Science.gov

Sample records for metal clusters adequate

  1. Metal interactions with boron clusters

    SciTech Connect

    Grimes, R.N.

    1982-01-01

    This book presents information on the following topics: the structural and bonding features of metallaboranes and metallacarboranes; transition-metal derivatives of nido-boranes and some related species; interactions of metal groups with the octahydrotriborate (1-) anion, B/sub 3/H/sub 8/; metallaboron cage compounds of the main group metals; closo-carborane-metal complexes containing metal-carbon and metal-boron omega-bonds; electrochemistry of metallaboron cage compounds; and boron clusters with transition metal-hydrogen bonds.

  2. 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.

  3. 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.

  4. Reactive cluster model of metallic glasses

    SciTech Connect

    Jones, Travis E.; Miorelli, Jonathan; Eberhart, Mark E.

    2014-02-28

    Though discovered more than a half century ago metallic glasses remain a scientific enigma. Unlike crystalline metals, characterized by short, medium, and long-range order, in metallic glasses short and medium-range order persist, though long-range order is absent. This fact has prompted research to develop structural descriptions of metallic glasses. Among these are cluster-based models that attribute amorphous structure to the existence of clusters that are incommensurate with crystalline periodicity. Not addressed, however, are the chemical factors stabilizing these clusters and promoting their interconnections. We have found that glass formers are characterized by a rich cluster chemistry that above the glass transformation temperature promotes exchange as well as static and vibronic sharing of atoms between clusters. The vibronic mechanism induces correlated motions between neighboring clusters and we hypothesize that the distance over which these motions are correlated mediates metallic glass stability and influences critical cooling rates.

  5. MODELING THE METALLICITY DISTRIBUTION OF GLOBULAR CLUSTERS

    SciTech Connect

    Muratov, Alexander L.; Gnedin, Oleg Y. E-mail: ognedin@umich.ed

    2010-08-01

    Observed metallicities of globular clusters reflect physical conditions in the interstellar medium of their high-redshift host galaxies. Globular cluster systems in most large galaxies display bimodal color and metallicity distributions, which are often interpreted as indicating two distinct modes of cluster formation. The metal-rich and metal-poor clusters have systematically different locations and kinematics in their host galaxies. However, the red and blue clusters have similar internal properties, such as their masses, sizes, and ages. It is therefore interesting to explore whether both metal-rich and metal-poor clusters could form by a common mechanism and still be consistent with the bimodal distribution. We present such a model, which prescribes the formation of globular clusters semi-analytically using galaxy assembly history from cosmological simulations coupled with observed scaling relations for the amount and metallicity of cold gas available for star formation. We assume that massive star clusters form only during mergers of massive gas-rich galaxies and tune the model parameters to reproduce the observed distribution in the Galaxy. A wide, but not the entire, range of model realizations produces metallicity distributions consistent with the data. We find that early mergers of smaller hosts create exclusively blue clusters, whereas subsequent mergers of more massive galaxies create both red and blue clusters. Thus, bimodality arises naturally as the result of a small number of late massive merger events. This conclusion is not significantly affected by the large uncertainties in our knowledge of the stellar mass and cold gas mass in high-redshift galaxies. The fraction of galactic stellar mass locked in globular clusters declines from over 10% at z > 3 to 0.1% at present.

  6. Fission and dipole resonances in metal clusters

    SciTech Connect

    Martin, T. P.; Billas, I. M. L.; Branz, W.; Heinebrodt, M.; Tast, F.; Malinowski, N.

    1997-06-20

    It is not obvious that metal clusters should behave like atomic nuclei--but they do. Of course the energy and distance scales are quite different. But aside from this, the properties of these two forms of condensed matter are amazingly similar. The shell model developed by nuclear physicists describes very nicely the electronic properties of alkali metal clusters. The giant dipole resonances in the excitation spectra of nuclei have their analogue in the plasmon resonances of metal clusters. Finally, the droplet model describing the fission of unstable nuclei can be successively applied to the fragmentation of highly charged metal clusters. The similarity between clusters and nuclei is not accidental. Both systems consist of fermions moving, nearly freely, in a confined space.

  7. 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)

  8. Structural evolution and metallicity of lead clusters

    NASA Astrophysics Data System (ADS)

    Götz, Daniel A.; Shayeghi, Armin; Johnston, Roy L.; Schwerdtfeger, Peter; Schäfer, Rolf

    2016-05-01

    The evolution of the metallic state in lead clusters and its structural implications are subject to ongoing discussions. Here we present molecular beam electric deflection studies of neutral PbN (N = 19-25, 31, 36, 54) clusters. Many of them exhibit dipole moments or anomalies of the polarizability indicating a non-metallic state. In order to resolve their structures, the configurational space is searched using the Pool Birmingham Cluster Genetic algorithm based on density functional theory. Spin-orbit effects on the geometries and dipole moments are taken into account by further relaxing them with two-component density functional theory. Geometries and dielectric properties from quantum chemical calculations are then used to simulate beam deflection profiles. Structures are assigned by the comparison of measured and simulated beam profiles. Energy gaps are calculated using time-dependent density functional theory. They are compared to Kubo gaps, which are an indicator of the metallicity in finite particles. Both, experimental and theoretical data suggest that lead clusters are not metallic up to at least 36 atoms.The evolution of the metallic state in lead clusters and its structural implications are subject to ongoing discussions. Here we present molecular beam electric deflection studies of neutral PbN (N = 19-25, 31, 36, 54) clusters. Many of them exhibit dipole moments or anomalies of the polarizability indicating a non-metallic state. In order to resolve their structures, the configurational space is searched using the Pool Birmingham Cluster Genetic algorithm based on density functional theory. Spin-orbit effects on the geometries and dipole moments are taken into account by further relaxing them with two-component density functional theory. Geometries and dielectric properties from quantum chemical calculations are then used to simulate beam deflection profiles. Structures are assigned by the comparison of measured and simulated beam profiles. Energy gaps

  9. Cage Destruction in Metal-Fullerene Clusters

    SciTech Connect

    Tast, F.; Malinowski, N.; Frank, S.; Heinebrodt, M.; Billas, I.M.; Martin, T.P.

    1996-10-01

    Mass spectrometric studies on free clusters composed of single fullerene molecules and transition metal atoms (C{sub 60}{ital M}{sub {ital x}} and C{sub 70}{ital M}{sub {ital x}}; {ital x}=0.150, {ital M}{element_of}{l_brace}Ti,V,Nb,Ta{r_brace}) reveal that they undergo a laser induced transformation from metal-fullerene clusters to metal carbide and metallo-carbohedrene clusters. Two types of fragmentation behavior are observed. Fullerenes doped with titanium or vanadium seem to be stable at low laser intensities, whereas tantalum and niobium severely destabilize the fullerene cage. Photofragmentation spectra of preselected C{sub 60}Ta{sub {ital x}} indicate that the C{sub 60} cage is destroyed for {ital x}{ge}3. {copyright} {ital 1996 The American Physical Society.}

  10. Shell structure in faceted metal clusters

    NASA Astrophysics Data System (ADS)

    Pavloff, Nicolas; Creagh, Stephen C.

    1993-12-01

    We study the quantized electronic energy levels in a three-dimensional icosahedral billiard modeling a faceted metal cluster. The first 2000 levels are determined numerically. The magic numbers are compared with experimental data and with the results for a spherical model. We discuss the supershell structure and propose its study as a test of cluster sphericity. We compare our results with the predictions of the semiclassical trace formula and point out the relevance of diffractive orbits.

  11. (Electronic structure and reactivities of transition metal clusters)

    SciTech Connect

    Not Available

    1992-01-01

    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.

  12. Radial distribution of metallicity in the LMC cluster systems

    NASA Technical Reports Server (NTRS)

    Kontizas, M.; Kontizas, E.; Michalitsianos, A. G.

    1993-01-01

    New determinations of the deprojected distances to the galaxy center for 94 star clusters and their metal abundances are used to investigate the variation of metallicity across the two LMC star cluster systems (Kontizas et al. 1990). A systematic radial trend of metallicity is observed in the extended outer cluster system, the outermost clusters being significantly metal poorer than the more central ones, with the exception of six clusters (which might lie out of the plane of the cluster system) out of 77. A radial metallicity gradient has been found, qualitatively comparable to that of the Milky Way for its system of the old disk clusters. If the six clusters are taken into consideration then the outer cluster system is well mixed up to 8 kpc. The spatial distribution of metallicities for the inner LMC cluster system, consisting of very young globulars does not show a systematic radial trend; they are all metal rich.

  13. Metals Cluster Brief. Vocational Education in Oregon.

    ERIC Educational Resources Information Center

    Little, Ralph

    This guide sets forth minimum approval criteria for metals occupational clusters training programs in Oregon. The information in the guide is intended for use by district-level curriculum planners, teachers, regional coordinators, or state education department staff involved with new program development or revisions of existing programs. The guide…

  14. Structural evolution and metallicity of lead clusters.

    PubMed

    Götz, Daniel A; Shayeghi, Armin; Johnston, Roy L; Schwerdtfeger, Peter; Schäfer, Rolf

    2016-06-01

    The evolution of the metallic state in lead clusters and its structural implications are subject to ongoing discussions. Here we present molecular beam electric deflection studies of neutral PbN (N = 19-25, 31, 36, 54) clusters. Many of them exhibit dipole moments or anomalies of the polarizability indicating a non-metallic state. In order to resolve their structures, the configurational space is searched using the Pool Birmingham Cluster Genetic algorithm based on density functional theory. Spin-orbit effects on the geometries and dipole moments are taken into account by further relaxing them with two-component density functional theory. Geometries and dielectric properties from quantum chemical calculations are then used to simulate beam deflection profiles. Structures are assigned by the comparison of measured and simulated beam profiles. Energy gaps are calculated using time-dependent density functional theory. They are compared to Kubo gaps, which are an indicator of the metallicity in finite particles. Both, experimental and theoretical data suggest that lead clusters are not metallic up to at least 36 atoms. PMID:27181365

  15. The structure of small metal clusters

    NASA Technical Reports Server (NTRS)

    Bauschlicher, C. W., Jr.; Pettersson, L. G. M.

    1986-01-01

    One metal atom surrounded by its 12 nearest neighbors is considered for both D(3d) (face-centered cubic-like) and D(3h) (hexagonal close-packed-like) geometries. For Al and Be, the neutral cluster and the positive and negative ions are considered for idealized (all bonds equal) and distorted geometries. The D(3d) geometry is found to be the lowest for Be13, while the D(3h) geometry is lower for Al13. This is the reverse of what is expected based upon the bulk metal structures, Be(hcp) and Al(fcc). Al13 is found to have only small distortions, while Be13 shows large distortions for both the D(3d) and D(3h) geometries. The ions have geometries which are similar to those found for the neutral systems. Both all-electron and effective core potential calculations were carried out on the X13 clusters; the agreement is very good.

