by the National Energy Research Scientific Computing Center (NERSC).« less

First Principles Studies of Electronic and Optical Excitations in Noble Metal and Titania Clusters

NASA Astrophysics Data System (ADS)

Baishya, Kopinjol

Clusters are metastable structures that form a bridge between the atomic and the bulk phase. Due to their small size, quantum confinement effects are very important in clusters. They also have large surface to volume ratio, and as such, surface effects are also important. Due to these effects the properties of clusters are quite different from those of the bulk. When the size of a cluster is increased, its properties change from atomic to bulk values usually in nontrivial ways, often displaying interesting effects. By studying the evolution of cluster properties as a function of size one can try to understand the evolution and origin of bulk properties. This thesis concentrates on two main topics, noble-metal clusters of Ag and Cu, and TiO2 nanocrystals. I present my study of the optical properties of these systems calculated using first principles methods. Noble metal clusters have intriguing physical and chemical properties due to their electronic structure that contains a fully filled and localized d orbital energetically and spatially very close to the half filled s orbital. In Chapters 3 and 4 of this thesis, I present a detailed study of the role of d electrons on the optical properties of Ag and Cu clusters. I also show that the optical spectra of these clusters can be explained remarkably well by the classical Mie-Gans theory which uses the bulk dielectric constant of the material to predict their optical absorption spectra. The fact that the concept of the bulk dielectric constant survives up to the sub-nanometer size range is one of the main findings of this thesis. TiO2 is arguably the most studied single-crystalline material in the field of surface science of metal oxides. In chapter 5 of this thesis I present results and analyses on the electronic and optical excitations in rutile TiO2 nanocrystals. The motivation for this study stems from the following observation: In modeling optical prooperties of DSSC configurations with various organic molecules, a typical approach has been to use a finite, appropriately passivated TiO2 nanocrystal in order to limit the computational demand. In real systems on the other hand, the size of nanocrystalline TiO2 is of the order of several hundreds of nanometers, and hence, they can be considered to be essentially bulk-like. The question is then, whether finite TiO2 nanoparticles can accurately model the optical properties of bulk TiO2. I show in my thesis that the optical absorption absorption spectra of such TiO2 nanocrystals do not have the particular features seen in the imaginary part of the bulk dielectric function of TiO 2 associated with the van Hove singularities in the electronic density of states. Instead, the absorption spectra of bulk-terminated TiO2 nanocrystals can be reproduced quite well by the Mie-Gans theory.

Intergalactic stellar populations in intermediate redshift clusters

NASA Astrophysics Data System (ADS)

Melnick, J.; Giraud, E.; Toledo, I.; Selman, F.; Quintana, H.

2012-11-01

A substantial fraction of the total stellar mass in rich clusters of galaxies resides in a diffuse intergalactic component usually referred to as the intracluster light (ICL). Theoretical models indicate that these intergalactic stars originate mostly from the tidal interaction of the cluster galaxies during the assembly history of the cluster, and that a significant fraction of these stars could have formed in situ from the late infall of cold metal-poor gas clouds on to the cluster. However, these models also overpredict the fraction of stellar mass in the ICL by a substantial margin, something that is still not well understood. The models also make predictions about the age distribution of the ICL stars, which may provide additional observational constraints. Here we present population synthesis models for the ICL of an intermediate redshift (z = 0.29) X-ray cluster that we have extensively studied in previous papers. The advantage of observing intermediate redshift clusters rather than nearby ones is that the former fit the field of view of multi-object spectrographs in 8-m telescopes and therefore permit us to encompass most of the ICL with only a few well-placed slits. In this paper we show that by stacking spectra at different locations within the ICL it is possible to reach sufficiently high signal-to-noise ratios to fit population synthesis models and derive meaningful results. The models provide ages and metallicities for the dominant populations at several different locations within the ICL and the brightest cluster galaxies (BCG) halo, as well as measures of the kinematics of the stars as a function of distance from the BCG. We thus find that the ICL in our cluster is dominated by old metal-rich stars, at odds with what has been found in nearby clusters where the stars that dominate the ICL are old and metal poor. While we see weak evidence of a young, metal-poor component, if real, these young stars would amount to less than 1 per cent of the total ICL mass, much less than the up to 30 per cent predicted by the models. We propose that the very metal-rich (i.e. 2.5× solar) stars in the ICL of our cluster, which comprise ˜40 per cent of the total mass, originate mostly from the central dumb-bell galaxy, while the remaining solar and metal-poor stars come from spiral, post-starburst (E+A) and metal-poor dwarf galaxies. About 16 per cent of the ICL stars are old and metal poor.

SPECTROSCOPY OF LUMINOUS COMPACT BLUE GALAXIES IN DISTANT CLUSTERS. II. PHYSICAL PROPERTIES OF dE PROGENITOR CANDIDATES

DOE Office of Scientific and Technical Information (OSTI.GOV)

Crawford, S. M.; Wirth, Gregory D.; Bershady, M. A.

2016-02-01

Luminous Compact Blue Galaxies (LCBGs) are an extreme star-bursting population of galaxies that were far more common at earlier epochs than today. Based on spectroscopic and photometric measurements of LCBGs in massive (M > 10{sup 15} M{sub ⊙}), intermediate redshift (0.5 < z < 0.9) galaxy clusters, we present their rest-frame properties including star formation rate, dynamical mass, size, luminosity, and metallicity. The appearance of these small, compact galaxies in clusters at intermediate redshift helps explain the observed redshift evolution in the size–luminosity relationship among cluster galaxies. In addition, we find the rest-frame properties of LCBGs appearing in galaxy clusters are indistinguishable from field LCBGs atmore » the same redshift. Up to 35% of the LCBGs show significant discrepancies between optical and infrared indicators of star formation, suggesting that star formation occurs in obscured regions. Nonetheless, the star formation for LCBGs shows a decrease toward the center of the galaxy clusters. Based on their position and velocity, we estimate that up to 10% of cluster LCBGs are likely to merge with another cluster galaxy. Finally, the observed properties and distributions of the LCBGs in these clusters lead us to conclude that we are witnessing the quenching of the progenitors of dwarf elliptical galaxies that dominate the number density of present-epoch galaxy clusters.« less

Single Electron Tunneling

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ruggiero, Steven T.

Financial support for this project has led to advances in the science of single-electron phenomena. Our group reported the first observation of the so-called ''Coulomb Staircase'', which was produced by tunneling into ultra-small metal particles. This work showed well-defined tunneling voltage steps of width e/C and height e/RC, demonstrating tunneling quantized on the single-electron level. This work was published in a now well-cited Physical Review Letter. Single-electron physics is now a major sub-field of condensed-matter physics, and fundamental work in the area continues to be conducted by tunneling in ultra-small metal particles. In addition, there are now single-electron transistors thatmore » add a controlling gate to modulate the charge on ultra-small photolithographically defined capacitive elements. Single-electron transistors are now at the heart of at least one experimental quantum-computer element, and single-electron transistor pumps may soon be used to define fundamental quantities such as the farad (capacitance) and the ampere (current). Novel computer technology based on single-electron quantum dots is also being developed. In related work, our group played the leading role in the explanation of experimental results observed during the initial phases of tunneling experiments with the high-temperature superconductors. When so-called ''multiple-gap'' tunneling was reported, the phenomenon was correctly identified by our group as single-electron tunneling in small grains in the material. The main focus throughout this project has been to explore single electron phenomena both in traditional tunneling formats of the type metal/insulator/particles/insulator/metal and using scanning tunneling microscopy to probe few-particle systems. This has been done under varying conditions of temperature, applied magnetic field, and with different materials systems. These have included metals, semi-metals, and superconductors. Amongst a number of results, we have verified that clusters of down to one, two, and three metal atoms can be identified with single-electron techniques. We have also, extended the regime of single-electron phenomenology through the observation of single-electron effects in metal droplets in the high-conductance regime.« less

Linked supramolecular building blocks for enhanced cluster formation

DOE PAGES

McLellan, Ross; Palacios, Maria A.; Beavers, Christine M.; ...

2015-01-09

Methylene-bridged calix[4]arenes have emerged as extremely versatile ligand supports in the formation of new polymetallic clusters possessing fascinating magnetic properties. Metal ion binding rules established for this building block allow one to partially rationalise the complex assembly process. The ability to covalently link calix[4]arenes at the methylene bridge provides significantly improved control over the introduction of different metal centres to resulting cluster motifs. Clusters assembled from bis-calix[4]arenes and transition metal ions or 3d-4f combinations display characteristic features of the analogous calix[4]arene supported clusters, thereby demonstrating an enhanced and rational approach towards the targeted synthesis of complex and challenging structures.

Thermodynamics of Small Alkali Metal Halide Cluster Ions: Comparison of Classical Molecular Simulations with Experiment and Quantum Chemistry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vlcek, Lukas; Uhlik, Filip; Moucka, Filip

We evaluate the ability of selected classical molecular models to describe the thermodynamic and structural aspects of gas-phase hydration of alkali halide ions and the formation of small water clusters. To understand the effect of many-body interactions (polarization) and charge penetration effects on the accuracy of a force field, we perform Monte Carlo simulations with three rigid water models using different functional forms to account for these effects: (i) point charge non-polarizable SPC/E, (ii) Drude point charge polarizable SWM4- DP, and (iii) Drude Gaussian charge polarizable BK3. Model predictions are compared with experimental Gibbs free energies and enthalpies of ionmore » hydration, and with microscopic structural properties obtained from quantum DFT calculations. We find that all three models provide comparable predictions for pure water clusters and cation hydration, but differ significantly in their description of anion hydration. None of the investigated classical force fields can consistently and quantitatively reproduce the experimental gas phase hydration thermodynamics. The outcome of this study highlights the relation between the functional form that describes the effective intermolecular interactions and the accuracy of the resulting ion hydration properties.« less

The Role of Bi3+ in Promoting and Stabilizing Iron Oxo Clusters in Strong Acid.

PubMed

Sadeghi, Omid; Amiri, Mehran; Reinheimer, Eric W; Nyman, May

2018-05-22

Metal oxo clusters and metal oxides assemble and precipitate from water in processes that depend on pH, temperature, and concentration. Other parameters that influence the structure, composition, and nuclearity of "molecular" and bulk metal oxides are poorly understood, and have thus not been exploited. Herein, we show that Bi 3+ drives the formation of aqueous Fe 3+ clusters, usurping the role of pH. We isolated and structurally characterized a Bi/Fe cluster, Fe 3 BiO 2 (CCl 3 COO) 8 (THF)(H 2 O) 2 , and demonstrated its conversion into an iron Keggin ion capped by six Bi 3+ irons (Bi 6 Fe 13 ). The reaction pathway was documented by X-ray scattering and mass spectrometry. Opposing the expected trend, increased cluster nuclearity required a pH decrease instead of a pH increase. We attribute this anomalous behavior of Bi/Fe(aq) solutions to Bi 3+ , which drives hydrolysis and condensation. Likewise, Bi 3+ stabilizes metal oxo clusters and metal oxides in strongly acidic conditions, which is important in applications such as water oxidation for energy storage. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Approximate treatment of semicore states in GW calculations with application to Au clusters.

PubMed

Xian, Jiawei; Baroni, Stefano; Umari, P

2014-03-28

We address the treatment of transition metal atoms in GW electronic-structure calculations within the plane-wave pseudo-potential formalism. The contributions of s and p semi-core electrons to the self-energy, which are essential to grant an acceptable accuracy, are dealt with using a recently proposed scheme whereby the exchange components are treated exactly at the G0W0 level, whereas a suitable approximation to the correlation components is devised. This scheme is benchmarked for small gold nano-clusters, resulting in ionization potentials, electron affinities, and density of states in very good agreement with those obtained from calculations where s and p semicore states are treated as valence orbitals, and allowing us to apply this same scheme to clusters of intermediate size, Au20 and Au32, that would be otherwise very difficult to deal with.

Approximate treatment of semicore states in GW calculations with application to Au clusters

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xian, Jiawei; Baroni, Stefano; CNR-IOM Democritos, Theory-Elettra group, Trieste

We address the treatment of transition metal atoms in GW electronic-structure calculations within the plane-wave pseudo-potential formalism. The contributions of s and p semi-core electrons to the self-energy, which are essential to grant an acceptable accuracy, are dealt with using a recently proposed scheme whereby the exchange components are treated exactly at the G{sub 0}W{sub 0} level, whereas a suitable approximation to the correlation components is devised. This scheme is benchmarked for small gold nano-clusters, resulting in ionization potentials, electron affinities, and density of states in very good agreement with those obtained from calculations where s and p semicore statesmore » are treated as valence orbitals, and allowing us to apply this same scheme to clusters of intermediate size, Au{sub 20} and Au{sub 32}, that would be otherwise very difficult to deal with.« less

First principles studies of electron tunneling in proteins

PubMed Central

Hayashi, Tomoyuki; Stuchebrukhov, Alexei A.

2014-01-01

A first principles study of electronic tunneling along the chain of seven Fe/S clusters in respiratory complex I, a key enzyme in the respiratory electron transport chain, is described. The broken-symmetry states of the Fe/S metal clusters calculated at both DFT and semi-empirical ZINDO levels were utilized to examine both the extremely weak electronic couplings between Fe/S clusters and the tunneling pathways, which provide a detailed atomistic-level description of the charge transfer process in the protein. One-electron tunneling approximation was found to hold within a reasonable accuracy, with only a moderate induced polarization of the core electrons. The method is demonstrated to be able to calculate accurately the coupling matrix elements as small as 10−4 cm−1. A distinct signature of the wave properties of electrons is observed as quantum interferences of multiple tunneling pathways. PMID:25383312

Metal nanostructures: from clusters to nanocatalysis and sensors

NASA Astrophysics Data System (ADS)

Smirnov, B. M.

2017-12-01

The properties of metal clusters and nanostructures composed of them are reviewed. Various existing methods for the generation of intense beams of metal clusters and their subsequent conversion into nanostructures are compared. Processes of the flow of a buffer gas with active molecules through a nanostructure are analyzed as a basis of using nanostructures for catalytic applications. The propagation of an electric signal through a nanostructure is studied by analogy with a macroscopic metal. An analysis is given of how a nanostructure changes its resistance as active molecules attach to its surface and are converted into negative ions. These negative ions induce the formation of positively charged vacancies inside the metal conductor and attract the vacancies to together change the resistance of the metal nanostructure. The physical basis is considered for using metal clusters and nanostructures composed of them to create new materials in the form of a porous metal film on the surface of an object. The fundamentals of nanocatalysis are reviewed. Semiconductor conductometric sensors consisting of bound nanoscale grains or fibers acting as a conductor are compared with metal sensors conducting via a percolation cluster, a fractal fiber, or a bunch of interwoven nanofibers formed in superfluid helium. It is shown that sensors on the basis of metal nanostructures are characterized by a higher sensitivity than semiconductor ones, but are not selective. Measurements using metal sensors involve two stages, one of which measures to high precision the attachment rate of active molecules to the sensor conductor, and in the other one the surface of metal nanostructures is cleaned from the attached molecules using a gas discharge plasma (in particular, capillary discharge) with a subsequent chromatography analysis for products of cleaning.

Ab Initio Calculations of Spin-Orbit Coupling for Heavy-Metal Containing Radicals

NASA Astrophysics Data System (ADS)

Cheng, Lan

2016-06-01

The perturbative treatment of spin-orbit coupling (SOC) on top of scalar-relativistic calculations is a cost-effective alternative to rigorous fully relativistic calculations. In this work the applicability of the perturbative scheme in the framework of spin-free exact two-component theory is demonstrated with calculations of SO splittings and SOC contributions to molecular properties in small heavy-metal containing radicals, including AuO, AuS, and ThO^+. The equation of motion coupled cluster techniques have been used to accurately account for the electron-correlation effects in these radicals, and basis-set effects are carefully analyzed. The computed results are compared with experimental measurements for SO splittings and dipole moments when available.

Process for metallization of a substrate by irradiative curing of a catalyst applied thereto

DOEpatents

Chen, Ken S.; Morgan, William P.; Zich, John L.

1999-01-01

An improved additive process for metallization of substrates is described whereby a catalyst solution is applied to a surface of a substrate. Metallic catalytic clusters can be formed in the catalyst solution on the substrate surface by irradiating the substrate. Electroless plating can then deposit metal onto the portion of the substrate surface having metallic clusters. Additional metallization thickness can be obtained by electrolytically plating the substrate surface after the electroless plating step.

Using numerical simulations to study the ICM metallicity fields in clusters and groups

NASA Astrophysics Data System (ADS)

Mazzei, Renato; Vijayaraghavan, Rukmani; Sarazin, Craig L.

2018-01-01

Most baryonic matter in clusters resides in the intracluster medium (ICM) as hot and diffuse gas. The metal content of this gas is deposited from dying stars, typically synthesized in type Ia or core-collapse supernovae. The ICM gas traces the formation history of the cluster and the compositional signature of its constituent galaxies as a function of time. Studying the metallicity content thus aids in understanding the gradual evolution of the cluster as it is constructed. Within this framework, galaxy and star formation and evolution can be studied by tracing metals in the ICM. In this work we use numerical simulations to study the evolution of ICM metallicity due to the stripping of galaxies’ gas. We model metallicity fields using cloud-in-cell techniques, to determine the ratio between the mass of particles tracing galaxy outflows and the mass of ICM gas at different spatial locations in each simulation time step. Integrated abundance maps are produced. We then project photons and construct mock X-ray images to investigate the relationship between ICM metallicity and observable information.

Tracing the Chemical Evolution of Metal-rich Galactic Bulge Globular Clusters

NASA Astrophysics Data System (ADS)

Munoz Gonzalez, Cesar; Saviane, Ivo; Geisler, Doug; Villanova, Sandro

2018-01-01

We present in this poster the metallicity characterization of the four metal rich Bulge Galactic Gobular Clusters, which have controversial metallicities. We analyzed our high-resolution spectra (using UVES-580nm and GIRAFFE-HR13 setups) for a large sample of RGB/AGB targets in each cluster in order to measure their metallicity and prove or discard the iron spread hypothesis. We have also characterized chemically stars with potentially different iron content by measuring light (O, Na, Mg, Al), alpha (Si, Ca, Ti), iron–peak (V, Cr, Ni, Mn) and s and r process (Y, Zr, Ba, Eu) elements. We have identified possible channels responsible for the chemical heterogeneity of the cluster populations, like AGB or massive fast-rotating stars contamination, or SN explosion. Also, we have analyzed the origin and evolution of these bulge GCs and their connection with the bulge itself.

Special and general superatoms.

PubMed

Luo, Zhixun; Castleman, A Welford

2014-10-21

Bridging the gap between atoms and macroscopic matter, clusters continue to be a subject of increasing research interest. Among the realm of cluster investigations, an exciting development is the realization that chosen stable clusters can mimic the chemical behavior of an atom or a group of the periodic table of elements. This major finding known as a superatom concept was originated experimentally from the study of aluminum cluster reactivity conducted in 1989 by noting a dramatic size dependence of the reactivity where cluster anions containing a certain number of Al atoms were unreactive toward oxygen while the other species were etched away. This observation was well interpreted by shell closings on the basis of the jellium model, and the related concept (originally termed "unified atom") spawned a wide range of pioneering studies in the 1990s pertaining to the understanding of factors governing the properties of clusters. Under the inspiration of a superatom concept, advances in cluster science in finding stable species not only shed light on magic clusters (i.e., superatomic noble gas) but also enlightened the exploration of stable clusters to mimic the chemical behavior of atoms leading to the discovery of superhalogens, alkaline-earth metals, superalkalis, etc. Among them, certain clusters could enable isovalent isomorphism of precious metals, indicating application potential for inexpensive superatoms for industrial catalysis, while a few superalkalis were found to validate the interesting "harpoon mechanism" involved in the superatomic cluster reactivity; recently also found were the magnetic superatoms of which the cluster-assembled materials could be used in spin electronics. Up to now, extensive studies in cluster science have allowed the stability of superatomic clusters to be understood within a few models, including the jellium model, also aromaticity and Wade-Mingos rules depending on the geometry and metallicity of the cluster. However, the scope of application of the jellium model and modification of the theory to account for nonspherical symmetry and nonmetal-doped metal clusters are still illusive to be further developed. It is still worth mentioning that a superatom concept has also been introduced in ligand-stabilized metal clusters which could also follow the major shell-closing electron count for a spherical, square-well potential. By proposing a new concept named as special and general superatoms, herein we try to summarize all these investigations in series, expecting to provide an overview of this field with a primary focus on the joint undertakings which have given rise to the superatom concept. To be specific, for special superatoms, we limit to clusters under a strict jellium model and simply classify them into groups based on their valence electron counts. While for general superatoms we emphasize on nonmetal-doped metal clusters and ligand-stabilized metal clusters, as well as a few isovalent cluster systems. Hopefully this summary of special and general superatoms benefits the further development of cluster-related theory, and lights up the prospect of using them as building blocks of new materials with tailored properties, such as inexpensive isovalent systems for industrial catalysis, semiconductive superatoms for transistors, and magnetic superatoms for spin electronics.

Enhanced electrocatalytic activity of the Au-electrodeposited Pt nanoparticles-coated conducting oxide for the quantum dot-sensitized solar cells

NASA Astrophysics Data System (ADS)

Yoon, Yeung-Pil; Kim, Jae-Hong; Kang, Soon-Hyung; Kim, Hyunsoo; Choi, Chel-Jong; Kim, Kyong-Kook; Ahn, Kwang-Soon

2014-08-01

Au was electrodeposited potentiostatically at 0.3 V for 5 min on nanoporous Pt nanoparticle-coated F-doped SnO2 (FTO/Pt) substrates. For comparison, Au-electrodeposited FTO (FTO/Au) and Au-uncoated FTO/Pt were prepared. FTO/Au showed large-sized Au clusters dispersed sparsely over FTO, which resulted in lower electrocatalytic activity than FTO/Pt. In contrast, FTO/Pt exhibited poor stability unlike FTO/Au due to poisoning by the adsorption of sulfur species. The Au-electrodeposited FTO/Pt (FTO/Pt/Au) consisted of small Au clusters deposited over the entire area of Pt due to the effective Au nucleation provided by nanoporous metallic Pt. FTO/Pt/Au exhibited enhanced electrocatalytic activity and excellent stability because the small Au particles well-dispersed over the nanoporous metallic Pt network provided numerous electrochemical reaction sites, and the Pt surface was not exposed to the electrolyte. When FTO/Pt/Au was used as the counter electrode (CE) of a quantum dot-sensitized solar cell, the significantly enhanced electrocatalytic activity of the FTO/Pt/Au CE facilitated the reduction reaction of Sn2- + 2e- (CE) → Sn-12- + S2- at the CE/electrolyte interface, resulting in a significantly hindered recombination reaction, Sn2- + 2e- (TiO2 in the photoanode) → Sn-12- + S2-, and significantly improved overall energy conversion efficiency.

Time-Dependent Thomas-Fermi Approach for Electron Dynamics in Metal Clusters

NASA Astrophysics Data System (ADS)

Domps, A.; Reinhard, P.-G.; Suraud, E.

1998-06-01

We propose a time-dependent Thomas-Fermi approach to the (nonlinear) dynamics of many-fermion systems. The approach relies on a hydrodynamical picture describing the system in terms of collective flow. We investigate in particular an application to electron dynamics in metal clusters. We make extensive comparisons with fully fledged quantal dynamical calculations and find overall good agreement. The approach thus provides a reliable and inexpensive scheme to study the electronic response of large metal clusters.

Raman bands in Ag nanoparticles obtained in extract of Opuntia ficus-indica plant

NASA Astrophysics Data System (ADS)

Bocarando-Chacon, J.-G.; Cortez-Valadez, M.; Vargas-Vazquez, D.; Rodríguez Melgarejo, F.; Flores-Acosta, M.; Mani-Gonzalez, P. G.; Leon-Sarabia, E.; Navarro-Badilla, A.; Ramírez-Bon, R.

2014-05-01

Silver nanoparticles have been obtained in an extract of Opuntia ficus-indica plant. The size and distribution of nanoparticles were quantified by atomic force microscopy (AFM). The diameter was estimated to be about 15 nm. In addition, energy dispersive X-ray spectroscopy (EDX) peaks of silver were observed in these samples. Three Raman bands have been experimentally detected at 83, 110 and 160 cm-1. The bands at 83 and 110 cm-1 are assigned to the silver-silver Raman modes (skeletal modes) and the Raman mode located at 160 cm-1 has been assigned to breathing modes. Vibrational assignments of Raman modes have been carried out based on the Density Functional Theory (DFT) quantum mechanical calculation. Structural and vibrational properties for small Agn clusters with 2≤n≤9 were determined. Calculated Raman modes for small metal clusters have an approximation trend of Raman bands. These Raman bands were obtained experimentally for silver nanoparticles (AgNP).

[Dynamic study of small metallic clusters]; Estudio Dinamico de Pequenos Agregados Metalicos

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lopez, M.J.; Jellinek, J.

1995-12-31

We present a brief introduction to computer simulation techniques (particularly to classical molecular dynamics) and their application to the study of the thermodynamic properties of a material system. The basic concepts are illustrated in the study of structural and energetic properties such as the liquid-solid transition and the fragmentation of small clusters of nickel. [Espanol] Presentamos una breve introducci{acute o}n de las t{acute e}cnicas de simulaci{acute o}n por ordenador (en particular de la Din{acute a}mica Molecular cl{acute a}sica) y de su aplicaci{acute o}n al estudio de las propiedades termodin{acute a}micas de un sistema material. Los conceptos b{acute a}sicos se ilustranmore » en el estudio de las propieades estructurales y energ{acute e}ticas, as{acute i} como de la transici{acute o}n de fase s{acute o}lido-l{acute i}quido y de las fragmentaciones de peque{tilde n}os agregados de n{acute i}quel.« less

Anthropogenic sources and environmentally relevant concentrations of heavy metals in surface water of a mining district in Ghana: a multivariate statistical approach.

PubMed

Armah, Frederick A; Obiri, Samuel; Yawson, David O; Onumah, Edward E; Yengoh, Genesis T; Afrifa, Ernest K A; Odoi, Justice O

2010-11-01

The levels of heavy metals in surface water and their potential origin (natural and anthropogenic) were respectively determined and analysed for the Obuasi mining area in Ghana. Using Hawth's tool an extension in ArcGIS 9.2 software, a total of 48 water sample points in Obuasi and its environs were randomly selected for study. The magnitude of As, Cu, Mn, Fe, Pb, Hg, Zn and Cd in surface water from the sampling sites were measured by flame Atomic Absorption Spectrophotometry (AAS). Water quality parameters including conductivity, pH, total dissolved solids and turbidity were also evaluated. Principal component analysis and cluster analysis, coupled with correlation coefficient analysis, were used to identify possible sources of these heavy metals. Pearson correlation coefficients among total metal concentrations and selected water properties showed a number of strong associations. The results indicate that apart from tap water, surface water in Obuasi has elevated heavy metal concentrations, especially Hg, Pb, As, Cu and Cd, which are above the Ghana Environmental Protection Agency (GEPA) and World Health Organisation (WHO) permissible levels; clearly demonstrating anthropogenic impact. The mean heavy metal concentrations in surface water divided by the corresponding background values of surface water in Obuasi decrease in the order of Cd > Cu > As > Pb > Hg > Zn > Mn > Fe. The results also showed that Cu, Mn, Cd and Fe are largely responsible for the variations in the data, explaining 72% of total variance; while Pb, As and Hg explain only 18.7% of total variance. Three main sources of these heavy metals were identified. As originates from nature (oxidation of sulphide minerals particularly arsenopyrite-FeAsS). Pb derives from water carrying drainage from towns and mine machinery maintenance yards. Cd, Zn, Fe and Mn mainly emanate from industry sources. Hg mainly originates from artisanal small-scale mining. It cannot be said that the difference in concentration of heavy metals might be attributed to difference in proximity to mining-related activities because this is inconsistent with the cluster analysis. Based on cluster analysis SN32, SN42 and SN43 all belong to group one and are spatially similar. But the maximum Cu concentration was found in SN32 while the minimum Cu concentration was found in SN42 and SN43.

Significant Transient Mobility of Platinum Clusters via a Hot Precursor State on the Alumina Surface.

PubMed

Beniya, Atsushi; Hirata, Hirohito; Watanabe, Yoshihide

2016-11-17

Relaxation dynamics of hot metal clusters on oxide surfaces play a crucial role in a variety of physical and chemical processes. However, their transient mobility has not been investigated as much as other systems such as atoms and molecules on metal surfaces due to experimental difficulties. To study the role of the transient mobility of clusters on the oxide surface, we investigated the initial adsorption process of size-selected Pt clusters on a thin Al 2 O 3 film. Soft-landing the size-selected clusters while suppressing the thermal migration resulted in the transient migration controlling the initial adsorption states as an isolated and aggregated cluster, as revealed using scanning tunneling microscopy. We demonstrate that transient migration significantly contributes to the initial cluster adsorption process; the cross section for aggregation is seven times larger than the expected value from geometrical considerations, indicating that metal clusters are highly mobile during a energy dissipation process on the oxide surface.

Globular cluster chemistry in fast-rotating dwarf stars belonging to intermediate-age open clusters

NASA Astrophysics Data System (ADS)

Pancino, Elena

2018-06-01

The peculiar chemistry observed in multiple populations of Galactic globular clusters is not generally found in other systems such as dwarf galaxies and open clusters, and no model can currently fully explain it. Exploring the boundaries of the multiple-population phenomenon and the variation of its extent in the space of cluster mass, age, metallicity, and compactness has proven to be a fruitful line of investigation. In the framework of a larger project to search for multiple populations in open clusters that is based on literature and survey data, I found peculiar chemical abundance patterns in a sample of intermediate-age open clusters with publicly available data. More specifically, fast-rotating dwarf stars (v sin i ≥ 50 km s-1) that belong to four clusters (Pleiades, Ursa Major, Come Berenices, and Hyades) display a bimodality in either [Na/Fe] or [O/Fe], or both, with the low-Na and high-O peak more populated than the high-Na and low-O peak. Additionally, two clusters show a Na-O anti-correlation in the fast-rotating stars, and one cluster shows a large [Mg/Fe] variation in stars with high [Na/Fe], reaching the extreme Mg depletion observed in NGC 2808. Even considering that the sample sizes are small, these patterns call for attention in the light of a possible connection with the multiple population phenomenon of globular clusters. The specific chemistry observed in these fast-rotating dwarf stars is thought to be produced by a complex interplay of different diffusion and mixing mechanisms, such as rotational mixing and mass loss, which in turn are influenced by metallicity, binarity, mass, age, variability, and so on. However, with the sample in hand, it was not possible to identify which stellar parameters cause the observed Na and O bimodality and Na-O anti-correlation. This suggests that other stellar properties might be important in addition to stellar rotation. Stellar binarity might influence the rotational properties and enhance rotational mixing and mass loss of stars in a dense environment like that of clusters (especially globulars). In conclusion, rotation and binarity appear as a promising research avenue for better understanding multiple stellar populations in globular clusters; this is certainly worth exploring further.

The colour-magnitude relation of globular clusters in Centaurus and Hydra. Constraints on star cluster self-enrichment with a link to massive Milky Way globular clusters

NASA Astrophysics Data System (ADS)

Fensch, J.; Mieske, S.; Müller-Seidlitz, J.; Hilker, M.

2014-07-01

Aims: We investigate the colour-magnitude relation of metal-poor globular clusters, the so-called blue tilt, in the Hydra and Centaurus galaxy clusters and constrain the primordial conditions for star cluster self-enrichment. Methods: We analyse U,I photometry for about 2500 globular clusters in the central regions of Hydra and Centaurus, based on VLT/FORS1 data. We measure the relation between mean colour and luminosity for the blue and red subpopulation of the globular cluster samples. We convert these relations into mass-metallicity space and compare the obtained GC mass-metallicity relation with predictions from the star cluster self-enrichment model by Bailin & Harris (2009, ApJ, 695, 1082). For this we include effects of dynamical and stellar evolution and a physically well motivated primordial mass-radius scaling. Results: We obtain a mass-metallicity scaling of Z ∝ M0.27 ± 0.05 for Centaurus GCs and Z ∝ M0.40 ± 0.06 for Hydra GCs, consistent with the range of observed relations in other environments. We find that the GC mass-metallicity relation already sets in at present-day masses of a few and is well established in the luminosity range of massive MW clusters like ω Centauri. The inclusion of a primordial mass-radius scaling of star clusters significantly improves the fit of the self-enrichment model to the data. The self-enrichment model accurately reproduces the observed relations for average primordial half-light radii rh ~ 1-1.5 pc, star formation efficiencies f⋆ ~ 0.3-0.4, and pre-enrichment levels of [Fe/H] - 1.7 dex. The slightly steeper blue tilt for Hydra can be explained either by a ~30% smaller average rh at fixed f⋆ ~ 0.3, or analogously by a ~20% smaller f⋆ at fixed rh ~ 1.5 pc. Within the self-enrichment scenario, the observed blue tilt implies a correlation between GC mass and width of the stellar metallicity distribution. We find that this implied correlation matches the trend of width with GC mass measured in Galactic GCs, including extreme cases like ω Centauri and M 54. Conclusions: First, we found that a primordial star cluster mass-radius relation provides a significant improvement to the self-enrichment model fits. Second we show that broadened metallicity distributions as found in some massive MW globular clusters may have arisen naturally from self-enrichment processes, without the need of a dwarf galaxy progenitor.

Small gas-phase dianions produced by sputtering and gas flooding

DOE Office of Scientific and Technical Information (OSTI.GOV)

Franzreb, Klaus; Williams, Peter

2005-12-08

We have extended our previous experiment [Schauer et al., Phys. Rev. Lett. 65, 625 (1990)] where we had produced small gas-phase dianion clusters of C{sub n}{sup 2-}(n{>=}7) by means of sputtering a graphite surface by Cs{sup +} ion bombardment. Our detection sensitivity for small C{sub n}{sup 2-} could now be increased by a factor of about 50 for odd n. Nevertheless, a search for the elusive pentamer dianion of C{sub 5}{sup 2-} was not successful. As an upper limit, the sputtered flux of C{sub 5}{sup 2-} must be at least a factor of 5000 lower than that of C{sub 7}{supmore » 2-}, provided that the lifetime of C{sub 5}{sup 2-} is sufficiently long to allow its detection by mass spectrometry. When oxygen gas (flooding with either O{sub 2} or with N{sub 2}O) was supplied to the Cs{sup +}-bombarded graphite surface, small dianions of OC{sub n}{sup 2-}(5{<=}n{<=}14) and O{sub 2}C{sub 7}{sup 2-} were observed in addition to C{sub n}{sup 2-}(n{>=}7). Similarly, Cs{sup +} sputtering of graphite with simultaneous SF{sub 6} gas flooding produced SC{sub n}{sup 2-}(6{<=}n{<=}18). Mixed nitrogen-carbon or fluorine-carbon dianion clusters could not be observed by these means. Attempts to detect mixed metal-fluoride dianions for SF{sub 6} gas flooding of various Cs{sup +}-bombarded metal surfaces were successful for the case of Zr, where metastable ZrF{sub 6}{sup 2-} was observed. Cs{sup +} bombardment of a silicon carbide (SiC) wafer produced SiC{sub n}{sup 2-} (n=6,8,10). When oxygen gas was supplied to the Cs{sup +}-bombarded SiC surface, small dianions of SiOC{sub n}{sup 2-} (n=4,6,8) and of SiO{sub 2}C{sub n}{sup 2-} (n=4,6) as well as a heavier unidentified dianion (at m/z=98.5) were observed. For toluene (C{sub 7}H{sub 8}) vapor flooding of a Cs{sup +}-bombarded graphite surface, several hydrocarbon dianion clusters of C{sub n}H{sub m}{sup 2-}(n{>=}7) were produced in addition to C{sub n}{sup 2-}(n{>=}7), while smaller C{sub n}H{sub m}{sup 2-} with n{<=}6 could not be observed. BeC{sub n}{sup 2-} (n=4,6,8,10), Be{sub 2}C{sub 6}{sup 2-}, as well as BeC{sub 8}H{sub m}{sup 2-} (with m=2 and/or m=1) were observed for toluene vapor flooding of a Cs{sup +}-bombarded beryllium metal foil. The metastable pentamer {sup 9}Be{sup 12}C{sub 4}{sup 2-} at m/z=28.5 was the smallest and lightest dianion molecule that we could detect. The small dianion clusters of SC{sub n}{sup 2-}, OC{sub n}{sup 2-}, BeC{sub n}{sup 2-}, and SiO{sub m}C{sub n}{sup 2-} (m=0,1,2) have different abundance patterns. A resemblance exists between the abundance patterns of BeC{sub n}{sup 2-} and SiC{sub n}{sup 2-}, even though calculated molecular structures of BeC{sub 6}{sup 2-} and SiC{sub 6}{sup 2-} are different. The abundance pattern of SC{sub n}{sup 2-} is fairly similar to that of C{sub n}{sup 2-}.« less

Integrated light chemical tagging analyses of seven M31 outer halo globular clusters from the Pan-Andromeda Archaeological Survey

NASA Astrophysics Data System (ADS)

Sakari, Charli M.; Venn, Kim A.; Mackey, Dougal; Shetrone, Matthew D.; Dotter, Aaron; Ferguson, Annette M. N.; Huxor, Avon

2015-04-01

Detailed chemical abundances are presented for seven M31 outer halo globular clusters (with projected distances from M31 greater than 30 kpc), as derived from high-resolution integrated light spectra taken with the Hobby-Eberly Telescope. Five of these clusters were recently discovered in the Pan-Andromeda Archaeological Survey (PAndAS) - this paper presents the first determinations of integrated Fe, Na, Mg, Ca, Ti, Ni, Ba, and Eu abundances for these clusters. Four of the target clusters (PA06, PA53, PA54, and PA56) are metal poor ([Fe/H] < -1.5), α-enhanced (though they are possibly less α-enhanced than Milky Way stars at the 1σ level), and show signs of star-to-star Na and Mg variations. The other three globular clusters (H10, H23, and PA17) are more metal rich, with metallicities ranging from [Fe/H] = -1.4 to -0.9. While H23 is chemically similar to Milky Way field stars, Milky Way globular clusters, and other M31 clusters, H10 and PA17, have moderately low [Ca/Fe], compared to Milky Way field stars and clusters. Additionally, PA17's high [Mg/Ca] and [Ba/Eu] ratios are distinct from Milky Way stars, and are in better agreement with the stars and clusters in the Large Magellanic Cloud. None of the clusters studied here can be conclusively linked to any of the identified streams from PAndAS; however, based on their locations, kinematics, metallicities, and detailed abundances, the most metal-rich PAndAS clusters H23 and PA17 may be associated with the progenitor of the Giant Stellar Stream, H10 may be associated with the SW cloud, and PA53 and PA56 may be associated with the eastern cloud.