  16. Metallicities and Reddenings For Young Globular Clusters

    NASA Astrophysics Data System (ADS)

    Sarajedini, Ata; Layden, Andrew

    1996-04-01

    We have obtained VI CCD photometry for the young globular clusters Ruprecht 106, Terzan 7, and Arp 2 using the 0.9m and 1.5m telescopes at Cerro Tololo Inter-American Observatory. The resulting V ~ (V-I) color-magnitude diagrams extend from the tip of the red giant branch to approximately 3 magnitudes below the horizontal branch. We have applied the SRM method of Sarajedini (1994) to the RGBs of these clusters in order to measure their reddenings and metallicities. Furthermore, we have formulated the SRM method in the V ~ (B-V) color-magnitude plane and applied it to published BV photometry for these young globular clusters. The implications of these derived parameters will be discussed.

  17. Jet-driven redistribution of metal in galaxy clusters

    NASA Astrophysics Data System (ADS)

    Morsony, Brian J.; Heinz, Sebastian; Reynolds, Christopher S.

    2016-04-01

    The ICM in galaxy clusters is metal enriched, typically to about 30% of solar metallicity, out to large radii. However, metals should form mostly in galaxies and remained bound to their progenitor systems. To enrich the ICM, effective mixing of gas needs to occur across large scales. We carry out numerical simulations of mixing driven by AGN jets in dynamical galaxy clusters. These jets lift gas out of the center of the cluster, redistributing metals and adding energy to the ICM. We compare our results to X-ray observations of metallicity in clusters.

  18. Jet-driven redistribution of metal in galaxy clusters

    NASA Astrophysics Data System (ADS)

    Morsony, Brian; Heinz, Sebastian; Reynolds, Christopher; Ruszkowski, Mateusz; Brueggen, Marcus

    2015-08-01

    The ICM in galaxy clusters is metal enriched, typically to about 30% of solar metallicity, out to large radii. However, metals should form mostly in galaxies and remained bound to their progenitor systems. To enrich the ICM, effective mixing of gas needs to occur across large scales. We carry out numerical simulations of mixing driven by AGN jets in dynamical galaxy clusters. These jets lift gas out of the center of the cluster, redistributing metals and adding energy to the ICM. We compare our results to X-ray observations of metallicity in clusters.

  19. Size-dependent catalytic activity of supported metal clusters

    NASA Astrophysics Data System (ADS)

    Xu, Z.; Xiao, F.-S.; Purnell, S. K.; Alexeev, O.; Kawi, S.; Deutsch, S. E.; Gates, B. C.

    1994-11-01

    BECAUSE catalysis by metals is a surface phenomenon, many technological catalysts contain small (typically nanometre-sized) supported metal particles with a large fraction of the atoms exposed1. Many reactions, such as hydrocarbon hydrogenations, are structure-insensitive, proceeding at approximately the same rate on metal particles of various sizes provided that they are larger than about 1 nm and show bulk-like metallic behaviour1. But it is not known whether the catalytic properties of metal particles become size-dependent as the particles become so small that they are no longer metallic in character. Here we investigate the catalytic behaviour of precisely defined clusters of just four and six iridium atoms on solid supports. We find that the Ir4 and Ir6 clusters differ in catalytic activity both from each other and from metallic Ir particles. This raises the possibility of tailoring the catalytic behaviour of metal clusters by controlling the cluster size.

  20. On the metallicity of open clusters. III. Homogenised sample

    NASA Astrophysics Data System (ADS)

    Netopil, M.; Paunzen, E.; Heiter, U.; Soubiran, C.

    2016-01-01

    Context. Open clusters are known as excellent tools for various topics in Galactic research. For example, they allow accurately tracing the chemical structure of the Galactic disc. However, the metallicity is known only for a rather low percentage of the open cluster population, and these values are based on a variety of methods and data. Therefore, a large and homogeneous sample is highly desirable. Aims: In the third part of our series we compile a large sample of homogenised open cluster metallicities using a wide variety of different sources. These data and a sample of Cepheids are used to investigate the radial metallicity gradient, age effects, and to test current models. Methods: We used photometric and spectroscopic data to derive cluster metallicities. The different sources were checked and tested for possible offsets and correlations. Results: In total, metallicities for 172 open cluster were derived. We used the spectroscopic data of 100 objects for a study of the radial metallicity distribution and the age-metallicity relation. We found a possible increase of metallicity with age, which, if confirmed, would provide observational evidence for radial migration. Although a statistical significance is given, more studies are certainly needed to exclude selection effects, for example. The comparison of open clusters and Cepheids with recent Galactic models agrees well in general. However, the models do not reproduce the flat gradient of the open clusters in the outer disc. Thus, the effect of radial migration is either underestimated in the models, or an additional mechanism is at work. Conclusions: Apart from the Cepheids, open clusters are the best tracers for metallicity over large Galactocentric distances in the Milky Way. For a sound statistical analysis, a sufficiently large and homogeneous sample of cluster metallicities is needed. Our compilation is currently by far the largest and provides the basis for several basic studies such as the statistical

  1. Molecular dynamical simulations of melting behaviors of metal clusters

    SciTech Connect

    Hamid, Ilyar; Fang, Meng; Duan, Haiming

    2015-04-15

    The melting behaviors of metal clusters are studied in a wide range by molecular dynamics simulations. The calculated results show that there are fluctuations in the heat capacity curves of some metal clusters due to the strong structural competition; For the 13-, 55- and 147-atom clusters, variations of the melting points with atomic number are almost the same; It is found that for different metal clusters the dynamical stabilities of the octahedral structures can be inferred in general by a criterion proposed earlier by F. Baletto et al. [J. Chem. Phys. 116 3856 (2002)] for the statically stable structures.

  2. High-nuclearity magnetic clusters: Magnetic interactions in clusters encapsulated by molecular metal oxides

    NASA Astrophysics Data System (ADS)

    Borras-Almenar, Juan José; Coronado, Eugenio; Galan-Mascaros, Jose Ramón; Gómez-García, Carlos J.

    1995-02-01

    The ability of the molecular metal oxides derived from the Keggin anion [PW 12O 40] 3- to accommodate magnetic ions at specific sites, giving rise to polymetallic clusters with increasing spin nuclearities is discussed. Examples of magnetic clusters with three, four and nine metal ions exhibiting ferromagnetic exchange couplings or a coexistence of ferro- and antiferromagnetic couplings are reported.

  3. Electronic Structure and Geometries of Small Compound Metal Clusters

    SciTech Connect

    1999-04-14

    During the tenure of the DOE grant DE-FG05-87EI145316 we have concentrated on equilibrium geometries, stability, and the electronic structure of transition metal-carbon clusters (met-cars), clusters designed to mimic the chemistry of atoms, and reactivity of homo-nuclear metal clusters and ions with various reactant molecules. It is difficult to describe all the research the authors have accomplished as they have published 38 papers. In this report, they outline briefly the salient features of their work on the following topics: (1) Designer Clusters: Building Blocks for a New Class of Solids; (2) Atomic Structure, Stability, and Electronic Properties of Metallo-Carbohedrenes; (3) Reactivity of Metal Clusters with H{sub 2} and NO; and (4) Anomalous Spectroscopy of Li{sub 4} Clusters.

  4. Ion beam induced nanosized Ag metal clusters in glass

    NASA Astrophysics Data System (ADS)

    Mahnke, H.-E.; Schattat, B.; Schubert-Bischoff, P.; Novakovic, N.

    2006-04-01

    Silver metal clusters have been formed in soda lime glass by high-energy heavy-ion irradiation at ISL. The metal cluster formation was detected with X-ray absorption spectroscopy (EXAFS) in fluorescence mode, and the shape of the clusters was imaged with transmission electron microscopy. While annealing in reducing atmosphere alone, leads to the formation of metal clusters in Ag-containing glasses, where the Ag was introduced by ion-exchange, such clusters are not very uniform in size and are randomly distributed over the Ag-containing glass volume. Irradiation with 600-MeV Au ions followed by annealing, however, results in clusters more uniform in size and arranged in chains parallel to the direction of the ion beam.

  5. Bridging the Gap: Electron Relay and Plasmonic Sensitization of Metal Nanocrystals for Metal Clusters.

    PubMed

    Xiao, Fang-Xing; Zeng, Zhiping; Liu, Bin

    2015-08-26

    In recent years, enormous attention has been paid to the construction of metal cluster-semiconductor nanocomposites because of the fascinating and unique properties of metal clusters; however, investigations on photoelectrochemical (PEC) and photocatalytic properties of metal cluster-semiconductor systems are still rare. Moreover, to date, intrinsic correlation between metal clusters and bulk metal nanocrystals has yet to be elucidated. In this work, a facile layer-by-layer (LbL) self-assembly strategy has been developed to judiciously and intimately integrate gold nanocrystals (Au) within the interface between gold clusters (Au(x)) and hierarchically ordered TiO2 nanotube arrays framework, by which imperative roles of Au nanocrystals as electron relay mediator and plasmonic sensitizer for Aux clusters were revealed. In addition, it was found that synergistic interaction between Au nanocrystals and Aux clusters contributed to promising visible-light-driven photocatalytical and PEC performances. It is anticipated that our work could provide a general way for rationally constructing metal and metal clusters codecorated semiconductor heterostructures and, more significantly, bridge the gap between metal clusters and metal nanocrystals for a diverse range of applications. PMID:26258281

  6. Star Clusters in M31. VII. Global Kinematics and Metallicity Subpopulations of the Globular Clusters

    NASA Astrophysics Data System (ADS)

    Caldwell, Nelson; Romanowsky, Aaron J.

    2016-06-01

    We carry out a joint spatial–kinematical–metallicity analysis of globular clusters (GCs) around the Andromeda Galaxy (M31), using a homogeneous, high-quality spectroscopic data set. In particular, we remove the contaminating young clusters that have plagued many previous analyses. We find that the clusters can be divided into three major metallicity groups based on their radial distributions: (1) an inner metal-rich group ([Fe/H] > -0.4); (2) a group with intermediate metallicity (with median [Fe/H] = ‑1) and (3) a metal-poor group, with [Fe/H] < -1.5. The metal-rich group has kinematics and spatial properties like those of the disk of M31, while the two more metal-poor groups show mild prograde rotation overall, with larger dispersions—in contrast to previous claims of stronger rotation. The metal-poor GCs are the least concentrated group; such clusters occur five times less frequently in the central bulge than do clusters of higher metallicity. Despite some well-known differences between the M31 and Milky Way GC systems, our revised analysis points to remarkable similarities in their chemodynamical properties, which could help elucidate the different formation stages of galaxies and their GCs. In particular, the M31 results motivate further exploration of a metal-rich GC formation mode in situ, within high-redshift, clumpy galactic disks.

  7. Simple and efficient separation of atomically precise noble metal clusters.

    PubMed

    Ghosh, Atanu; Hassinen, Jukka; Pulkkinen, Petri; Tenhu, Heikki; Ras, Robin H A; Pradeep, Thalappil

    2014-12-16

    There is an urgent need for accessible purification and separation strategies of atomically precise metal clusters in order to promote the study of their fundamental properties. Although the separation of mixtures of atomically precise gold clusters Au25L18, where L are thiolates, has been demonstrated by advanced separation techniques, we present here the first separation of metal clusters by thin-layer chromatography (TLC), which is simple yet surprisingly efficient. This method was successfully applied to a binary mixture of Au25L18 with different ligands, as well as to a binary mixture of different cluster cores, Au25 and Au144, protected with the same ligand. Importantly, TLC even enabled the challenging separation of a multicomponent mixture of mixed-monolayer-protected Au25 clusters with closely similar chemical ligand compositions. We anticipate that the realization of such simple yet efficient separation technique will progress the detailed investigation of cluster properties. PMID:25395064

  8. Structure of overheated metal clusters: MD simulation study

    SciTech Connect

    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.

  9. Infrared Multiple Photon Dissociation Spectroscopy Of Metal Cluster-Adducts

    NASA Astrophysics Data System (ADS)

    Cox, D. M.; Kaldor, A.; Zakin, M. R.

    1987-01-01

    Recent development of the laser vaporization technique combined with mass-selective detection has made possible new studies of the fundamental chemical and physical properties of unsupported transition metal clusters as a function of the number of constituent atoms. A variety of experimental techniques have been developed in our laboratory to measure ionization threshold energies, magnetic moments, and gas phase reactivity of clusters. However, studies have so far been unable to determine the cluster structure or the chemical state of chemisorbed species on gas phase clusters. The application of infrared multiple photon dissociation IRMPD to obtain the IR absorption properties of metal cluster-adsorbate species in a molecular beam is described here. Specifically using a high power, pulsed CO2 laser as the infrared source, the IRMPD spectrum for methanol chemisorbed on small iron clusters is measured as a function of the number of both iron atoms and methanols in the complex for different methanol isotopes. Both the feasibility and potential utility of IRMPD for characterizing metal cluster-adsorbate interactions are demonstrated. The method is generally applicable to any cluster or cluster-adsorbate system dependent only upon the availability of appropriate high power infrared sources.

  10. 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.

  11. Hybrid uranium-transition-metal oxide cage clusters.

    PubMed

    Ling, Jie; Hobbs, Franklin; Prendergast, Steven; Adelani, Pius O; Babo, Jean-Marie; Qiu, Jie; Weng, Zhehui; Burns, Peter C

    2014-12-15

    Transition-metal based polyoxometalate clusters have been known for decades, whereas those built from uranyl peroxide polyhedra have more recently emerged as a family of complex clusters. Here we report the synthesis and structures of six nanoscale uranyl peroxide cage clusters that contain either tungstate or molybdate polyhedra as part of the cage, as well as phosphate tetrahedra. These transition-metal-uranium hybrid clusters exhibit unique polyhedral connectivities and topologies that include 6-, 7-, 8-, 10-, and 12-membered rings of uranyl polyhedra and uranyl ions coordinated by bidentate peroxide in both trans and cis configurations. The transition-metal polyhedra appear to stabilize unusual units built of uranyl polyhedra, rather than templating their formation. PMID:25434424

  12. Towards a photometric metallicity scale for open clusters

    NASA Astrophysics Data System (ADS)

    Netopil, M.; Paunzen, E.

    2013-09-01

    Context. Open clusters are a useful tool when investigating several topics connected with stellar evolution; for example the age or distance can be more accurately determined than for field stars. However, one important parameter, the metallicity, is only known for a marginal percentage of open clusters. Aims: We aim at a consistent set of parameters for the open clusters investigated in our photometric Δa survey of chemically peculiar stars. Special attention is paid to expanding our knowledge of cluster metallicities and verifying their scale. Methods: Making use of a previously developed method based on normalised evolutionary grids and photometric data, the distance, age, reddening, and metallicity of open clusters were derived. To transform photometric measurements into effective temperatures to use as input for our method, a set of temperature calibrations for the most commonly used colour indices and photometric systems was compiled. Results: We analysed 58 open clusters in total. Our derived metallicity values were in excellent agreement with about 30 spectroscopically studied targets. The mean value of the absolute deviations was found to be 0.03 dex, with no noticeable offset or gradient. The method was also applied using recent evolutionary models based on the currently accepted lower solar abundance value Z ~ 0.014. No significant differences were found compared to grids using the former adopted solar value Z = 0.02. Furthermore, some divergent photometric datasets were identified and discussed. Conclusions: The method provides an accurate way of obtaining properly scaled metallicity values for open clusters. In light of present and future homogeneous photometric sky surveys, the sample of stellar clusters can be extended to the outskirts of the Milky Way, where spectroscopic studies are almost impossible. This will help for determining galactic metallicity gradients in more detail. Figure 7 is available in electronic form at http://www.aanda.org

  13. Effect of Graphene with Nanopores on Metal Clusters

    SciTech Connect

    Zhou, Hu; Chen, Xianlang; Wang, Lei; Zhong, Xing; Zhuang, Guilin; Li, Xiaonian; Mei, Donghai; Wang, Jianguo

    2015-10-07

    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, 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

  14. Molecular orbital analysis of dicarbido-transition-metal cluster compounds

    SciTech Connect

    Halet, J.; Mingos, D.M.P.

    1988-01-01

    Molecular orbital calculations on dicarbido-transition-metal carbonyl cluster compounds have shown that the bonding between C/sub 2/ and the metal cage results primarily from electron donation from the C/sub 2/ sigma/sub rho/- and ..pi..-bonding molecular orbitals and back donation from filled metallic molecular orbitals to the C/sub 2/ ..pi..* orbitals. The bonding therefore follows closely the Chatt-Dewar-Ducanson model that has been established previously for ethyne and ethene complexes but not for interstitial moieties. The C-C separation in the dicarbido clusters depends critically on the geometric constraints imposed by the metal cage and the extent of forward and back donation. In these clusters where the carbon atoms are in adjacent trigonal-prismatic sites the calculated formal bond order is between 1.0 and 1.5, which agrees well with the observed C-C bond lengths.

  15. Experimental studies of the chemistry of metal clusters

    SciTech Connect

    Parks, E.K.; Riley, S.J.

    1988-01-01

    The procedures for studying chemical reactions of metal clusters in a continuous-flow reactor are described, and examples of such studies are given. Experiments to be discussed include kinetics and thermodynamics measurements, and determination of the composition of clusters saturated with various adsorbate reagents. Specific systems to be covered include the reaction of iron clusters with ammonia and with hydrogen, the reaction of nickel clusters with hydrogen and with ammonia, and the reaction of platinum clusters with ethylene. The last two reactions are characterized by complex, multi-step processes that lead to adsorbate decomposition and hydrogen desorption from the clusters. Methods for probing these processes will be discussed. 26 refs., 8 figs.

  16. Term rules for simple metal clusters

    NASA Astrophysics Data System (ADS)

    Yoshida, Daisuke; Raebiger, Hannes

    2015-10-01

    Hund’s term rules are only valid for isolated atoms, but have no generalization for molecules or clusters of several atoms. We present a benchmark calculation of Al2 and Al3, for which we find the high and low-spin ground states 3Πu and , respectively. We show that the relative stabilities of all the molecular terms of Al2 and Al3 can be described by simple rules pertaining to bonding structures and symmetries, which serve as guiding principles to determine ground state terms of arbitrary multi-atom clusters.

  17. Term rules for simple metal clusters

    PubMed Central

    Yoshida, Daisuke; Raebiger, Hannes

    2015-01-01

    Hund’s term rules are only valid for isolated atoms, but have no generalization for molecules or clusters of several atoms. We present a benchmark calculation of Al2 and Al3, for which we find the high and low-spin ground states 3Πu and , respectively. We show that the relative stabilities of all the molecular terms of Al2 and Al3 can be described by simple rules pertaining to bonding structures and symmetries, which serve as guiding principles to determine ground state terms of arbitrary multi-atom clusters. PMID:26497089

  18. Photoionization profiles of metal clusters and the Fowler formula

    NASA Astrophysics Data System (ADS)

    Prem, Abhinav; Kresin, Vitaly V.

    2012-02-01

    Metal-cluster ionization potentials are important characteristics of these “artificial atoms,” but extracting these quantities from cluster photoabsorption spectra, especially in the presence of thermal smearing, remains a big challenge. Here we demonstrate that the classic Fowler theory of surface photoemission does an excellent job of fitting the photoabsorption profile shapes of neutral Inn=3-34 clusters [Wucher , New J. Phys.NJOPFM1367-263010.1088/1367-2630/10/10/103007 10, 103007 (2008)]. The deduced ionization potentials extrapolate precisely to the bulk work function, and the internal cluster temperatures are in close agreement with values expected for an ensemble of freely evaporating clusters. Supplementing an earlier application to potassium clusters, these results suggest that the Fowler formalism, which is straightforward and physical, may be of significant utility in metal-cluster spectroscopy. It is hoped also that the results will encourage a comprehensive theoretical analysis of the applicability of bulk-derived models to cluster photoionization behavior, and of the transition from atomic and molecular-type to surface-type photoemission.

  19. METAL PRODUCTION IN GALAXY CLUSTERS: THE NON-GALACTIC COMPONENT

    SciTech Connect

    Bregman, Joel N.; Anderson, Michael E.; Dai Xinyu E-mail: michevan@umich.ed

    2010-06-10

    The metallicity in galaxy clusters is expected to originate from the stars in galaxies, with a population dominated by high-mass stars likely being the most important stellar component, especially in rich clusters. We examine the relationship between the metallicity and the prominence of galaxies as measured by the star-to-baryon ratio, M{sub *}/M{sub bary}. Counter to expectations, we rule out a metallicity that is proportional to M{sub *}/M{sub bary}, where the best fit has the gas-phase metallicity decreasing with M{sub *}/M{sub bary}, or the metallicity of the gas plus the stars being independent of M{sub *}/M{sub bary}. This implies that the population of stars responsible for the metals is largely proportional to the total baryonic mass of the cluster, not to the galaxy mass within the cluster. If generally applicable, most of the heavy elements in the universe were not produced within galaxies.