Structure of overheated metal clusters: MD simulation study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vorontsov, Alexander

2015-08-17

The structure of overheated metal clusters appeared in condensation process was studied by computer simulation techniques. It was found that clusters with size larger than several tens of atoms have three layers: core part, intermediate dense packing layer and a gas- like shell with low density. The change of the size and structure of these layers with the variation of internal energy and the size of cluster is discussed.

Metal Cluster Models for Heterogeneous Catalysis: A Matrix-Isolation Perspective.

PubMed

Hübner, Olaf; Himmel, Hans-Jörg

2018-02-19

Metal cluster models are of high relevance for establishing new mechanistic concepts for heterogeneous catalysis. The high reactivity and particular selectivity of metal clusters is caused by the wealth of low-lying electronically excited states that are often thermally populated. Thereby the metal clusters are flexible with regard to their electronic structure and can adjust their states to be appropriate for the reaction with a particular substrate. The matrix isolation technique is ideally suited for studying excited state reactivity. The low matrix temperatures (generally 4-40 K) of the noble gas matrix host guarantee that all clusters are in their electronic ground-state (with only a very few exceptions). Electronically excited states can then be selectively populated and their reactivity probed. Unfortunately, a systematic research in this direction has not been made up to date. The purpose of this review is to provide the grounds for a directed approach to understand cluster reactivity through matrix-isolation studies combined with quantum chemical calculations. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nanocavity formation processes in MgO( 1 0 0 ) by light ion (D, He, Li) and heavy ion (Kr, Cu, Au) implantation

NASA Astrophysics Data System (ADS)

van Veen, A.; van Huis, M. A.; Fedorov, A. V.; Schut, H.; Labohm, F.; Kooi, B. J.; De Hosson, J. Th. M.

2002-05-01

In studies on the controlled growth of metallic precipitates in MgO it is attempted to use nanometer size cavities as precursors for formation of metallic precipitates. In MgO nanocavities can easily be generated by light gas ion bombardment at room temperature with typically 30 keV ion energy to a dose of 10 16 cm -2, followed by annealing to 1300 K. It has been shown earlier by transmission electron microscopy (TEM) that the cavities (thickness 2-3 nm and length/width 5-10 nm) have a perfectly rectangular shape bounded by {1 0 0} faces. The majority of the gas has been released at this temperature and the cavities are stable until annealing at 1500 K. The depth location of the cavities and the implanted ions is monitored by positron beam analysis, neutron depth profiling, RBS/channeling and energy dispersive spectroscopy. The presence of metallic nanoprecipitates is detected by optical absorption measurements and by high-resolution XTEM. Surprisingly, all the metallic implants induce, in addition to metallic precipitates in a band at the mean ion range, small rectangular and cubic nanocavities. These are most clearly observed at a depth shallower than the precipitate band. In the case of gold the cavities are produced in close proximity to the crystal surface. The results indicate that in MgO vacancy clustering dominates over Frenkel-pair recombination. Results of molecular dynamics calculations will be used to discuss the observed defect recovery and clustering processes in MgO.

Employing a portable X-Ray fluorescence (P-XRF) analyser and GIS to identify and map heavy metal pollution in soils of a traditional bonfire site

NASA Astrophysics Data System (ADS)

Dao, Ligang; Zhang, Chaosheng; Morrison, Liam

2010-05-01

Soils in the vicinity of bonfires are recipients of metal contaminants from burning of metal-containing materials. In order to better understand the impacts of bonfires on soils, a total of 218 surface soil samples were collected from a traditional bonfire site in Galway City, Ireland. Concentrations of Cu, Pb and Zn were determined using a portable X-ray Fluorescence (P-XRF) analyser. Strong variations were observed for these metals, and several samples contained elevated Zn concentrations which exceeded the intervention threshold of the Dutch criteria (720 mg kg-1). Spatial clusters and spatial outliers were detected using the local Moran's I index and were mapped using GIS. Two clear high value spatial clusters could be observed on the upper left side and centre part of the study area for Cu, Pb and Zn. Results of variogram analyses showed high nugget-sill-ratios for Cu, Pb and Zn, indicating strong spatial variation over short distances which could be resulted from anthropogenic activities. The spatial interpolation method of ordinary kriging was applied to produce the spatial interpolation maps for Cu, Pb and Zn, and the areas with elevated concentrations were in line with historical locations of the bonfires. The hazard maps showed small parts of the study area with Zn concentrations exceeding the Dutch intervention values. In order to prevent further contamination from bonfires, it is advised that tyres and other metal-containing wastes should not be burnt. The results in this study provide useful information for management of bonfires.

Chemical Enrichment History Of Abell 3112 Galaxy Cluster Out To The Virial Radius

NASA Astrophysics Data System (ADS)

Ezer, C.; Bulbul, E.; Ercan, E.; Smith, R.; Bautz, M.; Loewenstein, M.; McDonald, M.; Miller, E.

2017-10-01

The deep potential well of the galaxy clusters confines all metals produced via supernova explosions within the intra-cluster medium (ICM). The radial distributions of these metals along the ICM are direct records of the metal enrichment history. In this work, we investigate the chemical enrichment history of Abell 3112 galaxy cluster from cluster's core to out to radius R_{200} (˜ 1470 kpc) by analyzing a deep 1.2 Ms Suzaku observations with overlapping 72 ks Chandra observations. The fraction of supernova explosions enriching the ICM is obtained by fitting the X-ray spectra with a robust snapec model implemented in XSPEC. The ratio of supernova type Ia explosions to the core collapse supernova explosions is found in the range 0.12 - 0.16 and uniformly distributed out to R_{200}. The uniform spatial distribution of supernova enrichment indicates an early metal enrichment between the epoch of z ˜ 2 - 3. We also observe that W7, CDD, and WDD SN Ia models equally better explain the highest signal-to-noise region compared to 2D delayed detonation model CDDT. We further report the first time temperature (3.37 ± 0.77 keV) and metallicity (0.22 ± 0.08 Z_{⊙}) measurements of this archetypal cluster at its virial radius.

Estimating metallicities with isochrone fits to photometric data of open clusters

NASA Astrophysics Data System (ADS)

Monteiro, H.; Oliveira, A. F.; Dias, W. S.; Caetano, T. C.

2014-10-01

The metallicity is a critical parameter that affects the correct determination of stellar cluster's fundamental characteristics and has important implications in Galactic and Stellar evolution research. Fewer than 10% of the 2174 currently catalogued open clusters have their metallicity determined in the literature. In this work we present a method for estimating the metallicity of open clusters via non-subjective isochrone fitting using the cross-entropy global optimization algorithm applied to UBV photometric data. The free parameters distance, reddening, age, and metallicity are simultaneously determined by the fitting method. The fitting procedure uses weights for the observational data based on the estimation of membership likelihood for each star, which considers the observational magnitude limit, the density profile of stars as a function of radius from the center of the cluster, and the density of stars in multi-dimensional magnitude space. We present results of [Fe/H] for well-studied open clusters based on distinct UBV data sets. The [Fe/H] values obtained in the ten cases for which spectroscopic determinations were available in the literature agree, indicating that our method provides a good alternative to estimating [Fe/H] by using an objective isochrone fitting. Our results show that the typical precision is about 0.1 dex.

Reduction potentials of heterometallic manganese–oxido cubane complexes modulated by redox-inactive metals

PubMed Central

Tsui, Emily Y.; Agapie, Theodor

2013-01-01

Understanding the effect of redox-inactive metals on the properties of biological and heterogeneous water oxidation catalysts is important both fundamentally and for improvement of future catalyst designs. In this work, heterometallic manganese–oxido cubane clusters [MMn3O4] (M = Sr2+, Zn2+, Sc3+, Y3+) structurally relevant to the oxygen-evolving complex (OEC) of photosystem II were prepared and characterized. The reduction potentials of these clusters and other related mixed metal manganese–tetraoxido complexes are correlated with the Lewis acidity of the apical redox-inactive metal in a manner similar to a related series of heterometallic manganese–dioxido clusters. The redox potentials of the [SrMn3O4] and [CaMn3O4] clusters are close, which is consistent with the observation that the OEC is functional only with one of these two metals. Considering our previous studies of [MMn3O2] moieties, the present results with more structurally accurate models of the OEC ([MMn3O4]) suggest a general relationship between the reduction potentials of heterometallic oxido clusters and the Lewis acidities of incorporated cations that applies to diverse structural motifs. These findings support proposals that one function of calcium in the OEC is to modulate the reduction potential of the cluster to allow electron transfer. PMID:23744039

Imaging nanoclusters in the constant height mode of the dynamic SFM.

PubMed

Barth, Clemens; Pakarinen, Olli H; Foster, Adam S; Henry, Claude R

2006-04-14

For the first time, high quality images of metal nanoclusters which were recorded in the constant height mode of a dynamic scanning force microscope (dynamic SFM) are shown. Surfaces of highly ordered pyrolytic graphite (HOPG) were used as a test substrate since metal nanoclusters with well defined and symmetric shapes can be created by epitaxial growth. We performed imaging of gold clusters with sizes between 5 and 15 nm in both scanning modes, constant Δf mode and constant height mode, and compared the image contrast. We notice that clusters in constant height images appear much sharper, and exhibit more reasonable lateral shapes and sizes in comparison to images recorded in the constant Δf mode. With the help of numerical simulations we show that only a microscopically small part of the tip apex (nanotip) is probably the main contributor for the image contrast formation. In principle, the constant height mode can be used for imaging surfaces of any material, e.g. ionic crystals, as shown for the system Au/NaCl(001).

From clusters to bulk: A relativistic density functional investigation on a series of gold clusters Aun, n=6,…,147

NASA Astrophysics Data System (ADS)

Häberlen, Oliver D.; Chung, Sai-Cheong; Stener, Mauro; Rösch, Notker

1997-03-01

A series of gold clusters spanning the size range from Au6 through Au147 (with diameters from 0.7 to 1.7 nm) in icosahedral, octahedral, and cuboctahedral structure has been theoretically investigated by means of a scalar relativistic all-electron density functional method. One of the main objectives of this work was to analyze the convergence of cluster properties toward the corresponding bulk metal values and to compare the results obtained for the local density approximation (LDA) to those for a generalized gradient approximation (GGA) to the exchange-correlation functional. The average gold-gold distance in the clusters increases with their nuclearity and correlates essentially linearly with the average coordination number in the clusters. An extrapolation to the bulk coordination of 12 yields a gold-gold distance of 289 pm in LDA, very close to the experimental bulk value of 288 pm, while the extrapolated GGA gold-gold distance is 297 pm. The cluster cohesive energy varies linearly with the inverse of the calculated cluster radius, indicating that the surface-to-volume ratio is the primary determinant of the convergence of this quantity toward bulk. The extrapolated LDA binding energy per atom, 4.7 eV, overestimates the experimental bulk value of 3.8 eV, while the GGA value, 3.2 eV, underestimates the experiment by almost the same amount. The calculated ionization potentials and electron affinities of the clusters may be related to the metallic droplet model, although deviations due to the electronic shell structure are noticeable. The GGA extrapolation to bulk values yields 4.8 and 4.9 eV for the ionization potential and the electron affinity, respectively, remarkably close to the experimental polycrystalline work function of bulk gold, 5.1 eV. Gold 4f core level binding energies were calculated for sites with bulk coordination and for different surface sites. The core level shifts for the surface sites are all positive and distinguish among the corner, edge, and face-centered sites; sites in the first subsurface layer show still small positive shifts.

Reactions of mixed silver-gold cluster cations AgmAun+ (m+n=4,5,6) with CO: Radiative association kinetics and density functional theory computations

NASA Astrophysics Data System (ADS)

Neumaier, Marco; Weigend, Florian; Hampe, Oliver; Kappes, Manfred M.

2006-09-01

Near thermal energy reactive collisions of small mixed metal cluster cations AgmAun+ (m +n=4, 5, and 6) with carbon monoxide have been studied in the room temperature Penning trap of a Fourier transform ion-cyclotron-resonance mass spectrometer as a function of cluster size and composition. The tetrameric species AgAu3+ and Ag2Au2+ are found to react dissociatively by way of Au or Ag atom loss, respectively, to form the cluster carbonyl AgAu2CO+. In contrast, measurements on a selection of pentamers and hexamers show that CO is added with absolute rate constants that decrease with increasing silver content. Experimentally determined absolute rate constants for CO adsorption were analyzed using the radiative association kinetics model to obtain cluster cation-CO binding energies ranging from 0.77to1.09eV. High-level ab initio density functional theory (DFT) computations identifying the lowest-energy cluster isomers and the respective CO adsorption energies are in good agreement with the experimental findings clearly showing that CO binds in a "head-on" fashion to a gold atom in the mixed clusters. DFT exploration of reaction pathways in the case of Ag2Au2+ suggests that exoergicities are high enough to access the minimum energy products for all reactive clusters probed.

Microwave Heating of Metal Power Clusters

NASA Astrophysics Data System (ADS)

Rybakov, K. I.; Semenov, V. E.; Volkovskaya, I. I.

2018-01-01

The results of simulating the rapid microwave heating of spherical clusters of metal particles to the melting point are reported. In the simulation, the cluster is subjected to a plane electromagnetic wave. The cluster size is comparable to the wavelength; the perturbations of the field inside the cluster are accounted for within an effective medium approximation. It is shown that the time of heating in vacuum to the melting point does not exceed 1 s when the electric field strength in the incident wave is about 2 kV/cm at a frequency of 24 GHz or 5 kV/cm at a frequency of 2.45 GHz. The obtained results demonstrate feasibility of using rapid microwave heating for the spheroidization of metal particles with an objective to produce high-quality powders for additive manufacturing technologies.

Star clusters: age, metallicity and extinction from integrated spectra

NASA Astrophysics Data System (ADS)

González Delgado, Rosa M.; Cid Fernandes, Roberto

2010-01-01

Integrated optical spectra of star clusters in the Magellanic Clouds and a few Galactic globular clusters are fitted using high-resolution spectral models for single stellar populations. The goal is to estimate the age, metallicity and extinction of the clusters, and evaluate the degeneracies among these parameters. Several sets of evolutionary models that were computed with recent high-spectral-resolution stellar libraries (MILES, GRANADA, STELIB), are used as inputs to the starlight code to perform the fits. The comparison of the results derived from this method and previous estimates available in the literature allow us to evaluate the pros and cons of each set of models to determine star cluster properties. In addition, we quantify the uncertainties associated with the age, metallicity and extinction determinations resulting from variance in the ingredients for the analysis.

Assessment of eco-environmental geochemistry of heavy metals pollution of the river Gandak, a major tributary of the river Ganga in Northern India

NASA Astrophysics Data System (ADS)

Singh, Harendra; Kushwaha, Alok; Shukla, D. N.

2018-04-01

This study includes a seasonal analysis of sediment contamination of the River Gandak by heavy metals. It passes through the many small, medium and big cities of Uttar Pradesh and Bihar in Indian Territory. To explore the geochemical condition of the streambed sediment of the river, seven heavy metals, namely Co, Cu, Cr, Ni, Cd, Zn and Pb were analyzed. The newly deposited river bed sediment tests gathered on a seasonal basis from five stations for the years 2013-14 and 2014-15. Level of heavy metals in the sediments of the river was measured in the range between 10.54-16.78mg/kg for Co, 6.78-23.97mg/kg for Cu, 16.56-23.17mg/kg forCr, 9.71-18.11mg/kg for Ni, 0.364-1.068mg/kg forCd), 30.54-51.09mg/kg for Zn, 12.21-17.01mg/kg for Pb. Anthropogenic addition of heavy metals into the stream was controlled by utilizing metal Contamination Factor. Geo-accumulation values were found between (0-1) which indicates that sediment was uncontaminated to moderately contaminated, and can adversely influence the freshwater ecosystem of the river. A Good correlation was noted between Co, Zn, Pb, Ni, and Cu. Cluster analysis demonstrated three cluster groups of sites, which indicate that the metals originate from the same source mainly due to natural weathering of rocks, atmospheric deposition, human settlement and agriculture activity and is additionally confirmed by correlation analysis. However, on the basis of contamination indicators, it was found that the stream bed sediment is slightly contaminated with toxic metals. The conditions may harmful in the future because of the fast population growth in the river basin which might bring about irreparable biological harm in the long haul.

Self Assembly Nonlinear Optical Effects with Novel Small Metal Cluster Systems

DTIC Science & Technology

2013-07-29

Regents of the University of Michigan 3003 S. State St Ann Arbor, MI 48109 -1274 REPORT DOCUMENTATION PAGE b . ABSTRACT UU c. THIS PAGE UU 2. REPORT TYPE...Journal of Physical Chemistry Letters, (09 2011): 0. doi: 10.1021/jz200738t 10/30/2011 4.00 Travis B . Clark, Meghan E. Orr, Daniel C. Flynn, Theodore...jp2005925 10/30/2011 5.00 Mary Sajini Devadas , Junhyung Kim, Ekkehard Sinn, Dongil Lee, Theodore Goodson, Guda Ramakrishna. Unique Ultrafast Visible

Dehydration, Dehydrogenation, and Condensation of Alcohols on Supported Oxide Catalysts Based on Cyclic (WO3)3 and (MoO3)3 Clusters

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rousseau, Roger J.; Dixon, David A.; Kay, Bruce D.

2014-01-01

Supported early transition metal oxides have important applications in numerous catalytic reactions. In this article we review preparation and activity of well-defined model WO3 and MoO3 catalysts prepared via deposition of cyclic gas-phase (WO3)3 and (MoO3)3 clusters generated by sublimation of WO3 and MoO3 powders. Conversion of small aliphatic alcohols to alkenes, aldehydes/ketons, and ethers is employed to probe the structure-activity relationships on model WO3 and MoO3 catalysts ranging from unsupported (WO3)3 and (MoO3)3 clusters embedded in alcohol matrices, to (WO3)3 clusters supported on surfaces of other oxides, and epitaxial and nanoporous WO3 films. Detailed theoretical calculations reveal the underlyingmore » reaction mechanisms and provide insight into the origin of the differences in the WO3 and MoO3 reactivity. For the range of interrogated (WO3)3 they further shed light into the role structure and binding of (WO3)3 clusters with the support play in determining their catalytic activity.« less

Energy-consistent small-core pseudopotentials for 3d-transition metals adapted to quantum Monte Carlo calculations.

PubMed

Burkatzki, M; Filippi, Claudia; Dolg, M

2008-10-28

We extend our recently published set of energy-consistent scalar-relativistic Hartree-Fock pseudopotentials by the 3d-transition metal elements, scandium through zinc. The pseudopotentials do not exhibit a singularity at the nucleus and are therefore suitable for quantum Monte Carlo (QMC) calculations. The pseudopotentials and the accompanying basis sets (VnZ with n=T,Q) are given in standard Gaussian representation and their parameter sets are presented. Coupled cluster, configuration interaction, and QMC studies are carried out for the scandium and titanium atoms and their oxides, demonstrating the good performance of the pseudopotentials. Even though the choice of pseudopotential form is motivated by QMC, these pseudopotentials can also be employed in other quantum chemical approaches.

Photophysical characterization of fluorescent metal nanoclusters synthesized using oligonucleotides, proteins and small molecule ligands

NASA Astrophysics Data System (ADS)

Yeh, Hsin-Chih; Sharma, Jaswinder; Yoo, Hyojong; Martinez, Jennifer S.; Werner, James H.

2010-02-01

The size transition from bulk conducting metals to insulating nanoparticles and eventually to single atoms passes through the relatively unexplored few-atom nanocluster region. With dimensions close to the Fermi wavelength, these nanoclusters demonstrate molecule-like properties distinct from bulk metals or atoms, such as discrete and size-tunable electronic transitions which lead to photoluminescence. Current research aims to elucidate the fundamental photophysical properties of metal nanoclusters made by different means and based on different encapsulation agents. Here, we report the study of the photophysical properties, including quantum yields, lifetimes, extinction coefficients, blinking dynamics and sizes, of silver and gold nanoclusters synthesized using oligonucleotides, a protein (bovine serum albumin) and a Good's buffer molecule (MES, 2-(N-morpholino) ethanesulfonic acid) as encapsulation agents. We also investigate the change of photoluminescence as a function of temperature. Furthermore, we show that the fluorescent metal clusters can be used as a donor in forming a resonance energy transfer pair with a commercial organic quencher. These new fluorophores have great potential as versatile tools for a broad range of applications in biological and chemical detection.

Structures and physical properties of gaseous metal cationized biological ions.

PubMed

Burt, Michael B; Fridgen, Travis D

2012-01-01

Metal chelation can alter the activity of free biomolecules by modifying their structures or stabilizing higher energy tautomers. In recent years, mass spectrometric techniques have been used to investigate the effects of metal complexation with proteins, nucleobases and nucleotides, where small conformational changes can have significant physiological consequences. In particular, infrared multiple photon dissociation spectroscopy has emerged as an important tool for determining the structure and reactivity of gas-phase ions. Unlike other mass spectrometric approaches, this method is able to directly resolve structural isomers using characteristic vibrational signatures. Other activation and dissociation methods, such as blackbody infrared radiative dissociation or collision-induced dissociation can also reveal information about the thermochemistry and dissociative pathways of these biological ions. This information can then be used to provide information about the structures of the ionic complexes under study. In this article, we review the use of gas-phase techniques in characterizing metal-bound biomolecules. Particular attention will be given to our own contributions, which detail the ability of metal cations to disrupt nucleobase pairs, direct the self-assembly of nucleobase clusters and stabilize non-canonical isomers of amino acids.

Variable Stars In the Unusual, Metal-Rich Globular Cluster

NASA Technical Reports Server (NTRS)

Pritzl, Barton J.; Smith, Horace A.; Catelan, Marcio; Sweigart, Allen V.; Oegerle, William R. (Technical Monitor)

2002-01-01

We have undertaken a search for variable stars in the metal-rich globular cluster NGC 6388 using time-series BV photometry. Twenty-eight new variables were found in this survey, increasing the total number of variables found near NGC 6388 to approx. 57. A significant number of the variables are RR Lyrae (approx. 14), most of which are probable cluster members. The periods of the fundamental mode RR Lyrae are shown to be unusually long compared to metal-rich field stars. The existence of these long period RRab stars suggests that the horizontal branch of NGC 6388 is unusually bright. This implies that the metallicity-luminosity relationship for RR Lyrae stars is not universal if the RR Lyrae in NGC 6388 are indeed metal-rich. We consider the alternative possibility that the stars in NGC 6388 may span a range in [Fe/H]. Four candidate Population II Cepheids were also found. If they are members of the cluster, NGC 6388 would be the most metal-rich globular cluster to contain Population II Cepheids. The mean V magnitude of the RR Lyrae is found to be 16.85 +/- 0.05 resulting in a distance of 9.0 to 10.3 kpc, for a range of assumed values of (M(sub V)) for RR Lyrae. We determine the reddening of the cluster to be E(B - V) = 0.40 +/- 0.03 mag, with differential reddening across the face of the cluster. We discuss the difficulty in determining the Oosterhoff classification of NGC 6388 and NGC 6441 due to the unusual nature of their RR Lyrae, and address evolutionary constraints on a recent suggestion that they are of Oosterhoff type II.

Fission of Polyanionic Metal Clusters

NASA Astrophysics Data System (ADS)

König, S.; Jankowski, A.; Marx, G.; Schweikhard, L.; Wolfram, M.

2018-04-01

Size-selected dianionic lead clusters Pbn2 -, n =34 - 56 , are stored in a Penning trap and studied with respect to their decay products upon photoexcitation. Contrary to the decay of other dianionic metal clusters, these lead clusters show a variety of decay channels. The mass spectra of the fragments are compared to the corresponding spectra of the monoanionic precursors. This comparison leads to the conclusion that, in the cluster size region below about n =48 , the fission reaction Pbn2 -→Pbn-10 -+Pb10- is the major decay process. Its disappearance at larger cluster sizes may be an indication of a nonmetal to metal transition. Recently, the pair of Pb10- and Pbn-10 - were observed as pronounced fragments in electron-attachment studies [S. König et al., Int. J. Mass Spectrom. 421, 129 (2017), 10.1016/j.ijms.2017.06.009]. The present findings suggest that this combination is the fingerprint of the decay of doubly charged lead clusters. With this assumption, the dianion clusters have been traced down to Pb212 -, whereas the smallest size for the direct observation was as high as n =28 .

Magnetism, structures and stabilities of cluster assembled TM@Si nanotubes (TM = Cr, Mn and Fe): a density functional study.

PubMed

Dhaka, Kapil; Bandyopadhyay, Debashis

2016-08-02

The present study reports transition metal (TM = Cr, Mn and Fe) doped silicon nanotubes with tunable band structures and magnetic properties by careful selection of cluster assemblies as building blocks using the first-principles density functional theory. We found that the transition metal doping and in addition, the hydrogen termination process can stabilize the pure silicon nanoclusters or cluster assemblies and then it could be extended as magnetic nanotubes with finite magnetic moments. Study of the band structures and density of states (DOS) of different empty and TM doped nanotubes (Type 1 to Type 4) show that these nanotubes are useful as metals, semiconductors, semi-metals and half-metals. These designer magnetic materials could be useful in spintronics and magnetic devices of nanoscale order.

Dissociation kinetics of metal clusters on multiple electronic states including electronic level statistics into the vibronic soup

NASA Astrophysics Data System (ADS)

Shvartsburg, Alexandre A.; Siu, K. W. Michael

2001-06-01

Modeling the delayed dissociation of clusters had been over the last decade a frontline development area in chemical physics. It is of fundamental interest how statistical kinetics methods previously validated for regular molecules and atomic nuclei may apply to clusters, as this would help to understand the transferability of statistical models for disintegration of complex systems across various classes of physical objects. From a practical perspective, accurate simulation of unimolecular decomposition is critical for the extraction of true thermochemical values from measurements on the decay of energized clusters. Metal clusters are particularly challenging because of the multitude of low-lying electronic states that are coupled to vibrations. This has previously been accounted for assuming the average electronic structure of a conducting cluster approximated by the levels of electron in a cavity. While this provides a reasonable time-averaged description, it ignores the distribution of instantaneous electronic structures in a "boiling" cluster around that average. Here we set up a new treatment that incorporates the statistical distribution of electronic levels around the average picture using random matrix theory. This approach faithfully reflects the completely chaotic "vibronic soup" nature of hot metal clusters. We found that the consideration of electronic level statistics significantly promotes electronic excitation and thus increases the magnitude of its effect. As this excitation always depresses the decay rates, the inclusion of level statistics results in slower dissociation of metal clusters.

Supersonic Bare Metal Cluster Beams. Final Report

DOE R&D Accomplishments Database

Smalley, R. E.

1997-10-14

A major portion of the project involved elucidating the relation between reactivity and the electronic structure of transition-metal (TM) clusters of 2--200 atoms, which required the construction and continuous development of two principal apparati; the Fourier Transform-Ion Cyclotron Resonance (FT-ICR) apparatus, and Ultraviolet Photoelectron Spectroscopy (UPS). Together, these machines have enabled the most detailed probing of the structure and chemical reactivity of TM clusters. Clusters of all the transition metals were included in these studies. Fundamental aspects in chemisorption, reactivity, and heterogeneous catalysis have also become better understood as a result of these experiments for important classes of systems such as H{sub 2}, CO, and CO{sub 2} adsorbed onto clusters of many of the metals listed above. In particular, a correlation was found between reactivity of H{sub 2} with Fe, Co, and Ni clusters and differences between the cluster IP and EA. As recounted in a previous technical report, the DOE`s role in the initial discovery of fullerenes at Rice was central, and from the start investigations were made into metal atoms trapped in the fullerenes cage. More recently, the authors have discovered that 2--4 atoms of La, Y, or Sc can be produced by laser vaporization of composite graphite/metal-oxide disks. This work was largely motivated by the prospects of using such endohedral TM metals for their catalytic activity without the well-known difficulties of effective support media and lack of control over particle size. Thus, while it will certainly be important to discover ways to efficiently scale up production (e.g., the solar generation method explored with DOE support), the efforts have concentrated more on characterization, purification, and manipulation of doped fullerenes. For the past two years, much of the group`s effort has involved the production, purification, and characterization of carbon nanotubes.

Ligand combination strategy for the preparation of novel low-dimensional and open-framework metal cluster materials

NASA Astrophysics Data System (ADS)

Anokhina, Ekaterina V.

Low-dimensional and open-framework materials containing transition metals have a wide range of applications in redox catalysis, solid-state batteries, and electronic and magnetic devices. This dissertation reports on research carried out with the goal to develop a strategy for the preparation of low-dimensional and open-framework materials using octahedral metal clusters as building blocks. Our approach takes its roots from crystal engineering principles where the desired framework topologies are achieved through building block design. The key idea of this work is to induce directional bonding preferences in the cluster units using a combination of ligands with a large difference in charge density. This investigation led to the preparation and characterization of a new family of niobium oxychloride cluster compounds with original structure types exhibiting 1ow-dimensional or open-framework character. Most of these materials have framework topologies unprecedented in compounds containing octahedral clusters. Comparative analysis of their structural features indicates that the novel cluster connectivity patterns in these systems are the result of complex interplay between the effects of anisotropic ligand arrangement in the cluster unit and optimization of ligand-counterion electrostatic interactions. The important role played by these factors sets niobium oxychloride systems apart from cluster compounds with one ligand type or statistical ligand distribution where the main structure-determining factor is the total number of ligands. These results provide a blueprint for expanding the ligand combination strategy to other transition metal cluster systems and for the future rational design of cluster-based materials.

Polar Intermetallics Pr 5Co 2Ge 3 and Pr 7Co 2Ge 4 With Planar Hydrocarbon-Like Metal Clusters

DOE PAGES

Lin, Qisheng; Aguirre, Kaiser; Saunders, Scott M.; ...

2017-06-19

Planar hydrocarbon-like metal clusters may foster new insights linking organic molecules with conjugated π-π bonding interactions and inorganic structures in terms of their bonding characteristics. However, such clusters are uncommon in polar intermetallics. Herein, we report two polar intermetallic phases, Pr 5Co 2Ge 3 and Pr 7Co 2Ge 4, both of which feature such planar metal clusters, viz., ethylene-like [Co 2Ge 4] clusters plus the concatenated forms and polyacene-like [Co 2Ge 2] n ribbons in Pr 5Co 2Ge 3, and 1,2,4,5-tetramethylbenzene-like [Co4Ge6] cluster in Pr 7Co 2Ge 4. Just as in the related planar organic structures, these metal-metalloid species aremore » dominated by covalent bonding interactions. Both compounds magnetically order at low temperature with net ferromagnetic components: Pr 5Co 2Ge 3 via a series of transitions below 150 K; and Pr 7Co 2Ge 4 via a single ferromagnetic transition at 19 K. Spin-polarized electronic structure calculations for Pr 7Co 2Ge 4 reveal strong spin-orbit coupling within Pr and considerable magnetic contributions from Co atoms. This work suggests that similar structural chemistry can emerge for other rare earth-late transition metal-main group systems.« less

A Simple MO Treatment of Metal Clusters.

ERIC Educational Resources Information Center

Sahyun, M. R. V.

1980-01-01

Illustrates how a qualitative description of the geometry and electronic characteristics of homogeneous metal clusters can be obtained using semiempirical MO (molecular orbital theory) methods. Computer applications of MO methods to inorganic systems are also described. (CS)

Richard E. Smalley, Buckminsterfullerene (the Buckyball), and Nanotubes

Science.gov Websites

: 723-730; July 1997 Supersonic Bare Metal Cluster Beams. Technical Progress Report, March 16, 1984  – April 1, 1985 Includes early cold ion beam technology research Supersonic Bare Metal Cluster Beams

The origin of the Milky Way globular clusters

NASA Astrophysics Data System (ADS)

Renaud, Florent; Agertz, Oscar; Gieles, Mark

2017-03-01

We present a cosmological zoom-in simulation of a Milky Way-like galaxy used to explore the formation and evolution of star clusters. We investigate in particular the origin of the bimodality observed in the colour and metallicity of globular clusters, and the environmental evolution through cosmic times in the form of tidal tensors. Our results self-consistently confirm previous findings that the blue, metal-poor clusters form in satellite galaxies that are accreted on to the Milky Way, while the red, metal-rich clusters form mostly in situ, or, to a lower extent, in massive, self-enriched galaxies merging with the Milky Way. By monitoring the tidal fields these populations experience, we find that clusters formed in situ (generally centrally concentrated) feel significantly stronger tides than the accreted ones, both in the present day, and when averaged over their entire life. Furthermore, we note that the tidal field experienced by Milky Way clusters is significantly weaker in the past than at present day, confirming that it is unlikely that a power-law cluster initial mass function like that of young massive clusters, is transformed into the observed peaked distribution in the Milky Way with relaxation-driven evaporation in a tidal field.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Platero-Prats, Ana E.; Li, Zhanyong; Gallington, Leighanne C.

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 ofin situsynchrotron-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 °Cmore » produces metallic Cu 0of 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 2O cuprite phase. The dynamic restructuring of the system in different chemical environments underscores the importance of probing these systemsin situ.« less

Controlled Expansion of a Strong-Field Iron Nitride Cluster: Multi-Site Ligand Substitution as a Strategy for Activating Interstitial Nitride Nucleophilicity.

PubMed

Drance, Myles J; Mokhtarzadeh, Charles C; Melaimi, Mohand; Agnew, Douglas W; Moore, Curtis E; Rheingold, Arnold L; Figueroa, Joshua S

2018-05-02

Multimetallic clusters have long been investigated as molecular surrogates for reactive sites on metal surfaces. In the case of the μ 4 -nitrido cluster [Fe 4 (μ 4 -N)(CO) 12 ] - , this analogy is limited owing to the electron-withdrawing effect of carbonyl ligands on the iron nitride core. Described here is the synthesis and reactivity of [Fe 4 (μ 4 -N)(CO) 8 (CNAr Mes2 ) 4 ] - , an electron-rich analogue of [Fe 4 (μ 4 -N)(CO) 12 ] - , where the interstitial nitride displays significant nucleophilicity. This characteristic enables rational expansion with main-group and transition-metal centers to yield unsaturated sites. The resulting clusters display surface-like reactivity through coordination-sphere-dependent atom rearrangement and metal-metal cooperativity. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

LOW-METALLICITY YOUNG CLUSTERS IN THE OUTER GALAXY. II. SH 2-208

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yasui, Chikako; Kobayashi, Naoto; Izumi, Natsuko

We obtained deep near-infrared images of Sh 2-208, one of the lowest-metallicity H ii regions in the Galaxy, [O/H] = −0.8 dex. We detected a young cluster in the center of the H ii region with a limiting magnitude of K = 18.0 mag (10 σ ), which corresponds to a mass detection limit of ∼0.2 M {sub ⊙}. This enables the comparison of star-forming properties under low metallicity with those of the solar neighborhood. We identified 89 cluster members. From the fitting of the K -band luminosity function (KLF), the age and distance of the cluster are estimated to be ∼0.5more » Myr and ∼4 kpc, respectively. The estimated young age is consistent with the detection of strong CO emission in the cluster region and the estimated large extinction of cluster members ( A{sub V}  ∼ 4–25 mag). The observed KLF suggests that the underlying initial mass function (IMF) of the low-metallicity cluster is not significantly different from canonical IMFs in the solar neighborhood in terms of both high-mass slope and IMF peak (characteristic mass). Despite the very young age, the disk fraction of the cluster is estimated at only 27% ± 6%, which is significantly lower than those in the solar metallicity. Those results are similar to Sh 2-207, which is another star-forming region close to Sh 2-208 with a separation of 12 pc, suggesting that their star-forming activities in low-metallicity environments are essentially identical to those in the solar neighborhood, except for the disk dispersal timescale. From large-scale mid-infrared images, we suggest that sequential star formation is taking place in Sh 2-207, Sh 2-208, and the surrounding region, triggered by an expanding bubble with a ∼30 pc radius.« less

On the fate of laser-produced NH 2 in a constrained pulsed expansion of trimethylamine alane and NH 3

NASA Astrophysics Data System (ADS)

Demchuk, Alexander; Cahill, John J.; Simpson, Steven; Koplitz, Brent

2001-11-01

The effects of both 193 nm radiation and NH 3 on an expansion of trimethylamine alane (TMAA) have been studied. In neat TMAA, 193 nm radiation induces small but significant clustering. When NH 3 is introduced in the absence of 193 nm photons, no visible reaction occurs. However, when NH 3 is introduced along with 193 nm photons, the H 3Al:N(CH 3) 3 parent molecule is completely replaced by H 3AlNH 2. Moreover, the clustering channels observed with neat TMAA disappear. The apparent stability or inertness of the R 3MNH 2 (R=H, CH 3 or C 2H 5; M=Ga or Al) species in a variety of metal nitride reactive environments is discussed.