  20. STEM characterization of metal clusters in/on oxides

    NASA Astrophysics Data System (ADS)

    Mehraeen, Shareghe

    Dispersed metal clusters in or on a support matrix are key phenomenons in many technological fields. Two widely used examples of them which are investigated in this thesis are supported-metal clusters in heterogeneous catalysis and transition metal clusters in diluted magnetic semiconductors (DMS) applied in spintronics. The catalytic activity and selectivity of catalysts often depend sensitively on structure parameters, such as particles size and shape. With the same analogy, the magnetic properties of DMS oxides are sensitively related to the crystal defects of the host material as a consequence of doping the transition metal. Therefore it is essential to develop and understand the correlation between nanostructure and function of these materials. STEM Z-contrast imaging is the best candidate for this type of study because of a high degree of resolution it provides and the unique ability it offers to detect and differentiate between the clusters and oxide matrix due to the large difference between their atomic numbers. Moreover the technique development in the STEM field fosters the conjugation of electron energy Loss Spectroscopy (EELS) and Z-contrast imaging and their widespread use for nearly atomic level chemical analysis at interface, second phases, and isolated defects. The advanced preparation method of supported clusters catalysts which is by carbonyl ligands offers a controlled cluster size and shape. MgO-supported Os clusters and SiO2-supported Ta clusters prepared by this method are adsorbed on oxide to convert into single-sized supported metal aggregates. The last step of preparation method is by removal of the ligands (decarbonylation) which is very important because it determines the final size distribution and shape of such clusters. Reaching carbonylated decaosmium clusters with the size of theoretically 0.295 nm and the tetrahedral-shape geometry are the aim of the preparation method. The size distribution measurements of sub-nanoclusters of

  1. Is the Globular Cluster Colour-Metallicity Relation Universal?

    NASA Astrophysics Data System (ADS)

    Usher, Christopher; Sluggs Survey Team

    2015-01-01

    Visible at much greater distances than resolved stars, globular clusters are important tools for studying galaxy formation and assembly. Studies of extragalactic globular clusters typically use optical colours to derive metallicites. We use Keck DEIMOS spectroscopy and Subaru Suprime-Cam photometry from the SLUGGS Survey to investigate how the globular cluster colour-metallicity relation varies galaxy to galaxy and with globular cluster luminosity. As in previous studies we see variations in the shape of the relationship between (g - i) colour and the strength of the calcium triplet spectral feature. To measure weaker spectral features in the DEIMOS spectra, we stack the spectra by colour and by magnitude. Comparing spectra with the same colours and luminosities but from different galaxies, we see significant differences in the strengths of several spectral features, including the calcium triplet and weak iron lines. We interpret this as strong evidence that the globular cluster colour-metallicity relation varies galaxy-to-galaxy. We suggest differences in globular cluster ages between galaxies and in the abundances of light elements (helium, carbon, nitrogen and oxygen) between galaxies as possible explanations for the observed variations in the colour-metallicity relation.

  2. The effect of alkylating agents on model supported metal clusters

    SciTech Connect

    Erdem-Senatalar, A.; Blackmond, D.G.; Wender, I. . Dept. of Chemical and Petroleum Engineering); Oukaci, R. )

    1988-01-01

    Interactions between model supported metal clusters and alkylating agents were studied in an effort to understand a novel chemical trapping technique developed for identifying species adsorbed on catalyst surfaces. It was found that these interactions are more complex than had previously been suggested. Studies were completed using deuterium-labeled dimethyl sulfate (DMS), (CH{sub 3}){sub 2}SO{sub 4}, as a trapping agent to interact with the supported metal cluster ethylidyne tricobalt enneacarbonyl. Results showed that oxygenated products formed during the trapping reaction contained {minus}OCD{sub 3} groups from the DMS, indicating that the interaction was not a simple alkylation. 18 refs., 1 fig., 3 tabs.

  3. Theoretical studies of the electronic structure of small metal clusters

    NASA Technical Reports Server (NTRS)

    Jordan, K. D.

    1982-01-01

    Theoretical studies of the electronic structure of metal clusters, in particular clusters of Group IIA and IIB atoms were conducted. Early in the project it became clear that electron correlation involving d orbitals plays a more important role in the binding of these clusters than had been previously anticipated. This necessitated that computer codes for calculating two electron integrals and for constructing the resulting CI Hamiltonions be replaced with newer, more efficient procedures. Program modification, interfacing and testing were performed. Results of both plans are reported.

  4. Ionic recoil energies in the Coulomb explosion of metal clusters

    NASA Astrophysics Data System (ADS)

    Teuber, S.; Döppner, T.; Fennel, T.; Tiggesbäumker, J.; Meiwes-Broer, K. H.

    The photoionization of metal clusters in intense femtosecond laser fields has been studied. In contrast to an experiment on atoms, the interaction in this case leads to a very efficient and high charging of the particle where tens of electrons per atom are ejected from the cluster. The recoil energy distribution of the atomic fragment ions was measured which in the case of lead clusters exceeds 180 keV. Enhanced charging efficiency which we observed earlier for specific pulse conditions is not reflected in the recoil energy spectra. Both the average and the maximum energies decrease with increasing laser pulse width. This is in good agreement with molecular dynamics calculations.

  5. Interaction of metallic clusters with biologically active curcumin molecules

    NASA Astrophysics Data System (ADS)

    Gupta, Sanjeev K.; He, Haiying; Liu, Chunhui; Dutta, Ranu; Pandey, Ravindra

    2015-09-01

    We have investigated the interaction of subnano metallic Gd and Au clusters with curcumin, an important biomolecule having pharmacological activity. Gd clusters show different site preference to curcumin and much stronger interaction strength, in support of the successful synthesis of highly stable curcumin-coated Gd nanoparticles as reported recently. It can be attributed to significant charge transfer from the Gd cluster to curcumin together with a relatively strong hybridization of the Gd df-orbitals with curcumin p-orbitals. These results suggest that Gd nanoparticles can effectively be used as delivery carriers for curcumin at the cellular level for therapy and medical imaging applications.

  6. 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.

  7. 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.

  8. Theoretical dynamical studies of metal clusters and cluster-ligand systems

    SciTech Connect

    Jellinek, J.

    1995-06-01

    In what follows we use the term cluster to designate a cohesive group of like atoms (molecules), i.e., bare ({open_quotes}neet{close_quotes} {open_quotes}naked{close_quotes}) clusters. More generally, the term is also used for organo- and inorganometallic compounds, i.e., ligated clusters. Although the approaches and techniques used by the various disciplines to study metal-ligand interactions are quite different, many of the central subjects and issues are common for them. The common subjects include possible geometric structures and isomeric forms, structural (isomerization) transitions, stability, fluxionality, structure-reactivity correlation (or lack of it), role of coordination, etc. However, the precise interpretation of these issues and the details emphasized by the different disciplines are dictated by the nature of the objects studied and may not, therefore, be identical. For example, questions regarding structures, isomerization transitions, fluxionality or even melting of metal clusters refer to the state and properties of the metal network itself. The same questions, when asked in connection with organo- and inorganometallic compounds, often refer to the arrangements and rearrangements of the ligands attached to a metal framework of a fixed structure. Of course, when required, the state of and changes in the metal framework are considered as well. The fields of metal-containing molecular compounds, surface science, and physics and chemistry of clusters furnish complementary information on a broad variety of metal-ligand systems. A comprehensive understanding of the nature and properties of these systems, as defined by the type and number of metal atoms and ligands involved, can be achieved only through a mutual awareness of and continuing progress in all of these research areas.

  9. Hitomi observations of the Perseus Cluster / Constant metallicity in the outskirts of galaxy clusters

    NASA Astrophysics Data System (ADS)

    Werner, Norbert; Simionescu, Aurora; Urban, Ondrej; Allen, Steven

    2016-07-01

    X-ray observations with the Suzaku satellite reveal a remarkably homogeneous distribution of iron out to the virial radii of nearby galaxy clusters. Observations of the Virgo Cluster, that also allow us to measure the abundances of Si, S, and Mg out to the outskirts, show that the chemical composition of the intra-cluster medium is constant on large scales. These observations require that most of the metal enrichment and mixing of the intergalactic medium occurred before clusters formed, probably more than ten billion years ago, during the period of maximal star formation and black hole activity. We estimate the ratio between the number of SN Ia and the total number of supernovae enriching the intergalactic medium to be between 15-20%, generally consistent with the metal abundance patterns in our own Galaxy.

  10. 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.

  11. Flexible macrocycles as versatile supports for catalytically active metal clusters.

    PubMed

    Ryan, Jason D; Gagnon, Kevin J; Teat, Simon J; McIntosh, Ruaraidh D

    2016-07-12

    Here we present three structurally diverse clusters stabilised by the same macrocyclic polyphenol; t-butylcalix[8]arene. This work demonstrates the range of conformations the flexible ligand is capable of adopting, highlighting its versatility in metal coordination. In addition, a Ti complex displays activity for the ring-opening polymerisation of lactide. PMID:26892948

  12. Clustered field evaporation of metallic glasses in atom probe tomography.

    PubMed

    Zemp, J; Gerstl, S S A; Löffler, J F; Schönfeld, B

    2016-03-01

    Field evaporation of metallic glasses is a stochastic process combined with spatially and temporally correlated events, which are referred to as clustered evaporation (CE). This phenomenon is investigated by studying the distance between consecutive detector hits. CE is found to be a strongly localized phenomenon (up to 3nm in range) which also depends on the type of evaporating ions. While a similar effect in crystals is attributed to the evaporation of crystalline layers, CE of metallic glasses presumably has a different - as yet unknown - physical origin. The present work provides new perspectives on quantification methods for atom probe tomography of metallic glasses. PMID:26724469

  13. Separability Between Valence and Conduction Bands in Transition Metal Clusters

    SciTech Connect

    Apra, Edoardo; Carter, Emily A.; Fortunelli, Alessandro

    2004-07-30

    Simplified theories of transition metal electronic structure have been postulated for many decades. Here we test one such approximation, namely separate treatments of d (valence) and s/p (conduction) electrons in transition metal clusters, within a density functional formalism. Two different basic approaches are considered: (a) an independent-band approximation, in which the d- and s/p-bands interact only via the ?-dependent components of the Kohn-Sham operator; and (b) a more realistic approximation, in which the lowest-energy d- and s/p-orbitals (separately derived) are allowed to interact through explicit off-diagonal coupling matrix elements. Results are presented for the energy differences among three structural forms (icosahedral, cuboctahedral and truncated decahedral) of 13-atom Ni and Pt clusters. We demonstrate that an explicit decoupling of the d- and s/p-bands does not produce accurate results for the clusters considered here, not even for nickel, i.e., the transition metal for which d-s/p mixing should be at its minimum. By contrast, allowing the lowest energy orbitals of the two separate bands to interact improves the results considerably, and assures a fair description of metal-metal bonding. This suggests simplified models that exclude explicit d-s/p coupling should be employed with caution.

  14. Exploring the Formation of Galaxies through Metallicities of Globular Clusters

    NASA Astrophysics Data System (ADS)

    Kim, Sooyoung; Yoon, Suk-Jin; Chung, Chul; Caldwell, Nelson; Schiavon, Ricardo P.; Kang, Yong Beom; Rey, Soo-Chang; Lee, Young-Wook; Tamura, Naoyuki; Sohn, S. Tony; Arimoto, Nobuo; Kodama, Tadayuki; Yamada, Yoshihiko

    2014-06-01

    Globular clusters (GCs) are among the oldest stellar objects in the universe. They have long served the role of providing constraints on many aspects of galaxy evolution theory. Bimodal color distribution of GC systems in many luminous early-type galaxies is an observationally established phenomenon and has been interpreted as evidence of two GC subgroups with different metallicities. In this study, we use spectroscopic data on the GC systems of two giant galaxies, M31 (the Andromeda) and M87 (NGC 4486), to investigate the GC bimodality and the underlying metallicity distributions. Recent high signal-to-ratio spectroscopic data on M31 GCs revealed a clear bimodality in absorption-line index distributions of old GCs. Given that spectroscopy provides a more robust probe into stellar population than photometry, the reported spectral line index bimodality may indicate the presence of two distinct GC populations. However, here we show that the spectroscopic dichotomy of M31 GCs is due to the nonlinear nature of metallicity-to-index conversion and therefore one does not need two separate GC subsystems. We consider this as an analogy to the recent interpretation in which metallicity-color nonlinearity is the prime cause for observed GC color bimodality. We present spectra of ~130 old globular clusters (GCs) associated with the Virgo giant elliptical galaxy M87, obtained with the Multi-Object Spectrography (MOS) mode of Faint Object Camera and Spectrograph (FOCAS) on the Subaru telescope. The fundamental properties of globular clusters such as age, metallicity and elemental abundance ratio are investigated by comparing with a set of Simple Stellar Population (SSP) models. M87 GCs with reliable metallicity measurements exhibit significant inflection along the color-metallicity relations, through which observed color bimodality is reproduced using a broad, unimodal metallicity distribution. Our findings lend further support to this new interpretation of the GC color

  15. Development of Metal Cluster-Based Energetic Materials

    NASA Astrophysics Data System (ADS)

    Lightstone, James; Hooper, Joseph; Stoltz, Chad; Wilson, Becca; Mayo, Dennis; Eichhorn, Bryan; Bowen, Kit

    2011-06-01

    The energy available from the combustion of Al is 2 to 3 times that of conventional high explosives and as a result is often loaded into explosive and propellant formulations in micron and nano-particle form. However, even at the nano-scale the release of energy is slowed by the reaction kinetics of particle oxidation. In order to realize faster reaction rates, on the order of current CHNO explosives, the size of the particles of interest need to be reduced significantly into the molecular size-range (10's of atoms). Current research efforts at NSWC-IHD are utilizing gas-phase molecular beam studies, theoretical calculations, and condensed-phase production methods to identify novel metal cluster systems in which passivated metal clusters make up the subunit of a molecular metal-based energetic material. To date, small amounts of a metal-based compound with a subunit containing four Al atoms and four Cp* ligands has been produced and is currently being characterized using DSC and TGA. Additional Al based systems passivated with a variety of organic ligands are being systematically examined. Analytical and theoretical results obtained for Al4Cp*4 and the additional cluster systems under investigation along with their potential energetic applications will be presented.

  16. NGC 1252: a high altitude, metal poor open cluster remnant

    NASA Astrophysics Data System (ADS)

    de la Fuente Marcos, R.; de la Fuente Marcos, C.; Moni Bidin, C.; Carraro, G.; Costa, E.

    2013-09-01

    If stars form in clusters but most stars belong to the field, understanding the details of the transition from the former to the latter is imperative to explain the observational properties of the field. Aging open clusters are one of the sources of field stars. The disruption rate of open clusters slows down with age but, as an object gets older, the distinction between the remaining cluster or open cluster remnant (OCR) and the surrounding field becomes less and less obvious. As a result, finding good OCR candidates or confirming the OCR nature of some of the best candidates still remain elusive. One of these objects is NGC 1252, a scattered group of about 20 stars in Horologium. Here we use new wide-field photometry in the UBVI passbands, proper motions from the Yale/San Juan SPM 4.0 catalogue and high-resolution spectroscopy concurrently with results from N-body simulations to decipher NGC 1252's enigmatic character. Spectroscopy shows that most of the brightest stars in the studied area are chemically, kinematically and spatially unrelated to each other. However, after analysing proper motions, we find one relevant kinematic group. This sparse object is relatively close (˜1 kpc), metal poor and is probably not only one of the oldest clusters (3 Gyr) within 1.5 kpc from the Sun but also one of the clusters located farthest from the disc, at an altitude of nearly -900 pc. That makes NGC 1252 the first open cluster that can be truly considered a high Galactic altitude OCR: an unusual object that may hint at a star formation event induced on a high Galactic altitude gas cloud. We also conclude that the variable TW Horologii and the blue straggler candidate HD 20286 are unlikely to be part of NGC 1252. NGC 1252 17 is identified as an unrelated, Population II cannonball star moving at about 400 km s-1.

  17. Deep Mixing and Metallicity in Globular Cluster Red Giants

    NASA Astrophysics Data System (ADS)

    Martell, Sarah L.

    2007-12-01

    We present results from a study of carbon depletion and deep mixing in globular cluster red giants across a wide range of metallicity. CH bandstrengths are measured from low-resolution (R 1000) spectra and converted to [C/Fe] abundances by comparisons with synthetic spectra. Although some models of deep mixing predict that its efficiency will be reduced at high metallicity, no sign of such a cutoff is seen in our data, which span the range -2.29 < [Fe/H] < -1.29.

  18. The old, metal-poor, anticentre open cluster Trumpler 5

    NASA Astrophysics Data System (ADS)

    Donati, P.; Cocozza, G.; Bragaglia, A.; Pancino, E.; Cantat-Gaudin, T.; Carrera, R.; Tosi, M.

    2015-01-01

    As part of a long-term programme, we analyse the evolutionary status and properties of the old and populous open cluster Trumpler 5 (Tr 5), located in the Galactic anticentre direction, almost on the Galactic plane. Tr 5 was observed with Wide Field Imager@MPG/ESO Telescope using the Bessel U, B, and V filters. The cluster parameters have been obtained using the synthetic colour-magnitude diagram (CMD) method, i.e. the direct comparison of the observational CMD with a library of synthetic CMDs generated with different stellar evolution sets (Padova, FRANEC, and FST). Age, reddening, and distance are derived through the synthetic CMD method using stellar evolutionary models with subsolar metallicity (Z = 0.004 or Z = 0.006). Additional spectroscopic observations with Ultraviolet VLT Echelle Spectrograph@Very Large Telescope of three red clump stars of the cluster were used to determine more robustly the chemical properties of the cluster. Our analysis shows that Tr 5 has subsolar metallicity, with [Fe/H] = -0.403 ± 0.006 dex (derived from spectroscopy), age between 2.9 and 4 Gyr (the lower age is found using stellar models without core overshooting), reddening E(B - V) in the range 0.60-0.66 mag complicated by a differential pattern (of the order of ˜±0.1 mag), and distance modulus (m - M)0 = 12.4 ± 0.1 mag.

  19. Electronic Principles Governing the Stability and Reactivity of Ligated Metal and Silicon Encapsulated Transition Metal Clusters

    NASA Astrophysics Data System (ADS)

    Abreu, Marissa Baddick

    A thorough understanding of the underlying electronic principles guiding the stability and reactivity of clusters has direct implications for the identification of stable clusters for incorporation into clusters-assembled materials with tunable properties. This work explores the electronic principles governing the stability and reactivity of two types of clusters: ligated metal clusters and silicon encapsulated transition metal clusters. In the first case, the reactivity of iodine-protected aluminum clusters, Al13Ix - (x=0-4) and Al14Iy- (y=0-5), with the protic species methanol was studied. The symmetrical ground states of Al13Ix- showed no reactivity with methanol but reactivity was achieved in a higher energy isomer of Al 13I2- with iodines on adjacent aluminum atoms -- complementary Lewis acid-base active sites were induced on the opposite side of the cluster capable of breaking the O-H bond in methanol. Al 14Iy- (y=2-5) react with methanol, but only at the ligated adatom site. Reaction of methanol with Al14 - and Al14I- showed that ligation of the adatom was necessary for the reaction to occur there -- revealing the concept of a ligand-activated adatom. In the second case, the study focused heavily on CrSi12, a silicon encapsulated transition metal cluster whose stability and the reason for that stability has been debated heavily in the literature. Calculations of the energetic properties of CrSi n (n=6-16) revealed both CrSi12 and CrSi14 to have enhanced stability relative to other clusters; however CrSi12 lacks all the traditional markers of a magic cluster. Molecular orbital analysis of each of these clusters showed the CNFEG model to be inadequate in describing their stability. Because the 3dz2 orbital of Cr is unfilled in CrSi12, this cluster has only 16 effective valence electrons, meaning that the 18-electron rule is not applicable. The moderate stability of CrSi 12 can be accounted for by the crystal-field splitting of the 3d orbitals, which pushes the

  20. The Old, Super-Metal-Rich Open Cluster, NGC 6791

    NASA Astrophysics Data System (ADS)

    Boesgaard, Ann Merchant; Lum, Michael G. G.; Deliyannis, Constantine P.