Globular Cluster Abundances from High-resolution, Integrated-light Spectroscopy. II. Expanding the Metallicity Range for Old Clusters and Updated Analysis Techniques

NASA Astrophysics Data System (ADS)

Colucci, Janet E.; Bernstein, Rebecca A.; McWilliam, Andrew

2017-01-01

We present abundances of globular clusters (GCs) in the Milky Way and Fornax from integrated-light (IL) spectra. Our goal is to evaluate the consistency of the IL analysis relative to standard abundance analysis for individual stars in those same clusters. This sample includes an updated analysis of seven clusters from our previous publications and results for five new clusters that expand the metallicity range over which our technique has been tested. We find that the [Fe/H] measured from IL spectra agrees to ˜0.1 dex for GCs with metallicities as high as [Fe/H] = -0.3, but the abundances measured for more metal-rich clusters may be underestimated. In addition we systematically evaluate the accuracy of abundance ratios, [X/Fe], for Na I, Mg I, Al I, Si I, Ca I, Ti I, Ti II, Sc II, V I, Cr I, Mn I, Co I, Ni I, Cu I, Y II, Zr I, Ba II, La II, Nd II, and Eu II. The elements for which the IL analysis gives results that are most similar to analysis of individual stellar spectra are Fe I, Ca I, Si I, Ni I, and Ba II. The elements that show the greatest differences include Mg I and Zr I. Some elements show good agreement only over a limited range in metallicity. More stellar abundance data in these clusters would enable more complete evaluation of the IL results for other important elements. This paper includes data gathered with the 6.5 m Magellan Telescopes located at Las Campanas Observatory, Chile.

Exploring the origin of a large cavity in Abell 1795 using deep Chandra observations

NASA Astrophysics Data System (ADS)

Walker, S. A.; Fabian, A. C.; Kosec, P.

2014-12-01

We examine deep stacked Chandra observations of the galaxy cluster Abell 1795 (over 700 ks) to study in depth a large (34 kpc radius) cavity in the X-ray emission. Curiously, despite the large energy required to form this cavity (4PV = 4 × 1060 erg), there is no obvious counterpart to the cavity on the opposite side of the cluster, which would be expected if it has formed due to jets from the central active galactic nucleus (AGN) inflating bubbles. There is also no radio emission associated with the cavity, and no metal enhancement or filaments between it and the brightest cluster galaxy, which are normally found for bubbles inflated by AGN which have risen from the core. One possibility is that this is an old ghost cavity, and that gas sloshing has dominated the distribution of metals around the core. Projection effects, particularly the long X-ray bright filament to the south-east, may prevent us from seeing the companion bubble on the opposite side of the cluster core. We calculate that such a companion bubble would easily have been able to uplift the gas in the southern filament from the core. Interestingly, it has recently been found that inside the cavity is a highly variable X-ray point source coincident with a small dwarf galaxy. Given the remarkable spatial correlation of this point source and the X-ray cavity, we explore the possibility that an outburst from this dwarf galaxy in the past could have led to the formation of the cavity, but find this to be an unlikely scenario.

New gas phase inorganic ion cluster species and their atmospheric implications

NASA Technical Reports Server (NTRS)

Maerk, T. D.; Peterson, K. I.; Castleman, A. W., Jr.

1980-01-01

Recent experimental laboratory observations, with high-pressure mass spectroscopy, have revealed the existence of previously unreported species involving water clustered to sodium dimer ions, and alkali metal hydroxides clustered to alkali metal ions. The important implications of these results concerning the existence of such species are here discussed, as well as how from a practical aspect they confirm the stability of certain cluster species proposed by Ferguson (1978) to explain masses recently detected at upper altitudes using mass spectrometric techniques.

Cluster size selectivity in the product distribution of ethene dehydrogenation on niobium clusters.

PubMed

Parnis, J Mark; Escobar-Cabrera, Eric; Thompson, Matthew G K; Jacula, J Paul; Lafleur, Rick D; Guevara-García, Alfredo; Martínez, Ana; Rayner, David M

2005-08-18

Ethene reactions with niobium atoms and clusters containing up to 25 constituent atoms have been studied in a fast-flow metal cluster reactor. The clusters react with ethene at about the gas-kinetic collision rate, indicating a barrierless association process as the cluster removal step. Exceptions are Nb8 and Nb10, for which a significantly diminished rate is observed, reflecting some cluster size selectivity. Analysis of the experimental primary product masses indicates dehydrogenation of ethene for all clusters save Nb10, yielding either Nb(n)C2H2 or Nb(n)C2. Over the range Nb-Nb6, the extent of dehydrogenation increases with cluster size, then decreases for larger clusters. For many clusters, secondary and tertiary product masses are also observed, showing varying degrees of dehydrogenation corresponding to net addition of C2H4, C2H2, or C2. With Nb atoms and several small clusters, formal addition of at least six ethene molecules is observed, suggesting a polymerization process may be active. Kinetic analysis of the Nb atom and several Nb(n) cluster reactions with ethene shows that the process is consistent with sequential addition of ethene units at rates corresponding approximately to the gas-kinetic collision frequency for several consecutive reacting ethene molecules. Some variation in the rate of ethene pick up is found, which likely reflects small energy barriers or steric constraints associated with individual mechanistic steps. Density functional calculations of structures of Nb clusters up to Nb(6), and the reaction products Nb(n)C2H2 and Nb(n)C2 (n = 1...6) are presented. Investigation of the thermochemistry for the dehydrogenation of ethene to form molecular hydrogen, for the Nb atom and clusters up to Nb6, demonstrates that the exergonicity of the formation of Nb(n)C2 species increases with cluster size over this range, which supports the proposal that the extent of dehydrogenation is determined primarily by thermodynamic constraints. Analysis of the structural variations present in the cluster species studied shows an increase in C-H bond lengths with cluster size that closely correlates with the increased thermodynamic drive to full dehydrogenation. This correlation strongly suggests that all steps in the reaction are barrierless, and that weakening of the C-H bonds is directly reflected in the thermodynamics of the overall dehydrogenation process. It is also demonstrated that reaction exergonicity in the initial partial dehydrogenation step must be carried through as excess internal energy into the second dehydrogenation step.

Rubidium and Lead Abundances in Giant Stars of the Globular Clusters M13 and NGC 6752

NASA Astrophysics Data System (ADS)

Yong, David; Aoki, Wako; Lambert, David L.; Paulson, Diane B.

2006-03-01

We present measurements of the neutron-capture elements Rb and Pb in five giant stars of the globular cluster NGC 6752 and Pb measurements in four giants of the globular cluster M13. The abundances were derived by comparing synthetic spectra with high-resolution, high signal-to-noise ratio spectra obtained using HDS on the Subaru telescope and MIKE on the Magellan telescope. The program stars span the range of the O-Al abundance variation. In NGC 6752, the mean abundances are [Rb/Fe]=-0.17+/-0.06 (σ=0.14), [Rb/Zr]=-0.12+/-0.06 (σ=0.13), and [Pb/Fe]=-0.17+/-0.04 (σ=0.08). In M13 the mean abundance is [Pb/Fe]=-0.28+/-0.03 (σ=0.06). Within the measurement uncertainties, we find no evidence for star-to-star variation for either Rb or Pb within these clusters. None of the abundance ratios [Rb/Fe], [Rb/Zr], or [Pb/Fe] are correlated with the Al abundance. NGC 6752 may have slightly lower abundances of [Rb/Fe] and [Rb/Zr] compared to the small sample of field stars at the same metallicity. For M13 and NGC 6752 the Pb abundances are in accord with predictions from a Galactic chemical evolution model. If metal-poor intermediate-mass asymptotic giant branch stars did produce the globular cluster abundance anomalies, then such stars do not synthesize significant quantities of Rb or Pb. Alternatively, if such stars do synthesize large amounts of Rb or Pb, then they are not responsible for the abundance anomalies seen in globular clusters. Based in part on data collected at the Subaru Telescope, which is operated by the National Astronomical Observatory of Japan, and on observations made with the Magellan Clay Telescope at Las Campanas Observatory.

Spatial clustering of metal and metalloid mixtures in unregulated water sources on the Navajo Nation - Arizona, New Mexico, and Utah, USA.

PubMed

Hoover, Joseph H; Coker, Eric; Barney, Yolanda; Shuey, Chris; Lewis, Johnnye

2018-08-15

Contaminant mixtures are identified regularly in public and private drinking water supplies throughout the United States; however, the complex and often correlated nature of mixtures makes identification of relevant combinations challenging. This study employed a Bayesian clustering method to identify subgroups of water sources with similar metal and metalloid profiles. Additionally, a spatial scan statistic assessed spatial clustering of these subgroups and a human health metric was applied to investigate potential for human toxicity. These methods were applied to a dataset comprised of metal and metalloid measurements from unregulated water sources located on the Navajo Nation, in the southwest United States. Results indicated distinct subgroups of water sources with similar contaminant profiles and that some of these subgroups were spatially clustered. Several profiles had metal and metalloid concentrations that may have potential for human toxicity including arsenic, uranium, lead, manganese, and selenium. This approach may be useful for identifying mixtures in water sources, spatially evaluating the clusters, and help inform toxicological research investigating mixtures. Copyright © 2018 The Authors. Published by Elsevier B.V. All rights reserved.

Structure of fluorescent metal clusters on a DNA template.

NASA Astrophysics Data System (ADS)

Vdovichev, A. A.; Sych, T. S.; Reveguk, Z. V.; Smirnova, A. A.; Maksimov, D. A.; Ramazanov, R. R.; Kononov, A. I.

2016-08-01

Luminescent metal clusters are a subject of growing interest in recent years due to their bright emission from visible to near infrared range. Detailed structure of the fluorescent complexes of Ag and other metal clusters with ligands still remains a challenging task. In this joint experimental and theoretical study we synthesized Ag-DNA complexes on a DNA oligonucleotide emitting in violet- green spectral range. The structure of DNA template was determined by means of various spectral measurements (CD, MS, XPS). Comparison of the experimental fluorescent excitation spectra and calculated absorption spectra for different QM/MM optimized structures allowed us to determine the detailed structure of the green cluster containing three silver atoms in the stem of the DNA hairpin structure stabilized by cytosine-Ag+-cytosine bonds.

GLOBULAR CLUSTER ABUNDANCES FROM HIGH-RESOLUTION, INTEGRATED-LIGHT SPECTROSCOPY. II. EXPANDING THE METALLICITY RANGE FOR OLD CLUSTERS AND UPDATED ANALYSIS TECHNIQUES

DOE Office of Scientific and Technical Information (OSTI.GOV)

Colucci, Janet E.; Bernstein, Rebecca A.; McWilliam, Andrew

2017-01-10

We present abundances of globular clusters (GCs) in the Milky Way and Fornax from integrated-light (IL) spectra. Our goal is to evaluate the consistency of the IL analysis relative to standard abundance analysis for individual stars in those same clusters. This sample includes an updated analysis of seven clusters from our previous publications and results for five new clusters that expand the metallicity range over which our technique has been tested. We find that the [Fe/H] measured from IL spectra agrees to ∼0.1 dex for GCs with metallicities as high as [Fe/H] = −0.3, but the abundances measured for more metal-rich clustersmore » may be underestimated. In addition we systematically evaluate the accuracy of abundance ratios, [X/Fe], for Na i, Mg i, Al i, Si i, Ca i, Ti i, Ti ii, Sc ii, V i, Cr i, Mn i, Co i, Ni i, Cu i, Y ii, Zr i, Ba ii, La ii, Nd ii, and Eu ii. The elements for which the IL analysis gives results that are most similar to analysis of individual stellar spectra are Fe i, Ca i, Si i, Ni i, and Ba ii. The elements that show the greatest differences include Mg i and Zr i. Some elements show good agreement only over a limited range in metallicity. More stellar abundance data in these clusters would enable more complete evaluation of the IL results for other important elements.« less

Perturbative treatment of spin-orbit-coupling within spin-free exact two-component theory using equation-of-motion coupled-cluster methods

NASA Astrophysics Data System (ADS)

Cheng, Lan; Wang, Fan; Stanton, John F.; Gauss, Jürgen

2018-01-01

A scheme is reported for the perturbative calculation of spin-orbit coupling (SOC) within the spin-free exact two-component theory in its one-electron variant (SFX2C-1e) in combination with the equation-of-motion coupled-cluster singles and doubles method. Benchmark calculations of the spin-orbit splittings in 2Π and 2P radicals show that the accurate inclusion of scalar-relativistic effects using the SFX2C-1e scheme extends the applicability of the perturbative treatment of SOC to molecules that contain heavy elements. The contributions from relaxation of the coupled-cluster amplitudes are shown to be relatively small; significant contributions from correlating the inner-core orbitals are observed in calculations involving third-row and heavier elements. The calculation of term energies for the low-lying electronic states of the PtH radical, which serves to exemplify heavy transition-metal containing systems, further demonstrates the quality that can be achieved with the pragmatic approach presented here.

Vilnius Multicolor CCD Photometry of the Open Cluster NGC 752

NASA Astrophysics Data System (ADS)

Bartašiūtė, S.; Janusz, R.; Boyle, R. P.; Philip, A. G. Davis

We have performed multicolor CCD observations of the central area of NGC 752 to search for faint, low-mass members of this open cluster. Four 12'x12' fields were taken on the 1.8 m Vatican Advanced Technology Telescope (Mt. Graham, Arizona) using a 4K CCD camera and eight intermediate-band filters of the Strömvil system. In this paper we present a catalog of photometry for 405 stars down to the limiting magnitude V=18.5, which contains V magnitudes and color indices of the Vilnius system, together with photometric determinations of spectral types, absolute magnitudes MV, interstellar reddening values EY-V and metallicity parameters [Fe/H]. The good quality multicolor data made it possible to identify the locus of the lower main sequence to four magnitudes beyond the previous (photographic) limit. A relatively small number of photometric members identified at faint magnitudes seems to be indicative of actual dissolution of the cluster from the low-mass end.

Synthesis and characterization of Mn quantum dots by bioreduction with water hyacinth.

PubMed

Rosano-Ortega, G; Schabes-Retchkiman, P; Zorrilla, C; Liu, H B; Canizal, G; Avila-Pérez, P; Ascencio, J A

2006-01-01

The bio-reduction method is reported as a part of a complimentary self-sustained technology, where bioremediation and metal particle production are related. The use of the characterization methods in this self sustainable technique open the expectative to be used for several other elements and with other plants, which will be discussed. However, the particular case of Mn nanoparticles involves an important option to generate nanoparticles in the range of 1-4 nanometers with a well controlled size and with a structure based on an fcc-like geometry for the smallest clusters and with more complex arrays for cluster greater than four shells, which involves magnetic moments significantly related to their atomistic configuration. At the same time, the use of the characterization methods establishes the dependence of the nanoparticle's size on the pH conditions used during the synthesis; small clusters in the range of 1-2 nm were generated using pH=5, and it was shown that for the smallest aggregates, simple polyhedron shapes are stable.

A SURVEY OF CN AND CH VARIATIONS IN GALACTIC GLOBULAR CLUSTERS FROM SLOAN DIGITAL SKY SURVEY SPECTROSCOPY

DOE Office of Scientific and Technical Information (OSTI.GOV)

Smolinski, Jason P.; Beers, Timothy C.; Lee, Young Sun

We present a homogeneous survey of the CN and CH band strengths in eight Galactic globular clusters observed during the course of the Sloan Extension for Galactic Understanding and Exploration sub-survey of the Sloan Digital Sky Survey. We confirm the existence of a bimodal CN distribution among red giant branch (RGB) stars in all of the clusters with metallicity greater than [Fe/H] = -1.7; the lowest metallicity cluster with an observed CN bimodality is M53, with [Fe/H] {approx_equal} -2.1. There is also some evidence for individual CN groups on the subgiant branches of M92, M2, and M13, and on themore » RGBs of M92 and NGC 5053. Finally, we quantify the correlation between overall cluster metallicity and the slope of the CN band strength-luminosity plot as a means of further demonstrating the level of CN enrichment in cluster giants. Our results agree well with previous studies reported in the literature.« less

DOES THE OOSTERHOFF DICHOTOMY EXIST IN THE ANDROMEDA GALAXY? I. THE CASE OF G11

DOE Office of Scientific and Technical Information (OSTI.GOV)

Contreras Ramos, Rodrigo; Clementini, Gisella; Federici, Luciana, E-mail: rodrigo.contreras@oabo.inaf.it, E-mail: gisella.clementini@oabo.inaf.it, E-mail: luciana.federici@oabo.inaf.it

We present the first evidence that Oosterhoff type II globular clusters exist in the Andromeda galaxy (M31). On the basis of time-series photometry of the moderately metal-poor ([Fe/H] {approx}-1.6 dex) M31 globular cluster G11, obtained with the Wide Field Planetary Camera 2 on board the Hubble Space Telescope, we detected and derived periods for 14 RR Lyrae stars, of which five are found to lie inside the cluster tidal radius. They include three fundamental-mode (RRab) and two first-overtone (RRc) pulsators, with average periods (P{sub ab} ) = 0.70 days, and (P{sub c} ) = 0.40 days, respectively. These mean periodsmore » and the position of the cluster variable stars in the period-amplitude and period-metallicity diagrams all suggest that G11 is likely to be an Oosterhoff type II globular cluster. This appears to be in agreement with the general behavior of Milky Way globular clusters with similar metallicity and horizontal branch morphology.« less

Photochemical cleavage of metal--carbon nanocrystals and their reconstruction into met--cars clusters

NASA Astrophysics Data System (ADS)

Pilgrim, J. S.; Duncan, M. A.

1994-10-01

Titanium and zirconium metal--carbon clusters are produced by laser vaporization in a pulsed nozzle source and detected with time-of-flight mass spectrometry. In addition to the now-familiar "met-cars" stoichiometry (M8C12), larger magic number clusters are produced with near 1:1 metal--carbon ratios. The special stoichiometries observed correspond to face-centered cubic crystal fragments, with a strong preference for fragments with symmetrical x,y,z dimensions. Mass-selected photodissociation experiments are used to investigate the structural patterns and stabilities of these systems. Photodissociation of the larger "nanocrystal" clusters leads to cleavage along crystal planes, producing smaller crystals also having highly symmetric dimensions. Photoexcitation of all these crystallites, in particular the 3 × 3 × 3 species, also leads to surface reconstruction, forming the M8C12 met-cars cluster and/or the M8C13 cluster, the latter of which is assigned to a met--cars cage with an endohedral carbon atom.

Heavy metal contamination of agricultural soils affected by mining activities around the Ganxi River in Chenzhou, Southern China.

PubMed

Ma, Li; Sun, Jing; Yang, Zhaoguang; Wang, Lin

2015-12-01

Heavy metal contamination attracted a wide spread attention due to their strong toxicity and persistence. The Ganxi River, located in Chenzhou City, Southern China, has been severely polluted by lead/zinc ore mining activities. This work investigated the heavy metal pollution in agricultural soils around the Ganxi River. The total concentrations of heavy metals were determined by inductively coupled plasma-mass spectrometry. The potential risk associated with the heavy metals in soil was assessed by Nemerow comprehensive index and potential ecological risk index. In both methods, the study area was rated as very high risk. Multivariate statistical methods including Pearson's correlation analysis, hierarchical cluster analysis, and principal component analysis were employed to evaluate the relationships between heavy metals, as well as the correlation between heavy metals and pH, to identify the metal sources. Three distinct clusters have been observed by hierarchical cluster analysis. In principal component analysis, a total of two components were extracted to explain over 90% of the total variance, both of which were associated with anthropogenic sources.

Melting phenomena: effect of composition for 55-atom Ag-Pd bimetallic clusters.

PubMed

Cheng, Daojian; Wang, Wenchuan; Huang, Shiping

2008-05-14

Understanding the composition effect on the melting processes of bimetallic clusters is important for their applications. Here, we report the relationship between the melting point and the metal composition for the 55-atom icosahedral Ag-Pd bimetallic clusters by canonical Monte Carlo simulations, using the second-moment approximation of the tight-binding potentials (TB-SMA) for the metal-metal interactions. Abnormal melting phenomena for the systems of interest are found. Our simulation results reveal that the dependence of the melting point on the composition is not a monotonic change, but experiences three different stages. The melting temperatures of the Ag-Pd bimetallic clusters increase monotonically with the concentration of the Ag atoms first. Then, they reach a plateau presenting almost a constant value. Finally, they decrease sharply at a specific composition. The main reason for this change can be explained in terms of the relative stability of the Ag-Pd bimetallic clusters at different compositions. The results suggest that the more stable the cluster, the higher the melting point for the 55-atom icosahedral Ag-Pd bimetallic clusters at different compositions.

Making sense of the conflicting magic numbers in WSi{sub n} clusters

DOE Office of Scientific and Technical Information (OSTI.GOV)

Abreu, Marissa Baddick; Reber, Arthur C.; Khanna, Shiv N.

2015-08-21

First principles studies on the geometric structure, stability, and electronic structure of WSi{sub n} clusters, n = 6-16, have been carried out to show that the observed differing “magic sizes” for WSi{sub n} clusters are associated with the nature of the growth processes. The WSi{sub 12} cluster, observed as a magic species in experiments reacting transition metal ions with silane, is not stable due to a filled shell of 18 electrons, as previously proposed, but due to its atomic structure that arrests further growth because of an endohedral transition metal site. In fact, it is found that all of thesemore » clusters, n = 6-16, have filled 5d shells except for WSi{sub 12}, which has a 5d{sup 8} configuration that is caused by crystal field splitting. The stability of WSi{sub 15}{sup +}, observed as highly stable in clusters generated by vaporizing silicon and metal carbonyls, is shown to be associated with a combination of geometric and electronic features. The findings are compared with previous results on CrSi{sub n} clusters.« less

New insights into designing metallacarborane based room temperature hydrogen storage media.

PubMed

Bora, Pankaj Lochan; Singh, Abhishek K

2013-10-28

Metallacarboranes are promising towards realizing room temperature hydrogen storage media because of the presence of both transition metal and carbon atoms. In metallacarborane clusters, the transition metal adsorbs hydrogen molecules and carbon can link these clusters to form metal organic framework, which can serve as a complete storage medium. Using first principles density functional calculations, we chalk out the underlying principles of designing an efficient metallacarborane based hydrogen storage media. The storage capacity of hydrogen depends upon the number of available transition metal d-orbitals, number of carbons, and dopant atoms in the cluster. These factors control the amount of charge transfer from metal to the cluster, thereby affecting the number of adsorbed hydrogen molecules. This correlation between the charge transfer and storage capacity is general in nature, and can be applied to designing efficient hydrogen storage systems. Following this strategy, a search for the best metallacarborane was carried out in which Sc based monocarborane was found to be the most promising H2 sorbent material with a 9 wt.% of reversible storage at ambient pressure and temperature.

A heavy-metal home

NASA Image and Video Library

2016-05-30

This 10.5-billion-year-old globular cluster, NGC 6496, is home to heavy-metal stars of a celestial kind! The stars comprising this spectacular spherical cluster are enriched with much higher proportions of metals — elements heavier than hydrogen and helium, are in astronomy curiously known as metals — than stars found in similar clusters. A handful of these high-metallicity stars are also variable stars, meaning that their brightness fluctuates over time. NGC 6496 hosts a selection of long-period variables — giant pulsating stars whose brightness can take up to, and even over, a thousand days to change — and short-period eclipsing binaries, which dim when eclipsed by a stellar companion. The nature of the variability of these stars can reveal important information about their mass, radius, luminosity, temperature, composition, and evolution, providing astronomers with measurements that would be difficult or even impossible to obtain through other methods. NGC 6496 was discovered in 1826 by Scottish astronomer James Dunlop. The cluster resides at about 35 000 light-years away in the southern constellation of Scorpius (The Scorpion).

New insights into designing metallacarborane based room temperature hydrogen storage media

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bora, Pankaj Lochan; Singh, Abhishek K.

Metallacarboranes are promising towards realizing room temperature hydrogen storage media because of the presence of both transition metal and carbon atoms. In metallacarborane clusters, the transition metal adsorbs hydrogen molecules and carbon can link these clusters to form metal organic framework, which can serve as a complete storage medium. Using first principles density functional calculations, we chalk out the underlying principles of designing an efficient metallacarborane based hydrogen storage media. The storage capacity of hydrogen depends upon the number of available transition metal d-orbitals, number of carbons, and dopant atoms in the cluster. These factors control the amount of chargemore » transfer from metal to the cluster, thereby affecting the number of adsorbed hydrogen molecules. This correlation between the charge transfer and storage capacity is general in nature, and can be applied to designing efficient hydrogen storage systems. Following this strategy, a search for the best metallacarborane was carried out in which Sc based monocarborane was found to be the most promising H{sub 2} sorbent material with a 9 wt.% of reversible storage at ambient pressure and temperature.« less

Chemical evolution of the Magellanic Clouds

NASA Astrophysics Data System (ADS)

Barbuy, B.; de Freitas Pacheco, J. A.; Idiart, T.

We have obtained integrated spectra for 14 clusters in the Magellanic Clouds, on which the spectral indices Hβ, Mg2, Fe5270, Fe5335 were measured. Selecting indices whose behaviour depends essentially on age and metallicity (Hβ and ), together with (B-V) and (V-K) colours, we were able to determine age and metallicities for these clusters, using calibrations based on single stellar population models (Borges et al. 1995). A chemical evolution model which follows a star formation history as indicated by the field population is checked with the age and metallicity data for our sample star clusters.

Cúmulos estelares de edad intermedia de la Nube Mayor de Magallanes: determinación de parámetros fundamentales a partir de fotometría de Washington

NASA Astrophysics Data System (ADS)

Palma, T.; Clariá, J. J.; Geisler, D.; Piatti, A. E.; Ahumada, A. V.

Based on CCD images obtained in the Washington system at Cerro Tololo Inter-American Observatory, we determine ages and metallicities of 8 unstudied star clusters of the Large Magellanic Cloud (LMC). We find that they are intermediate-age (1-2 Gyr) and relatively metal-poor, although the metallicities are mainly determined from isochrones and are not strongly constrained. The study of this cluster sample will soon be extended to almost a hundred practically unstudied LMC star clusters. FULL TEXT IN SPANISH

An intermetallic Au24Ag20 superatom nanocluster stabilized by labile ligands.

PubMed

Wang, Yu; Su, Haifeng; Xu, Chaofa; Li, Gang; Gell, Lars; Lin, Shuichao; Tang, Zichao; Häkkinen, Hannu; Zheng, Nanfeng

2015-04-08

An intermetallic nanocluster containing 44 metal atoms, Au24Ag20(2-SPy)4(PhC≡C)20Cl2, was successfully synthesized and structurally characterized by single-crystal analysis and density funtional theory computations. The 44 metal atoms in the cluster are arranged as a concentric three-shell Au12@Ag20@Au12 Keplerate structure having a high symmetry. For the first time, the co-presence of three different types of anionic ligands (i.e., phenylalkynyl, 2-pyridylthiolate, and chloride) was revealed on the surface of metal nanoclusters. Similar to thiolates, alkynyls bind linearly to surface Au atoms using their σ-bonds, leading to the formation of two types of surface staple units (PhC≡C-Au-L, L = PhC≡C(-) or 2-pyridylthiolate) on the cluster. The co-presence of three different surface ligands allows the site-specific surface and functional modification of the cluster. The lability of PhC≡C(-) ligands on the cluster was demonstrated, making it possible to keep the metal core intact while removing partial surface capping. Moreover, it was found that ligand exchange on the cluster occurs easily to offer various derivatives with the same metal core but different surface functionality and thus different solubility.

LATE POP III STAR FORMATION DURING THE EPOCH OF REIONIZATION: RESULTS FROM THE RENAISSANCE SIMULATIONS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xu, Hao; Norman, Michael L.; O’Shea, Brian W.

2016-06-01

We present results on the formation of Population III (Pop III) stars at redshift 7.6 from the Renaissance Simulations, a suite of extremely high-resolution and physics-rich radiation transport hydrodynamics cosmological adaptive-mesh refinement simulations of high-redshift galaxy formation performed on the Blue Waters supercomputer. In a survey volume of about 220 comoving Mpc{sup 3}, we found 14 Pop III galaxies with recent star formation. The surprisingly late formation of Pop III stars is possible due to two factors: (i) the metal enrichment process is local and slow, leaving plenty of pristine gas to exist in the vast volume; and (ii) strongmore » Lyman–Werner radiation from vigorous metal-enriched star formation in early galaxies suppresses Pop III formation in (“not so”) small primordial halos with mass less than ∼3 × 10{sup 7} M {sub ⊙}. We quantify the properties of these Pop III galaxies and their Pop III star formation environments. We look for analogs to the recently discovered luminous Ly α emitter CR7, which has been interpreted as a Pop III star cluster within or near a metal-enriched star-forming galaxy. We find and discuss a system similar to this in some respects, however, the Pop III star cluster is far less massive and luminous than CR7 is inferred to be.« less

Influence of silver and copper doping on luminescent properties of zinc-phosphate glasses after x-ray irradiation

NASA Astrophysics Data System (ADS)

Murashov, Alexander A.; Sidorov, Alexander I.; Shakhverdov, Teimur A.; Stolyarchuk, Maxim V.

2017-11-01

It is shown, experimentally, that in silver- and copper-containing zinc-phosphate glasses, metal molecular clusters are formed during the glass synthesis. X-ray irradiation of these glasses led to the considerable increase of its luminescence in visible spectral range. This effect is caused by the transformation of the charged metal molecular clusters into the neutral state. Luminescence and excitation spectra of the glass, doped with silver and copper simultaneously, change significantly in comparison with the spectra of glasses doped with one metal. The reason for this can be the formation of hybrid AgnCum molecular clusters. The computer simulation of the structure and optical properties of such clusters by the time-dependent density functional theory method is presented. It is shown that the optimal luminescent material for photonics application, in comparison with other studied materials, is glass, containing hybrid molecular clusters.

Fischer–Tropsch Synthesis at a Low Pressure on Subnanometer Cobalt Oxide Clusters: The Effect of Cluster Size and Support on Activity and Selectivity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lee, Sungsik; Lee, Byeongdu; Seifert, Sönke

2015-05-21

In this study, the catalytic activity and changes in the oxidation state during the Fischer Tropsch (FT) reaction was investigated on subnanometer size-selected cobalt clusters deposited on oxide (Al2O3, MgO) and carbon-based (ultrananocrystalline diamond UNCD) supports by temperature programmed reaction (TPRx) combined with in-situ grazing-incidence X-ray absorption characterization (GIXAS). The activity and selectivity of ultrasmall cobalt clusters exhibits a very strong dependence on cluster size and support. The evolution of the oxidation state of metal cluster during the reaction reveals that metal-support interaction plays a key role in the reaction.

Chemical Abundances of Seven Outer Halo M31 Globular Clusters from the Pan-Andromeda Archaeological Survey

NASA Astrophysics Data System (ADS)

Sakari, Charli M.

2017-03-01

Observations of stellar streams in M31's outer halo suggest that M31 is actively accreting several dwarf galaxies and their globular clusters (GCs). Detailed abundances can chemically link clusters to their birth environments, establishing whether or not a GC has been accreted from a satellite dwarf galaxy. This talk presents the detailed chemical abundances of seven M31 outer halo GCs (with projected distances from M31 greater than 30 kpc), as derived from high-resolution integrated-light spectra taken with the Hobby Eberly Telescope. Five of these clusters were recently discovered in the Pan-Andromeda Archaeological Survey (PAndAS)-this talk presents the first determinations of integrated Fe, Na, Mg, Ca, Ti, Ni, Ba, and Eu abundances for these clusters. Four of the target clusters (PA06, PA53, PA54, and PA56) are metal-poor ([Fe/H] < -1.5), α-enhanced (though they are possibly less alpha-enhanced than Milky Way stars at the 1 sigma level), and show signs of star-to-star Na and Mg variations. The other three GCs (H10, H23, and PA17) are more metal-rich, with metallicities ranging from [Fe/H] = -1.4 to -0.9. While H23 is chemically similar to Milky Way field stars, Milky Way GCs, and other M31 clusters, H10 and PA17 have moderately-low [Ca/Fe], compared to Milky Way field stars and clusters. Additionally, PA17's high [Mg/Ca] and [Ba/Eu] ratios are distinct from Milky Way stars, and are in better agreement with the stars and clusters in the Large Magellanic Cloud (LMC). None of the clusters studied here can be conclusively linked to any of the identified streams from PAndAS; however, based on their locations, kinematics, metallicities, and detailed abundances, the most metal-rich PAndAS clusters H23 and PA17 may be associated with the progenitor of the Giant Stellar Stream, H10 may be associated with the SW Cloud, and PA53 and PA56 may be associated with the Eastern Cloud.

A Wide-Field Photometric Survey for Extratidal Tails Around Five Metal-Poor Globular Clusters in the Galactic Halo

NASA Astrophysics Data System (ADS)

Chun, Sang-Hyun; Kim, Jae-Woo; Sohn, Sangmo T.; Park, Jang-Hyun; Han, Wonyong; Kim, Ho-Il; Lee, Young-Wook; Lee, Myung Gyoon; Lee, Sang-Gak; Sohn, Young-Jong

2010-02-01

Wide-field deep g'r'i' images obtained with the Megacam of the Canada-France-Hawaii Telescope are used to investigate the spatial configuration of stars around five metal-poor globular clusters M15, M30, M53, NGC 5053, and NGC 5466, in a field-of-view ~3°. Applying a mask filtering algorithm to the color-magnitude diagrams of the observed stars, we sorted cluster's member star candidates that are used to examine the characteristics of the spatial stellar distribution surrounding the target clusters. The smoothed surface density maps and the overlaid isodensity contours indicate that all of the five metal-poor globular clusters exhibit strong evidence of extratidal overdensity features over their tidal radii, in the form of extended tidal tails around the clusters. The orientations of the observed extratidal features show signatures of tidal tails tracing the clusters' orbits, inferred from their proper motions, and effects of dynamical interactions with the Galaxy. Our findings include detections of a tidal bridge-like feature and an envelope structure around the pair of globular clusters M53 and NGC 5053. The observed radial surface density profiles of target clusters have a deviation from theoretical King models, for which the profiles show a break at 0.5-0.7rt , extending the overdensity features out to 1.5-2rt . Both radial surface density profiles for different angular sections and azimuthal number density profiles confirm the overdensity features of tidal tails around the five metal-poor globular clusters. Our results add further observational evidence that the observed metal-poor halo globular clusters originate from an accreted satellite system, indicative of the merging scenario of the formation of the Galactic halo. Based on observations carried out at the Canada-France-Hawaii Telescope, operated by the National Research Council of Canada, the Centre National de la Recherche Scientifique de France, and the University of Hawaii. This is part of the Searching for the Galactic Halo project using the CFHT, organized by the Korea Astronomy and Space Science Institute.

DFT Studies of Adsorption of Cu7-atom Nanoclusters on TiO2 Surfaces and Application to Methanol Steam Reforming Reactions

NASA Astrophysics Data System (ADS)

Taft, Michael J., Sr.

Alcohol conversion to hydrogen, via steam reforming, is an alternative energy process that is promising for the future of clean energy economies. With advancements in fuel cell technologies, on-board hydrogen reforming could leverage already existing automotive designs and fuel infrastructure. The design of catalytic materials with tunable properties requires a level of insight that has yet to be achieved experimentally. The central objective of this project is to develop a working model of metal-oxide surface mediated copper clusters, since such catalytic beds have a wide-range of applications. More specifically, we investigate the catalytic framework of this process with theoretical models of the active metal (Cu) and metal­oxide support (TiO2). We employ a Density Functional Theory (DFT)-Generalized Gradient Approximation (GGA) approach for the quantum level electronic structure calculations of Cu, TiO2 and CH3OH. Additionally, we have generated anatase (A(001), A(101)) and rutile (R(100), R(110)) surface morphologies and 7­atom copper cluster complexes with those planes. To examine the possible influence of TiO2 on the adsorption properties of our active metal, Cu7, we have carried out adsorption studies with CH3OH. Our final data and observations predict that the Cu7 cluster adopts a symmetric pentagonal bipyramidal geometry with D5h symmetry. We find that the anatase morphology has a greater overall stability than rutile. The adsorption strength of the Cu7 cluster has been predicted in this study to be according to the following order: A(001) > A(101)> R(110). Indeed, the R(100) surface appears to be an unfavorable surface for metal cluster binding. Our data indicates that copper cluster stabilization on the metal-oxide surface depends on the nature of the crystal face. Again, we studied the adsorption properties of methanol on nascent Cu7 cluster, Cu7-TiO 2 complex and on pure TiO2-surface in A(001) polymorphic form. The calculations revealed that methanol adsorbs more efficiently on TiO2-bound copper clusters than either the copper cluster alone or the surface of TiO2. Additionally, we find that the metal-oxide support plays a significant role in stabilizing the catalytic reactions of CH3OH adsorption. Here, we have shown that TiO2 clearly enhances the catalytic properties of copper clusters.

Density functional theory study on the metal-support interaction between a Au9 cluster and an anatase TiO2(001) surface.

PubMed

Jiang, Zong-You; Zhao, Zong-Yan

2017-08-23

Noble metals supported on TiO 2 surfaces have shown extraordinary photocatalytic properties in many important processes such as hydrogenation, water splitting, degradation of hazards, and so on. Using density functional theory calculations, this work has systematically investigated the microstructure and electronic structure of three different Au 9 isomers loaded on anatase TiO 2 (001) surface. The calculated results show that the interaction between the Au 9 cluster and the TiO 2 support is closely related to the adsorption site and the stability of the Au 9 cluster in the gas phase. The adsorption energy of the 2D configuration is larger than that of the 3D configuration of the Au 9 cluster, owing to the stronger interactions between more adsorption sites. The stable adsorption site for Au 9 clusters deposited on the anatase TiO 2 (001) surface tends to be the O 2c -O 2c hollow site. The presentation of the MIGS of the Au 9 cluster, the disappearance of surface states of the TiO 2 (001) surface, and the shifting of the Fermi level from the top of the valence band to the bottom of the conduction band suggest strong interactions between the Au 9 clusters and the TiO 2 (001) surface. Importantly, the electron transfer from the Au 9 clusters to the TiO 2 support occurs mainly through Au-O 2c interactions, which are mainly localized at the contact layer of the Au 9 clusters. These conclusions are useful to understand various physical and chemical properties of noble metal clusters loaded onto an oxide surface, and helpful to design novel metal/semiconductor functional composite materials and devices.