    2015-08-01

    Stellar evolution and Galactic evolution have both been greatly advanced by the study of star clusters. In addition the elemental abundance results from clusters have revealed information about Galactic chemical evolution and nucleosynthesis. The cluster, NGC 6791, has a number of bizarre properties that make it especially interesting for comparative cluster studies. It is old (8.3 Gyr) yet metal-rich ([Fe/H] = +0.30). It has a heliocentric distance of 4 kpc and a galactic latitude of +11 degrees which makes it 1 kpc above the galactic plane. Its boxy orbit has a high eccentricity (~0.5) with a perigalactic distance of 3 kpc and an apogalactic distance of 10 kpc. The orbital period of ~130 Myr indicates that it has crossed the Galactic plane several times yet has remained as an intact cluster. We have determined abundances from high-resolution (R = 46,000) Keck/HIRES spectra of turn-off stars in this open cluster NGC 6791. We have a solid determination of [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 are corrected for small nLTE effects. We find consistent ratios of [O/Fe]n with a mean of -0.06 +/-0.02, indicating 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 old, metal-rich field stars. The Fe-peak elements, Cr and Ni, have values of [Cr/Fe] = +0.05 +/-0.02 and [Ni/Fe] = +0.04 +/-0.01. Determinations of upper limits were found for Li by spectrum synthesis; this is consistent with the upper limits in this temperature range for turn-off/subgiant stars in the relatively old, super-metal-rich cluster NGC 6253. We speculate that no stars in NGC 6791 have retained the Li with which they formed.

  1. Metal Adatoms and Clusters on Ultrathin Zirconia Films

    PubMed Central

    2016-01-01

    Nucleation and growth of transition metals on zirconia has been studied by scanning tunneling microscopy (STM) and density functional theory (DFT) calculations. Since STM requires electrical conductivity, ultrathin ZrO2 films grown by oxidation of Pt3Zr(0001) and Pd3Zr(0001) were used as model systems. DFT studies were performed for single metal adatoms on supported ZrO2 films as well as the (1̅11) surface of monoclinic ZrO2. STM shows decreasing cluster size, indicative of increasing metal–oxide interaction, in the sequence Ag < Pd ≈ Au < Ni ≈ Fe. Ag and Pd nucleate mostly at steps and domain boundaries of ZrO2/Pt3Zr(0001) and form three-dimensional clusters. Deposition of low coverages of Ni and Fe at room temperature leads to a high density of few-atom clusters on the oxide terraces. Weak bonding of Ag to the oxide is demonstrated by removing Ag clusters with the STM tip. DFT calculations for single adatoms show that the metal–oxide interaction strength increases in the sequence Ag < Au < Pd < Ni on monoclinic ZrO2, and Ag ≈ Au < Pd < Ni on the supported ultrathin ZrO2 film. With the exception of Au, metal nucleation and growth on ultrathin zirconia films follow the usual rules: More reactive (more electropositive) metals result in a higher cluster density and wet the surface more strongly than more noble metals. These bind mainly to the oxygen anions of the oxide. Au is an exception because it can bind strongly to the Zr cations. Au diffusion may be impeded by changing its charge state between −1 and +1. We discuss differences between the supported ultrathin zirconia films and the surfaces of bulk ZrO2, such as the possibility of charge transfer to the substrate of the films. Due to their large in-plane lattice constant and the variety of adsorption sites, ZrO2{111} surfaces are more reactive than many other oxygen-terminated oxide surfaces. PMID:27213024

  2. The metal content of the bulge globular cluster NGC 6528

    NASA Astrophysics Data System (ADS)

    Zoccali, M.; Barbuy, B.; Hill, V.; Ortolani, S.; Renzini, A.; Bica, E.; Momany, Y.; Pasquini, L.; Minniti, D.; Rich, R. M.

    2004-08-01

    High resolution spectra of five stars in the bulge globular cluster NGC 6528 were obtained at the 8m VLT UT2-Kueyen telescope with the UVES spectrograph. Out of the five stars, two of them showed evidence of binarity. The target stars belong to the horizontal and red giant branch stages, at 4000 < Tefflt; 4800 K. Multiband V, I, J, H, Ks photometry was used to derive initial effective temperatures and gravities. The main purpose of this study is the determination of metallicity and elemental ratios for this template bulge cluster, as a basis for the fundamental calibration of metal-rich populations. The present analysis provides a metallicity [Fe/H] = -0.1±0.2 and the α-elements O, Mg and Si, show [α/Fe] ≈ +0.1, whereas Ca and Ti are around the solar value or below, resulting in an overall metallicity Z ≈ Z⊙. Observations collected both at the European Southern Observatory, Paranal and La Silla, Chile (ESO programme 65.L-0340) and with the NASA/ESA Hubble Space Telescope, obtained at the Space Telescope Science Institute, operated by AURA Inc. under contract to NASA. Tables \\ref{targets}, \\ref{logobs}, \\ref{tablines} and Fig. \\ref{chart} are only available in electronic form at http://www.edpsciences.org

  3. FURTHER DEFINITION OF THE MASS-METALLICITY RELATION IN GLOBULAR CLUSTER SYSTEMS AROUND BRIGHTEST CLUSTER GALAXIES

    SciTech Connect

    Cockcroft, Robert; Harris, William E.; Wehner, Elizabeth M. H.; Whitmore, Bradley C.; Rothberg, Barry E-mail: harris@physics.mcmaster.ca E-mail: whitmore@stsci.edu

    2009-09-15

    We combine the globular cluster (GC) data for 15 brightest cluster galaxies and use this material to trace the mass-metallicity relations (MMRs) in their globular cluster systems (GCSs). This work extends previous studies which correlate the properties of the MMR with those of the host galaxy. Our combined data sets show a mean trend for the metal-poor subpopulation that corresponds to a scaling of heavy-element abundance with cluster mass Z {approx} M {sup 0.30{+-}}{sup 0.05}. No trend is seen for the metal-rich subpopulation which has a scaling relation that is consistent with zero. We also find that the scaling exponent is independent of the GCS specific frequency and host galaxy luminosity, except perhaps for dwarf galaxies. We present new photometry in (g',i') obtained with Gemini/GMOS for the GC populations around the southern giant ellipticals NGC 5193 and IC 4329. Both galaxies have rich cluster populations which show up as normal, bimodal sequences in the color-magnitude diagram. We test the observed MMRs and argue that they are statistically real, and not an artifact caused by the method we used. We also argue against asymmetric contamination causing the observed MMR as our mean results are no different from other contamination-free studies. Finally, we compare our method to the standard bimodal fitting method (KMM or RMIX) and find our results are consistent. Interpretation of these results is consistent with recent models for GC formation in which the MMR is determined by GC self-enrichment during their brief formation period.

  4. Metallicity distributions of globular cluster systems in galaxies

    NASA Astrophysics Data System (ADS)

    Eerik, H.; Tenjes, P.

    We collected a sample of 100 galaxies for which different observers have determined colour indices of globular cluster candidates. The sample includes representatives of galaxies of various morphological types and different luminosities. Colour indices (in most cases (V-I), but also (B-I) and (C-T_1)) were transformed into metallicities [Fe/H] according to a relation by Kissler-Patig (1998). These data were analysed with the KMM software in order to estimate similarity of the distribution with uni- or bimodal Gaussian distribution. We found that 45 of 100 systems have bimodal metallicity distributions. Mean metallicity of the metal-poor component for these galaxies is < [Fe/H]> = -1.40 +/- 0.02, of the metal-rich component < [Fe/H]> = -0.69 +/- 0.03. Dispersions of the distributions are 0.15 and 0.18, respectively. Distribution of unimodal metallicities is rather wide. These data will be analysed in a subsequent paper in order to find correlations with parameters of galaxies and galactic environment.

  5. Fabrication of nanoelectrodes and metal clusters by electrodeposition.

    PubMed

    Velmurugan, Jeyavel; Mirkin, Michael V

    2010-09-10

    Most nanometer-sized electrodes reported to date are made from either Pt or Au. For technical reasons, it is difficult to make nanoelectrodes from many other metals (e.g. Hg) by heat-sealing microwires into glass capillaries or by other established techniques. Such nanoelectrodes can be useful for a wide range of analytical and physicochemical applications from high sensitivity stripping analysis (Hg) to pH nano-sensors to studies of electrocatalysis. In this paper, nanometer-sized metal electrodes are prepared by electrodeposition of Hg or Pt on disk-type, polished or recessed nanoelectrodes. The deposition of Hg is monitored chronoamperometrically to produce near-hemispherical electrodes, which are characterized by voltammetry and scanning electrochemical microscopy (SECM). The well-shaped deposits of a solid metal (Pt) at Au nanoelectrodes are prepared and imaged by scanning electron microscopy (SEM). Catalytic metal clusters can also be prepared using this methodology. Electrodes with the metal surface flush with glass insulator, most suitable for quantitative voltammetric and SECM experiments are fabricated by electrodeposition of a metal inside an etched nanocavity. PMID:20645378

  6. An age difference of two billion years between a metal-rich and a metal-poor globular cluster.

    PubMed

    Hansen, B M S; Kalirai, J S; Anderson, J; Dotter, A; Richer, H B; Rich, R M; Shara, M M; Fahlman, G G; Hurley, J R; King, I R; Reitzel, D; Stetson, P B

    2013-08-01

    Globular clusters trace the formation history of the spheroidal components of our Galaxy and other galaxies, which represent the bulk of star formation over the history of the Universe. The clusters exhibit a range of metallicities (abundances of elements heavier than helium), with metal-poor clusters dominating the stellar halo of the Galaxy, and higher-metallicity clusters found within the inner Galaxy, associated with the stellar bulge, or the thick disk. Age differences between these clusters can indicate the sequence in which the components of the Galaxy formed, and in particular which clusters were formed outside the Galaxy and were later engulfed along with their original host galaxies, and which were formed within it. Here we report an absolute age of 9.9 ± 0.7 billion years (at 95 per cent confidence) for the metal-rich globular cluster 47 Tucanae, determined by modelling the properties of the cluster's white-dwarf cooling sequence. This is about two billion years younger than has been inferred for the metal-poor cluster NGC 6397 from the same models, and provides quantitative evidence that metal-rich clusters like 47 Tucanae formed later than metal-poor halo clusters like NGC 6397. PMID:23903747

  7. Vibrationally resolved anion photoelectron spectroscopy of metal clusters

    NASA Astrophysics Data System (ADS)

    Miller, Stephen R.