The metallicity spread and the age-metallicity relation of ω Centauri

DOE Office of Scientific and Technical Information (OSTI.GOV)

Villanova, S.; Geisler, D.; Gratton, R. G.

2014-08-20

ω Centauri is a peculiar globular cluster formed by a complex stellar population. To investigate it, we studied 172 stars belonging to the five SGBs that we can identify in our photometry, in order to measure their [Fe/H] content as well as estimate their age dispersion and the age-metallicity relation. The first important result is that all of these SGBs have a distribution in metallicity with a spread that exceeds the observational errors and typically displays several peaks that indicate the presence of several subpopulations. We were able to identify at least six of them based on their mean [Fe/H]more » content. These metallicity-based subpopulations are seen to varying extents in each of the five SGBs. Taking advantage of the age sensitivity of the SGB, we showed that, first of all, at least half of the subpopulations have an age spread of at least 2 Gyr. Then, we obtained an age-metallicity relation that is the most complete to date for this cluster. Interpretation of the age-metallicity relation is not straightforward, but it is possible that the cluster (or what we can call its progenitor) was initially composed of two populations with different metallicities. Because of their age, it is very unlikely that the most metal-rich derives from the most metal-poor by some kind of chemical evolution process, so they can be assumed to be two independent primordial objects, or perhaps two separate parts of a single larger object, that merged in the past to form the present-day cluster.« less

Synthesis and Characterization of Novel Compound Clusters

DTIC Science & Technology

1997-08-26

also be intrinsically stable, they cannot be formed by this plasma chemistry presumably because the metals are less reactive. Plasma chemistry reactions...samples without the presence of hydrogen. Vaporization of these composite samples produces the metal carbide clusters in many cases where plasma chemistry does...antimony or bismuth cannot be produced by the hydrocarbon plasma chemistry method, but they are produced readily from composite sample (metal film on

The SEGUE Stellar Parameter Pipeline. II. Validation with Galactic Globular and Open Clusters

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lee, Y.S.; Beers, T.C.; Sivarani, T.

2007-10-01

The authors validate the performance and accuracy of the current SEGUE (Sloan Extension for Galactic Understanding and Exploration) Stellar Parameter Pipeline (SSPP), which determines stellar atmospheric parameters (effective temperature, surface gravity, and metallicity) by comparing derived overall metallicities and radial velocities from selected likely members of three globular clusters (M 13, M 15, and M 2) and two open clusters (NGC 2420 and M 67) to the literature values. Spectroscopic and photometric data obtained during the course of the original Sloan Digital Sky Survey (SDSS-1) and its first extension (SDSS-II/SEGUE) are used to determine stellar radial velocities and atmospheric parametermore » estimates for stars in these clusters. Based on the scatter in the metallicities derived for the members of each cluster, they quantify the typical uncertainty of the SSPP values, {sigma}([Fe/H]) = 0.13 dex for stars in the range of 4500 K {le} T{sub eff} {le} 7500 K and 2.0 {le} log g {le} 5.0, at least over the metallicity interval spanned by the clusters studied (-2.3 {le} [Fe/H] < 0). The surface gravities and effective temperatures derived by the SSPP are also compared with those estimated from the comparison of the color-magnitude diagrams with stellar evolution models; they find satisfactory agreement. At present, the SSPP underestimates [Fe/H] for near-solar-metallicity stars, represented by members of M 67 in this study, by {approx} 0.3 dex.« less

FORS2/VLT survey of Milky Way globular clusters. II. Fe and Mg abundances of 51 Milky Way globular clusters on a homogeneous scale

NASA Astrophysics Data System (ADS)

Dias, B.; Barbuy, B.; Saviane, I.; Held, E. V.; Da Costa, G. S.; Ortolani, S.; Gullieuszik, M.; Vásquez, S.

2016-05-01

Context. Globular clusters trace the formation and evolution of the Milky Way and surrounding galaxies, and outline their chemical enrichment history. To accomplish these tasks it is important to have large samples of clusters with homogeneous data and analysis to derive kinematics, chemical abundances, ages and locations. Aims: We obtain homogeneous metallicities and α-element enhancement for 51 Galactic bulge, disc, and halo globular clusters that are among the most distant and/or highly reddened in the Galaxy's globular cluster system. We also provide membership selection based on stellar radial velocities and atmospheric parameters. The implications of our results are discussed. Methods: We observed R ~ 2000 spectra in the wavelength interval 456-586 nm for over 800 red giant stars in 51 Galactic globular clusters. We applied full spectrum fitting with the code ETOILE together with libraries of observed and synthetic spectra. We compared the mean abundances of all clusters with previous work and with field stars. We used the relation between mean metallicity and horizontal branch morphology defined by all clusters to select outliers for discussion. Results: [Fe/H], [Mg/Fe], and [α/Fe] were derived in a consistent way for almost one-third of all Galactic globular clusters. We find our metallicities are comparable to those derived from high-resolution data to within σ = 0.08 dex over the interval -2.5< [Fe/H] < 0.0. Furthermore, a comparison of previous metallicity scales with our values yields σ< 0.16 dex. We also find that the distribution of [Mg/Fe] and [α/Fe] with [Fe/H] for the 51 clusters follows the general trend exhibited by field stars. It is the first time that the following clusters have been included in a large sample of homogeneous stellar spectroscopic observations and metallicity derivation: BH 176, Djorg 2, Pal 10, NGC 6426, Lynga 7, and Terzan 8. In particular, only photometric metallicities were available previously for the first three clusters, and the available metallicity for NGC 6426 was based on integrated spectroscopy and photometry. Two other clusters, HP 1 and NGC 6558, are confirmed as candidates for the oldest globular clusters in the Milky Way. Conclusions: Stellar spectroscopy in the visible at R ~ 2000 for a large sample of globular clusters is a robust and efficient way to trace the chemical evolution of the host galaxy and to detect interesting objects for follow-up at higher resolution and with forthcoming giant telescopes. The technique used here can also be applied to globular cluster systems in nearby galaxies with current instruments and to distant galaxies with the advent of ELTs. Based on observations collected at the European Southern Observatory/Paranal, Chile, under programmes 68.B-0482(A), 69.D-0455(A), 71.D-0219(A), 077.D-0775(A), and 089.D-0493(B).Full Tables 1 and A.2 with the derived average parameters for the 758 red giant stars are only available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (http://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/590/A9

The Herschel Virgo Cluster Survey - XVI. A cluster inventory

NASA Astrophysics Data System (ADS)

Davies, J. I.; Bianchi, S.; Baes, M.; Bendo, G. J.; Clemens, M.; De Looze, I.; di Serego Alighieri, S.; Fritz, J.; Fuller, C.; Pappalardo, C.; Hughes, T. M.; Madden, S.; Smith, M. W. L.; Verstappen, J.; Vlahakis, C.

2014-03-01

Herschel far-infrared (FIR) observations are used to construct Virgo cluster galaxy luminosity functions and to show that the cluster lacks the very bright and the numerous faint sources detected in field galaxy surveys. The FIR spectral energy distributions are fitted to obtain dust masses and temperatures and the dust mass function. The cluster is overdense in dust by about a factor of 100 compared to the field. The same emissivity (β)-temperature relation applies for different galaxies as that found for different regions of M31. We use optical and H I data to show that Virgo is overdense in stars and atomic gas by about a factor of 100 and 20, respectively. Metallicity values are used to measure the mass of metals in the gas phase. The mean metallicity is ˜0.7 solar, and ˜50 per cent of the metals are in the dust. For the cluster as a whole, the mass density of stars in galaxies is eight times that of the gas and the gas mass density is 130 times that of the metals. We use our data to consider the chemical evolution of the individual galaxies, inferring that the measured variations in the effective yield are due to galaxies having different ages, being affected to varying degrees by gas loss. Four galaxy scaling relations are considered: mass-metallicity, mass-velocity, mass-star formation rate and mass-radius - we suggest that initial galaxy mass is the prime driver of a galaxy's ultimate destiny. Finally, we use X-ray observations and galaxy dynamics to assess the dark and baryonic matter content compared to the cosmological model.

Medium-resolution Spectroscopy of Red Giant Branch Stars in ω Centauri

NASA Astrophysics Data System (ADS)

An, Deokkeun; Lee, Young Sun; In Jung, Jae; Rey, Soo-Chang; Rhee, Jaehyon; Lee, Jae-Woo; Lee, Young-Wook; Joe, Young Hoon

2017-10-01

We present [Fe/H] and [Ca/Fe] of ˜600 red giant branch (RGB) members of the globular cluster Omega Centauri (ω {Cen}). We collect medium-resolution (R˜ 2000) spectra using the Blanco 4 m telescope at the Cerro Tololo Inter-American Observatory equipped with Hydra, the fiber-fed multi-object spectrograph. We demonstrate that blending of stellar light in optical fibers severely limits the accuracy of spectroscopic parameters in the crowded central region of the cluster. When photometric temperatures are taken in the spectroscopic analysis, our kinematically selected cluster members, excluding those that are strongly affected by flux from neighboring stars, include relatively fewer stars at intermediate metallicity ([{Fe}/{{H}}]˜ -1.5) than seen in the previous high-resolution survey for brighter giants in Johnson & Pilachowski. As opposed to the trend of increasing [Ca/Fe] with [Fe/H] found by those authors, our [Ca/Fe] estimates, based on Ca II H & K measurements, show essentially the same mean [Ca/Fe] for most of the metal-poor and metal-intermediate populations in this cluster, suggesting that mass- or metallicity-dependent SN II yields may not be necessary in their proposed chemical evolution scenario. Metal-rich cluster members in our sample show a large spread in [Ca/Fe], and do not exhibit a clear bimodal distribution in [Ca/Fe]. We also do not find convincing evidence for a radial metallicity gradient among RGB stars in ω {Cen}.

Infrared Astronomy at Extremely Faint Light Levels in Support of the LAIRTS Program.

DTIC Science & Technology

1987-09-01

Elliptical and Irregular Galaxies (T. X. Thuan), Ap. J., 299, 881-895 (1985). 2. IC 3475: A Stripped Dwarf Galaxy in the Virgo Cluster (L. Vigroux, T. X...imply a metallicity range for BCDs and dis between 1/30 and 1/3 of the sun’s metallicity, while the near-IR colors of the dEs (in the Virgo cluster of... clusters . A paper is in preparation which will study the stellar populations in these first brightest galaxies, as a function of the cluster

Geographical and pedological drivers of distribution and risks to soil fauna of seven metals (Cd, Cu, Cr, Ni, Pb, V and Zn) in British soils.

PubMed

Spurgeon, David J; Rowland, Philip; Ainsworth, Gillian; Rothery, Peter; Long, Sara; Black, Helaina I J

2008-05-01

Concentrations of seven metals were measured in over 1000 samples as part of an integrated survey. Sixteen metal pairs were significantly positively correlated. Cluster analysis identified two clusters. Metals from the largest (Cr, Cu, Ni, V, Zn), but not the smallest (Cd, Pb) cluster were significantly negatively correlated with spatial location and soil pH and organic matter content. Cd and Pb were not correlated with these parameters, due possibly to the masking effect of recent extensive release. Analysis of trends with soil properties in different habitats indicated that general trends may not necessarily be applicable to all areas. A risk assessment indicated that Zn poses the most widespread direct risk to soil fauna and Cd the least. Any risks associated with high metal concentrations are, however, likely to be greatest in habitats such as arable and horticultural, improved grassland and built up areas where soil metal concentrations are more frequently elevated.

On the Scatter of the Present-day Stellar Metallicity–Mass Relation of Cluster Dwarf Galaxies

NASA Astrophysics Data System (ADS)

Engler, Christoph; Lisker, Thorsten; Pillepich, Annalisa

2018-04-01

We examine the scatter of the relation between stellar mass and stellar metallicity for cluster dwarf galaxies in the cosmological simulation Illustris. The mass-metallicity relation exhibits the smallest intrinsic scatter at the galaxies' times of peak stellar mass, suggesting stellar mass stripping to be the primary effect responsible for the rather broad relation at present. However, for about 40% of galaxies in the high-metallicity tail of the relation, we find mass stripping to coincide with an increased enrichment of stellar metallicity, possibly caused by the stripping of low-metallicity stars in the galaxy outskirts.

XMM-Newton Observations of the Toothbrush and Sausage Clusters

NASA Astrophysics Data System (ADS)

Kara, S.; Mernier, F.; Ezer, C.; Akamatsu, H.; Ercan, E.

2017-10-01

Galaxy clusters are the largest gravitationally-bound objects in the universe. The member galaxies are embedded in a hot X-ray emitting Intra Cluster Medium (ICM) that has been enriched with metals produced by supernovae over the last billion years. Here we report new results from XMM-Newton archival observations of the merging clusters 1RXSJ0603.3+4213 and CIZA J2242.8+5301. These two clusters, also known as the Toothbrush and Sausage clusters, respectively, show a large radio relic associated with a merger shock North of their respective core. We show the distribution of the metal abundances with respect to the merger structures in these two clusters. The results are derived from spatially resolved X-ray spectra from the EPIC instrument on board XMM-Newton.

Synthesis and Characterization of Platinum-Ruthenium-Tin Catalysts

NASA Astrophysics Data System (ADS)

Uffalussy, Karen

Magnesia-supported trimetallic Pt-Ru-Sn catalysts prepared through a cluster and a conventional synthetic route have been investigated in terms of their structural properties and their catalytic activity for the hydrogenation of citral and crotonaldehyde. FTIR results indicate that the majority of the stabilizing ligands remain attached to the PtRu5(μ-SnPh 2)(C)(CO)15 cluster used following impregnation onto the MgO support. Under H2 reduction conditions, partial and full ligand removal are both observed at 473 and 573 K, respectively. HRSTEM analysis shows that cluster-derived samples exhibit significantly smaller average metal particle sizes, as well as narrower particle size distributions than the corresponding conventionally prepared ones. EDX measurements show that in the cluster-derived catalysts, the majority of the metal particles present are trimetallic in nature, with metal compositions similar to those of the original cluster. In contrast, the conventionally prepared materials contain mostly bimetallic and monometallic particles with variable compositions. XPS was used to determine how the variation in method of Sn addition to bimetallic Pt-Ru affects the electronic state for the trimetallic Pt-Ru-Sn/MgO system prepared by impregnation using multimetallic clusters, metal-salts, and the combination of both precursor types. Results show that the PtRu5Sn/MgO material has a significantly higher percentage of Sn0 in comparison to Pt-Ru-Sn/MgO and PtRu5-Sn/MgO, and a corresponding shift in both Pt and Ru peaks can be correlated to this relative change in Sn oxidation state. The formation of smaller metal particles and electronic modification of Pt and Ru by Sn in the cluster-derived catalysts and the presence of the three metals in these particles in close proximity result in higher activity and selectivity to the unsaturated alcohols for the hydrogenation of both citral and crotonaldehyde.

Electron-Poor Polar Intermetallics: Complex Structures, Novel Clusters, and Intriguing Bonding with Pronounced Electron Delocalization.

PubMed

Lin, Qisheng; Miller, Gordon J

2018-01-16

Intermetallic compounds represent an extensive pool of candidates for energy related applications stemming from magnetic, electric, optic, caloric, and catalytic properties. The discovery of novel intermetallic compounds can enhance understanding of the chemical principles that govern structural stability and chemical bonding as well as finding new applications. Valence electron-poor polar intermetallics with valence electron concentrations (VECs) between 2.0 and 3.0 e - /atom show a plethora of unprecedented and fascinating structural motifs and bonding features. Therefore, establishing simple structure-bonding-property relationships is especially challenging for this compound class because commonly accepted valence electron counting rules are inappropriate. During our efforts to find quasicrystals and crystalline approximants by valence electron tuning near 2.0 e - /atom, we observed that compositions close to those of quasicrystals are exceptional sources for unprecedented valence electron-poor polar intermetallics, e.g., Ca 4 Au 10 In 3 containing (Au 10 In 3 ) wavy layers, Li 14.7 Mg 36.8 Cu 21.5 Ga 66 adopting a type IV clathrate framework, and Sc 4 Mg x Cu 15-x Ga 7.5 that is incommensurately modulated. In particular, exploratory syntheses of AAu 3 T (A = Ca, Sr, Ba and T = Ge, Sn) phases led to interesting bonding features for Au, such as columns, layers, and lonsdaleite-type tetrahedral frameworks. Overall, the breadth of Au-rich polar intermetallics originates, in part, from significant relativistics effect on the valence electrons of Au, effects which result in greater 6s/5d orbital mixing, a small effective metallic radius, and an enhanced Mulliken electronegativity, all leading to ultimate enhanced binding with nearly all metals including itself. Two other successful strategies to mine electron-poor polar intermetallics include lithiation and "cation-rich" phases. Along these lines, we have studied lithiated Zn-rich compounds in which structural complexity can be realized by small amounts of Li replacing Zn atoms in the parent binary compounds CaZn 2 , CaZn 3 , and CaZn 5 ; their phase formation and bonding schemes can be rationalized by Fermi surface-Brillouin zone interactions between nearly free-electron states. "Cation-rich", electron-poor polar intermetallics have emerged using rare earth metals as the electropositive ("cationic") component together metal/metalloid clusters that mimic the backbones of aromatic hydrocarbon molecules, which give evidence of extensive electronic delocalization and multicenter bonding. Thus, we can identify three distinct, valence electron-poor, polar intermetallic systems that have yielded unprecedented phases adopting novel structures containing complex clusters and intriguing bonding characteristics. In this Account, we summarize our recent specific progress in the developments of novel Au-rich BaAl 4 -type related structures, shown in the "gold-rich grid", lithiation-modulated Ca-Li-Zn phases stabilized by different bonding characteristics, and rare earth-rich polar intermetallics containing unprecedented hydrocarbon-like planar Co-Ge metal clusters and pronounced delocalized multicenter bonding. We will focus mainly on novel structural motifs, bonding analyses, and the role of valence electrons for phase stability.

Physical properties of star clusters in the outer LMC as observed by the DES

DOE PAGES

Pieres, A.; Santiago, B.; Balbinot, E.; ...

2016-05-26

The Large Magellanic Cloud (LMC) harbors a rich and diverse system of star clusters, whose ages, chemical abundances, and positions provide information about the LMC history of star formation. We use Science Verification imaging data from the Dark Energy Survey to increase the census of known star clusters in the outer LMC and to derive physical parameters for a large sample of such objects using a spatially and photometrically homogeneous data set. Our sample contains 255 visually identified cluster candidates, of which 109 were not listed in any previous catalog. We quantify the crowding effect for the stellar sample producedmore » by the DES Data Management pipeline and conclude that the stellar completeness is < 10% inside typical LMC cluster cores. We therefore develop a pipeline to sample and measure stellar magnitudes and positions around the cluster candidates using DAOPHOT. We also implement a maximum-likelihood method to fit individual density profiles and colour-magnitude diagrams. For 117 (from a total of 255) of the cluster candidates (28 uncatalogued clusters), we obtain reliable ages, metallicities, distance moduli and structural parameters, confirming their nature as physical systems. The distribution of cluster metallicities shows a radial dependence, with no clusters more metal-rich than [Fe/H] ~ -0.7 beyond 8 kpc from the LMC center. Furthermore, the age distribution has two peaks at ≃ 1.2 Gyr and ≃ 2.7 Gyr.« less

Physical properties of star clusters in the outer LMC as observed by the DES

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pieres, A.; Santiago, B.; Balbinot, E.

The Large Magellanic Cloud (LMC) harbors a rich and diverse system of star clusters, whose ages, chemical abundances, and positions provide information about the LMC history of star formation. We use Science Verification imaging data from the Dark Energy Survey to increase the census of known star clusters in the outer LMC and to derive physical parameters for a large sample of such objects using a spatially and photometrically homogeneous data set. Our sample contains 255 visually identified cluster candidates, of which 109 were not listed in any previous catalog. We quantify the crowding effect for the stellar sample producedmore » by the DES Data Management pipeline and conclude that the stellar completeness is < 10% inside typical LMC cluster cores. We therefore develop a pipeline to sample and measure stellar magnitudes and positions around the cluster candidates using DAOPHOT. We also implement a maximum-likelihood method to fit individual density profiles and colour-magnitude diagrams. For 117 (from a total of 255) of the cluster candidates (28 uncatalogued clusters), we obtain reliable ages, metallicities, distance moduli and structural parameters, confirming their nature as physical systems. The distribution of cluster metallicities shows a radial dependence, with no clusters more metal-rich than [Fe/H] ~ -0.7 beyond 8 kpc from the LMC center. Furthermore, the age distribution has two peaks at ≃ 1.2 Gyr and ≃ 2.7 Gyr.« less

Mineral constituents profile of biochar derived from diversified waste biomasses: implications for agricultural applications.

PubMed

Zhao, Ling; Cao, Xinde; Wang, Qun; Yang, Fan; Xu, Shi

2013-01-01

The wide distribution and high heterogeneity of different elements in biochars derived from diverse feedstocks make it difficult to regulate their application in soil and to evaluate the maximum potential contribution of the nutrients and trace metals as well as the potential risk of toxic metals. This study classified 20 biochars, covering six typical categories, into three clusters according to their similarity and distance on nutrients and minerals using cluster analysis. Four principle components (PC) were extracted using factor analysis to reduce dimension and clearly characterize the mineral profile of these biochars. The contribution of each group of elements in the PCs to every cluster was clarified. PC1 had a high loading for Mg, Cu, Zn, Al, and Fe; PC2 was related to N, K, and Mn; and PC3 and PC4 mainly represented P and Ca. Cluster 1 included bone dregs and eggshell biochars with PC3 and PC4 as the main contributors. Cluster 2 included waterweeds and waste paper biochars, which were close to shrimp hull and chlorella biochars, with the main contributions being from PC2 and PC4. Cluster 3 included biochars with PC1 as the main contributor. At a soil biochar amendment rate of 50 t ha, the soil nutrients were significantly elevated, whereas the rise in toxic metals was negligible compared with Class I of the China Environmental Quality Standards for Soil. Biochar can potentially supply soil nutrients and trace metals, and different cluster biochars can be applied appropriately to different soils so that excessive or deficient nutrient and metal applications can be avoided. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

High-resolution electron spectroscopy of lanthanide (Ce, Pr, and Nd) complexes of cyclooctatetraene: the role of 4f electrons.

PubMed

Kumari, Sudesh; Roudjane, Mourad; Hewage, Dilrukshi; Liu, Yang; Yang, Dong-Sheng

2013-04-28

Cerium, praseodymium, and neodymium complexes of 1,3,5,7-cyclooctatetraene (COT) complexes were produced in a laser-vaporization metal cluster source and studied by pulsed-field ionization zero electron kinetic energy spectroscopy and quantum chemical calculations. The computations included the second-order Møller-Plesset perturbation theory, the coupled cluster method with single, double, and perturbative triple excitations, and the state-average complete active space self-consistent field method. The spectrum of each complex exhibits multiple band systems and is assigned to ionization of several low-energy electronic states of the neutral complex. This observation is different from previous studies of M(COT) (M = Sc, Y, La, and Gd), for which a single band system was observed. The presence of the multiple low-energy electronic states is caused by the splitting of the partially filled lanthanide 4f orbitals in the ligand field, and the number of the low-energy states increases rapidly with increasing number of the metal 4f electrons. On the other hand, the 4f electrons have a small effect on the geometries and vibrational frequencies of these lanthanide complexes.

Lasers '81

DOE Office of Scientific and Technical Information (OSTI.GOV)

Collins, C.B.

1982-01-01

Progress in lasers is discussed. The subjects addressed include: excimer lasers, surface spectroscopy, modern laser spectroscopy, free electron lasers, cavities and propagation, lasers in medicine, X-ray and gamma ray lasers, laser spectroscopy of small molecules and clusters, optical bistability, excitons, nonlinear optics in the X-ray and gamma ray regions, collective atomic phenomena, tunable IR lasers, far IR/submillimeter lasers, and laser-assisted collisions. Also treated are: special applications, multiphoton processes in atoms and small molecules, nuclear pumped lasers, material processing and applications, polarization, high energy lasers, laser chemistry, IR molecular lasers, laser applications of collision and dissociation phenomena, solid state laser materials,more » phase conjugation, advances in laser technology for fusion, metal vapor lasers, picosecond phenomena, laser ranging and geodesy, and laser photochemistry of complex molecules.« less

Photodissociation Studies of Metal-Containing Clusters and Complexes

NASA Astrophysics Data System (ADS)

Pilgrim, Jeffrey Scott

1995-01-01

There have been two major areas of investigation for researchers working with laser ablation in molecular beams. The first area is the study of weakly-bound complexes. These complexes are bound by electrostatic interactions. In the present study the weakly bound interactions of the rare gases with the magnesium ion are investigated with electronic spectroscopy. The second major area is the study of metal and metal-containing clusters. Examples of previous investigations are the alkali metal clusters and the fullerenes. The present investigation is on metal -carbon clusters. The so-called metallo-carbohedrenes and metal-carbon nanocrystals are studied. Resonance enhanced photodissociation spectroscopy is used to obtain electronic excitation spectra of the Mg^+-rare gas species in the ultraviolet region. This investigation is facilitated by a reflectron time-of-flight mass spectrometer. The interaction of the rare gas with the metal ion is attributed to a "solvation" of the atomic ion transition. Simple bonding arguments predict that the excited state is more bound than the ground state for these complexes. This will result in a shift of the complex vibronic origin to lower energy from the atomic ion transition. This is exactly what is observed in the experiment with progressively larger shifts for the heavier rare gases. The electronic excitation spectra allow the vibrational frequencies and anharmonicities for these complexes to be obtained for the excited state. In turn, the excited state bond dissociation energies can be determined. Finally, conservation of energy allows calculation of the ground state bond dissociation energies. In the metal-carbon systems the stability of the metallo-carbohedrene, met-car, stoichiometry is shown to extend into the transition period at least to the iron group. Photodissociation with a 532 nm laser causes a loss of metal atoms for met-cars formed with first row transition metals and a loss of metal-carbon units for met-cars formed from second-row transition metal atoms. Larger metal-carbon clusters are found to be face-centered-cubic nanocrystals. Photodissociation of these nanocrystals causes fragmentation into smaller nanocrystals. In addition, nanocrystals also dissociatively rearrange into the met -car structure. Two of the metal-carbon nanocrystals ( rm Ti_{14}C_{13 }^+ and rm V_{14 }C_{13}^+) fragment into the met-car with a trapped carbon atom.

How to Spot a Disrupted Galactic Satellite

NASA Astrophysics Data System (ADS)

Kohler, Susanna

2016-03-01

Many satellites dwarf galaxies and globular clusters are thought to be orbiting our galaxy, but detecting them can be a tricky business. In particular, satellites can be disrupted by the galactic potential and spread out into streams, making them so diffuse that were unable to spot them in photometric observations.In a recent study, a team of scientists led by John Vickers (Chinese Academy of Sciences) has cleverly worked around this difficulty by searching for groups of stars that have clustered velocities and metallicities differing from the background field.Searching Through StarsRadial velocity and metallicity of LAMOST stars near the physical location of Lamost 1. Circles are stars within 1.5 of the target location, small dots are stars within 5. [Vickers et al. 2016]The team trawled the Large Sky Area Multi-Object Fibre Spectroscopic Telescope (LAMOST) catalog, which contains spectroscopic information for 2.5 million stars. Vickers and collaborators first hunted for stars that shared an approximate physical location and had similar velocities (because the stars of a satellite will maintain similar velocities even after the satellite is disrupted). Next, they discarded any of these clumps that didnt also share a similar metallicity.Vickers and collaborators then compared the resulting set of 21 candidate streams to catalogs of known globular clusters, open clusters, and nearby galaxies. Three of the candidate clumps, clustered in a 3 area on the sky, do not correspond to any known objects. The authors postulate that these are all part of a disrupted satellite, which they dub Lamost 1.Characterizing a Former ClusterFitting the spectroscopic data for the member stars, the authors are able to estimate a number of characteristics of Lamost 1, with the best fit implying an age of 11 Gyr, a total mass of about 20,000 solar masses, and a distance from us of about 8,500 light-years.Based on the stellar motions, the authors believe that the clump is on an eccentric orbit and is currently at its furthest distance from the Galactic center. They suggest that the elliptic orbit and advanced age of the clump indicate it is most likely to be a disrupted globular cluster, rather than a dwarf galaxy.Interestingly, when the authors went back to search for a stellar overdensity corresponding to Lamost 1 in photometric data, they were unable to detect it. This reaffirms that their approach of searching for velocity and metallicity clumping is an important tool for discovering otherwise-invisible diffuse streams.BonusCheck out this cool graphic Vickers made using Stellarium and Aladin to demonstratewhere in the sky the stars ofLamost 1 are located. Lamost 1sstars are the red dots in the constellation Draco.CitationJohn J. Vickers et al 2016 ApJ 816 L2. doi:10.3847/2041-8205/816/1/L2

Packing of Russian doll clusters to form a nanometer-scale CsCl-type compound in a Cr–Zn–Sn complex metallic alloy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xie, Weiwei; Cava, Robert J.; Miller, Gordon J.

A new cubic complex metallic alloy phase, Cr 22Zn 72Sn 24, with a lattice parameter near 2.5 nm was discovered in crystals grown using a Zn/Sn flux. The structure consists of Russian doll clusters or a 3-d network of Cr-centered icosahedra (shown) with bcc-metal fragments in void spaces.

Packing of Russian doll clusters to form a nanometer-scale CsCl-type compound in a Cr–Zn–Sn complex metallic alloy

DOE PAGES

Xie, Weiwei; Cava, Robert J.; Miller, Gordon J.

2017-07-03

A new cubic complex metallic alloy phase, Cr 22Zn 72Sn 24, with a lattice parameter near 2.5 nm was discovered in crystals grown using a Zn/Sn flux. The structure consists of Russian doll clusters or a 3-d network of Cr-centered icosahedra (shown) with bcc-metal fragments in void spaces.

Hubble Friday - Heavy Metal Stars

NASA Image and Video Library

2017-12-08

Hubble rocks out with heavy metal stars! This 10.5-billion-year-old globular cluster, NGC 6496, is home to heavy-metal stars of a celestial kind! The stars comprising this spectacular spherical cluster are enriched with much higher proportions of metals — elements heavier than hydrogen and helium are curiously known as metals in astronomy — than stars found in similar clusters. A handful of these high-metallicity stars are also variable stars, meaning that their brightness fluctuates over time. NGC 6496 hosts a selection of long-period variables — giant pulsating stars whose brightness can take up to, and even over, a thousand days to change — and short-period eclipsing binaries, which dim when eclipsed by a stellar companion. The nature of the variability of these stars can reveal important information about their mass, radius, luminosity, temperature, composition, and evolution, providing astronomers with measurements that would be difficult or even impossible to obtain through other methods. NGC 6496 was discovered in 1826 by Scottish astronomer James Dunlop. The cluster resides at about 35,000 light-years away in the southern constellation of Scorpius (The Scorpion). Image credit: ESA/Hubble & NASA, Acknowledgement: Judy Schmidt Text credit: European Space Agency Read more: go.nasa.gov/1U2wqGW

Reactivity and Catalytic Activity of Hydrogen Atom Chemisorbed Silver Clusters.

PubMed

Manzoor, Dar; Pal, Sourav

2015-06-18

Metal clusters of silver have attracted recent interest of researchers as a result of their potential in different catalytic applications and low cost. However, due to the completely filled d orbital and very high first ionization potential of the silver atom, the silver-based catalysts interact very weakly with the reacting molecules. In the current work, density functional theory calculations were carried out to investigate the effect of hydrogen atom chemisorption on the reactivity and catalytic properties of inert silver clusters. Our results affirm that the hydrogen atom chemisorption leads to enhancement in the binding energy of the adsorbed O2 molecule on the inert silver clusters. The increase in the binding energy is also characterized by the decrease in the Ag-O and increase in the O-O bond lengths in the case of the AgnH silver clusters. Pertinent to the increase in the O-O bond length, a significant red shift in the O-O stretching frequency is also noted in the case of the AgnH silver clusters. Moreover, the hydrogen atom chemisorbed silver clusters show low reaction barriers and high heat of formation of the final products for the environmentally important CO oxidation reaction as compared to the parent catalytically inactive clusters. The obtained results were compared with those of the corresponding gold and hydrogen atom chemisorbed gold clusters obtained at the same level of theory. It is expected the current computational study will provide key insights for future advances in the design of efficient nanosilver-based catalysts through the adsorption of a small atom or a ligand.

Helium cluster isolation spectroscopy

NASA Astrophysics Data System (ADS)

Higgins, John Paul

Clusters of helium, each containing ~103- 104 atoms, are produced in a molecular beam and are doped with alkali metal atoms (Li, Na, and K) and large organic molecules. Electronic spectroscopy in the visible and UV regions of the spectrum is carried out on the dopant species. Since large helium clusters are liquid and attain an equilibrium internal temperature of 0.4 K, they interact weakly with atoms or molecules absorbed on their surface or resident inside the cluster. The spectra that are obtained are characterized by small frequency shifts from the positions of the gas phase transitions, narrow lines, and cold vibrational temperatures. Alkali atoms aggregate on the helium cluster surface to form dimers and trimers. The spectra of singlet alkali dimers exhibit the presence of elementary excitations in the superfluid helium cluster matrix. It is found that preparation of the alkali molecules on the surface of helium clusters leads to the preferential formation of high-spin, van der Waals bound, triplet dimers and quartet trimers. Four bound-bound and two bound-free transitions are observed in the triplet manifold of the alkali dimers. The quartet trimers serve as an ideal system for the study of a simple unimolecular reaction in the cold helium cluster environment. Analysis of the lowest quartet state provides valuable insight into three-body forces in a van der Waals trimer. The wide range of atomic and molecular systems studied in this thesis constitutes a preliminary step in the development of helium cluster isolation spectroscopy, a hybrid technique combining the advantages of high resolution spectroscopy with the synthetic, low temperature environment of matrices.

Bonding properties of FCC-like Au 44 (SR) 28 clusters from X-ray absorption spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Rui; Chevrier, Daniel M.; Zeng, Chenjie

Thiolate-protected gold clusters with precisely controlled atomic composition have recently emerged as promising candidates for a variety of applications because of their unique optical, electronic, and catalytic properties. The recent discovery of the Au44(SR)28 total structure is considered as an interesting finding in terms of the face-centered cubic (FCC)-like core structure in small gold-thiolate clusters. Herein, the unique bonding properties of Au44(SR)28 is analyzed using temperature-dependent X-ray absorption spectroscopy (XAS) measurements at the Au L3-edge and compared with other FCC-like clusters such as Au36(SR)24 and Au28(SR)20. A negative thermal expansion was detected for the Au–Au bonds of the metal coremore » (the first Au–Au shell) and was interpreted based on the unique Au core structure consisting of the Au4 units. EXAFS fitting results from Au28(SR)20, Au36(SR)24, and Au44(SR)28 show a size-dependent negative thermal expansion behavior in the first Au–Au shell, further highlighting the importance of the Au4 units in determining the Au core bonding properties and shedding light on the growth mechanism of these FCC-like Au clusters.« less

Tuning electronic and magnetic properties of Mn-mullite oxide sub-nanoclusters via MnOn polyhedron units.

PubMed

Li, Hui; Cho, Kyeongjae; Li, Shunfang; Wang, Weichao

2018-06-13

Ternary oxide nano-clusters compared to unary metallic and binary ones potentially exhibit more remarkable properties due to their higher stoichiometric flexibility in addition to cluster size variations. Herein, by combining with the structural searching scheme CALYPSO, we have built a series of Mn-mullite oxide clusters (SmxMnyOz)n {(xyz) = (125); (115); n = 1-4, 8} prior to investigation of their geometric and electronic structures via first-principles calculations. In small size regime (n < 4), (SmxMnyOz)n prefer nonstoichiometric (Sm1Mn1O5)n phases composed of nonmagnetic MnO4 tetrahedrons. When n ≧ 4, the clusters tend to develop as stoichiometric (Sm1Mn2O5)n species, including magnetic MnOn polyhedrons and Mn-Mn dimers, which contribute 3d-orbitals (dz2 and/or dx2-y2) around the Fermi levels. The different magnetic behaviors of nonstoichiometric and stoichiometric species originate from the distinct couplings of MnOn polyhedronal units, wherein Mn atoms experience different ligand fields and thus display different spin states. Such findings enable the tuning of electronic properties and potential applications in heterogeneous catalysis, electrochemical catalysis, and the related fields via engineering cluster size and stoichiometry.

Interaction of scandium and titanium atoms with a carbon surface containing five- and seven-membered rings

DOE Office of Scientific and Technical Information (OSTI.GOV)

Krasnov, P. O., E-mail: kpo1980@gmail.com; Eliseeva, N. S.; Kuzubov, A. A., E-mail: alex_xx@rambler.ru

2012-01-15

The use of carbon nanotubes coated by atoms of transition metals to store molecular hydrogen is associated with the problem of the aggregation of these atoms, which leads to the formation of metal clusters. The quantum-chemical simulation of cluster models of the carbon surface of a graphene type with scandium and titanium atoms has been performed. It has been shown that the presence of five- and seven-membered rings, in addition to six-membered rings, in these structures makes it possible to strongly suppress the processes of the migration of metal atoms over the surface, preventing their clustering.

Metal abundance of Tal 13

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zinn, R.; Diaz, A.I.

1982-08-01

Low-resolution spectrograms have been obtained of the three RR Lyrae variables in the distant and very sparse globular cluster Pal 13. A comparison of these spectrograms with similar ones of several RR Lyrae variables in the globular clusters M4, M5, and M22 reveals that Pal 13 is intermediate to M5 and M22 in metal abundance. A value of (Fe/H) = -1.67 +- 0.15 is obtained for Pal 13 by adopting Zinn's (1980a (Astrophys. J. Suppl. 42,19)) values of (Fe/H) for these other clusters. Pal 13 is another example of a distant halo object that is not extremely metal poor.

Molecular dynamics simulations of the structure evolutions of Cu-Zr metallic glasses under irradiation

NASA Astrophysics Data System (ADS)

Lang, Lin; Tian, Zean; Xiao, Shifang; Deng, Huiqiu; Ao, Bingyun; Chen, Piheng; Hu, Wangyu

2017-02-01

Molecular dynamics simulations have been performed to investigate the structural evolution of Cu64.5Zr35.5 metallic glasses under irradiation. The largest standard cluster analysis (LSCA) method was used to quantify the microstructure within the collision cascade regions. It is found that the majority of clusters within the collision cascade regions are full and defective icosahedrons. Not only the smaller structures (common neighbor subcluster) but also primary clusters greatly changed during the collision cascades; while most of these radiation damages self-recover quickly in the following quench states. These findings indicate the Cu-Zr metallic glasses have excellent irradiation-resistance properties.

NGC 6273: Towards Defining A New Class of Galactic Globular Clusters?

NASA Astrophysics Data System (ADS)

Johnson, Christian I.; Rich, Robert Michael; Pilachowski, Catherine A.; Caldwell, Nelson; Mateo, Mario L.; Ira Bailey, John; Crane, Jeffrey D.

2016-01-01

A growing number of observations have found that several Galactic globular clusters exhibit abundance dispersions beyond the well-known light element (anti-)correlations. These clusters tend to be very massive, have >0.1 dex intrinsic metallicity dispersions, have complex sub-giant branch morphologies, and have correlated [Fe/H] and s-process element enhancements. Interestingly, nearly all of these clusters discovered so far have [Fe/H]~-1.7. In this context, we have examined the chemical composition of 18 red giant branch (RGB) stars in the massive, metal-poor Galactic bulge globular cluster NGC 6273 using high signal-to-noise, high resolution (R~27,000) spectra obtained with the Michigan/Magellan Fiber System (M2FS) and MSpec spectrograph mounted on the Magellan-Clay 6.5m telescope at Las Campanas Observatory. We find that the cluster exhibits a metallicity range from [Fe/H]=-1.80 to -1.30 and is composed of two dominant populations separated in [Fe/H] and [La/Fe] abundance. The increase in [La/Eu] as a function of [La/H] suggests that the increase in [La/Fe] with [Fe/H] is due to almost pure s-process enrichment. The most metal-rich star in our sample is not strongly La-enhanced, but is α-poor and may belong to a third "anomalous" stellar population. The two dominant populations exhibit the same [Na/Fe]-[Al/Fe] correlation found in other "normal" globular clusters. Therefore, NGC 6273 joins ω Centauri, M 22, M 2, and NGC 5286 as a possible new class of Galactic globular clusters.

Activation of CO2 by supported Cu clusters.

PubMed

Iyemperumal, Satish Kumar; Deskins, N Aaron

2017-11-01

Catalytic reduction of carbon dioxide to useful chemicals is a potent way to mitigate this greenhouse gas, but the challenge lies in finding active reduction catalysts. Using density functional theory we studied CO 2 activation over TiO 2 -supported Cu clusters of size 1-4 atoms. The linear to bent transformation of CO 2 is necessary for activation, and we found that all the clusters stabilized bent CO 2 , along with a significant gain of electrons on the CO 2 (indicative of activation). On all the TiO 2 supported Cu clusters, the interfacial sites were found to stabilize the bent CO 2 adsorption, where the active site of adsorption on Cu dimer, trimer and tetramer was on the Cu atom farthest away from the TiO 2 surface. Particularly, the Cu dimer stabilized bent CO 2 very strongly, although this species was found to be unstable on the surface. A synthesis technique that could stabilize the Cu dimer could therefore lead to a very active catalyst. Furthermore we found (using vibrational and charge analysis) that the active sites for the CO 2 activation predominantly had 0 and +1 oxidation states; the oxidation state of Cu is known to directly affect CO 2 reduction activity. Our study shows TiO 2 -supported small Cu clusters can be active catalysts for CO 2 reduction and also provides further motivation for theoretical and experimental studies of metal clusters.

Far-infrared spectra of yttrium-doped gold clusters Au(n)Y (n=1-9).

PubMed

Lin, Ling; Claes, Pieterjan; Gruene, Philipp; Meijer, Gerard; Fielicke, André; Nguyen, Minh Tho; Lievens, Peter

2010-06-21

The geometric, spectroscopic, and electronic properties of neutral yttrium-doped gold clusters Au(n)Y (n=1-9) are studied by far-infrared multiple photon dissociation (FIR-MPD) spectroscopy and quantum chemical calculations. Comparison of the observed and calculated vibrational spectra allows the structures of the isomers present in the molecular beam to be determined. Most of the isomers for which the IR spectra agree best with experiment are calculated to be the energetically most stable ones. Attachment of xenon to the Au(n)Y cluster can cause changes in the IR spectra, which involve band shifts and band splittings. In some cases symmetry changes, as a result of the attachment of xenon atoms, were also observed. All the Au(n)Y clusters considered prefer a low spin state. In contrast to pure gold clusters, which exhibit exclusively planar lowest-energy structures for small sizes, several of the studied species are three-dimensional. This is particularly the case for Au(4)Y and Au(9)Y, while for some other sizes (n=5, 8) the 3D structures have an energy similar to that of their 2D counterparts. Several of the lowest-energy structures are quasi-2D, that is, slightly distorted from planar shapes. For all the studied species the Y atom prefers high coordination, which is different from other metal dopants in gold clusters.

Integrated spectral properties of 22 small angular diameter galactic open clusters

NASA Astrophysics Data System (ADS)

Ahumada, A. V.; Clariá, J. J.; Bica, E.

2007-10-01

Aims:Flux-calibrated integrated spectra of a sample of 22 Galactic open clusters of small angular diameter are presented. With one exception (ESO 429-SC2), all objects have Galactic longitudes in the range 208° < l < 33°. The spectra cover the range ≈3600-6800 Å, with a resolution of ≈14 Å. The properties of the present cluster sample are compared with those of well-studied clusters located in two 90° sectors, centred at l = 257° and l = 347°. The dissolution rate of Galactic open clusters in these two sectors is examined. Methods: Using the equivalent widths of the Balmer lines and comparing line intensities and continuum distribution of the cluster spectra with those of template cluster spectra with known properties, we derive both foreground reddening values and ages. Thus, we provide information independent of that determined through colour-magnitude diagrams. Results: The derived E(B-V) values for the whole sample vary from 0.0 in ESO 445-SC74 to 1.90 in Pismis 24, while the ages range from ~3 Myr (NGC 6604 and BH 151) to ~3.5 Gyr (Ruprecht 2). For six clusters (Dolidze 34, ESO 429-SC2, ESO 445-SC74, Ruprecht 2, BH 151 and Hogg 9) the foreground E(B-V) colour excesses and ages are determined for the first time. The results obtained for the remaining clusters show, in general terms, good agreement with previous photometric results. Conclusions: The age and reddening distributions of the present sample match those of known clusters in the two selected Galactic sectors. The present results would favour a major dissolution rate of star clusters in these two sectors. Two new solar-metallicity templates are defined corresponding to the age groups of (4-5) Myr and 30 Myr among those of Piatti et al. (2002, MNRAS, 335, 233). The Piatti et al. templates of 20 Myr and (3-4) Gyr are here redefined. Based on observations made at Complejo Astronómico El Leoncito, which is operated under agreement between the Consejo Nacional de Investigaciones Científicas y Técnicas de la República Argentina (CONICET) and the National Universities of La Plata, Córdoba and San Juan, Argentina. Tables [see full text]- [see full text] and Appendix are only available in electronic form at http://www.aanda.org

Catalyst Architecture for Stable Single Atom Dispersion Enables Site-Specific Spectroscopic and Reactivity Measurements of CO Adsorbed to Pt Atoms, Oxidized Pt Clusters, and Metallic Pt Clusters on TiO2.

PubMed

DeRita, Leo; Dai, Sheng; Lopez-Zepeda, Kimberly; Pham, Nicholas; Graham, George W; Pan, Xiaoqing; Christopher, Phillip

2017-10-11

Oxide-supported precious metal nanoparticles are widely used industrial catalysts. Due to expense and rarity, developing synthetic protocols that reduce precious metal nanoparticle size and stabilize dispersed species is essential. Supported atomically dispersed, single precious metal atoms represent the most efficient metal utilization geometry, although debate regarding the catalytic activity of supported single precious atom species has arisen from difficulty in synthesizing homogeneous and stable single atom dispersions, and a lack of site-specific characterization approaches. We propose a catalyst architecture and characterization approach to overcome these limitations, by depositing ∼1 precious metal atom per support particle and characterizing structures by correlating scanning transmission electron microscopy imaging and CO probe molecule infrared spectroscopy. This is demonstrated for Pt supported on anatase TiO 2 . In these structures, isolated Pt atoms, Pt iso , remain stable through various conditions, and spectroscopic evidence suggests Pt iso species exist in homogeneous local environments. Comparing Pt iso to ∼1 nm preoxidized (Pt ox ) and prereduced (Pt metal ) Pt clusters on TiO 2 , we identify unique spectroscopic signatures of CO bound to each site and find CO adsorption energy is ordered: Pt iso ≪ Pt metal < Pt ox . Pt iso species exhibited a 2-fold greater turnover frequency for CO oxidation than 1 nm Pt metal clusters but share an identical reaction mechanism. We propose the active catalytic sites are cationic interfacial Pt atoms bonded to TiO 2 and that Pt iso exhibits optimal reactivity because every atom is exposed for catalysis and forms an interfacial site with TiO 2 . This approach should be generally useful for studying the behavior of supported precious metal atoms.

Growth Behavior and Electronic Structure of Noble Metal-Doped Germanium Clusters.

PubMed

Mahtout, Sofiane; Siouani, Chaouki; Rabilloud, Franck

2018-01-18

Structures, energetics, and electronic properties of noble metal-doped germanium (MGe n with M = Cu, Ag, Au; n = 1-19) clusters are systematically investigated by using the density functional theory (DFT) approach. The endohedral structures in which the metal atom is encapsulated inside of a germanium cage appear at n = 10 when the dopant is Cu and n = 12 for M = Ag and Au. While Cu doping enhances the stability of the corresponding germanium frame, the binding energies of AgGe n and AuGe n are always lower than those of pure germanium clusters. Our results highlight the great stability of the CuGe 10 cluster in a D 4d structure and, to a lesser extent, that of AgGe 15 and AuGe 15 , which exhibits a hollow cage-like geometry. The sphere-type geometries obtained for n = 10-15 present a peculiar electronic structure in which the valence electrons of the noble metal and Ge atoms are delocalized and exhibit a shell structure associated with the quasi-spherical geometry. It is found that the coinage metal is able to give both s- and d-type electrons to be reorganized together with the valence electrons of Ge atoms through a pooling of electrons. The cluster size dependence of the stability, the frontier orbital energy gap, the vertical ionization potentials, and electron affinities are given.

Benthic foraminiferal assemblages as bio-indicators of metals contamination in sediments, Qarun Lake as a case study, Egypt

NASA Astrophysics Data System (ADS)

Abd El Naby, Ahmed; Al Menoufy, Safia; Gad, Ahmed

2018-03-01

Qarun Lake, in the Fayoum Depression of the Western Desert of Egypt, lies within the deepest area in the River Nile flood plain. The drainage water in the Qarun Lake is derived from the discharge of the natural and artificial drainage systems in the Fayoum. Mixed domestic and agricultural pollutants, including heavy metals, nitrates, phosphates, sulfates and pesticides, are discharged into Qarun Lake. Forty-six samples, collected from the undisturbed layer of sediments were used for benthic foraminiferal analysis. Concentrations of some selected trace metal elements (Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Sr, V, and Zn) were also determined. Statistical analysis of the abiotic variables (Texture distribution of sediments, Physico-chemical parameters, and metals concentrations) and of the biotic variables (distribution of benthic foraminiferal species) were also performed. The Q-mode cluster analysis of benthic foraminiferal distribution has provided evidence that the Qarun Lake can be subdivided into two cluster groups (A and B), reflecting environmental changes in the lake ecosystem. Cluster B can also be subdivided into two sub-clusters (B1 and B2). The presence of only pollution tolerant taxa with higher faunal density and lower diversity and the absence of the other foraminiferal assemblages in cluster A were attributed to the high concentration of trace metal elements and the strong environmental stress at the eastern and central parts of the Qarun Lake.

A CN Band Survey of Red Giants in the Globular Cluster M53

NASA Astrophysics Data System (ADS)

Martell, S. L.; Smith, G. H.

2004-12-01

We investigate the star-to-star variations in λ 3883 CN bandstrength among red giant stars in the low-metallicity globular cluster M53 ([Fe/H] = --2.0). Our data were taken with the Kast spectrograph on the 3-meter Shane telescope at Lick Observatory in April 2001. Star-to-star variations in CN bandstrength are common in intermediate- and high-metallicity globular clusters ([Fe/H] ≥ --1.6). Our data were obtained to test whether that variation will also be present in a low-metallicity globular cluster, or whether it will be suppressed by the overall lack of metals in the stars. Our preliminary result is that the λ 3883 CN band is weak in our program stars, which span the brightest magnitude of the red giant branch. On visual inspection, the M53 giants appear to be similar in their CN bandstrength to the four CN-weak giants in NGC 6752 whose average spectrum is plotted in Fig. 4 of Norris et al. (1981, ApJ, 244, 205). This work is planned to form part of a larger study of the metallicity dependence of CN bandstrength and carbon abundance behavior on the upper giant branch of globular clusters. This work is supported by NSF grant AST 00-98453 and by an award from the ARCS foundation, Northern California Chapter.

Quasars, clusters and cosmology

NASA Astrophysics Data System (ADS)

Dhanda, Neelam

PART A: Acceleration of the Universe and Modified Gravity: We study the power of next-generation galaxy cluster surveys (such as eROSITA and WFXT) in constraining the cosmological parameters and especially the growth history of the Universe, using the information from galaxy cluster redshift and mass-function evolution and from cluster power spectrum. We use the Fisher Matrix formalism to evaluate the potential for the galaxy cluster surveys to make predictions about cosmological parameters like the gravitational growth index gamma. The primary purpose of this study has been to check whether we can rule out one or the other of the underlying gravity theories in light of the present uncertainty of mass-observable relations and their scatter evolution. We found that these surveys will provide better constraints on various cosmological parameters even after we admit a lack of complete knowledge about the galaxy cluster structure, and when we combine the information from the cluster number count redshift and mass evolution with that from the cluster power spectrum. Based on this, we studied the ability of different surveys to constrain the growth history of the Universe. It was found that whereas eROSITA surveys will need strong priors on cluster structure evolution to conclusively rule out one or the other of the two gravity models, General Relativity and DGP Braneworld Gravity; WFXT surveys do hold the special promise of differentiating growth and telling us whether it is GR or not, with its wide-field survey having the ability to say so even with 99% confidence. PART B: Chemical Evolution in Quasars: We studied chemical evolution in the broad emission line region (BELR) of nitrogen rich quasars drawn from the SDSS Quasar Catalogue IV. Using tools of emission-line spectroscopy, we made detailed abundance measurements of ˜ 40 quasars and estimated their metallicities using the line-intensity ratio method. It was found that quasars with strong nitrogen lines are indicators of high metallicities. Some of these quasars have reached metallicities as high as Z ˜ 20 Z⊙ . Our detailed analysis showed that except in three QSOs, most of the different line-intensity ratios implied the similar metallicities. This verifies that this abundance analysis technique does produce meaningful results. The exceptions are the line-intensity ratio NIV]/CIV, which gives systematically low metallicities and the line-intensity ratio NV/He II, which gives systematically high metallicities. We compared our findings with the predictions of the galactic chemical evolution models. From this study it was concluded that such high metallicities are reached either by requiring a top-heavy Initial Mass Function (IMF) for the quasar host galaxy as suggested by theoretical models, or by physically catastrophic events such as mergers that trigger star formation in already evolved systems which then leads to extreme metallicities in such quasars.

Ages of Extragalactic Intermediate-Age Star Clusters

NASA Technical Reports Server (NTRS)

Flower, P. J.

1983-01-01

A dating technique for faint, distant star clusters observable in the local group of galaxies with the space telescope is discussed. Color-magnitude diagrams of Magellanic Cloud clusters are mentioned along with the metallicity of star clusters.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Johnson, Christian I.; Caldwell, Nelson; Rich, R. Michael

We present radial velocities and chemical abundances for red giant branch stars in the Galactic bulge globular clusters NGC 6342 and NGC 6366. The velocities and abundances are based on measurements of high-resolution ( R ≳ 20,000) spectra obtained with the MMT–Hectochelle and WIYN–Hydra spectrographs. We find that NGC 6342 has a heliocentric radial velocity of +112.5 km s{sup −1} ( σ = 8.6 km s{sup −1}), NGC 6366 has a heliocentric radial velocity of −122.3 km s{sup −1} ( σ = 1.5 km s{sup −1}), and both clusters have nearly identical metallicities ([Fe/H] ≈ −0.55). NGC 6366 shows evidencemore » of a moderately extended O–Na anti-correlation, but more data are needed for NGC 6342 to determine if this cluster also exhibits the typical O–Na relation likely found in all other Galactic globular clusters. The two clusters are distinguished from similar metallicity field stars as having larger [Na/Fe] spreads and enhanced [La/Fe] ratios, but we find that NGC 6342 and NGC 6366 display α and Fe-peak element abundance patterns that are typical of other metal-rich ([Fe/H] > −1) inner Galaxy clusters. However, the median [La/Fe] abundance may vary from cluster-to-cluster.« less

LASER APPLICATIONS AND OTHER TOPICS IN QUANTUM ELECTRONICS: On gamma-ray spectra of metal nuclei in a metal-carbon cluster

NASA Astrophysics Data System (ADS)

Rivlin, Lev A.

2007-07-01

The resonance absorption and emission gamma-ray spectra are constructed for nuclear transitions in metals in large metal-carbon clusters. The possibilities of observing gamma lines with the natural linewidth in an isolated molecule and the suppression of the excess line broadening in an ensemble of molecules are estimated. The possibility of the appearance of the hidden population inversion of nuclear states and the quantum amplification of the type of coherent stimulated scattering is also analysed.

On the lithium dip in the metal poor open cluster NGC 2243

NASA Astrophysics Data System (ADS)

François, P.; Pasquini, L.; Biazzo, K.; Bonifacio, P.; Palsa, R.

2014-05-01

Lithium is a key element for studying the mixing mechanisms operating in stellar interiors. It can also be used to probe the chemical evolution of the Galaxy and the Big Bang nucleosynthesis. Measuring the abundance of Lithium in stars belonging to Open Clusters (hereafter OC) allows a detailed comparison with stellar evolutionary models. NGC 2243 is particularly interesting thanks to its relative low metallicity ([Fe/H]=-0.54 ± 0.10 dex). We performed a detailed analysis of high-resolution spectra obtained with the multi-object facility FLAMES at the VLT 8.2m telescope. Lithium abundance has been measured in 27 stars. We found a Li dip center of 1.06 M⊙, which is significantly smaller than that observed in solar metallicity and metal-rich clusters. This finding confirms and strengthens the conclusion that the mass of the stars in the Li dip strongly depends on stellar metallicity. The mean Li abundance of the cluster is log n(Li) = 2.70 dex, which is substantially higher than that observed in 47 Tue. We derived an iron abundance of [Fe/H]=-0.54±0.10 dex for NGC 2243, in agreement (within the errors) with previous findings.

Abell 1142 and the Missing Central Galaxy – A Cluster in Transition?

NASA Astrophysics Data System (ADS)

Jones, Alexander; Su, Yuanyuan; Buote, David; Forman, William; van Weeren, Reinout; Jones, Christine; Gastaldello, Fabio; Kraft, Ralph; Randall, Scott

2018-01-01

Two types of galaxy clusters exist: cool core (CC) clusters which exhibit centrally-peaked metallicity and X-ray emission and non-cool core (NCC) clusters, possessing comparably homogeneous metallicity and X-ray emission distributions. However, the origin of this dichotomy is still unknown. The current prevailing theories state that either there is a primordial entropy limit, above which a CC is unable to form, or that clusters can change type through major mergers and radiative cooling. Abell 1142 is a galaxy cluster that can provide a unique probe of the root of this cluster-type division. It is formed of two merging sub-clusters, each with its own brightest cluster galaxies (BCG). Its enriched X-ray centroid (possible CC remnant) lies between these two BCGs. We present the thermal and chemical distributions of this system using deep (180ks) XMM-Newton observations to shed light on the role of mergers in the evolution of galaxy clusters.

Electronic Interactions of Size-Selected Oxide Clusters on Metallic and Thin Film Oxide Supports

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xue, Meng; Nakayama, Miki; Liu, Ping

The interfacial electronic structure of various size-selected metal oxide nanoclusters (M 3O x; M = Mo, Nb, Ti) on Cu(111) and a thin film of Cu 2O supports were investigated in this paper by a combination of experimental methods and density functional theory (DFT). These systems explore electron transfer at the metal–metal oxide interface which can modify surface structure, metal oxidation states, and catalytic activity. Electron transfer was probed by measurements of surface dipoles derived from coverage dependent work function measurements using two-photon photoemission (2PPE) and metal core level binding energy spectra from X-ray photoelectron spectroscopy (XPS). The measured surfacemore » dipoles are negative for all clusters on Cu(111) and Cu 2O/Cu(111), but those on the Cu 2O surface are much larger in magnitude. In addition, sub-stoichiometric or “reduced” clusters exhibit smaller surface dipoles on both the Cu(111) and Cu 2O surfaces. Negative surface dipoles for clusters on Cu(111) suggest Cu → cluster electron transfer, which is generally supported by DFT-calculated Bader charge distributions. For Cu 2O/Cu(111), calculations of the surface electrostatic potentials show that the charge distributions associated with cluster adsorption structures or distortions at the cluster–Cu 2O–Cu(111) interface are largely responsible for the observed negative surface dipoles. Changes observed in the XPS spectra for the Mo 3d, Nb 3d, and Ti 2p core levels of the clusters on Cu(111) and Cu 2O/Cu(111) are interpreted with help from the calculated Bader charges and cluster adsorption structures, the latter providing information about the presence of inequivalent cation sites. Finally, the results presented in this work illustrate how the combined use of different experimental probes along with theoretical calculations can result in a more realistic picture of cluster–support interactions and bonding.« less

Electronic Interactions of Size-Selected Oxide Clusters on Metallic and Thin Film Oxide Supports

DOE PAGES

Xue, Meng; Nakayama, Miki; Liu, Ping; ...

2017-09-13

The interfacial electronic structure of various size-selected metal oxide nanoclusters (M 3O x; M = Mo, Nb, Ti) on Cu(111) and a thin film of Cu 2O supports were investigated in this paper by a combination of experimental methods and density functional theory (DFT). These systems explore electron transfer at the metal–metal oxide interface which can modify surface structure, metal oxidation states, and catalytic activity. Electron transfer was probed by measurements of surface dipoles derived from coverage dependent work function measurements using two-photon photoemission (2PPE) and metal core level binding energy spectra from X-ray photoelectron spectroscopy (XPS). The measured surfacemore » dipoles are negative for all clusters on Cu(111) and Cu 2O/Cu(111), but those on the Cu 2O surface are much larger in magnitude. In addition, sub-stoichiometric or “reduced” clusters exhibit smaller surface dipoles on both the Cu(111) and Cu 2O surfaces. Negative surface dipoles for clusters on Cu(111) suggest Cu → cluster electron transfer, which is generally supported by DFT-calculated Bader charge distributions. For Cu 2O/Cu(111), calculations of the surface electrostatic potentials show that the charge distributions associated with cluster adsorption structures or distortions at the cluster–Cu 2O–Cu(111) interface are largely responsible for the observed negative surface dipoles. Changes observed in the XPS spectra for the Mo 3d, Nb 3d, and Ti 2p core levels of the clusters on Cu(111) and Cu 2O/Cu(111) are interpreted with help from the calculated Bader charges and cluster adsorption structures, the latter providing information about the presence of inequivalent cation sites. Finally, the results presented in this work illustrate how the combined use of different experimental probes along with theoretical calculations can result in a more realistic picture of cluster–support interactions and bonding.« less

Protein-protected luminescent noble metal quantum clusters: an emerging trend in atomic cluster nanoscience

PubMed Central

Xavier, Paulrajpillai Lourdu; Chaudhari, Kamalesh; Baksi, Ananya; Pradeep, Thalappil

2012-01-01

Noble metal quantum clusters (NMQCs) are the missing link between isolated noble metal atoms and nanoparticles. NMQCs are sub-nanometer core sized clusters composed of a group of atoms, most often luminescent in the visible region, and possess intriguing photo-physical and chemical properties. A trend is observed in the use of ligands, ranging from phosphines to functional proteins, for the synthesis of NMQCs in the liquid phase. In this review, we briefly overview recent advancements in the synthesis of protein protected NMQCs with special emphasis on their structural and photo-physical properties. In view of the protein protection, coupled with direct synthesis and easy functionalization, this hybrid QC-protein system is expected to have numerous optical and bioimaging applications in the future, pointers in this direction are visible in the literature. PMID:22312454

Spectrum syntheses of high-resolution integrated light spectra of Galactic globular clusters

NASA Astrophysics Data System (ADS)

Sakari, Charli M.; Shetrone, Matthew; Venn, Kim; McWilliam, Andrew; Dotter, Aaron

2013-09-01

Spectrum syntheses for three elements (Mg, Na and Eu) in high-resolution integrated light spectra of the Galactic globular clusters 47 Tuc, M3, M13, NGC 7006 and M15 are presented, along with calibration syntheses of the solar and Arcturus spectra. Iron abundances in the target clusters are also derived from integrated light equivalent width analyses. Line profiles in the spectra of these five globular clusters are well fitted after careful consideration of the atomic and molecular spectral features, providing levels of precision that are better than equivalent width analyses of the same integrated light spectra, and that are comparable to the precision in individual stellar analyses. The integrated light abundances from the 5528 and 5711 Å Mg I lines, the 6154 and 6160 Å Na I lines, and the 6645 Å Eu II line fall within the observed ranges from individual stars; however, these integrated light abundances do not always agree with the average literature abundances. Tests with the second parameter clusters M3, M13 and NGC 7006 show that assuming an incorrect horizontal branch morphology is likely to have only a small ( ≲ 0.06 dex) effect on these Mg, Na and Eu abundances. These tests therefore show that integrated light spectrum syntheses can be applied to unresolved globular clusters over a wide range of metallicities and horizontal branch morphologies. Such high precision in integrated light spectrum syntheses is valuable for interpreting the chemical abundances of globular cluster systems around other galaxies.

Black hole binaries dynamically formed in globular clusters

NASA Astrophysics Data System (ADS)

Park, Dawoo; Kim, Chunglee; Lee, Hyung Mok; Bae, Yeong-Bok; Belczynski, Krzysztof

2017-08-01

We investigate properties of black hole (BH) binaries formed in globular clusters via dynamical processes, using directN-body simulations. We pay attention to effects of BH mass function on the total mass and mass ratio distributions of BH binaries ejected from clusters. First, we consider BH populations with two different masses in order to learn basic differences from models with single-mass BHs only. Secondly, we consider continuous BH mass functions adapted from recent studies on massive star evolution in a low metallicity environment, where globular clusters are formed. In this work, we consider only binaries that are formed by three-body processes and ignore stellar evolution and primordial binaries for simplicity. Our results imply that most BH binary mergers take place after they get ejected from the cluster. Also, mass ratios of dynamically formed binaries should be close to 1 or likely to be less than 2:1. Since the binary formation efficiency is larger for higher-mass BHs, it is likely that a BH mass function sampled by gravitational-wave observations would be weighed towards higher masses than the mass function of single BHs for a dynamically formed population. Applying conservative assumptions regarding globular cluster populations such as small BH mass fraction and no primordial binaries, the merger rate of BH binaries originated from globular clusters is estimated to be at least 6.5 yr-1 Gpc-3. Actual rate can be up to more than several times of our conservative estimate.

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

PubMed

Platero-Prats, Ana E; Li, Zhanyong; Gallington, Leighanne C; Peters, Aaron W; Hupp, Joseph T; Farha, Omar K; Chapman, Karena W

2017-09-01

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. These 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.

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

DOE PAGES

Platero-Prats, Ana E.; Li, Zhanyong; Gallington, Leighanne C.; ...

2017-04-03

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 ofin situsynchrotron-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 °Cmore » produces metallic Cu 0of 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 2O cuprite phase. The dynamic restructuring of the system in different chemical environments underscores the importance of probing these systemsin situ.« less

Sinter-Resistant Platinum Catalyst Supported by Metal-Organic Framework.

PubMed

Kim, In Soo; Li, Zhanyong; Zheng, Jian; Platero-Prats, Ana E; Mavrandonakis, Andreas; Pellizzeri, Steven; Ferrandon, Magali; Vjunov, Aleksei; Gallington, Leighanne C; Webber, Thomas E; Vermeulen, Nicolaas A; Penn, R Lee; Getman, Rachel B; Cramer, Christopher J; Chapman, Karena W; Camaioni, Donald M; Fulton, John L; Lercher, Johannes A; Farha, Omar K; Hupp, Joseph T; Martinson, Alex B F

2018-01-22

Single atoms and few-atom clusters of platinum are uniformly installed on the zirconia nodes of a metal-organic framework (MOF) NU-1000 via targeted vapor-phase synthesis. The catalytic Pt clusters, site-isolated by organic linkers, are shown to exhibit high catalytic activity for ethylene hydrogenation while exhibiting resistance to sintering up to 200 °C. In situ IR spectroscopy reveals the presence of both single atoms and few-atom clusters that depend upon synthesis conditions. Operando X-ray absorption spectroscopy and X-ray pair distribution analyses reveal unique changes in chemical bonding environment and cluster size stability while on stream. Density functional theory calculations elucidate a favorable reaction pathway for ethylene hydrogenation with the novel catalyst. These results provide evidence that atomic layer deposition (ALD) in MOFs is a versatile approach to the rational synthesis of size-selected clusters, including noble metals, on a high surface area support. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

The complex star cluster system of NGC 1316 (Fornax A)

NASA Astrophysics Data System (ADS)

Sesto, Leandro A.; Faifer, Favio R.; Forte, Juan C.

2016-10-01

This paper presents Gemini-gri' high-quality photometry for cluster candidates in the field of NGC 1316 (Fornax A) as part of a study that also includes GMOS spectroscopy. A preliminary discussion of the photometric data indicates the presence of four stellar cluster populations with distinctive features in terms of age, chemical abundance and spatial distribution. Two of them seem to be the usually old (metal poor and metal rich) populations typically found in elliptical galaxies. In turn, an intermediate-age (5 Gyr) globular cluster population is the dominant component of the sample (as reported by previous papers). We also find a younger cluster population with a tentative age of ≈ 1 Gyr.

Addressing individual metal ion centers in supramolecules by STS

NASA Astrophysics Data System (ADS)

Alam, M. S.; Ako, A. M.; Ruben, M.; Thompson, L. K.; Lehn, J.-M.

2005-03-01

As the information of STM measurements arises from electronic structure, separating information on the topography is not straightforward for complex molecules. Scanning tunneling spectroscopy (STS) measurements give information about the molecular energy levels, which are next to the molecules Fermi level. Using a home built STM working under ambient conditions, we succeeded to combine high resolution topography mapping with simultaneous current-voltage characteristics (STS) measurements on single molecules deposited on highly oriented pyrolytic graphite surfaces. We present our recent results on grid-type molecules [Co4L4] (L=4,6-bis(2',2''-bipyridyl-6-yl)pyrimidine) and [Mn9L6] (L=2POAP-2H) as well as on ring-shaped Fe ion chains [Fe6Cl6L6] (L=1-Ecosyliminodiethanol). Small, regular molecule clusters as well as separated single molecules were observed. We found a rather large contrast at the expected location of the metal centers in our molecules, i.e. the location of the individual metal ions in their organic matrix is directly addressable by STS.

Asymmetric pathways in the electrochemical conversion reaction of NiO as battery electrode with high storage capacity

PubMed Central

Boesenberg, Ulrike; Marcus, Matthew A.; Shukla, Alpesh K.; Yi, Tanghong; McDermott, Eamon; Teh, Pei Fen; Srinivasan, Madhavi; Moewes, Alexander; Cabana, Jordi

2014-01-01

Electrochemical conversion reactions of transition metal compounds create opportunities for large energy storage capabilities exceeding modern Li-ion batteries. However, for practical electrodes to be envisaged, a detailed understanding of their mechanisms is needed, especially vis-à-vis the voltage hysteresis observed between reduction and oxidation. Here, we present such insight at scales from local atomic arrangements to whole electrodes. NiO was chosen as a simple model system. The most important finding is that the voltage hysteresis has its origin in the differing chemical pathways during reduction and oxidation. This asymmetry is enabled by the presence of small metallic clusters and, thus, is likely to apply to other transition metal oxide systems. The presence of nanoparticles also influences the electrochemical activity of the electrolyte and its degradation products and can create differences in transport properties within an electrode, resulting in localized reactions around converted domains that lead to compositional inhomogeneities at the microscale. PMID:25410966

Asymmetric pathways in the electrochemical conversion reaction of NiO as battery electrode with high storage capacity

DOE PAGES

Boesenberg, Ulrike; Marcus, Matthew A.; Shukla, Alpesh K.; ...

2014-11-20

Electrochemical conversion reactions of transition metal compounds create opportunities for large energy storage capabilities exceeding modern Li-ion batteries. However, for practical electrodes to be envisaged, a detailed understanding of their mechanisms is needed, especially vis-à-vis the voltage hysteresis observed between reduction and oxidation. Here, we present such insight at scales from local atomic arrangements to whole electrodes. NiO was chosen as a simple model system. The most important finding is that the voltage hysteresis has its origin in the differing chemical pathways during reduction and oxidation. This asymmetry is enabled by the presence of small metallic clusters and, thus, ismore » likely to apply to other transition metal oxide systems. Lastly, the presence of nanoparticles also influences the electrochemical activity of the electrolyte and its degradation products and can create differences in transport properties within an electrode, resulting in localized reactions around converted domains that lead to compositional inhomogeneities at the microscale.« less

SBA Innovation Clusters

DTIC Science & Technology

2012-03-02

Programs and services to help you start, grow and succeed www.sba.gov U.S. Small Business Administration Your Small Business Resource 1Approved for...Public Release SBA Innovation Clusters RADM Steven G. Smith USN (Ret) Advanced Defense Technology Cluster Coordinator U.S. Small Business ...UNIT NUMBER 7. PERFORMING ORGANIZATION NAME(S) AND ADDRESS(ES) U.S. Small Business Administration ,Advanced Defense Technology Cluster,409 3rd St, SW

Properties of Ammonium Ion–Water Clusters: Analyses of Structure Evolution, Noncovalent Interactions, and Temperature and Humidity Effects

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pei, Shi-Tu; Jiang, Shuai; Liu, Yi-Rong

2015-03-03

Although ammonium ion–water clusters are abundant in the biosphere, some information regarding these clusters, such as their growth route, the influence of temperature and humidity, and the concentrations of various hydrated clusters, is lacking. In this study, theoretical calculations are performed on ammonium ion–water clusters. These theoretical calculations are focused on determining the following characteristics: (1) the pattern of cluster growth; (2) the percentages of clusters of the same size at different temperatures and humidities; (3) the distributions of different isomers for the same size clusters at different temperatures; (4) the relative strengths of the noncovalent interactions for clusters ofmore » different sizes. The results suggest that the dipole moment may be very significant for the ammonium ion–water system, and some new stable isomers were found. The nucleation of ammonium ions and water molecules is favorable at low temperatures; thus, the clusters observed at high altitudes might not be present at low altitudes. High humidity can contribute to the formation of large ammonium ion–water clusters, whereas the formation of small clusters may be favorable under low-humidity conditions. The potential energy surfaces (PES) of these different sized clusters are complicated and differ according to the distribution of isomers at different temperatures. Some similar structures are observed between NH4+(H2O)n and M(H2O)n (where M represents an alkali metal ion or water molecule); when n = 8, the clusters begin to form the closed-cage geometry. As the cluster size increases, these interactions become progressively weaker. The successive binding energy at the DF-MP2-F12/VDZ-F12 level is better than that at the PW91PW91/6-311++G(3df, 3pd) level and is consistent with the experimentally determined values.« less

Properties of ammonium ion-water clusters: analyses of structure evolution, noncovalent interactions, and temperature and humidity effects.

PubMed

Pei, Shi-Tu; Jiang, Shuai; Liu, Yi-Rong; Huang, Teng; Xu, Kang-Ming; Wen, Hui; Zhu, Yu-Peng; Huang, Wei

2015-03-26

Although ammonium ion-water clusters are abundant in the biosphere, some information regarding these clusters, such as their growth route, the influence of temperature and humidity, and the concentrations of various hydrated clusters, is lacking. In this study, theoretical calculations are performed on ammonium ion-water clusters. These theoretical calculations are focused on determining the following characteristics: (1) the pattern of cluster growth; (2) the percentages of clusters of the same size at different temperatures and humidities; (3) the distributions of different isomers for the same size clusters at different temperatures; (4) the relative strengths of the noncovalent interactions for clusters of different sizes. The results suggest that the dipole moment may be very significant for the ammonium ion-water system, and some new stable isomers were found. The nucleation of ammonium ions and water molecules is favorable at low temperatures; thus, the clusters observed at high altitudes might not be present at low altitudes. High humidity can contribute to the formation of large ammonium ion-water clusters, whereas the formation of small clusters may be favorable under low-humidity conditions. The potential energy surfaces (PES) of these different sized clusters are complicated and differ according to the distribution of isomers at different temperatures. Some similar structures are observed between NH4(+)(H2O)n and M(H2O)n (where M represents an alkali metal ion or water molecule); when n = 8, the clusters begin to form the closed-cage geometry. As the cluster size increases, these interactions become progressively weaker. The successive binding energy at the DF-MP2-F12/VDZ-F12 level is better than that at the PW91PW91/6-311++G(3df, 3pd) level and is consistent with the experimentally determined values.