    Vibrationally resolved anion photoelectron spectroscopy of metal clusters Vibrationally resolved anion photoelectron spectroscopy (APES) and density functional theory (DFT) are applied to the study of structure and reactivity in small metal containing molecules. The studies described fall into two general categories: the study of bare metal clusters and the study of metal/organic ligand reactions. The current lack of spectroscopic data for small, bare gas-phase metal compounds makes the experimental study of such compounds important for understanding structure and bonding in open-shell metallic species. The heteronuclear diatomic anions MCu- (M = Cr, Mo) were prepared in a flowing afterglow ion-molecule reactor, and studied experimentally with APES. Anion and neutral vibrational frequencies and MCu electron affinities were obtained for both systems. The experiments were supplemented by DFT calculations. The combined use of experiment and theory allows for the assignment of both photoelectron spectra, including a reassignment of the CrCu ground state reported in the literature. Similarly, DFT was used to assign the anionic/neutral electronic states observed in the photoelectron spectra of Al3- and Al3O-. The study of partially ligated organometallic complexes offers a means of examining the interactions between metal atoms and individual ligand molecules. DFT was used to assign electronic states observed in the photoelectron spectra of NbC2H2-, NbC4H4 -NbC6H6- and VC6H 6-. Comparison of the NbnHn - (n = 2, 4, 6) spectra (obtained through the reaction of C2 H4 and Nb) with DFT results provides the first direct spectroscopic evidence of the conversion of ethylene to benzene by a gas phase metal atom. Experiments were used to probe the reactivity of Y with C2H 4 in an effort to examine the generality of the metal induced C 2H4 dehydrogenation/cyclization reactions. Some of the key products in the Y reactions were YC2H-, YC 2H2-, and YC6H5 -. However, the results

  8. Charging dynamics of metal clusters in intense laser fields

    NASA Astrophysics Data System (ADS)

    Döppner, T.; Teuber, S.; Schumacher, M.; Tiggesbäumker, J.; Meiwes-Broer, K. H.

    2000-09-01

    Clusters of heavy metal atoms in strong femtosecond laser-light fields undergo multi-ionization with the loss of hundreds of electrons. The cross section largely exceeds that of corresponding isolated atoms, which leads in the case of PbN to a complete ionization of the 4f shell with a light intensity of 1.2×1015 W/cm2. Experimental investigations on Pb and Pt clusters with variable pulse widths and, for the first time, with the pump&probe technique give insight into the dynamics of the coupling of electromagnetic radiation into the clusters. Both approaches support the picture according to which, after an initial charging, the clusters expand due to Coulomb forces. This expansion is accompanied by a reduction of the electron density and at the same time by an increase of the optical sensitivity. Once the plasmon energy of the diluted nanoplasma approaches the photon energy, the charging efficiency increases significantly. The experimental observations are confirmed by random-phase approximation (RPA) calculations of the optical response, including molecular-dynamics simulations of the expanding systems.

  9. Water clusters in mixed ionic complexes with metal dipicolinate anions

    NASA Astrophysics Data System (ADS)

    Das, Babulal; Baruah, Jubaraj B.

    2013-02-01

    Formations of three different types of hydrogen-bonded water clusters in the interstices of mixed ionic complexes with metal dipicolinate anions are reported. In the complex [Co(phen)2(H2O)2][Zn(dpa)2]ṡ7H2O (1) (where phen = 1,10-phenanthroline, dpa = dipicolinate), both the cation and anion is hydrophilic in nature, exhibits an unusual 2D infinite cyclic water decamers (H2O)10 stabilized by four identical zinc dipicolinato complex anions. Modulating the cationic unit to a hydrophobic environment by replacing the aqua ligand with 2,2'-bipyridine ligand the water cluster can be modified. The complex [Ni(phen)2ṡbpy][Co(dpa)2]ṡ8H2O (2) (where bpy = 2,2'-bipyridine) has unprecedented discrete hydrogen bonded hexadecameric (H2O)16 water clusters encapsulated between eight anionic units. A rare wavelike infinite water chain (H2O)n is observed in complex [Co(phen)3][Mn(dpa)2]ṡ12H2O (3), in this case the water chain fills the interstitial space created by packing of large hydrophilic anionic units and hydrophobic cationic units. The reported clusters are indefinitely stable in their respective complex at ambient temperature, but the water loss is irreversible when thermally decomposed.

  10. Shell structure of magnesium and other divalent metal clusters

    SciTech Connect

    Diederich, Th.; Doeppner, T.; Fennel, Th.; Tiggesbaeumker, J.; Meiwes-Broer, K.-H.

    2005-08-15

    Clusters of the divalent metals magnesium, cadmium, and zinc have been grown in ultracold helium nanodroplets and studied by high-resolution mass spectrometry, with a special emphasis on magnesium. The mass spectra of all materials show similar characteristic features independent of the chosen ionization technique - i.e., electron impact ionization as well as nanosecond and femtosecond multiphoton excitation. In the lower-size range the abundance distributions can be explained by an electronic shell structure. The associated electron delocalization - i.e., metallic bonding - is found to set in at about N=20 atoms. For Mg{sub N} we have resolved crossings of electronic levels at the highest-occupied molecular orbital which result in additional magic numbers compared to the alkali metals: e.g., Mg{sub 40} with 80 electrons. This specific electronic shell structure is also present in the intensity pattern of doubly charged Mg{sub N}. For larger clusters (N{>=}92) a coexistence of electronic shell effects and geometrical packing is observed and a clear signature of icosahedral structure is present beyond N{>=}147.

  11. The electronic structure of free aluminum clusters: Metallicity and plasmons

    SciTech Connect

    Andersson, Tomas; Zhang Chaofan; Svensson, Svante; Maartensson, Nils; Bjoerneholm, Olle; Tchaplyguine, Maxim

    2012-05-28

    The electronic structure of free aluminum clusters with {approx}3-4 nm radius has been investigated using synchrotron radiation-based photoelectron and Auger electron spectroscopy. A beam of free clusters has been produced using a gas-aggregation source. The 2p core level and the valence band have been probed. Photoelectron energy-loss features corresponding to both bulk and surface plasmon excitation following photoionization of the 2p level have been observed, and the excitation energies have been derived. In contrast to some expectations, the loss features have been detected at energies very close to those of the macroscopic solid. The results are discussed from the point of view of metallic properties in nanoparticles with a finite number of constituent atoms.

  12. The electronic structure of free aluminum clusters: Metallicity and plasmons

    NASA Astrophysics Data System (ADS)

    Andersson, Tomas; Zhang, Chaofan; Tchaplyguine, Maxim; Svensson, Svante; Mârtensson, Nils; Björneholm, Olle

    2012-05-01

    The electronic structure of free aluminum clusters with ˜3-4 nm radius has been investigated using synchrotron radiation-based photoelectron and Auger electron spectroscopy. A beam of free clusters has been produced using a gas-aggregation source. The 2p core level and the valence band have been probed. Photoelectron energy-loss features corresponding to both bulk and surface plasmon excitation following photoionization of the 2p level have been observed, and the excitation energies have been derived. In contrast to some expectations, the loss features have been detected at energies very close to those of the macroscopic solid. The results are discussed from the point of view of metallic properties in nanoparticles with a finite number of constituent atoms.

  13. Properties of Red Giant Branches of Star Clusters in the Magellanic Clouds and Their Relation with Cluster Metallicity

    NASA Astrophysics Data System (ADS)

    Kučinskas, A.; Dobrovolskas, V.; Černiauskas, A.; Tanabé, T.

    We derive a new calibration that relates the observed cluster RGB slope in the Ks vs. J--Ks color-magnitude diagram with cluster metallicity. The new calibration is derived using a sample of intermediate age (1--8 Gyr) clusters in the Large and Small Magellanic Clouds with precise JHKs photometry available from the SIRIUS photometric survey of the Magellanic Clouds. Cluster metallicities are literature data obtained either from high resolution or infrared calcium triplet spectroscopy of individual cluster RGB stars. We find systematic differences between the RGB slope vs. metallicity relation derived in this work and that of Valenti et al. (2004), the latter obtained using a sample of old Galactic globular clusters. The possible origin of the discrepancies is discussed briefly.

  14. 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

  15. Oligomeric rare-earth metal cluster complexes with endohedral transition metal atoms

    SciTech Connect

    Steinberg, Simon; Zimmermann, Sina; Brühmann, Matthias; Meyer, Eva; Rustige, Christian; Wolberg, Marike; Daub, Kathrin; Bell, Thomas; Meyer, Gerd

    2014-11-15

    Comproportionation reactions of rare-earth metal trihalides (RX{sub 3}) with the respective rare-earth metals (R) and transition metals (T) led to the formation of 22 oligomeric R cluster halides encapsulating T, in 19 cases for the first time. The structures of these compounds were determined by single-crystal X-ray diffraction and are composed of trimers ((T{sub 3}R{sub 11})X{sub 15}-type, P6{sub 3}/m), tetramers ((T{sub 4}R{sub 16})X{sub 28}(R{sub 4}) (P-43m), (T{sub 4}R{sub 16})X{sub 20} (P4{sub 2}/nnm), (T{sub 4}R{sub 16})X{sub 24}(RX{sub 3}){sub 4} (I4{sub 1}/a) and (T{sub 4}R{sub 16})X{sub 23} (C2/m) types of structure) and pentamers ((Ru{sub 5}La{sub 14}){sub 2}Br{sub 39}, Cc) of (TR{sub r}){sub n} (n=2–5) clusters. These oligomers are further enveloped by inner (X{sup i}) as well as outer (X{sup a}) halido ligands, which possess diverse functionalities and interconnect like oligomers through i–i, i–a and/or a–i bridges. The general features of the crystal structures for these new compounds are discussed and compared to literature entries as well as different structure types with oligomeric T centered R clusters. Dimers and tetramers originating from the aggregation of (TR{sub 6}) octahedra via common edges are more frequent than trimers and pentamers, in which the (TR{sub r}) clusters share common faces. - Graphical abstract: Rare earth-metal cluster complexes with endohedral transition metal atoms (TR{sub 6}) may connect via common edges or faces to form dimers, trimers, tetramers and pentamers of which the tetramers are the most prolific. Packing effects and electron counts play an important role. - Highlights: • Rare-earth metal cluster complexes encapsulate transition metal atoms. • Oligomers are built via connection of octahedral clusters via common edges or faces. • Dimers through pentamers with closed structures are known. • Tetramers including a tetrahedron of endohedral atoms are the most prolific.

  16. Superatoms and Metal-Semiconductor Motifs for Cluster Materials

    SciTech Connect

    Castleman, A. W.

    2013-10-11

    A molecular understanding of catalysis and catalytically active materials is of fundamental importance in designing new substances for applications in energy and fuels. We have performed reactivity studies and ultrafast ionization and coulomb explosion studies on a variety of catalytically-relevant materials, including transition metal oxides of Fe, Co, Ni, Cu, Ti, V, Nb, and Ta. We demonstrate that differences in charge state, geometry, and elemental composition of clusters of such materials determine chemical reactivity and ionization behavior, crucial steps in improving performance of catalysts.

  17. Zintl cluster chemistry in the alkali-metal-gallium systems

    SciTech Connect

    Henning, R.