Nonlocality and particle-clustering effects on the optical response of composite materials with metallic nanoparticles

NASA Astrophysics Data System (ADS)

Chen, C. W.; Chung, H. Y.; Chiang, H.-P.; Lu, J. Y.; Chang, R.; Tsai, D. P.; Leung, P. T.

2010-10-01

The optical properties of composites with metallic nanoparticles are studied, taking into account the effects due to the nonlocal dielectric response of the metal and the coalescing of the particles to form clusters. An approach based on various effective medium theories is followed, and the modeling results are compared with those from the cases with local response and particles randomly distributed through the host medium. Possible observations of our modeling results are illustrated via a calculation of the transmission of light through a thin film made of these materials. It is found that the nonlocal effects are particularly significant when the particles coalesce, leading to blue-shifted resonances and slightly lower values in the dielectric functions. The dependence of these effects on the volume fraction and fractal dimension of the metal clusters is studied in detail.

Theoretical research program to predict the properties of molecules and clusters containing transition metal atoms

NASA Technical Reports Server (NTRS)

Walch, S.

1984-01-01

The primary focus of this research has been the theoretical study of transition metal (TM) chemistry. A major goal of this work is to provide reliable information about the interaction of H atoms with iron metal. This information is needed to understand the effect of H atoms on the processes of embrittlement and crack propagation in iron. The method in the iron hydrogen studies is the cluster method in which the bulk metal is modelled by a finite number of iron atoms. There are several difficulties in the application of this approach to the hydrogen iron system. First the nature of TM-TM and TM-H bonding for even diatomic molecules was not well understood when these studies were started. Secondly relatively large iron clusters are needed to provide reasonable results.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yoon, Yeung-Pil; Kim, Jae-Hong; Ahn, Kwang-Soon, E-mail: kstheory@ynu.ac.kr

Au was electrodeposited potentiostatically at 0.3 V for 5 min on nanoporous Pt nanoparticle-coated F-doped SnO{sub 2} (FTO/Pt) substrates. For comparison, Au-electrodeposited FTO (FTO/Au) and Au-uncoated FTO/Pt were prepared. FTO/Au showed large-sized Au clusters dispersed sparsely over FTO, which resulted in lower electrocatalytic activity than FTO/Pt. In contrast, FTO/Pt exhibited poor stability unlike FTO/Au due to poisoning by the adsorption of sulfur species. The Au-electrodeposited FTO/Pt (FTO/Pt/Au) consisted of small Au clusters deposited over the entire area of Pt due to the effective Au nucleation provided by nanoporous metallic Pt. FTO/Pt/Au exhibited enhanced electrocatalytic activity and excellent stability because the small Aumore » particles well-dispersed over the nanoporous metallic Pt network provided numerous electrochemical reaction sites, and the Pt surface was not exposed to the electrolyte. When FTO/Pt/Au was used as the counter electrode (CE) of a quantum dot-sensitized solar cell, the significantly enhanced electrocatalytic activity of the FTO/Pt/Au CE facilitated the reduction reaction of S{sub n}{sup 2− }+ 2e{sup −} (CE) → S{sub n−1}{sup 2−} + S{sup 2−} at the CE/electrolyte interface, resulting in a significantly hindered recombination reaction, S{sub n}{sup 2− }+ 2e{sup −} (TiO{sub 2} in the photoanode) → S{sub n-1}{sup 2−} + S{sup 2−}, and significantly improved overall energy conversion efficiency.« less

The Ages of 55 Globular Clusters as Determined Using an Improved \\Delta V^HB_TO Method along with Color-Magnitude Diagram Constraints, and Their Implications for Broader Issues

NASA Astrophysics Data System (ADS)

VandenBerg, Don A.; Brogaard, K.; Leaman, R.; Casagrande, L.

2013-10-01

Ages have been derived for 55 globular clusters (GCs) for which Hubble Space Telescope Advanced Camera for Surveys photometry is publicly available. For most of them, the assumed distances are based on fits of theoretical zero-age horizontal-branch (ZAHB) loci to the lower bound of the observed distributions of HB stars, assuming reddenings from empirical dust maps and metallicities from the latest spectroscopic analyses. The age of the isochrone that provides the best fit to the stars in the vicinity of the turnoff (TO) is taken to be the best estimate of the cluster age. The morphology of isochrones between the TO and the beginning part of the subgiant branch (SGB) is shown to be nearly independent of age and chemical abundances. For well-defined color-magnitude diagrams (CMDs), the error bar arising just from the "fitting" of ZAHBs and isochrones is ≈ ± 0.25 Gyr, while that associated with distance and chemical abundance uncertainties is ~ ± 1.5-2 Gyr. The oldest GCs in our sample are predicted to have ages of ≈13.0 Gyr (subject to the aforementioned uncertainties). However, the main focus of this investigation is on relative GC ages. In conflict with recent findings based on the relative main-sequence fitting method, which have been studied in some detail and reconciled with our results, ages are found to vary from mean values of ≈12.5 Gyr at [Fe/H] <~ - 1.7 to ≈11 Gyr at [Fe/H] >~ -1. At intermediate metallicities, the age-metallicity relation (AMR) appears to be bifurcated: one branch apparently contains clusters with disk-like kinematics, whereas the other branch, which is displaced to lower [Fe/H] values by ≈0.6 dex at a fixed age, is populated by clusters with halo-type orbits. The dispersion in age about each component of the AMR is ~ ± 0.5 Gyr. There is no apparent dependence of age on Galactocentric distance (R G) nor is there a clear correlation of HB type with age. As previously discovered in the case of M3 and M13, subtle variations have been found in the slope of the SGB in the CMDs of other metal-poor ([Fe/H] <~ - 1.5) GCs. They have been tentatively attributed to cluster-to-cluster differences in the abundance of helium. Curiously, GCs that have relatively steep "M13-like" SGBs tend to be massive systems, located at small R G, that show the strongest evidence of in situ formation of multiple stellar populations. The clusters in the other group are typically low-mass systems (with 2-3 exceptions, including M3) that, at the present time, should not be able to retain the matter lost by mass-losing stars due either to the development of GC winds or to ram-pressure stripping by the halo interstellar medium. The apparent separation of the two groups in terms of their present-day gas retention properties is difficult to understand if all GCs were initially ~20 times their current masses. The lowest-mass systems, in particular, may have never been massive enough to retain enough gas to produce a significant population of second-generation stars. In this case, the observed light element abundance variations, which are characteristic of all GCs, were presumably present in the gas out of which the observed cluster stars formed.

Metal mixtures in urban and rural populations in the US: The Multi-Ethnic Study of Atherosclerosis and the Strong Heart Study.

PubMed

Pang, Yuanjie; Peng, Roger D; Jones, Miranda R; Francesconi, Kevin A; Goessler, Walter; Howard, Barbara V; Umans, Jason G; Best, Lyle G; Guallar, Eliseo; Post, Wendy S; Kaufman, Joel D; Vaidya, Dhananjay; Navas-Acien, Ana

2016-05-01

Natural and anthropogenic sources of metal exposure differ for urban and rural residents. We searched to identify patterns of metal mixtures which could suggest common environmental sources and/or metabolic pathways of different urinary metals, and compared metal-mixtures in two population-based studies from urban/sub-urban and rural/town areas in the US: the Multi-Ethnic Study of Atherosclerosis (MESA) and the Strong Heart Study (SHS). We studied a random sample of 308 White, Black, Chinese-American, and Hispanic participants in MESA (2000-2002) and 277 American Indian participants in SHS (1998-2003). We used principal component analysis (PCA), cluster analysis (CA), and linear discriminant analysis (LDA) to evaluate nine urinary metals (antimony [Sb], arsenic [As], cadmium [Cd], lead [Pb], molybdenum [Mo], selenium [Se], tungsten [W], uranium [U] and zinc [Zn]). For arsenic, we used the sum of inorganic and methylated species (∑As). All nine urinary metals were higher in SHS compared to MESA participants. PCA and CA revealed the same patterns in SHS, suggesting 4 distinct principal components (PC) or clusters (∑As-U-W, Pb-Sb, Cd-Zn, Mo-Se). In MESA, CA showed 2 large clusters (∑As-Mo-Sb-U-W, Cd-Pb-Se-Zn), while PCA showed 4 PCs (Sb-U-W, Pb-Se-Zn, Cd-Mo, ∑As). LDA indicated that ∑As, U, W, and Zn were the most discriminant variables distinguishing MESA and SHS participants. In SHS, the ∑As-U-W cluster and PC might reflect groundwater contamination in rural areas, and the Cd-Zn cluster and PC could reflect common sources from meat products or metabolic interactions. Among the metals assayed, ∑As, U, W and Zn differed the most between MESA and SHS, possibly reflecting disproportionate exposure from drinking water and perhaps food in rural Native communities compared to urban communities around the US. Copyright © 2016 Elsevier Inc. All rights reserved.

Dissolved heavy metal concentrations of the Kralkızı, Dicle and Batman dam reservoirs in the Tigris River basin, Turkey.

PubMed

Varol, Memet

2013-10-01

Water samples were collected at monthly intervals during 1 year of monitoring from Kralkızı, Dicle and Batman dam reservoirs in the Tigris River basin to assess the concentrations of dissolved heavy metals and to determine their spatial and seasonal variations. The results indicated that dissolved heavy metal concentrations in the reservoirs were very low, reflecting the natural background levels. The lowest total metal concentrations in the three dam reservoirs were detected at sampling sites close to the dam wall. However, the highest total concentrations were observed at sites, which are located at the entrance of the streams to the reservoirs. Fe, Cr and Ni were the most abundant elements in the reservoirs, whereas Cd and As were the less abundant. The mean concentrations of dissolved metals in the dam reservoirs never exceeded the maximum permitted concentrations established by EC (European Community), WHO and USEPA drinking water quality guidelines. All heavy metals showed significant seasonal variations. As, Cd, Cr, Cu, Fe, Ni and Pb displayed higher values in the dry season, while higher values for Zn in the wet season. Cluster analysis grouped all ten sampling sites into three clusters. Clusters 1 and 2, and cluster 3 corresponded to relatively low polluted and moderate polluted regions, respectively. PCA/FA demonstrated the dissolved metals in the dam reservoirs controlled by natural sources. Copyright © 2013 Elsevier Ltd. All rights reserved.

Be Stars in M31

NASA Astrophysics Data System (ADS)

Peters, Matthew L.; Wisniewski, John; Choi, Yumi; Williams, Ben; Lomax, Jamie; Bjorkman, Karen; Durbin, Meredith; Johnson, Lent Cliff; Lewis, Alexia; Lutz, Julie; Sigut, Aaron; Wallach, Aislynn; Dalcanton, Julianne

2018-01-01

We identify Be candidate stars in M31 using two-epoch F625W + F658N photometry from HST/ACS+WFC3 combined with the Panchromatic Hubble Andromeda Treasury (PHAT) Catalog. Using the PHAT catalog allows us to extract stellar parameters such as surface temperature and gravity, thereby allowing us to identify the main sequence B type stars in the field of view. Be candidate stars are identified by comparing their HST narrow-band Hα excess magnitudes with that predicted by Kurucz spectra. We find 314 Be candidate stars out of 5699 B + Be candidate stars (5.51%) in our first epoch and 301 Be candidate stars out of 5769 B + Be candidate stars (5.22%) in our second epoch. Our Be fraction, while lower than that of the SMC, LMC, and MW, is possibly consistent with the fact the M31 has a higher metallicity than the other galaxies because Be fraction varies inversely with metallicity. We note that earlier spectral types have the largest Be fraction, and that the Be fraction strictly declines as the spectral type increases to later types. We then match our Be candidate stars with clusters, establishing that 39 of 314 are cluster stars in epoch one and 36 of 301 stars are cluster stars in epoch two. We assign ages, using the cluster age to characterize cluster Be candidate stars and star formation histories to characterize field Be candidate stars. Finally, we determine which Be candidate stars exhibited disk loss or disk growth between epochs, finding that, of the Be stars that did not show source confusion or low SNR in one of the epochs, 65 / 265 (24.5%) showed disk loss or renewal, while 200 / 265 (75.5%) showed only small changes in Hα excess. Our research provides context for the parameters of candidate Be stars in M31, which will be useful in further determining the nature of Be stars. This paper was supported by a grant from STScI via GO-13857.

THE SIZE DIFFERENCE BETWEEN RED AND BLUE GLOBULAR CLUSTERS IS NOT DUE TO PROJECTION EFFECTS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Webb, Jeremy J.; Harris, William E.; Sills, Alison, E-mail: webbjj@mcmaster.ca

Metal-rich (red) globular clusters in massive galaxies are, on average, smaller than metal-poor (blue) globular clusters. One of the possible explanations for this phenomenon is that the two populations of clusters have different spatial distributions. We test this idea by comparing clusters observed in unusually deep, high signal-to-noise images of M87 with a simulated globular cluster population in which the red and blue clusters have different spatial distributions, matching the observations. We compare the overall distribution of cluster effective radii as well as the relationship between effective radius and galactocentric distance for both the observed and simulated red and bluemore » sub-populations. We find that the different spatial distributions does not produce a significant size difference between the red and blue sub-populations as a whole or at a given galactocentric distance. These results suggest that the size difference between red and blue globular clusters is likely due to differences during formation or later evolution.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Goudfrooij, Paul, E-mail: goudfroo@stsci.edu

We study mass functions of globular clusters derived from Hubble Space Telescope/Advanced Camera for Surveys images of the early-type merger remnant galaxy NGC 1316, which hosts a significant population of metal-rich globular clusters of intermediate age ({approx}3 Gyr). For the old, metal-poor ({sup b}lue{sup )} clusters, the peak mass of the mass function M{sub p} increases with internal half-mass density {rho}{sub h} as M{sub p}{proportional_to}{rho}{sub h}{sup 0.44}, whereas it stays approximately constant with galactocentric distance R{sub gal}. The mass functions of these clusters are consistent with a simple scenario in which they formed with a Schechter initial mass function andmore » evolved subsequently by internal two-body relaxation. For the intermediate-age population of metal-rich ({sup r}ed{sup )} clusters, the faint end of the previously reported power-law luminosity function of the clusters with R{sub gal} > 9 kpc is due to many of those clusters having radii larger than the theoretical maximum value imposed by the tidal field of NGC 1316 at their R{sub gal}. This renders disruption by two-body relaxation ineffective. Only a few such diffuse clusters are found in the inner regions of NGC 1316. Completeness tests indicate that this is a physical effect. Using comparisons with star clusters in other galaxies and cluster disruption calculations using published models, we hypothesize that most red clusters in the low-{rho}{sub h} tail of the initial distribution have already been destroyed in the inner regions of NGC 1316 by tidal shocking, and that several remaining low-{rho}{sub h} clusters will evolve dynamically to become similar to 'faint fuzzies' that exist in several lenticular galaxies. Finally, we discuss the nature of diffuse red clusters in early-type galaxies.« less

Experimental and theoretical study on activation of the C-H bond in pyridine by [M(m)]- (M = Cu, Ag, Au, m = 1-3).

PubMed

Liu, Xiao-Jing; Hamilton, I P; Han, Ke-Li; Tang, Zi-Chao

2010-09-21

Activation of the C-H bond of pyridine by [M(m)](-) (M = Cu, Ag, Au, m = 1-3) is investigated by experiment and theory. Complexes of coinage metal clusters and the pyridyl group, [M(m)-C(5)H(4)N](-), are produced from reactions between metal clusters formed by laser ablation of coinage metal samples and pyridine molecules seeded in argon carrier gas. We examine the structure and formation mechanism of these pyridyl-coinage metal complexes. Our study shows that C(5)H(4)N bonds to the metal clusters through a M-C sigma bond and [M(m)-C(5)H(4)N](-) is produced via a stepwise mechanism. The first step is a direct insertion reaction between [M(m)](-) and C(5)H(5)N with activation of the C-H bond to yield the intermediate [HM(m)-C(5)H(4)N](-). The second step is H atom abstraction by a neutral metal atom to yield [M(m)-C(5)H(4)N](-).

Electrophobic interaction induced impurity clustering in metals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhou, Hong-Bo; Wang, Jin-Long; Jiang, W.

2016-10-01

We introduce the concept of electrophobic interaction, analogous to hydrophobic interaction, for describing the behavior of impurity atoms in a metal, a 'solvent of electrons'. We demonstrate that there exists a form of electrophobic interaction between impurities with closed electron shell structure, which governs their dissolution behavior in a metal. Using He, Be and Ar as examples, we predict by first-principles calculations that the electrophobic interaction drives He, Be or Ar to form a close-packed cluster with a clustering energy that follows a universal power-law scaling with the number of atoms (N) dissolved in a free electron gas, as wellmore » as W or Al lattice, as Ec is proportional to (N2/3-N). This new concept unifies the explanation for a series of experimental observations of close-packed inert-gas bubble formation in metals, and significantly advances our fundamental understanding and capacity to predict the solute behavior of impurities in metals, a useful contribution to be considered in future material design of metals for nuclear, metallurgical, and energy applications.« less

A Spectroscopic Analysis of the Galactic Globular Cluster NGC 6273 (M19)

NASA Astrophysics Data System (ADS)

Johnson, Christian I.; Rich, R. Michael; Pilachowski, Catherine A.; Caldwell, Nelson; Mateo, Mario; Bailey, John I., III; Crane, Jeffrey D.

2015-08-01

A combined effort utilizing spectroscopy and photometry has revealed the existence of a new globular cluster class. These “anomalous” clusters, which we refer to as “iron-complex” clusters, are differentiated from normal clusters by exhibiting large (≳0.10 dex) intrinsic metallicity dispersions, complex sub-giant branches, and correlated [Fe/H] and s-process enhancements. In order to further investigate this phenomenon, we have measured radial velocities and chemical abundances for red giant branch stars in the massive, but scarcely studied, globular cluster NGC 6273. The velocities and abundances were determined using high resolution (R ˜ 27,000) spectra obtained with the Michigan/Magellan Fiber System (M2FS) and MSpec spectrograph on the Magellan-Clay 6.5 m telescope at Las Campanas Observatory. We find that NGC 6273 has an average heliocentric radial velocity of +144.49 km s-1 (σ = 9.64 km s-1) and an extended metallicity distribution ([Fe/H] = -1.80 to -1.30) composed of at least two distinct stellar populations. Although the two dominant populations have similar [Na/Fe], [Al/Fe], and [α/Fe] abundance patterns, the more metal-rich stars exhibit significant [La/Fe] enhancements. The [La/Eu] data indicate that the increase in [La/Fe] is due to almost pure s-process enrichment. A third more metal-rich population with low [X/Fe] ratios may also be present. Therefore, NGC 6273 joins clusters such as ω Centauri, M2, M22, and NGC 5286 as a new class of iron-complex clusters exhibiting complicated star formation histories. This paper includes data gathered with the 6.5 m Magellan Telescopes located at Las Campanas Observatory, Chile.

Formation of metallic magnetic clusters in a Kondo-lattice metal: Evidence from an optical study

PubMed Central

Kovaleva, N. N.; Kugel, K. I.; Bazhenov, A. V.; Fursova, T. N.; Löser, W.; Xu, Y.; Behr, G.; Kusmartsev, F. V.

2012-01-01

Magnetic materials are usually divided into two classes: those with localised magnetic moments, and those with itinerant charge carriers. We present a comprehensive experimental (spectroscopic ellipsomerty) and theoretical study to demonstrate that these two types of magnetism do not only coexist but complement each other in the Kondo-lattice metal, Tb2PdSi3. In this material the itinerant charge carriers interact with large localised magnetic moments of Tb(4f) states, forming complex magnetic lattices at low temperatures, which we associate with self-organisation of magnetic clusters. The formation of magnetic clusters results in low-energy optical spectral weight shifts, which correspond to opening of the pseudogap in the conduction band of the itinerant charge carriers and development of the low- and high-spin intersite electronic transitions. This phenomenon, driven by self-trapping of electrons by magnetic fluctuations, could be common in correlated metals, including besides Kondo-lattice metals, Fe-based and cuprate superconductors. PMID:23189239

Adsorption of Atoms of 3 d Metals on the Surfaces of Aluminum and Magnesium Oxide Films

NASA Astrophysics Data System (ADS)

Ramonova, A. G.; Kibizov, D. D.; Kozyrev, E. N.; Zaalishvili, V. B.; Grigorkina, G. S.; Fukutani, K.; Magkoev, T. T.

2018-01-01

The adsorption and formation of submonolayer structures of Ti, Cr, Fe, Ni, Cu on the surfaces of aluminum and magnesium oxide films formed on Mo(110) under ultrahigh vacuum conditions are studied via X-ray, ultraviolet photo-, and Auger electron spectroscopy (XPS, UVES, AES); spectroscopy of energy losses of high-resolution electrons (SELHRE); spectroscopy of the backscattering of low-energy ions (SBSLEI); infrared absorption spectroscopy (IAS); and the diffraction of slow electrons (DSE). Individual atoms and small clusters of all the investigated metals deposited on oxides acquire a positive charge, due presumably to interaction with surface defects. As the concentration of adatoms increases when the adsorption centers caused by defects are filled, charge transfer from adatoms to substrates is reduced. This is accompanied by further depolarization caused by the lateral interaction of adatoms.

New ALMA constraints on the star-forming interstellar medium at low metallicity: a 50 pc view of the blue compact dwarf galaxy SBS 0335-052

NASA Astrophysics Data System (ADS)

Cormier, D.; Bendo, G. J.; Hony, S.; Lebouteiller, V.; Madden, S. C.; Galliano, F.; Glover, S. C. O.; Klessen, R. S.; Abel, N. P.; Bigiel, F.; Clark, P. C.

2017-06-01

Properties of the cold interstellar medium of low-metallicity galaxies are not well known due to the faintness and extremely small scale on which emission is expected. We present deep ALMA band 6 (230 GHz) observations of the nearby, low-metallicity (12 + log (O/H) = 7.25) blue compact dwarf galaxy SBS 0335-052 at an unprecedented resolution of 0.2 arcsec (52 pc). The 12CO J = 2→1 line is not detected and we report a 3σ upper limit of LCO(2-1) = 3.6 × 104 K km s-1 pc2. Assuming that molecular gas is converted into stars with a given depletion time, ranging from 0.02 to 2 Gyr, we find lower limits on the CO-to-H2 conversion factor αCO in the range 102-104 M⊙ pc-2 (K km s-1)-1. The continuum emission is detected and resolved over the two main super star clusters. Re-analysis of the IR-radio spectral energy distribution suggests that the mm-fluxes are not only free-free emission but are most likely also associated with a cold dust component coincident with the position of the brightest cluster. With standard dust properties, we estimate its mass to be as large as 105 M⊙. Both line and continuum results suggest the presence of a large cold gas reservoir unseen in CO even with ALMA.

Entrapment of metal clusters in metal-organic framework channels by extended hooks anchored at open metal sites.

PubMed

Zheng, Shou-Tian; Zhao, Xiang; Lau, Samuel; Fuhr, Addis; Feng, Pingyun; Bu, Xianhui

2013-07-17

Reported here are the new concept of utilizing open metal sites (OMSs) for architectural pore design and its practical implementation. Specifically, it is shown here that OMSs can be used to run extended hooks (isonicotinates in this work) from the framework walls to the channel centers to effect the capture of single metal ions or clusters, with the concurrent partitioning of the large channel spaces into multiple domains, alteration of the host-guest charge relationship and associated guest-exchange properties, and transfer of OMSs from the walls to the channel centers. The concept of the extended hook, demonstrated here in the multicomponent dual-metal and dual-ligand system, should be generally applicable to a range of framework types.

Peptide protected gold clusters: chemical synthesis and biomedical applications

NASA Astrophysics Data System (ADS)

Yuan, Qing; Wang, Yaling; Zhao, Lina; Liu, Ru; Gao, Fuping; Gao, Liang; Gao, Xueyun

2016-06-01

Bridging the gap between atoms and nanoparticles, noble metal clusters with atomic precision continue to attract considerable attention due to their important applications in catalysis, energy transformation, biosensing and biomedicine. Greatly different to common chemical synthesis, a one-step biomimetic synthesis of peptide-conjugated metal clusters has been developed to meet the demand of emerging bioapplications. Under mild conditions, multifunctional peptides containing metal capturing, reactive and targeting groups are rationally designed and elaborately synthesized to fabricate atomically precise peptide protected metal clusters. Among them, peptide-protected Au Cs (peptide-Au Cs) possess a great deal of exceptional advantages such as nanometer dimensions, high photostability, good biocompatibility, accurate chemical formula and specific protein targeting capacity. In this review article, we focus on the recent advances in potential theranostic fields by introducing the rising progress of peptide-Au Cs for biological imaging, biological analysis and therapeutic applications. The interactions between Au Cs and biological systems as well as potential mechanisms are also our concerned theme. We expect that the rapidly growing interest in Au Cs-based theranostic applications will attract broader concerns across various disciplines.

THE PREPARATION OF CURRICULUM MATERIALS AND THE DEVELOPMENT OF TEACHERS FOR AN EXPERIMENTAL APPLICATION OF THE CLUSTER CONCEPT OF VOCATIONAL EDUCATION AT THE SECONDARY SCHOOL LEVEL. VOLUME III, INSTRUCTIONAL PLANS FOR THE METAL FORMING AND FABRICATION CLUSTER.

ERIC Educational Resources Information Center

MALEY, DONALD

DESIGNED FOR USE WITH 11TH AND 12TH GRADE STUDENTS, THIS CURRICULUM GUIDE FOR THE OCCUPATIONAL CLUSTER IN METAL FORMING AND FABRICATION WAS DEVELOPED BY PARTICIPATING TEACHERS FROM RESULTS OF THE RESEARCH PROCEDURES DESCRIBED IN VOLUME I (VT 004 162). THE COURSE DESCRIPTION, NEED FOR THE COURSE, COURSE OBJECTIVES, PROCEDURES AND INSTRUCTIONAL PLAN…

Validity of the classical monte carlo method to model the magnetic properties of a large transition-metal cluster: Mn19.

PubMed

Lima, Nicola; Caneschi, Andrea; Gatteschi, Dante; Kritikos, Mikael; Westin, L Gunnar

2006-03-20

The susceptibility of the large transition-metal cluster [Mn19O12(MOE)14(MOEH)10].MOEH (MOE = OC2H2O-CH3) has been fitted through classical Monte Carlo simulation, and an estimation of the exchange coupling constants has been done. With these results, it has been possible to perform a full-matrix diagonalization of the cluster core, which was used to provide information on the nature of the low-lying levels.

Hydrogen storage in metal-organic frameworks: An investigation of structure-property relationships

NASA Astrophysics Data System (ADS)

Rowsell, Jesse

Metal-organic frameworks (MOFs) have been identified as candidate hydrogen storage materials due to their ability to physisorb large quantities of small molecules. Thirteen compounds (IRMOF-1, -2, -3, -6, -8, -9, -11, -13, -18, -20, MOF-74, MOF-177 and HKUST-1) have been prepared and fully characterized for the evaluation of their dihydrogen (H2) adsorption properties. All compounds display approximately type I isotherms with no hysteresis at 77 K up to 1 atm. The amount adsorbed ranges from 0.89 to 2.54 wt%; however, saturation is not achieved under these conditions. The influences of link functionalization, catenation and topology are examined for the eleven MOFs composed of Zn4O(O2C-)6 clusters. Enhanced H2 uptake by catenated compounds is rationalized by increased overlap of the surface potentials within their narrower pores. This is corroborated by the larger isosteric heat of adsorption of IRMOF-11 compared to IRMOF-1. Inelastic neutron scattering spectroscopic analysis of four Zn4O-based materials (IRMOF-1, -8, -11, and MOF-74) under a range of H2 loading suggests the presence of multiple localized adsorption sites on both the inorganic and organic moieties. To determine the structural details of the adsorption sites, variable temperature single crystal X-ray diffraction was used to analyze adsorbed argon and dinitrogen molecules in IRMOF-1. The principle binding site was found to be the same for both adsorbates and is located on faces of the octahedral Zn4O(O2C-)6 clusters with close contacts to three carboxylate groups. A total of eight symmetry-independent adsorption sites were identified for argon at 30 K. Similar sites were observed for dinitrogen, suggesting that they are good model adsorbates for the behaviour of dihydrogen. Two additional materials composed of inorganic clusters with coordinatively unsaturated metal sites (MOF-74, HKUST-1) were examined and their increased capacities and isosteric heats of adsorption provide further evidence that the interaction is strongest at the inorganic clusters. This enhancement becomes less important at high pressure, where large pore volume proves to be the greater contributor to capacity.

Sinter-Resistant Platinum Catalyst Supported by Metal-Organic Framework

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, In Soo; Li, Zhanyong; Zheng, Jian

Installed on the zirconia nodes of a metal-organic framework (MOF) NU-1000 via targeted vapor-phase synthesis. The catalytic Pt clusters, site-isolated by organic linkers, are shown to exhibit high catalytic activity for ethylene hydrogenation while exhibiting resistance to sintering up to 200 degrees C. In situ IR spectroscopy reveals the presence of both single atoms and few-atom clusters that depend upon synthesis conditions. Operando X-ray absorption spectroscopy and Xray pair distribution analyses reveal unique changes in chemical bonding environment and cluster size stability while on stream. Density functional theory calculations elucidate a favorable reaction pathway for ethylene hydrogenation with the novelmore » catalyst. These results provide evidence that atomic layer deposition (ALD) in MOFs is a versatile approach to the rational synthesis of size-selected clusters, including noble metals, on a high surface area support.« less

Growth of Ni nanoclusters on irradiated graphene: a molecular dynamics study.

PubMed

Valencia, F J; Hernandez-Vazquez, E E; Bringa, E M; Moran-Lopez, J L; Rogan, J; Gonzalez, R I; Munoz, F

2018-04-23

We studied the soft landing of Ni atoms on a previously damaged graphene sheet by means of molecular dynamics simulations. We found a monotonic decrease of the cluster frequency as a function of its size, but few big clusters comprise an appreciable fraction of the total number of Ni atoms. The aggregation of Ni atoms is also modeled by means of a simple phenomenological model. The results are in clear contrast with the case of hard or energetic landing of metal atoms, where there is a tendency to form mono-disperse metal clusters. This behavior is attributed to the high diffusion of unattached Ni atoms, together with vacancies acting as capture centers. The findings of this work show that a simple study of the energetics of the system is not enough in the soft landing regime, where it is unavoidable to also consider the growth process of metal clusters.

Generalized vibrating potential model for collective excitations in spherical, deformed and superdeformed systems: (1) Atomic nuclei, (2) Metal clusters

NASA Astrophysics Data System (ADS)

Nesterenko, V. O.; Kleinig, W.

1995-01-01

The self-consistent vibrating potential model (VPM) is extended for description of Eλ collective excitations in atomic nuclei and metal clusters with practically any kind of static deformation. The model is convenient for a qualitative analysis and provides the RPA accuracy of numerical calculations. The VPM is applied to study Eλ giant resonances in spherical metal clusters and deformed and superdeformed nuclei. It is shown that the deformation splitting of superdeformed nuclei results in a very complicated ("jungle-like") structure of the resonances, which makes the experimental observation of E2 and E3 giant resonances in superdeformed nuclei quite problematic. Calculations of E1 giant resonances in spherical sodium clusters Na8, Na20 and Na40 are presented, as a test of the VPM in this field. The results are in qualitative agreement with the experimental data.

Trace Element Compositions of Pallasite Olivine Grains and Pallasite Origin

NASA Technical Reports Server (NTRS)

Mittlefehldt, David W.; Herrin, J. S.

2010-01-01

Pallasites are mixtures of metal with magnesian olivine. Most have similar metal compositions and olivine oxygen isotopic compositions; these are the main-group pallasites (PMG). The Eagle Station grouplet of pallasites (PES) have distinctive metal and olivine compositions and oxygen isotopic compositions. Pallasites are thought to have formed at the core-mantle boundary of their parent asteroids by mixing molten metal with solid olivine of either cumulatic or restitic origin. We have continued our investigation of pallasite olivines by doing in situ trace element analyses in order to further constrain their origin. We determined Al, P, Ca, Ga and first row transition element contents of olivine grains from suite of PMG and PES by LA-ICP-MS at JSC. Included in the PMG suite are some that have anomalous metal compositions (PMG-am) and atypically ferroan olivines (PMG-as). Our EMPA work has shown that there are unanticipated variations in olivine Fe/Mn, even within those PMG that have uni-form Fe/Mg. Manganese is homologous with Fe2+, and thus can be used the same way to investigate magmatic fractionation processes. It has an advantage for pallasite studies in that it is unaffected by redox exchange with the metal. PMG can be divided into three clusters on the basis of Mn/Mg; low, medium and high that can be thought of as less, typically and more fractionated in an igneous sense. The majority of PMG have medium Mn/Mg ratios. PMG-am occur in all three clusters; there does not seem to be any relationship between putative olivine igneous fractionation and metal composition. The PMG-as and one PMG-am make up the high Mn/Mg cluster; no PMG are in this cluster. The high Mn/Mg cluster ought to be the most fractionated (equivalent to the most Fe-rich in igneous suites), yet they have among the lowest contents of incompatible lithophile elements Al and Ti and the two PMG-as in this cluster also have low Ca and Sc contents. This is inconsistent with simple igneous fractionation on a single, initially homogeneous parent asteroid. For Al and Ti, the low and high Mn/Mg clusters have generally uniform contents, while the medium cluster has wide ranges. This is also true of analyses of duplicate grains from the medium cluster pallasites which can have very different Al and Ti contents. Those from the low and high clusters do not. These observations suggest that pallasite olivines are not cumulates, but rather are restites from high degrees of melting. The moderately siderophile elements P and Ga show wide ranges in the high Mn/Mg cluster, but very uniform compositions in the medium cluster, opposite the case for Al and Ti. There is no correlation of P or Ga and Fe/Mn as might be expected if redox processes controlled the contents of moderately siderophile elements in the olivines. The lack of correlation of P could reflect equilibration with phosphates, although there is no correlation of Ca with P as might be expected

Robustness of cluster synchronous patterns in small-world networks with inter-cluster co-competition balance

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Jianbao; Ma, Zhongjun, E-mail: mzj1234402@163.com; Chen, Guanrong

All edges in the classical Watts and Strogatz's small-world network model are unweighted and cooperative (positive). By introducing competitive (negative) inter-cluster edges and assigning edge weights to mimic more realistic networks, this paper develops a modified model which possesses co-competitive weighted couplings and cluster structures while maintaining the common small-world network properties of small average shortest path lengths and large clustering coefficients. Based on theoretical analysis, it is proved that the new model with inter-cluster co-competition balance has an important dynamical property of robust cluster synchronous pattern formation. More precisely, clusters will neither merge nor split regardless of adding ormore » deleting nodes and edges, under the condition of inter-cluster co-competition balance. Numerical simulations demonstrate the robustness of the model against the increase of the coupling strength and several topological variations.« less

Robustness of cluster synchronous patterns in small-world networks with inter-cluster co-competition balance

NASA Astrophysics Data System (ADS)

Zhang, Jianbao; Ma, Zhongjun; Chen, Guanrong

2014-06-01

All edges in the classical Watts and Strogatz's small-world network model are unweighted and cooperative (positive). By introducing competitive (negative) inter-cluster edges and assigning edge weights to mimic more realistic networks, this paper develops a modified model which possesses co-competitive weighted couplings and cluster structures while maintaining the common small-world network properties of small average shortest path lengths and large clustering coefficients. Based on theoretical analysis, it is proved that the new model with inter-cluster co-competition balance has an important dynamical property of robust cluster synchronous pattern formation. More precisely, clusters will neither merge nor split regardless of adding or deleting nodes and edges, under the condition of inter-cluster co-competition balance. Numerical simulations demonstrate the robustness of the model against the increase of the coupling strength and several topological variations.

Modeling of the HiPco process for carbon nanotube production. II. Reactor-scale analysis

NASA Technical Reports Server (NTRS)

Gokcen, Tahir; Dateo, Christopher E.; Meyyappan, M.

2002-01-01

The high-pressure carbon monoxide (HiPco) process, developed at Rice University, has been reported to produce single-walled carbon nanotubes from gas-phase reactions of iron carbonyl in carbon monoxide at high pressures (10-100 atm). Computational modeling is used here to develop an understanding of the HiPco process. A detailed kinetic model of the HiPco process that includes of the precursor, decomposition metal cluster formation and growth, and carbon nanotube growth was developed in the previous article (Part I). Decomposition of precursor molecules is necessary to initiate metal cluster formation. The metal clusters serve as catalysts for carbon nanotube growth. The diameter of metal clusters and number of atoms in these clusters are some of the essential information for predicting carbon nanotube formation and growth, which is then modeled by the Boudouard reaction with metal catalysts. Based on the detailed model simulations, a reduced kinetic model was also developed in Part I for use in reactor-scale flowfield calculations. Here this reduced kinetic model is integrated with a two-dimensional axisymmetric reactor flow model to predict reactor performance. Carbon nanotube growth is examined with respect to several process variables (peripheral jet temperature, reactor pressure, and Fe(CO)5 concentration) with the use of the axisymmetric model, and the computed results are compared with existing experimental data. The model yields most of the qualitative trends observed in the experiments and helps to understanding the fundamental processes in HiPco carbon nanotube production.

Effective cluster model of dielectric enhancement in metal-insulator composites

NASA Astrophysics Data System (ADS)

Doyle, W. T.; Jacobs, I. S.

1990-11-01

The electrical permittivity of a suspension of conducting spheres at high volume loading exhibits a large enhancement above the value predicted by the Clausius-Mossotti approximation. The permittivity enhancement is a dielectric anomaly accompanying a metallization transition that occurs when conducting particles are close packed. In disordered suspensions, close encounters can cause a permittivity enhancement at any volume loading. We attribute the permittivity enhancements typically observed in monodisperse disordered suspensions of conducting spheres to local metallized regions of high density produced by density fluctuations. We model a disordered suspension as a mixture, or mesosuspension, of isolated spheres and random close-packed spherical clusters of arbitrary size. Multipole interactions within the clusters are treated exactly. External interactions between clusters and isolated spheres are treated in the dipole approximation. Model permittivities are compared with Guillien's experimental permittivity measurements [Ann. Phys. (Paris) Ser. 11, 16, 205 (1941)] on liquid suspensions of Hg droplets in oil and with Turner's conductivity measurements [Chem. Eng. Sci. 31, 487 (1976)] on fluidized bed suspensions of ion-exchange resin beads in aqueous solution. New permittivity measurements at 10 GHz on solid suspensions of monodisperse metal spheres in polyurethane are presented and compared with the model permittivities. The effective spherical cluster model is in excellent agreement with the experiments over the entire accessible range of volume loading.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lin, Qisheng; Aguirre, Kaiser; Saunders, Scott M.

Planar hydrocarbon-like metal clusters may foster new insights linking organic molecules with conjugated π-π bonding interactions and inorganic structures in terms of their bonding characteristics. However, such clusters are uncommon in polar intermetallics. Herein, we report two polar intermetallic phases, Pr 5Co 2Ge 3 and Pr 7Co 2Ge 4, both of which feature such planar metal clusters, viz., ethylene-like [Co 2Ge 4] clusters plus the concatenated forms and polyacene-like [Co 2Ge 2] n ribbons in Pr 5Co 2Ge 3, and 1,2,4,5-tetramethylbenzene-like [Co4Ge6] cluster in Pr 7Co 2Ge 4. Just as in the related planar organic structures, these metal-metalloid species aremore » dominated by covalent bonding interactions. Both compounds magnetically order at low temperature with net ferromagnetic components: Pr 5Co 2Ge 3 via a series of transitions below 150 K; and Pr 7Co 2Ge 4 via a single ferromagnetic transition at 19 K. Spin-polarized electronic structure calculations for Pr 7Co 2Ge 4 reveal strong spin-orbit coupling within Pr and considerable magnetic contributions from Co atoms. This work suggests that similar structural chemistry can emerge for other rare earth-late transition metal-main group systems.« less

Community-level physiological profiles of microorganisms inhabiting soil contaminated with heavy metals

NASA Astrophysics Data System (ADS)

Kuźniar, Agnieszka; Banach, Artur; Stępniewska, Zofia; Frąc, Magdalena; Oszust, Karolina; Gryta, Agata; Kłos, Marta; Wolińska, Agnieszka

2018-01-01

The aim of the study was to assess the differences in the bacterial community physiological profiles in soils contaminated with heavy metals versus soils without metal contaminations. The study's contaminated soil originated from the surrounding area of the Szopienice non-ferrous metal smelter (Silesia Region, Poland). The control was soil unexposed to heavy metals. Metal concentration was appraised by flame atomic absorption spectrometry, whereas the the community-level physiological profile was determined with the Biolog EcoPlatesTM system. The soil microbiological activity in both sites was also assessed via dehydrogenase activity. The mean concentrations of metals (Cd and Zn) in contaminated soil samples were in a range from 147.27 to 12265.42 mg kg-1, and the heavy metal contamination brought about a situation where dehydrogenase activity inhibition was observed mostly in the soil surface layers. Our results demonstrated that there is diversity in the physiological profiles of microorganisms inhabiting contaminated and colntrol soils; therefore, for assessment purposes, these were treated as two clusters. Cluster I included colntrol soil samples in which microbial communities utilised most of the available substrates. Cluster II incorporated contaminated soil samples in which a smaller number of the tested substrates was utilised by the contained microorganisms. The physiological profiles of micro-organisms inhabiting the contaminated and the colntrol soils are distinctly different.

Hubble Admires a Youthful Globular Star Cluster

NASA Image and Video Library

2017-12-08

Hubble sees an unusal global cluster that is enriching the interstellar medium with metals Globular clusters offer some of the most spectacular sights in the night sky. These ornate spheres contain hundreds of thousands of stars, and reside in the outskirts of galaxies. The Milky Way contains over 150 such clusters — and the one shown in this NASA/ESA Hubble Space Telescope image, named NGC 362, is one of the more unusual ones. As stars make their way through life they fuse elements together in their cores, creating heavier and heavier elements — known in astronomy as metals — in the process. When these stars die, they flood their surroundings with the material they have formed during their lifetimes, enriching the interstellar medium with metals. Stars that form later therefore contain higher proportions of metals than their older relatives. By studying the different elements present within individual stars in NGC 362, astronomers discovered that the cluster boasts a surprisingly high metal content, indicating that it is younger than expected. Although most globular clusters are much older than the majority of stars in their host galaxy, NGC 362 bucks the trend, with an age lying between 10 and 11 billion years old. For reference, the age of the Milky Way is estimated to be above 13 billion years. This image, in which you can view NGC 362’s individual stars, was taken by Hubble’s Advanced Camera for Surveys (ACS). Credit: ESA/Hubble& NASA NASA image use policy. NASA Goddard Space Flight Center enables NASA’s mission through four scientific endeavors: Earth Science, Heliophysics, Solar System Exploration, and Astrophysics. Goddard plays a leading role in NASA’s accomplishments by contributing compelling scientific knowledge to advance the Agency’s mission. Follow us on Twitter Like us on Facebook Find us on Instagram

A Density Functional Theory Investigation of Nin , Pdn , and Ptn Clusters (n=1-4) Adsorbed on Buckminsterfullerene.

PubMed

Pham, Nguyet N T; Le, Hung M

2017-05-19

In this study, we examine the adsorptions of Ni, Pd, and Pt clusters on C 60 by using a computational approach. Our calculation results show that the base structure of C 60 can host Ni n /Pd n /Pt n (n=1-4) clusters with good adsorption stability and the complexes establish either two or no unpaired electrons. The binding energy of Pd and Pt clusters increases as the number of metal atoms increases, implying that the coverage of C 60 with Pd or Pt preferentially establishes a large-size metal cluster. A single metal atom favorably occupies the C-C bridge site. For dimer clusters, the three metals of interest share a similar binding fashion, in which two metal atoms establish direct interactions with the C-C bridge sites. For trimer adsorptions, the formation of linear and triangular structures is observed. Both Pt 3 and Ni 3 preferably constitute isosceles triangles on C 60 , whilst Pd 3 favorably establishes a linear shape. Finally, for each of the Ni 4 and Pd 4 adsorption cases, we observed three stable binding configurations: rhombus, tetrahedron, and Y-form. Whereas Ni 4 establishes a tetrahedral form, Pd 4 attains the most stable form with the Y-shape geometry on C 60 . Overall, we observe that the trend of Pd binding to C 60 tends to go beyond the fashion of Ni and Pt. In terms of magnetic alignment, the Pd n -C 60 systems seem to be non-magnetic in most cases, unlike the Ni and Pt cases, the structures of which possess magnetic moments of 2 μB in their most stable forms. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Trigonal Mn3 and Co3 Clusters Supported by Weak-Field Ligands: A Structural, Spectroscopic, Magnetic, and Computational Investigation into the Correlation of Molecular and Electronic Structure

PubMed Central

Fout, Alison R.; Xiao, Dianne J.; Zhao, Qinliang; Harris, T. David; King, Evan R.; Eames, Emily V.; Zheng, Shao-Liang; Betley, Theodore A.

2012-01-01

Transamination of divalent transition metal starting materials (M2(N(SiMe3)2)4, M = Mn, Co) with hexadentate ligand platforms RLH6 (RLH6 = MeC(CH2NPh-o-NR)3 where R = H, Ph, Mes (Mes = Mesityl)) or H,CyLH6 = 1,3,5-C6H9(NHPh-o-NH2)3 with added pyridine or tertiary phosphine co-ligands afforded trinuclear complexes of the type (RL)Mn3(py)3 and (RL)Co3(PMe2R’)3 (R’ = Me, Ph). While the sterically less encumbered ligand varieties, HL or PhL, give rise to local square-pyramidal geometries at each of the bound metal atoms, with four anilides forming an equatorial plane and an exogenous pyridine or phosphine in the apical site, the mesityl-substituted ligand (MesL) engenders local tetrahedral coordination. Both the neutral Mn3 and Co3 clusters feature S = 1/2 ground states, as determined by dc magnetometry, 1H NMR spectroscopy, and low-temperature EPR spectroscopy. Within the Mn3 clusters, the long internuclear Mn–Mn separations suggest minimal direct metal-metal orbital overlap. Accordingly, fits to variable-temperature magnetic susceptibility data reveal the presence of weak antiferromagnetic superexchange interactions through the bridging anilide ligands with exchange couplings ranging from J = −16.8 to −42 cm−1. Conversely, the short Co–Co interatomic distances suggest a significant degree of direct metal-metal orbital overlap, akin to the related Fe3 clusters. With the Co3 series, the S = 1/2 ground state can be attributed to population of a single molecular orbital manifold that arises from mixing of the metal- and o-phenylenediamide (OPDA) ligand-based frontier orbitals. Chemical oxidation of the neutral Co3 clusters affords diamagnetic cationic clusters of the type [(RL)Co3(PMe2R)3]+. DFT calculations on the neutral (S = ½) and cationic (S = 0) Co3 clusters reveal that oxidation occurs at an oribital with contributions from both the Co3 core and OPDA subunits. The predicted bond elongations within the ligand OPDA units are corroborated by the ligand bond perturbations observed by X-ray crystallography. PMID:22991939

Giant Faraday Rotation through Ultrasmall Fe0 n Clusters in Superparamagnetic FeO-SiO2 Vitreous Films.

PubMed

Nakatsuka, Yuko; Pollok, Kilian; Wieduwilt, Torsten; Langenhorst, Falko; Schmidt, Markus A; Fujita, Koji; Murai, Shunsuke; Tanaka, Katsuhisa; Wondraczek, Lothar

2017-04-01

Magnetooptical (MO) glasses and, in particular, Faraday rotators are becoming key components in lasers and optical information processing, light switching, coding, filtering, and sensing. The common design of such Faraday rotator materials follows a simple path: high Faraday rotation is achieved by maximizing the concentration of paramagnetic ion species in a given matrix material. However, this approach has reached its limits in terms of MO performance; hence, glass-based materials can presently not be used efficiently in thin film MO applications. Here, a novel strategy which overcomes this limitation is demonstrated. Using vitreous films of x FeO·(100 - x )SiO 2 , unusually large Faraday rotation has been obtained, beating the performance of any other glassy material by up to two orders of magnitude. It is shown that this is due to the incorporation of small, ferromagnetic clusters of atomic iron which are generated in line during laser deposition and rapid condensation of the thin film, generating superparamagnetism. The size of these clusters underbids the present record of metallic Fe incorporation and experimental verification in glass matrices.

Cooling Flow Spectra in Ginga Galaxy Clusters

NASA Technical Reports Server (NTRS)

White, Raymond E., III

1997-01-01

The primary focus of this research project has been a joint analysis of Ginga LAC and Einstein SSS X-ray spectra of the hot gas in galaxy clusters with cooling flows is reported. We studied four clusters (A496, A1795, A2142 & A2199) and found their central temperatures to be cooler than in the exterior, which is expected from their having cooling flows. More interestingly, we found central metal abundance enhancements in two of the clusters, A496 and A2142. We have been assessing whether the abundance gradients (or lack thereof) in intracluster gas is correlated with galaxy morphological gradients in the host clusters. In rich, dense galaxy clusters, elliptical and SO galaxies are generally found in the cluster cores, while spiral galaxies are found in the outskirts. If the metals observed in clusters came from proto-ellipticals and proto-S0s blowing winds, then the metal distribution in intracluster gas may still reflect the distribution of their former host galaxies. In a research project which was inspired by the success of the Ginga LAC/Einstein SSS work, we analyzed X-ray spectra from the HEAO-A2 MED and the Einstein SSS to look for temperature gradients in cluster gas. The HEAO-A2 MED was also a non-imaging detector with a large field of view compared to the SSS, so we used the differing fields of view of the two instruments to extract spatial information. We found some evidence of cool gas in the outskirts of clusters, which may indicate that the nominally isothermal mass density distributions in these clusters are steepening in the outer parts of these clusters.

Density-based clustering of small peptide conformations sampled from a molecular dynamics simulation.

PubMed

Kim, Minkyoung; Choi, Seung-Hoon; Kim, Junhyoung; Choi, Kihang; Shin, Jae-Min; Kang, Sang-Kee; Choi, Yun-Jaie; Jung, Dong Hyun

2009-11-01

This study describes the application of a density-based algorithm to clustering small peptide conformations after a molecular dynamics simulation. We propose a clustering method for small peptide conformations that enables adjacent clusters to be separated more clearly on the basis of neighbor density. Neighbor density means the number of neighboring conformations, so if a conformation has too few neighboring conformations, then it is considered as noise or an outlier and is excluded from the list of cluster members. With this approach, we can easily identify clusters in which the members are densely crowded in the conformational space, and we can safely avoid misclustering individual clusters linked by noise or outliers. Consideration of neighbor density significantly improves the efficiency of clustering of small peptide conformations sampled from molecular dynamics simulations and can be used for predicting peptide structures.

Radial distribution of metals in the hot intra-cluster medium as observed by XMM-Newton

NASA Astrophysics Data System (ADS)

Mernier, F.; de Plaa, J.; Kaastra, J.; Zhang, Y.; Akamatsu, H.; Gu, L.; Mao, J.; Pinto, C.; Reiprich, T.; Sanders, J.

2017-10-01

The hot intra-cluster medium (ICM), which accounts for ˜80% of the baryonic content in galaxy clusters, is rich in heavy elements. Since these metals have been produced by stars and supernovae before enriching the ICM, measuring metal abundance distributions in galaxy clusters and groups provides essential clues to determine the main astrophysical source(s) and epoch(s) of the ICM enrichment. In this work, we present radial abundance profiles averaged over 44 nearby cool-core galaxy clusters, groups, and massive ellipticals (the CHEERS sample) measured with XMM-Newton EPIC. While most of the Fe of the Universe is thought to be synthesised by Type Ia supernovae (SNIa), lighter elements, such as O, Mg, Si or S, are mostly produced by core-collapse supernovae (SNcc). The derived average radial profiles of the O, Mg, Si, S, Ar, Ca, Fe, and Ni abundances out to ˜ 0.5 r_{500} allows us to accurately compare the distributions of SNIa and SNcc products in clusters and groups. By comparing our results with recent chemo-dynamical simulations, we discuss the interpretation of the profiles in the context of early and late ICM enrichments.

Pd n Ag (4-n) and Pd n Pt (4-n) clusters on MgO (100): a density functional surface genetic algorithm investigation

DOE PAGES

Heard, Christopher J.; Heiles, Sven; Vajda, Stefan; ...

2014-08-07

We employed the novel surface mode of the Birmingham Cluster Genetic Algorithm (S-BCGA) for the global optimisation of noble metal tetramers upon an MgO(100) substrate at the GGA-DFT level of theory. The effect of element identity and alloying in surface-bound neutral subnanometre clusters is determined by energetic comparison between all compositions of Pd nAg (4-n) and Pd nPt (4-n). And while the binding strengths to the surface increase in the order Pt > Pd > Ag, the excess energy profiles suggest a preference for mixed clusters for both cases. The binding of CO is also modelled, showing that the adsorptionmore » site can be predicted solely by electrophilicity. Comparison to CO binding on a single metal atom shows a reversal of the 5s-d activation process for clusters, weakening the cluster surface interaction on CO adsorption. Charge localisation determines homotop, CO binding and surface site preferences. Furthermore, the electronic behaviour, which is intermediate between molecular and metallic particles allows for tunable features in the subnanometre size range.« less

Geographic clustering of elevated blood heavy metal levels in pregnant women.

PubMed

King, Katherine E; Darrah, Thomas H; Money, Eric; Meentemeyer, Ross; Maguire, Rachel L; Nye, Monica D; Michener, Lloyd; Murtha, Amy P; Jirtle, Randy; Murphy, Susan K; Mendez, Michelle A; Robarge, Wayne; Vengosh, Avner; Hoyo, Cathrine

2015-10-09

Cadmium (Cd), lead (Pb), mercury (Hg), and arsenic (As) exposure is ubiquitous and has been associated with higher risk of growth restriction and cardiometabolic and neurodevelopmental disorders. However, cost-efficient strategies to identify at-risk populations and potential sources of exposure to inform mitigation efforts are limited. The objective of this study was to describe the spatial distribution and identify factors associated with Cd, Pb, Hg, and As concentrations in peripheral blood of pregnant women. Heavy metals were measured in whole peripheral blood of 310 pregnant women obtained at gestational age ~12 weeks. Prenatal residential addresses were geocoded and geospatial analysis (Getis-Ord Gi* statistics) was used to determine if elevated blood concentrations were geographically clustered. Logistic regression models were used to identify factors associated with elevated blood metal levels and cluster membership. Geospatial clusters for Cd and Pb were identified with high confidence (p-value for Gi* statistic <0.01). The Cd and Pb clusters comprised 10.5 and 9.2 % of Durham County residents, respectively. Medians and interquartile ranges of blood concentrations (μg/dL) for all participants were Cd 0.02 (0.01-0.04), Hg 0.03 (0.01-0.07), Pb 0.34 (0.16-0.83), and As 0.04 (0.04-0.05). In the Cd cluster, medians and interquartile ranges of blood concentrations (μg/dL) were Cd 0.06 (0.02-0.16), Hg 0.02 (0.00-0.05), Pb 0.54 (0.23-1.23), and As 0.05 (0.04-0.05). In the Pb cluster, medians and interquartile ranges of blood concentrations (μg/dL) were Cd 0.03 (0.02-0.15), Hg 0.01 (0.01-0.05), Pb 0.39 (0.24-0.74), and As 0.04 (0.04-0.05). Co-exposure with Pb and Cd was also clustered, the p-values for the Gi* statistic for Pb and Cd was <0.01. Cluster membership was associated with lower education levels and higher pre-pregnancy BMI. Our data support that elevated blood concentrations of Cd and Pb are spatially clustered in this urban environment compared to the surrounding areas. Spatial analysis of metals concentrations in peripheral blood or urine obtained routinely during prenatal care can be useful in surveillance of heavy metal exposure.

Site-Directed Synthesis of Cobalt Oxide Clusters in a Metal–Organic Framework

DOE PAGES

Peters, Aaron W.; Otake, Kenichi; Platero-Prats, Ana E.; ...

2018-04-19

Here, direct control over structure and location of catalytic species deposited on amorphous supports represents a formidable challenge in heterogeneous catalysis. In contrast, a structurally well-defined, crystalline metal–organic framework (MOF) can be rationally designed using post-synthetic techniques to allow for desired structural or locational changes of deposited metal ions. Herein, naphthalene dicarboxylate linkers are incorporated in the MOF, NU-1000, to block the small cavities where few-atom clusters of cobalt oxide preferentially grow, inducing catalyst deposition towards hither-to ill-favored grafting sites orientated toward NU-1000’s mesoporous channels. Despite the different cobalt oxide location, the resulting material is still an active propane oxidativemore » dehydrogenation catalyst at low temperature, reaching a turnover frequency of 0.68 ± 0.05 h –1 at 230 °C and confirming the utility of MOFs as crystalline supports to guide rational design of catalysts.« less

Site-Directed Synthesis of Cobalt Oxide Clusters in a Metal–Organic Framework

DOE Office of Scientific and Technical Information (OSTI.GOV)

Peters, Aaron W.; Otake, Kenichi; Platero-Prats, Ana E.

Here, direct control over structure and location of catalytic species deposited on amorphous supports represents a formidable challenge in heterogeneous catalysis. In contrast, a structurally well-defined, crystalline metal–organic framework (MOF) can be rationally designed using post-synthetic techniques to allow for desired structural or locational changes of deposited metal ions. Herein, naphthalene dicarboxylate linkers are incorporated in the MOF, NU-1000, to block the small cavities where few-atom clusters of cobalt oxide preferentially grow, inducing catalyst deposition towards hither-to ill-favored grafting sites orientated toward NU-1000’s mesoporous channels. Despite the different cobalt oxide location, the resulting material is still an active propane oxidativemore » dehydrogenation catalyst at low temperature, reaching a turnover frequency of 0.68 ± 0.05 h –1 at 230 °C and confirming the utility of MOFs as crystalline supports to guide rational design of catalysts.« less

Electrocatalyst for alcohol oxidation at fuel cell anodes

DOEpatents

Adzic, Radoslav [East Setauket, NY; Kowal, Andrzej [Cracow, PL

2011-11-02

In some embodiments a ternary electrocatalyst is provided. The electrocatalyst can be used in an anode for oxidizing alcohol in a fuel cell. In some embodiments, the ternary electrocatalyst may include a noble metal particle having a surface decorated with clusters of SnO.sub.2 and Rh. The noble metal particles may include platinum, palladium, ruthenium, iridium, gold, and combinations thereof. In some embodiments, the ternary electrocatalyst includes SnO.sub.2 particles having a surface decorated with clusters of a noble metal and Rh. Some ternary electrocatalysts include noble metal particles with clusters of SnO.sub.2 and Rh at their surfaces. In some embodiments the electrocatalyst particle cores are nanoparticles. Some embodiments of the invention provide a fuel cell including an anode incorporating the ternary electrocatalyst. In some aspects a method of using ternary electrocatalysts of Pt, Rh, and SnO.sub.2 to oxidize an alcohol in a fuel cell is described.

Massive Star Cluster Populations in Irregular Galaxies as Probable Younger Counterparts of Old Metal-rich Globular Cluster Populations in Spheroids

NASA Astrophysics Data System (ADS)

Kravtsov, V. V.

2006-09-01

Peak metallicities of metal-rich populations of globular clusters (MRGCs) belonging to early-type galaxies and spheroidal subsystems of spiral galaxies (spheroids) of different mass fall within the somewhat conservative -0.7<=[Fe/H]<=-0.3 range. Indeed, if possible age effects are taken into account, this metallicity range might become smaller. Irregular galaxies such as the Large Magellanic Cloud (LMC), with longer timescales of formation and lower star formation (SF) efficiency, do not contain old MRGCs with [Fe/H]>-1.0, but they are observed to form populations of young/intermediate-age massive star clusters (MSCs) with masses exceeding 104 Msolar. Their formation is widely believed to be an accidental process fully dependent on external factors. From the analysis of available data on the populations and their hosts, including intermediate-age populous star clusters in the LMC, we find that their most probable mean metallicities fall within -0.7<=[Fe/H]<=-0.3, as the peak metallicities of MRGCs do, irrespective of signs of interaction. Moreover, both the disk giant metallicity distribution function (MDF) in the LMC and the MDFs for old giants in the halos of massive spheroids exhibit a significant increase toward [Fe/H]~-0.5. That is in agreement with a correlation found between SF activity in galaxies and their metallicity. The formation of both the old MRGCs in spheroids and MSC populations in irregular galaxies probably occurs at approximately the same stage of the host galaxies' chemical evolution and is related to the essentially increased SF activity in the hosts around the same metallicity that is achieved very early in massive spheroids, later in lower mass spheroids, and much later in irregular galaxies. Changes in the interstellar dust, particularly in elemental abundances in dust grains and in the mass distribution function of the grains, may be among the factors regulating star and MSC formation activity in galaxies. Strong interactions and mergers affecting the MSC formation presumably play an additional role, although they can substantially intensify the internally regulated MSC formation process. Several implications of our suggestions are briefly discussed.

Stellar Population Properties of Ultracompact Dwarfs in M87: A Mass–Metallicity Correlation Connecting Low-metallicity Globular Clusters and Compact Ellipticals

NASA Astrophysics Data System (ADS)

Zhang, Hong-Xin; Puzia, Thomas H.; Peng, Eric W.; Liu, Chengze; Côté, Patrick; Ferrarese, Laura; Duc, Pierre-Alain; Eigenthaler, Paul; Lim, Sungsoon; Lançon, Ariane; Muñoz, Roberto P.; Roediger, Joel; Sánchez-Janssen, Ruben; Taylor, Matthew A.; Yu, Jincheng

2018-05-01

We derive stellar population parameters for a representative sample of ultracompact dwarfs (UCDs) and a large sample of massive globular clusters (GCs) with stellar masses ≳ 106 M ⊙ in the central galaxy M87 of the Virgo galaxy cluster, based on model fitting to the Lick-index measurements from both the literature and new observations. After necessary spectral stacking of the relatively faint objects in our initial sample of 40 UCDs and 118 GCs, we obtain 30 sets of Lick-index measurements for UCDs and 80 for GCs. The M87 UCDs have ages ≳ 8 Gyr and [α/Fe] ≃ 0.4 dex, in agreement with previous studies based on smaller samples. The literature UCDs, located in lower-density environments than M87, extend to younger ages and smaller [α/Fe] (at given metallicities) than M87 UCDs, resembling the environmental dependence of the stellar nuclei of dwarf elliptical galaxies (dEs) in the Virgo cluster. The UCDs exhibit a positive mass–metallicity relation (MZR), which flattens and connects compact ellipticals at stellar masses ≳ 108 M ⊙. The Virgo dE nuclei largely follow the average MZR of UCDs, whereas most of the M87 GCs are offset toward higher metallicities for given stellar masses. The difference between the mass–metallicity distributions of UCDs and GCs may be qualitatively understood as a result of their different physical sizes at birth in a self-enrichment scenario or of galactic nuclear cluster star formation efficiency being relatively low in a tidal stripping scenario for UCD formation. The existing observations provide the necessary but not sufficient evidence for tidally stripped dE nuclei being the dominant contributors to the M87 UCDs.

MASS OUTFLOW AND CHROMOSPHERIC ACTIVITY OF RED GIANT STARS IN GLOBULAR CLUSTERS. II. M13 AND M92

DOE Office of Scientific and Technical Information (OSTI.GOV)

Meszaros, Sz.; Dupree, A. K.; Szalai, T.

High-resolution spectra of 123 red giant stars in the globular cluster M13 and 64 red giant stars in M92 were obtained with Hectochelle at the MMT telescope. Emission and line asymmetries in H{alpha} and Ca II K are identified, characterizing motions in the extended atmospheres and seeking differences attributable to metallicity in these clusters and M15. On the red giant branch, emission in H{alpha} generally appears in stars with T {sub eff} {approx}< 4500 K and log L/L {sub sun}{approx}> 2.75. Fainter stars showing emission are asymptotic giant branch (AGB) stars or perhaps binary stars. The line-bisector for H{alpha} revealsmore » the onset of chromospheric expansion in stars more luminous than log (L/L {sub sun}) {approx} 2.5 in all clusters, and this outflow velocity increases with stellar luminosity. However, the coolest giants in the metal-rich M13 show greatly reduced outflow in H{alpha} most probably due to decreased T {sub eff} and changing atmospheric structure. The Ca II K{sub 3} outflow velocities are larger than shown by H{alpha} at the same luminosity and signal accelerating outflows in the chromospheres. Stars clearly on the AGB show faster chromospheric outflows in H{alpha} than RGB objects. While the H{alpha} velocities on the RGB are similar for all metallicities, the AGB stars in the metal-poor M15 and M92 have higher outflow velocities than in the metal-rich M13. Comparison of these chromospheric line profiles in the paired metal-poor clusters, M15 and M92, shows remarkable similarities in the presence of emission and dynamical signatures, and does not reveal a source of the 'second-parameter' effect.« less

The Lack of Influence of Metallicity on Cooling and Collapse of Ionized Gas in Small Protogalactic Halos

NASA Astrophysics Data System (ADS)

Jappsen, A.-K.; Glover, S. C. O.; Klessen, R. S.; Mac Low, M.-M.

2005-12-01

We study the influence of low levels of metal enrichment on the cooling and collapse of ionized gas in small protogalactic halos. We use three-dimensional, smoothed particle hydrodynamics simulations, run with the publicly available parallel code GADGET (Springel et al. 2001). We implement a sink particle algorithm. This allows us to safely represent gas that has collapsed beyond the resolution limit without causing numerical errors within the resolved regions of the simulation. We also include the necessary framework for following the non-equilibrium chemistry of H2 in the protogalactic gas, and a treatment of radiative heating and cooling. Our initial conditions represent protogalaxies forming within a fossil H ii region---a previously ionized H ii region that has not yet had time to cool and recombine. Prior to cosmological reionization, such regions should be relatively common, since the characteristic lifetimes of the likely ionizing sources are significantly shorter than a Hubble time. We show that in these regions, H2 is the dominant and most effective coolant, even in the presence of small amounts of metals. It is the amount of H2 which forms that controls whether or not the gas can collapse and form stars. For metallicities Z ≤ 10-3 Z⊙, we find that metal line cooling alters the density and temperature evolution of the gas by less than 1% compared to the metal-free case at densities below 1 cm-3 and temperatures above 2000 K. However, at higher densities and lower temperatures, metal line cooling does become rather more important, and will affect the ability of the gas to fragment. We also show that an external ultraviolet background delays or suppresses the cooling and collapse of the gas regardless of whether or not it is metal-enriched. RSK and A-KJ acknowledge support from the Emmy Noether Program of the Deutsche Forschungsgemeinschaft (grant no. KL1358/1). M-MML acknowledges support from NSF grants AST99-85392 and AST03-07854, and NASA grant NAG5-10103. SCOG acknowledges support from NSF grant AST03-07793, and NASA grant NAG5-13028. The simulations were performed on the cluster "sanssouci" at Astrophysikalisches Institut Potsdam.

Surface mediated assembly of small, metastable gold nanoclusters

NASA Astrophysics Data System (ADS)

Pettibone, John M.; Osborn, William A.; Rykaczewski, Konrad; Talin, A. Alec; Bonevich, John E.; Hudgens, Jeffrey W.; Allendorf, Mark D.

2013-06-01

The unique properties of metallic nanoclusters are attractive for numerous commercial and industrial applications but are generally less stable than nanocrystals. Thus, developing methodologies for stabilizing nanoclusters and retaining their enhanced functionality is of great interest. We report the assembly of PPh3-protected Au9 clusters from a heterogeneous mixture into films consisting of sub 3 nm nanocluster assemblies. The depositing nanoclusters are metastable in solution, but the resulting nanocluster assemblies are stabilized indefinitely in air or fresh solvent. The films exhibit distinct structure from Au nanoparticles observed by X-ray diffraction, and film dissolution data support the preservation of small nanoclusters. UV-Vis spectroscopy, electrospray ionization mass spectrometry, X-ray photoelectron spectroscopy and electron microscopy are used to elucidate information regarding the nanocluster formation and assembly mechanism. Preferential deposition of nanocluster assemblies can be achieved on multiple substrates, including polymer, Cr, Si, SiO2, SiNx, and metal-organic frameworks (MOFs). Unlike other vapor phase coating processes, nanocluster assembly on the MIL-68(In) MOF crystal is capable of preferentially coating the external surface and stabilizing the crystal structure in hydrothermal conditions, which should enhance their storage, separation and delivery capabilities.The unique properties of metallic nanoclusters are attractive for numerous commercial and industrial applications but are generally less stable than nanocrystals. Thus, developing methodologies for stabilizing nanoclusters and retaining their enhanced functionality is of great interest. We report the assembly of PPh3-protected Au9 clusters from a heterogeneous mixture into films consisting of sub 3 nm nanocluster assemblies. The depositing nanoclusters are metastable in solution, but the resulting nanocluster assemblies are stabilized indefinitely in air or fresh solvent. The films exhibit distinct structure from Au nanoparticles observed by X-ray diffraction, and film dissolution data support the preservation of small nanoclusters. UV-Vis spectroscopy, electrospray ionization mass spectrometry, X-ray photoelectron spectroscopy and electron microscopy are used to elucidate information regarding the nanocluster formation and assembly mechanism. Preferential deposition of nanocluster assemblies can be achieved on multiple substrates, including polymer, Cr, Si, SiO2, SiNx, and metal-organic frameworks (MOFs). Unlike other vapor phase coating processes, nanocluster assembly on the MIL-68(In) MOF crystal is capable of preferentially coating the external surface and stabilizing the crystal structure in hydrothermal conditions, which should enhance their storage, separation and delivery capabilities. Electronic supplementary information (ESI) available: Further details on stored plating solution preparation, film characterization, solution processing, MOF crystal FIB reconstruction and stability are available. See DOI: 10.1039/c3nr01708g

Absolute Magnitude Calibration for Dwarfs Based on the Colour-Magnitude Diagrams of Galactic Clusters

NASA Astrophysics Data System (ADS)

Karaali, S.; Gökçe, E. Yaz; Bilir, S.; Güçtekin, S. Tunçel

2014-07-01

We present two absolute magnitude calibrations for dwarfs based on colour-magnitude diagrams of Galactic clusters. The combination of the Mg absolute magnitudes of the dwarf fiducial sequences of the clusters M92, M13, M5, NGC 2420, M67, and NGC 6791 with the corresponding metallicities provides absolute magnitude calibration for a given (g - r)0 colour. The calibration is defined in the colour interval 0.25 ≤ (g - r)0 ≤ 1.25 mag and it covers the metallicity interval - 2.15 ≤ [Fe/H] ≤ +0.37 dex. The absolute magnitude residuals obtained by the application of the procedure to another set of Galactic clusters lie in the interval - 0.15 ≤ ΔMg ≤ +0.12 mag. The mean and standard deviation of the residuals are < ΔMg > = - 0.002 and σ = 0.065 mag, respectively. The calibration of the MJ absolute magnitude in terms of metallicity is carried out by using the fiducial sequences of the clusters M92, M13, 47 Tuc, NGC 2158, and NGC 6791. It is defined in the colour interval 0.90 ≤ (V - J)0 ≤ 1.75 mag and it covers the same metallicity interval of the Mg calibration. The absolute magnitude residuals obtained by the application of the procedure to the cluster M5 ([Fe/H] = -1.40 dex) and 46 solar metallicity, - 0.45 ≤ [Fe/H] ≤ +0.35 dex, field stars lie in the interval - 0.29 and + 0.35 mag. However, the range of 87% of them is rather shorter, - 0.20 ≤ ΔMJ ≤ +0.20 mag. The mean and standard deviation of all residuals are < ΔMJ > =0.05 and σ = 0.13 mag, respectively. The derived relations are applicable to stars older than 4 Gyr for the Mg calibration, and older than 2 Gyr for the MJ calibration. The cited limits are the ages of the youngest calibration clusters in the two systems.

Photometrically-derived properties of massive-star clusters obtained with different massive-star evolution tracks and deterministic models

NASA Astrophysics Data System (ADS)

Wofford, Aida; Charlot, Stéphane; Eldridge, John

2015-08-01

We compute libraries of stellar + nebular spectra of populations of coeval stars with ages of <100 Myr and metallicities of Z=0.001 to 0.040, using different sets of massive-star evolution tracks, i.e., new Padova tracks for single non-rotating stars, the Geneva tracks for single non-rotating and rotating stars, and the Auckland tracks for single non-rotating and binary stars. For the stellar component, we use population synthesis codes galaxev, starburst99, and BPASS, depending on the set of tracks. For the nebular component we use photoionization code cloudy. From these spectra, we obtain magnitudes in filters F275W, F336W, F438W, F547M, F555W, F657N, and F814W of the Hubble Space Telescope (HST) Wide Field Camera Three. We use i) our computed magnitudes, ii) new multi-band photometry of massive-star clusters in nearby (<11 Mpc) galaxies spanning the metallicity range 12+log(O/H)=7.2-9.2, observed as part of HST programs 13364 (PI Calzetti) and 13773 (PI Chandar), and iii) Bayesian inference to a) establish how well the different models are able to constrain the metallicities, extinctions, ages, and masses of the star clusters, b) quantify differences in the cluster properties obtained with the different models, and c) assess how properties of lower-mass clusters are affected by the stochastic sampling of the IMF. In our models, the stellar evolution tracks, stellar atmospheres, and nebulae have similar chemical compositions. Different metallicities are available with different sets of tracks and we compare results from models of similar metallicities. Our results have implications for studies of the formation and evolution of star clusters, the cluster age and mass functions, and the star formation histories of galaxies.

Effects of single atom doping on the ultrafast electron dynamics of M1Au24(SR)18 (M = Pd, Pt) nanoclusters

NASA Astrophysics Data System (ADS)

Zhou, Meng; Qian, Huifeng; Sfeir, Matthew Y.; Nobusada, Katsuyuki; Jin, Rongchao

2016-03-01

Atomically precise, doped metal clusters are receiving wide research interest due to their synergistic properties dependent on the metal composition. To understand the electronic properties of doped clusters, it is highly desirable to probe the excited state behavior. Here, we report the ultrafast relaxation dynamics of doped M1@Au24(SR)18 (M = Pd, Pt; R = CH2CH2Ph) clusters using femtosecond visible and near infrared transient absorption spectroscopy. Three relaxation components are identified for both mono-doped clusters: (1) sub-picosecond relaxation within the M1Au12 core states; (2) core to shell relaxation in a few picoseconds; and (3) relaxation back to the ground state in more than one nanosecond. Despite similar relaxation pathways for the two doped nanoclusters, the coupling between the metal core and surface ligands is accelerated by over 30% in the case of the Pt dopant compared with the Pd dopant. Compared to Pd doping, the case of Pt doping leads to much more drastic changes in the steady state and transient absorption of the clusters, which indicates that the 5d orbitals of the Pt atom are more strongly mixed with Au 5d and 6s orbitals than the 4d orbitals of the Pd dopant. These results demonstrate that a single foreign atom can lead to entirely different excited state spectral features of the whole cluster compared to the parent Au25(SR)18 cluster. The detailed excited state dynamics of atomically precise Pd/Pt doped gold clusters help further understand their properties and benefit the development of energy-related applications.Atomically precise, doped metal clusters are receiving wide research interest due to their synergistic properties dependent on the metal composition. To understand the electronic properties of doped clusters, it is highly desirable to probe the excited state behavior. Here, we report the ultrafast relaxation dynamics of doped M1@Au24(SR)18 (M = Pd, Pt; R = CH2CH2Ph) clusters using femtosecond visible and near infrared transient absorption spectroscopy. Three relaxation components are identified for both mono-doped clusters: (1) sub-picosecond relaxation within the M1Au12 core states; (2) core to shell relaxation in a few picoseconds; and (3) relaxation back to the ground state in more than one nanosecond. Despite similar relaxation pathways for the two doped nanoclusters, the coupling between the metal core and surface ligands is accelerated by over 30% in the case of the Pt dopant compared with the Pd dopant. Compared to Pd doping, the case of Pt doping leads to much more drastic changes in the steady state and transient absorption of the clusters, which indicates that the 5d orbitals of the Pt atom are more strongly mixed with Au 5d and 6s orbitals than the 4d orbitals of the Pd dopant. These results demonstrate that a single foreign atom can lead to entirely different excited state spectral features of the whole cluster compared to the parent Au25(SR)18 cluster. The detailed excited state dynamics of atomically precise Pd/Pt doped gold clusters help further understand their properties and benefit the development of energy-related applications. Electronic supplementary information (ESI) available: The pump dependent transient absorption spectra and the corresponding global analysis results. See DOI: 10.1039/c6nr01008c

NGC 6067: a young and massive open cluster with high metallicity

NASA Astrophysics Data System (ADS)

Alonso-Santiago, J.; Negueruela, I.; Marco, A.; Tabernero, H. M.; González-Fernández, C.; Castro, N.

2017-08-01

NGC 6067 is a young open cluster hosting the largest population of evolved stars among known Milky Way clusters in the 50-150 Ma age range. It thus represents the best laboratory in our Galaxy to constrain the evolutionary tracks of 5-7 M⊙ stars. We have used high-resolution spectra of a large sample of bright cluster members (45), combined with archival photometry, to obtain accurate parameters for the cluster as well as stellar atmospheric parameters. We derive a distance of 1.78 ± 0.12 kpc, an age of 90 ± 20 Ma and a tidal radius of 14.8^{+6.8}_{-3.2} arcmin. We estimate an initial mass above 5700 M⊙, for a present-day evolved population of two Cepheids, two A supergiants and 12 red giants with masses ≈6 M⊙. We also determine chemical abundances of Li, O, Na, Mg, Si, Ca, Ti, Ni, Rb, Y and Ba for the red clump stars. We find a supersolar metallicity, [Fe/H] = +0.19 ± 0.05, and a homogeneous chemical composition, consistent with the Galactic metallicity gradient. The presence of a Li-rich red giant, star 276 with A(Li) = 2.41, is also detected. An overabundance of Ba is found, supporting the enhanced s-process. The ratio of yellow to red giants is much smaller than 1, in agreement with models with moderate overshooting, but the properties of the cluster Cepheids do not seem consistent with current Padova models for supersolar metallicity.

Have We Finally Found Pop III Stars?

NASA Astrophysics Data System (ADS)

Kohler, Susanna

2015-08-01

Elusive Population: Population III stars — the theoretical generation of extremely metal-poor stars that should have been formed in the early universe before metals existed — have been conspicuously absent in observations. But a team led by David Sobral (Institute of Astrophysics and Space Sciences, University of Lisbon, and Leiden Observatory) may have changed this paradigm with their recent detection of an extremely bright galaxy in the early universe. The team's broad survey of distant galaxies using ESO's Very Large Telescope provides a glimpse of the universe as it was only 800 million years after the Big Bang. The survey uncovered several unusually bright galaxies — including the brightest galaxy ever seen at this distance, an important discovery by itself. But further scrutiny of this galaxy, named CR7, produced an even more exciting find: a bright pocket of the galaxy contained no sign of any metals. Follow-up with other telescopes confirmed this initial detection. Formation Waves: Sobral and his team postulate that we are observing this galaxy at just the right time to have caught a cluster of Population III stars — the bright, metal-free region of the galaxy — at the end of a wave of early star formation. The observations of CR7 also suggest the presence of regular stars in clumps around the metal-free pocket. These older, surrounding clusters may have formed stars first, helping to ionize a local bubble in the galaxy and allowing us to now observe the light from CR7. It was previously thought that Population III stars might only be found in small, dim galaxies, making them impossible for us to detect. But CR7 provides an interesting alternative: this galaxy is bright, and the candidate Population III stars are surrounded by clusters of normal stars. This suggests that these first-generation stars might in fact be easier to detect than was originally thought. Additional follow-up observations with other telescopes will help to confirm the identity of these stars. In particular, the James Webb Space Telescope is expected to further advance the pursuit of the earliest galaxies and stars in the universe. Citation: David Sobral et al. 2015, ApJ, 808, 139. doi:10.1088/0004-637X/808/2/139

STELLAR POPULATIONS AND EVOLUTION OF EARLY-TYPE CLUSTER GALAXIES: CONSTRAINTS FROM OPTICAL IMAGING AND SPECTROSCOPY OF z = 0.5-0.9 GALAXY CLUSTERS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jorgensen, Inger; Chiboucas, Kristin, E-mail: ijorgensen@gemini.edu, E-mail: kchiboucas@gemini.edu

2013-03-15

We present an analysis of stellar populations and evolutionary history of galaxies in three similarly rich galaxy clusters MS0451.6-0305 (z = 0.54), RXJ0152.7-1357 (z = 0.83), and RXJ1226.9+3332 (z = 0.89). Our analysis is based on high signal-to-noise ground-based optical spectroscopy and Hubble Space Telescope imaging for a total of 17-34 members in each cluster. Using the dynamical masses together with the effective radii and the velocity dispersions, we find no indication of evolution of sizes or velocity dispersions with redshift at a given galaxy mass. We establish the Fundamental Plane (FP) and scaling relations between absorption line indices andmore » velocity dispersions. We confirm that the FP is steeper at z Almost-Equal-To 0.86 compared to the low-redshift FP, indicating that under the assumption of passive evolution the formation redshift, z{sub form}, depends on the galaxy velocity dispersion (or alternatively mass). At a velocity dispersion of {sigma} = 125 km s{sup -1} (Mass = 10{sup 10.55} M{sub Sun }) we find z{sub form} = 1.24 {+-} 0.05, while at {sigma} = 225 km s{sup -1} (Mass = 10{sup 11.36} M{sub Sun }) the formation redshift is z{sub form} = 1.95{sup +0.3}{sub -0.2}, for a Salpeter initial mass function. The three clusters follow similar scaling relations between absorption line indices and velocity dispersions as those found for low-redshift galaxies. The zero point offsets for the Balmer lines depend on cluster redshifts. However, the offsets indicate a slower evolution, and therefore higher formation redshift, than the zero point differences found from the FP, if interpreting the data using a passive evolution model. Specifically, the strength of the higher order Balmer lines H{delta} and H{gamma} implies z{sub form} > 2.8. The scaling relations for the metal indices in general show small and in some cases insignificant zero point offsets, favoring high formation redshifts for a passive evolution model. Based on the absorption line indices and recent stellar population models from Thomas et al., we find that MS0451.6-0305 has a mean metallicity [M/H] approximately 0.2 dex below that of the other clusters and our low-redshift sample. We confirm our previous result that RXJ0152.7-1357 has a mean abundance ratio [{alpha}/Fe] approximately 0.3 dex higher than that of the other clusters. The differences in [M/H] and [{alpha}/Fe] between the high-redshift clusters and the low-redshift sample are inconsistent with a passive evolution scenario for early-type cluster galaxies over the redshift interval studied. Low-level star formation may be able to bring the metallicity of MS0451.6-0305 in agreement with the low-redshift sample, while we speculate whether galaxy mergers can lead to sufficiently large changes in the abundance ratios for the RXJ0152.7-1357 galaxies to allow them to reach the low-redshift sample values in the time available.« less

Ab Initio Cluster Calculations for the Adsorption of Small Molecules on Oxide Surfaces - from Single Molecules to Monolayers

NASA Astrophysics Data System (ADS)

Pykavy, M.; Staemmler, V.; Rittner, F.

2000-04-01

Quantum chemical ab initio cluster calculations were performed for the adsorption of small molecules on metal oxide surfaces. Two systems were studied in detail: The adsorption of N2 on the (110) surface plane of TiO2 (rutile) and the adsorption of CO on the polar (0001) surface of Cr2O3. In both cases a full five-dimensional potential for the interaction of a single molecule with the respective surface was calculated. For N2/TiO2 (110) the minimum was found for the end-on adsorption of N2 atop a coordinately unsaturated surface Ti atom, with an adsorption energy of (35 ± 5) kJ/mol. In the case of CO/Cr2O3 (0001) the CO molecule is adsorbed strongly tilted (almost side-on) along a line connecting two Cr3+ ions at the surface; the calculated adsorption energy is 22 kJ/mol. In conjunction with empirical pair potentials for the N2/N2 and CO/CO interaction in the gas phase, Monte Carlo simulations were carried out to determine adsorption isotherms and the geometric structure of adsorbed monolayers.

The Au(n) cluster probe in secondary ion mass spectrometry: influence of the projectile size and energy on the desorption/ionization rate from biomolecular solids.

PubMed

Novikov, Alexey; Caroff, Martine; Della-Negra, Serge; Depauw, Joël; Fallavier, Mireille; Le Beyec, Yvon; Pautrat, Michèle; Schultz, J Albert; Tempez, Agnès; Woods, Amina S

2005-01-01

A Au-Si liquid metal ion source which produces Au(n) clusters over a large range of sizes was used to study the dependence of both the molecular ion desorption yield and the damage cross-section on the size (n = 1 to 400) and on the kinetic energy (E = 10 to 500 keV) of the clusters used to bombard bioorganic surfaces. Three pure peptides with molecular masses between 750 and 1200 Da were used without matrix. [M+H](+) and [M+cation](+) ion emission yields were enhanced by as much as three orders of magnitude when bombarding with Au(400) (4+) instead of monatomic Au(+), yet very little damage was induced in the samples. A 100-fold increase in the molecular ion yield was observed when the incident energy of Au(9) (+) was varied from 10 to 180 keV. Values of emission yields and damage cross-sections are presented as a function of cluster size and energy. The possibility to adjust both cluster size and energy, depending on the application, makes the analysis of biomolecules by secondary ion mass spectrometry an extremely powerful and flexible technique, particularly when combined with orthogonal time-of-flight mass spectrometry that then allows fast measurements using small primary ion beam currents. Copyright (c) 2005 John Wiley & Sons, Ltd.

Room-temperature current blockade in atomically defined single-cluster junctions

NASA Astrophysics Data System (ADS)

Lovat, Giacomo; Choi, Bonnie; Paley, Daniel W.; Steigerwald, Michael L.; Venkataraman, Latha; Roy, Xavier

2017-11-01

Fabricating nanoscopic devices capable of manipulating and processing single units of charge is an essential step towards creating functional devices where quantum effects dominate transport characteristics. The archetypal single-electron transistor comprises a small conducting or semiconducting island separated from two metallic reservoirs by insulating barriers. By enabling the transfer of a well-defined number of charge carriers between the island and the reservoirs, such a device may enable discrete single-electron operations. Here, we describe a single-molecule junction comprising a redox-active, atomically precise cobalt chalcogenide cluster wired between two nanoscopic electrodes. We observe current blockade at room temperature in thousands of single-cluster junctions. Below a threshold voltage, charge transfer across the junction is suppressed. The device is turned on when the temporary occupation of the core states by a transiting carrier is energetically enabled, resulting in a sequential tunnelling process and an increase in current by a factor of ∼600. We perform in situ and ex situ cyclic voltammetry as well as density functional theory calculations to unveil a two-step process mediated by an orbital localized on the core of the cluster in which charge carriers reside before tunnelling to the collector reservoir. As the bias window of the junction is opened wide enough to include one of the cluster frontier orbitals, the current blockade is lifted and charge carriers can tunnel sequentially across the junction.

Atomically manufactured nickel-silicon quantum dots displaying robust resonant tunneling and negative differential resistance

NASA Astrophysics Data System (ADS)

Cheng, Jian-Yih; Fisher, Brandon L.; Guisinger, Nathan P.; Lilley, Carmen M.

2017-12-01

Providing a spin-free host material in the development of quantum information technology has made silicon a very interesting and desirable material for qubit design. Much of the work and experimental progress has focused on isolated phosphorous atoms. In this article, we report on the exploration of Ni-Si clusters that are atomically manufactured via self-assembly from the bottom-up and behave as isolated quantum dots. These small quantum dot structures are probed at the atomic-scale with scanning tunneling microscopy and spectroscopy, revealing robust resonance through discrete quantized energy levels within the Ni-Si clusters. The resonance energy is reproducible and the peak spacing of the quantum dot structures increases as the number of atoms in the cluster decrease. Probing these quantum dot structures on degenerately doped silicon results in the observation of negative differential resistance in both I-V and dI/dV spectra. At higher surface coverage of nickel, a well-known √19 surface modification is observed and is essentially a tightly packed array of the clusters. Spatial conductance maps reveal variations in the local density of states that suggest the clusters are influencing the electronic properties of their neighbors. All of these results are extremely encouraging towards the utilization of metal modified silicon surfaces to advance or complement existing quantum information technology.

Atomically manufactured nickel–silicon quantum dots displaying robust resonant tunneling and negative differential resistance

DOE PAGES

Cheng, Jian -Yih; Fisher, Brandon L.; Guisinger, Nathan P.; ...

2017-05-22

Providing a spin-free host material in the development of quantum information technology has made silicon a very interesting and desirable material for qubit design. Much of the work and experimental progress has focused on isolated phosphorous atoms. In this article, we report on the exploration of Ni–Si clusters that are atomically manufactured via self-assembly from the bottom-up and behave as isolated quantum dots. These small quantum dot structures are probed at the atomic-scale with scanning tunneling microscopy and spectroscopy, revealing robust resonance through discrete quantized energy levels within the Ni–Si clusters. The resonance energy is reproducible and the peak spacingmore » of the quantum dot structures increases as the number of atoms in the cluster decrease. Probing these quantum dot structures on degenerately doped silicon results in the observation of negative differential resistance in both I–V and dI/dV spectra. At higher surface coverage of nickel, a well-known √19 surface modification is observed and is essentially a tightly packed array of the clusters. Spatial conductance maps reveal variations in the local density of states that suggest the clusters are influencing the electronic properties of their neighbors. Furthermore, all of these results are extremely encouraging towards the utilization of metal modified silicon surfaces to advance or complement existing quantum information technology.« less

Atomically manufactured nickel–silicon quantum dots displaying robust resonant tunneling and negative differential resistance

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cheng, Jian -Yih; Fisher, Brandon L.; Guisinger, Nathan P.

Providing a spin-free host material in the development of quantum information technology has made silicon a very interesting and desirable material for qubit design. Much of the work and experimental progress has focused on isolated phosphorous atoms. In this article, we report on the exploration of Ni–Si clusters that are atomically manufactured via self-assembly from the bottom-up and behave as isolated quantum dots. These small quantum dot structures are probed at the atomic-scale with scanning tunneling microscopy and spectroscopy, revealing robust resonance through discrete quantized energy levels within the Ni–Si clusters. The resonance energy is reproducible and the peak spacingmore » of the quantum dot structures increases as the number of atoms in the cluster decrease. Probing these quantum dot structures on degenerately doped silicon results in the observation of negative differential resistance in both I–V and dI/dV spectra. At higher surface coverage of nickel, a well-known √19 surface modification is observed and is essentially a tightly packed array of the clusters. Spatial conductance maps reveal variations in the local density of states that suggest the clusters are influencing the electronic properties of their neighbors. Furthermore, all of these results are extremely encouraging towards the utilization of metal modified silicon surfaces to advance or complement existing quantum information technology.« less

Red giants observed by CoRoT and APOGEE: The evolution of the Milky Way's radial metallicity gradient

NASA Astrophysics Data System (ADS)

Anders, F.; Chiappini, C.; Minchev, I.; Miglio, A.; Montalbán, J.; Mosser, B.; Rodrigues, T. S.; Santiago, B. X.; Baudin, F.; Beers, T. C.; da Costa, L. N.; García, R. A.; García-Hernández, D. A.; Holtzman, J.; Maia, M. A. G.; Majewski, S.; Mathur, S.; Noels-Grotsch, A.; Pan, K.; Schneider, D. P.; Schultheis, M.; Steinmetz, M.; Valentini, M.; Zamora, O.

2017-04-01

Using combined asteroseismic and spectroscopic observations of 418 red-giant stars close to the Galactic disc plane (6 kpc < RGal ≲ 13 kpc, | ZGal| < 0.3 kpc), we measure the age dependence of the radial metallicity distribution in the Milky Way's thin disc over cosmic time. The slope of the radial iron gradient of the young red-giant population (-0.058 ± 0.008 [stat.] ±0.003 [syst.] dex/kpc) is consistent with recent Cepheid measurements. For stellar populations with ages of 1-4 Gyr the gradient is slightly steeper, at a value of -0.066 ± 0.007 ± 0.002 dex/kpc, and then flattens again to reach a value of -0.03 dex/kpc for stars with ages between 6 and 10 Gyr. Our results are in good agreement with a state-of-the-art chemo-dynamical Milky-Way model in which the evolution of the abundance gradient and its scatter can be entirely explained by a non-varying negative metallicity gradient in the interstellar medium, together with stellar radial heating and migration. We also offer an explanation for why intermediate-age open clusters in the solar neighbourhood can be more metal-rich, and why their radial metallicity gradient seems to be much steeper than that of the youngest clusters. Already within 2 Gyr, radial mixing can bring metal-rich clusters from the innermost regions of the disc to Galactocentric radii of 5 to 8 kpc. We suggest that these outward-migrating clusters may be less prone to tidal disruption and therefore steepen the local intermediate-age cluster metallicity gradient. Our scenario also explains why the strong steepening of the local iron gradient with age is not seen in field stars. In the near future, asteroseismic data from the K2 mission will allow for improved statistics and a better coverage of the inner-disc regions, thereby providing tighter constraints on theevolution of the central parts of the Milky Way.

Properties of the Open Cluster Tombaugh 1 from High-resolution Spectroscopy and uvbyCaHβ Photometry

NASA Astrophysics Data System (ADS)

Sales Silva, João V.; Carraro, Giovanni; Anthony-Twarog, Barbara J.; Moni Bidin, Christian; Costa, Edgardo; Twarog, Bruce A.

2016-01-01

Open clusters can be the key to deepening our knowledge on various issues involving the structure and evolution of the Galactic disk and details of stellar evolution because a cluster’s properties are applicable to all its members. However, the number of open clusters with detailed analysis from high-resolution spectroscopy or precision photometry imposes severe limitations on studies of these objects. To expand the number of open clusters with well-defined chemical abundances and fundamental parameters, we investigate the poorly studied, anticenter open cluster Tombaugh 1. Using precision uvbyCaHβ photometry and high-resolution spectroscopy, we derive the cluster’s reddening, obtain photometric metallicity estimates, and, for the first time, present a detailed abundance analysis of 10 potential cluster stars (nine clump stars and one Cepheid). Using the radial position from the cluster center and multiple color indices, we have isolated a sample of unevolved, probable single-star members of Tombaugh 1. From 51 stars, the cluster reddening is found to be E(b-y) = 0.221 ± 0.006 or E(B-V) = 0.303 ± 0.008, where the errors refer to the internal standard errors of the mean. The weighted photometric metallicity from m1 and hk is [Fe/H] = -0.10 ± 0.02, while a match to the Victoria-Regina Strömgren isochrones leads to an age of 0.95 ± 0.10 Gyr and an apparent modulus of (m-M) = 13.10 ± 0.10. Radial velocities identify six giants as probable cluster members, and the elemental abundances of Fe, Na, Mg, Al, Si, Ca, Ti, Cr, Ni, Y, Ba, Ce, and Nd have been derived for both the cluster and the field stars. Tombaugh 1 appears to be a typical inner thin disk, intermediate-age open cluster of slightly subsolar metallicity, located just beyond the solar circle, with solar elemental abundance ratios except for the heavy s-process elements, which are a factor of two above solar. Its metallicity is consistent with a steep metallicity gradient in the galactocentric region between 9.5 and 12 kpc. Our study also shows that Cepheid XZ CMa is not a member of Tombaugh 1 and reveals that this Cepheid presents signs of barium enrichment, making it a probable binary star. Based on observations carried out at Las Campanas Observatory (program ID: CN2009B-042) and Cerro Tololo Inter-American Observatory.

Changes in cluster magnetism and suppression of local superconductivity in amorphous FeCrB alloy irradiated by Ar+ ions

NASA Astrophysics Data System (ADS)

Okunev, V. D.; Samoilenko, Z. A.; Szymczak, H.; Szewczyk, A.; Szymczak, R.; Lewandowski, S. J.; Aleshkevych, P.; Malinowski, A.; Gierłowski, P.; Więckowski, J.; Wolny-Marszałek, M.; Jeżabek, M.; Varyukhin, V. N.; Antoshina, I. A.

2016-02-01

We show that сluster magnetism in ferromagnetic amorphous Fe67Cr18B15 alloy is related to the presence of large, D=150-250 Å, α-(Fe Cr) clusters responsible for basic changes in cluster magnetism, small, D=30-100 Å, α-(Fe, Cr) and Fe3B clusters and subcluster atomic α-(Fe, Cr, B) groupings, D=10-20 Å, in disordered intercluster medium. For initial sample and irradiated one (Φ=1.5×1018 ions/cm2) superconductivity exists in the cluster shells of metallic α-(Fe, Cr) phase where ferromagnetism of iron is counterbalanced by antiferromagnetism of chromium. At Φ=3×1018 ions/cm2, the internal stresses intensify and the process of iron and chromium phase separation, favorable for mesoscopic superconductivity, changes for inverse one promoting more homogeneous distribution of iron and chromium in the clusters as well as gigantic (twice as much) increase in density of the samples. As a result, in the cluster shells ferromagnetism is restored leading to the increase in magnetization of the sample and suppression of local superconductivity. For initial samples, the temperature dependence of resistivity ρ(T) T2 is determined by the electron scattering on quantum defects. In strongly inhomogeneous samples, after irradiation by fluence Φ=1.5×1018 ions/cm2, the transition to a dependence ρ(T) T1/2 is caused by the effects of weak localization. In more homogeneous samples, at Φ=3×1018 ions/cm2, a return to the dependence ρ(T) T2 is observed.

State of the metal core in nanosecond exploding wires and related phenomena

NASA Astrophysics Data System (ADS)

Sarkisov, G. S.; Sasorov, P. V.; Struve, K. W.; McDaniel, D. H.

2004-08-01

Experiments show that an expanding metal wire core that results from a nanosecond electrical explosion in vacuum consists primarily of three different states: solid, microdrop, and gas-plasma. The state of the wire core depends both on the amount of energy deposited before the voltage breakdown and on the heating conditions. For small amounts of deposited energy (on the order of solid-stage enthalpy), the wire core remains in a solid state or is partially disintegrated. For a high level of deposited energy (more than vaporization energy) the wire core is in a gas-plasma state. For an intermediate level of deposited energy (more than melting but less than vaporization), the wire disintegrates into hot liquid microdrops or clusters of submicron size. For a wire core in the cluster state, interferometry demonstrates weak (or even absent) phaseshift. Light emission shows a "firework effect"—the long late-time radiation related to the emission by the expanding cylinder of hot microparticles. For the wire core in a gas-plasma state, interferometry demonstrates a large phaseshift and a fast reduction in light emission due to adiabatic cooling of the expanding wire core. The simulation of this firework effect agrees well with experimental data, assuming submicron size and a temperature approaching boiling for the expanded microparticles cylinder.

Physicochemical model of detonation synthesis of nanoparticles from metal carboxylates

NASA Astrophysics Data System (ADS)

Tolochko, B. P.; Chernyshev, A. P.; Ten, K. A.; Pruuel, E. R.; Zhogin, I. L.; Zubkov, P. I.; Lyakhov, N. Z.; Luk'yanchikov, L. A.; Sheromov, M. A.

2008-02-01

We have shown previously that when metal carboxylates are subjected to a shock-wave action, diamond nanoparticles and nanoparticles of metals (Ag, Bi, Co, Fe, Pb) are formed and their characteristic size is about 30-200 Å. The metal nanoparticles formed are covered by an amorphous-carbon layer up to 20 Å thick. In this work we put forward a physicochemical model of the formation of diamond and metal nanoparticles from metal carboxylates upon shock-wave action. The energy released upon detonation inside the precursor is lower than in regions not occupied by the stearates. The characteristic time of temperature equalization has been estimated to be on the order of ˜10-3 s, which is greater by a factor of ˜103 than the characteristic reaction time. Due to the adiabatic nature of the processes occurring, the typical temperature of a "particle" will be lower than the temperature of the surrounding medium. In the framework of the model suggested, it has been assumed that the growth of metal clusters should occur by the diffusion mechanism; i.e., the "building material" is supplied through diffusion. The calculation using our previous experimental data on the reaction time and average size of metal particles has shown that the diffusion properties of the medium in which the metal nanoparticles are formed are close to those of the liquid state of the substance. The temperature and pressure under detonation conditions markedly exceed the analogous parameters characteristic of experiments on the thermodestruction of metal carboxylates. The small time of existence of the reaction mixture is compensated by the high mobility and concentration of reagents.

193Ir Mössbauer spectroscopy of Pt-IrO 2 nanoparticle catalysts developed for detection and removal of carbon monoxide from air

NASA Astrophysics Data System (ADS)

Sawicki, J. A.; Marcinkowska, K.; Wagner, F. E.

2010-08-01

Mössbauer spectroscopy of 73.0 keV gamma-ray transition in 193Ir and supplementary analytical techniques were used to study the microstructure and chemical form of polymer-supported hydrophobic bimetallic Pt-Ir catalysts for detection and removal of CO from humid air at ambient conditions. The catalysts, typically with a composition of 9 wt.% Pt and 1 wt.% Ir, were prepared by incipient wetness impregnation of polystyrene-divinylbenzene (SDB) granules with ethanol solutions of hexachloroplatinic and hexachloroiridic acids. This procedure, followed by reduction in H 2 or CO at only 200 °C or 250 °C, resulted in formation of highly-dispersed Pt-Ir particles usually smaller than 20 nm and having high catalytic activity and selectivity. Mössbauer spectra of 73.0 keV gamma-ray transition in 193Ir were taken after consecutive steps of preparation and exposure of catalysts to better understand and further improve the fabrication processes. In the as-impregnated state, iridium was found mostly as Ir(III) in [IrCl 6] 3- ions, with only a small fraction of Ir(IV) in [IrCl 6] 2- ions. The iridium in bimetallic clusters formed by reduction in hydrogen showed a strong tendency towards oxidation on exposure to air at room temperature, while Pt remained mostly metallic. In the most active and stable catalysts, the Ir and Pt in metallic regions of the clusters did not tend to segregate, unlike in Pt-Ir/silica-supported catalysts studied by us earlier. Further, this study shows that the IrO 2-like regions in the clusters exhibit stronger deviations from local symmetry and stoichiometry of crystalline IrO 2 than observed previously in Pt-Ir/silica catalysts. Our study also indicates that in the examined Pt-IrO 2 nanoparticles iridium largely provides the dissociative O 2 adsorption sites, while the CO adsorption occurs primarily at metallic Pt sites.

Rubredoxin-related Maturation Factor Guarantees Metal Cofactor Integrity during Aerobic Biosynthesis of Membrane-bound [NiFe] Hydrogenase*

PubMed Central

Fritsch, Johannes; Siebert, Elisabeth; Priebe, Jacqueline; Zebger, Ingo; Lendzian, Friedhelm; Teutloff, Christian; Friedrich, Bärbel; Lenz, Oliver

2014-01-01

The membrane-bound [NiFe] hydrogenase (MBH) supports growth of Ralstonia eutropha H16 with H2 as the sole energy source. The enzyme undergoes a complex biosynthesis process that proceeds during cell growth even at ambient O2 levels and involves 14 specific maturation proteins. One of these is a rubredoxin-like protein, which is essential for biosynthesis of active MBH at high oxygen concentrations but dispensable under microaerobic growth conditions. To obtain insights into the function of HoxR, we investigated the MBH protein purified from the cytoplasmic membrane of hoxR mutant cells. Compared with wild-type MBH, the mutant enzyme displayed severely decreased hydrogenase activity. Electron paramagnetic resonance and infrared spectroscopic analyses revealed features resembling those of O2-sensitive [NiFe] hydrogenases and/or oxidatively damaged protein. The catalytic center resided partially in an inactive Niu-A-like state, and the electron transfer chain consisting of three different Fe-S clusters showed marked alterations compared with wild-type enzyme. Purification of HoxR protein from its original host, R. eutropha, revealed only low protein amounts. Therefore, recombinant HoxR protein was isolated from Escherichia coli. Unlike common rubredoxins, the HoxR protein was colorless, rather unstable, and essentially metal-free. Conversion of the atypical iron-binding motif into a canonical one through genetic engineering led to a stable reddish rubredoxin. Remarkably, the modified HoxR protein did not support MBH-dependent growth at high O2. Analysis of MBH-associated protein complexes points toward a specific interaction of HoxR with the Fe-S cluster-bearing small subunit. This supports the previously made notion that HoxR avoids oxidative damage of the metal centers of the MBH, in particular the unprecedented Cys6[4Fe-3S] cluster. PMID:24448806

Water Oxidation Catalysis via Size-Selected Iridium Clusters

DOE Office of Scientific and Technical Information (OSTI.GOV)

Halder, Avik; Liu, Cong; LIU, ZHUN

The detailed mechanism and efficacy of four electron electrochemical water oxidation depend critically upon the detailed atomic structure of each catalytic site, which are numerous and diverse in most metal oxides anodes. In order to limit the diversity of sites, arrays of discrete iridium clusters with identical metal atom number (Ir-2, Ir-4, or Ir-8) were deposited in submonolayer coverage on conductive oxide supports, and the electrochemical properties and activity of each was evaluated. Exceptional electroactivity for the oxygen evolving reaction (OER) was observed for all cluster samples in acidic electrolyte. Reproducible cluster-size-dependent trends in redox behavior were also resolved. First-principlesmore » computational models of the individual discrete-size clusters allow correlation of catalytic-site structure and multiplicity with redox behavior.« less

ASCA Observations of Distant Clusters of Galaxies

NASA Astrophysics Data System (ADS)

Tsuru, T. G.

We present results from ASCA observation of distant clusters of galaxies. The observed clusters are as follows; CL0016+16, A370, A959, AC118, Zw3136, MS1305.4+2941, A1851, A963, A2163, MS0839.8+2938, A665, A1689, A2218, A586 and A1413. The covering range of the redshifts is 0.14-0.55 and their average red-shift is 0.245. The negative correlation between the metal abundance and the plasma temperature seen in near clusters is also detected in the distant clusters. No apparent difference between the two correlation. It suggests no strong metal evolution has been made from z = 0.2-0.3 to z = 0. Data of velocity dispersion is available for seven clusters among our samples. All the betaspec of them are above the average of near clusters. The average betaspec for the distant clusters obtained to be betaspec = 1.85 with an rms scatter of 0.62. The value is significantly higher than the near clusters' value of betaspec = 0.94 plus or minus 0.08 with an rms scatter of 0.46.

Modelling Catalyst Surfaces Using DFT Cluster Calculations

PubMed Central

Czekaj, Izabela; Wambach, Jörg; Kröcher, Oliver

2009-01-01

We review our recent theoretical DFT cluster studies of a variety of industrially relevant catalysts such as TiO2, γ-Al2O3, V2O5-WO3-TiO2 and Ni/Al2O3. Aspects of the metal oxide surface structure and the stability and structure of metal clusters on the support are discussed as well as the reactivity of surfaces, including their behaviour upon poisoning. It is exemplarily demonstrated how such theoretical considerations can be combined with DRIFT and XPS results from experimental studies. PMID:20057947

Theoretical colours and isochrones for some Hubble Space Telescope colour systems

NASA Technical Reports Server (NTRS)

Edvardsson, B.; Bell, R. A.

1989-01-01

Synthetic spectra for effective temperatures of 4000-7250 K, logarithmic surface gravities typical of dwarfs and subgiants, and metallicities from solar values to 0.001 of the solar metallicity were used to derive a grid of synthetic surface brightness magnitudes for 21 of the Hubble Space Telescope Wide Field Camera (WFC) band passes. The absolute magnitudes of these 21 band passes are also obtained for a set of globular cluster isochrones with different helium abundances, metallicities, oxygen abundances, and ages. The usefulness and efficiency of different sets of broad and intermediate bandwidth WFC colors for determining ages and metallicities for globular clusters are evaluated.

Using photometrically selected metal-poor stars to study dwarf galaxies and the Galactic stellar halo

NASA Astrophysics Data System (ADS)

Youakim, Kris; Starkenburg, Else; Martin, Nicolas; Pristine Team

2018-06-01

The Pristine survey is a narrow-band photometric survey designed to efficiently search for extremely metal-poor (EMP) stars. In the first three years of the survey, it has demonstrated great efficiency at finding EMP stars, and also great promise for increasing the current, small sample of the most metal-poor stars. The present sky coverage is ~2500 square degrees in the Northern Galactic Halo, including several individual fields targeting dwarf galaxies. By efficiently identifying member stars in the outskirts of known faint dwarf galaxies, the dynamical histories and chemical abundance patterns of these systems can be understood in greater detail. Additionally, with reliable photometric metallicities over a large sky coverage it is possible to perform a large scale clustering analysis in the Milky Way halo, and investigate the characteristic scale of substructure at different metallicities. This can reveal important details about the process of building up the halo through dwarf galaxy accretion, and offer insight into the connection between dwarf galaxies and the Milky Way halo. In this talk I will outline our results on the search for the most pristine stars, with a focus on how we are using this information to advance our understanding of dwarf galaxies and their contribution to the formation of the Galactic stellar halo.

Defects in Amorphous Semiconductors: The Case of Amorphous Indium Gallium Zinc Oxide

NASA Astrophysics Data System (ADS)

de Jamblinne de Meux, A.; Pourtois, G.; Genoe, J.; Heremans, P.

2018-05-01

Based on a rational classification of defects in amorphous materials, we propose a simplified model to describe intrinsic defects and hydrogen impurities in amorphous indium gallium zinc oxide (a -IGZO). The proposed approach consists of organizing defects into two categories: point defects, generating structural anomalies such as metal—metal or oxygen—oxygen bonds, and defects emerging from changes in the material stoichiometry, such as vacancies and interstitial atoms. Based on first-principles simulations, it is argued that the defects originating from the second group always act as perfect donors or perfect acceptors. This classification simplifies and rationalizes the nature of defects in amorphous phases. In a -IGZO, the most important point defects are metal—metal bonds (or small metal clusters) and peroxides (O - O single bonds). Electrons are captured by metal—metal bonds and released by the formation of peroxides. The presence of hydrogen can lead to two additional types of defects: metal-hydrogen defects, acting as acceptors, and oxygen-hydrogen defects, acting as donors. The impact of these defects is linked to different instabilities observed in a -IGZO. Specifically, the diffusion of hydrogen and oxygen is connected to positive- and negative-bias stresses, while negative-bias illumination stress originates from the formation of peroxides.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Leenheer, J.A.; Brown, G.K.; Cabaniss, S.E.

Fulvic acid, isolated from the Suwannee River, Georgia, was assessed for its ability to bind Ca{sup 2+}, Cd{sup 2+}, Cu{sup 2+}, Ni{sup 2+}, and Zn{sup 2+} ions at pH 6 before and after extensive fractionation that was designed to reveal the nature of metal binding functional groups. The binding constant for Ca{sup 2+} ion had the greatest increase of all the ions in a metal binding fraction that was selected for intensive characterization for the purpose of building quantitative average model structures. The metal binding fraction was characterized by quantitative {sup 13}C NMR, {sup 1}H NMR, and FT-IR spectrometry andmore » elemental, titrimetric, and molecular weight determinations. The characterization data revealed that carboxyl groups were clustered in short-chain aliphatic dibasic acid structures. The Ca{sup 2+} binding data suggested that ether-substituted oxysuccinic acid structures are good models for the metal binding sites at pH 6. Structural models were derived based upon oxidation and photolytic rearrangements of cutin, lignin, and tannin precursors. These structural models rich in substituted dibasic acid structures revealed polydentate binding sites with the potential for both inner-sphere and outer-sphere type binding. The majority of the fulvic acid molecule was involved with metal binding rather than a small substructural unit.« less

The Role of Structural and Compositional Heterogeneities in the Insulator-to-Metal Transition in Hole-Doped APd3O4 (A = Ca, Sr).

PubMed

Lamontagne, Leo K; Laurita, Geneva; Knight, Michael; Yusuf, Huma; Hu, Jerry; Seshadri, Ram; Page, Katharine

2017-05-01

The cubic semiconducting compounds APd 3 O 4 (A = Ca, Sr) can be hole-doped by Na substitution on the A site and driven toward more conducting states. This process has been followed here by a number of experimental techniques to understand the evolution of electronic properties. While an insulator-to-metal transition is observed in Ca 1-x Na x Pd 3 O 4 for x ≥ 0.15, bulk metallic behavior is not observed for Sr 1-x Na x Pd 3 O 4 up to x = 0.20. Given the very similar crystal and (calculated) electronic structures of the two materials, the distinct behavior is a matter of interest. We present evidence of local disorder in the A = Sr materials through the analysis of the neutron pair distribution function, which is potentially at the heart of the distinct behavior. Solid-state 23 Na nuclear magnetic resonance studies additionally suggest a percolative insulator-to-metal transition mechanism, wherein presumably small regions with a signal resembling metallic NaPd 3 O 4 form almost immediately upon Na substitution, and this signal grows monotonically with substitution. Some signatures of increased local disorder and a propensity for Na clustering are seen in the A = Sr compounds.