    1998-03-27

    Previous research into the alkali-metal-gallium systems has revealed a large variety of networked gallium deltahedra. The clusters are analogues to borane clusters and follow the same electronic requirements of 2n+2 skeletal electrons for closo-deltahedra. This work has focused on compounds that do not follow the typical electron counting rules. The first isolated gallium cluster was found in Cs{sub 8}Ga{sub 11}. The geometry of the Ga{sub 11}{sup 7{minus}} unit is not deltahedral but can be described as a penta-capped trigonal prism. The reduction of the charge from a closo-Ga{sub 11}{sup 13{minus}} to Ga{sub 11}{sup 7{minus}} is believed to be the driving force of the distortion. The compound is paramagnetic because of an extra electron but incorporation of a halide atom into the structure captures the unpaired electron and forms a diamagnetic compound. A second isolated cluster has been found in Na{sub 10}Ga{sub 10}Ni where the tetra-capped trigonal prismatic gallium is centered by nickel. Stabilization of the cluster occurs through Ni-Ga bonding. A simple two-dimensional network occurs in the binary K{sub 2}Ga{sub 3} Octahedra are connected through four waist atoms to form a layered structure with the potassium atoms sitting between the layers. Na{sub 30.5}Ga{sub 60{minus}x}Ag{sub x} is nonstoichiometric and needs only a small amount of silver to form (x {approximately} 2--6). The structure is composed of three different clusters which are interconnected to form a three-dimensional structure. The RbGa{sub 3{minus}x}Au{sub x} system is also nonstoichiometric with a three-dimensional structure composed of Ga{sub 8} dodecahedra and four-bonded gallium atoms. Unlike Na{sub 30.5}Ga{sub 60{minus}x}Ag{sub x}, the RbGa{sub 3} binary is also stable. The binary is formally a Zintl phase but the ternary is not. Some chemistry in the alkali-metal-indium system also has been explored. A new potassium-indium binary is discussed but the structure has not been completely

  18. Nearby Spiral Galaxy Globular Cluster Systems. II. Globular Cluster Metallicities in NGC 300

    NASA Astrophysics Data System (ADS)

    Nantais, Julie B.; Huchra, John P.; Barmby, Pauline; Olsen, Knut A. G.

    2010-03-01

    We present new metallicity estimates for globular cluster (GC) candidates in the Sd spiral NGC 300, one of the nearest spiral galaxies outside the Local Group. We have obtained optical spectroscopy for 44 Sculptor Group GC candidates with the Boller and Chivens (B&C) spectrograph on the Baade Telescope at Las Campanas Observatory. There are two GCs in NGC 253 and 12 objects in NGC 300 with globular-cluster-like spectral features, nine of which have radial velocities above 0 km s-1. The remaining three, due to their radial velocities being below the expected 95% confidence limit for velocities of NGC 300 halo objects, are flagged as possible foreground stars. The non-cluster-like candidates included 13 stars, 15 galaxies, and an H II region. One GC, four galaxies, two stars, and the H II region from our sample were identified in archival Hubble Space Telescope images. For the GCs, we measure spectral indices and estimate metallicities using an empirical calibration based on Milky Way GCs. The GCs of NGC 300 appear similar to those of the Milky Way. Excluding possible stars and including clusters from the literature, the GC system (GCS) has a velocity dispersion of 68 km s-1 and has no clear evidence of rotation. The mean metallicity for our full cluster sample plus one literature object is [Fe/H] = -0.94, lying above the relationship between mean GC metallicity and overall galaxy luminosity. Excluding the three low-velocity candidates, we obtain a mean [Fe/H] = -0.98, still higher than expected, raising the possibility of significant foreground star contamination even in this sample. Visual confirmation of genuine GCs using high-resolution space-based imagery could greatly reduce the potential problem of interlopers in small samples of GCSs in low-radial-velocity galaxies. Data for this project were obtained at the Baade 6.5 m telescope, Las Campanas Observatory, Chile. This publication makes use of data products from the Two Micron All Sky Survey, which is a joint

  19. Radical AdoMet enzymes in complex metal cluster biosynthesis.

    PubMed

    Duffus, Benjamin R; Hamilton, Trinity L; Shepard, Eric M; Boyd, Eric S; Peters, John W; Broderick, Joan B

    2012-11-01

    Radical S-adenosylmethionine (AdoMet) enzymes comprise a large superfamily of proteins that engage in a diverse series of biochemical transformations through generation of the highly reactive 5'-deoxyadenosyl radical intermediate. Recent advances into the biosynthesis of unique iron-sulfur (FeS)-containing cofactors such as the H-cluster in [FeFe]-hydrogenase, the FeMo-co in nitrogenase, as well as the iron-guanylylpyridinol (FeGP) cofactor in [Fe]-hydrogenase have implicated new roles for radical AdoMet enzymes in the biosynthesis of complex inorganic cofactors. Radical AdoMet enzymes in conjunction with scaffold proteins engage in modifying ubiquitous FeS precursors into unique clusters, through novel amino acid decomposition and sulfur insertion reactions. The ability of radical AdoMet enzymes to modify common metal centers to unusual metal cofactors may provide important clues into the stepwise evolution of these and other complex bioinorganic catalysts. This article is part of a Special Issue entitled: Radical SAM enzymes and Radical Enzymology. PMID:22269887

  20. Properties of Red Giant Branches of Star Clusters in the Magellanic Clouds and Their Relation with Cluster Metallicity. II. Mean Photometric Colors of Cluster RGBs

    NASA Astrophysics Data System (ADS)

    Kučinskas, A.; Dobrovolskas, V.; Lazauskaitė, R.; Tanabé, T.

    We derive new calibrations that relate the mean J-Ks photometric colors of red giant branch (RGB) stars at MKs=-5.5 and -5.0 with cluster metallicity. The new calibrations are derived using a sample of intermediate age (1--8 Gyr) clusters in the Large and Small Magellanic Clouds, with the JHKs photometry taken from the SIRIUS photometric survey of the Magellanic Clouds. Cluster metallicities are literature data, obtained either from the high resolution or infrared calcium triplet spectroscopy of individual RGB stars. We find systematic differences between the RGB color vs. metallicity relations derived in this work and those determined by Valenti et al. (2004), the latter ones obtained for a sample of old Galactic globular clusters. In terms of age, this discrepancy corresponds to ˜ 5 Gyr and therefore can be attributed to the age difference between the two cluster samples used in the derivation of the corresponding RGB color vs. metallicity relations.

  1. The transformation of organic amines by transition metal cluster compounds. Progress report, 1992--1993

    SciTech Connect

    Adams, R.D.

    1993-01-01

    The paper reports results on the following five studies: (1) The activation of tertiary amines by osmium cluster complexes; (2) Nucleophilic ring opening of thietane ligand in metal carbonyl cluster complexes; (3) Ring opening of a nitrogen containing strained ring heterocycle by an osmium cluster complex; (4) Insertion of an alkynes into a metal-metal bond -- evidence for an intramolecular insertion with a trans-stereochemistry; and (5) Cyclobutyne -- the ligand. Plans for future research are also briefly discussed. Two studies are planned: (1) studies of the synthesis and reactivity of strained ring ligands in metal cluster compounds; and (2) studies of the reactivity of dimetallic complexes with alkynes.

  2. 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)

  3. Size control of noble metal clusters and metallic heterostructures through the reduction kinetics of metal precursors

    NASA Astrophysics Data System (ADS)

    Sevonkaev, Igor V.; Herein, Daniel; Jeske, Gerald; Goia, Dan V.

    2014-07-01

    Eight precious metal salts/complexes were reduced in propylene glycol at temperatures ranging between 110 and 170 °C. We found that the reduction temperature and the size of precipitated metallic nanoparticles formed were significantly affected by the structure and reactivity of the metal precursors. The choice of noble metal precursor offers flexibility for designing, fabricating and controlling the size of metallic heterostructures with tunable properties.Eight precious metal salts/complexes were reduced in propylene glycol at temperatures ranging between 110 and 170 °C. We found that the reduction temperature and the size of precipitated metallic nanoparticles formed were significantly affected by the structure and reactivity of the metal precursors. The choice of noble metal precursor offers flexibility for designing, fabricating and controlling the size of metallic heterostructures with tunable properties. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr03045a

  4. High-dispersion spectroscopy of giants in metal-poor globular clusters. I - Iron abundances

    NASA Technical Reports Server (NTRS)

    Minniti, Dante; Geisler, Doug; Peterson, Ruth C.; Claria, Juan J.

    1993-01-01

    High-resolution, high-SNR CCD spectra have been obtained for 16 giants in eight metal-poor Galactic globular clusters. Fe abundances accurate to 0.15 dex have been determined by a fully consistent set of model atmospheres and spectrum synthesis techniques. A metallicity scale is presented for metal-poor clusters that should prove useful for calibrating a wide variety of photometric and low-resolution spectroscopic metallicity indicators.

  5. Permanent excimer superstructures by supramolecular networking of metal quantum clusters.

    PubMed

    Santiago-Gonzalez, Beatriz; Monguzzi, Angelo; Azpiroz, Jon Mikel; Prato, Mirko; Erratico, Silvia; Campione, Marcello; Lorenzi, Roberto; Pedrini, Jacopo; Santambrogio, Carlo; Torrente, Yvan; De Angelis, Filippo; Meinardi, Francesco; Brovelli, Sergio

    2016-08-01

    Excimers are evanescent quasi-particles that typically form during collisional intermolecular interactions and exist exclusively for their excited-state lifetime. We exploited the distinctive structure of metal quantum clusters to fabricate permanent excimer-like colloidal superstructures made of ground-state noninteracting gold cores, held together by a network of hydrogen bonds between their capping ligands. This previously unknown aggregation state of matter, studied through spectroscopic experiments and ab initio calculations, conveys the photophysics of excimers into stable nanoparticles, which overcome the intrinsic limitation of excimers in single-particle applications-that is, their nearly zero formation probability in ultra-diluted solutions. In vitro experiments demonstrate the suitability of the superstructures as nonresonant intracellular probes and further reveal their ability to scavenge reactive oxygen species, which enhances their potential as anticytotoxic agents for biomedical applications. PMID:27493181

  6. Contribution of radiation chemistry to the study of metal clusters.

    PubMed

    Belloni, J

    1998-11-01

    Radiation chemistry dates from the discovery of radioactivity one century ago by H. Becquerel and P. and M. Curie. The complex phenomena induced by ionizing radiation have been explained progressively. At present, the methodology of radiation chemistry, particularly in the pulsed mode, provides a powerful means to study not only the early processes after the energy absorption, but more generally a broad diversity of chemical and biochemical reaction mechanisms. Among them, the new area of metal cluster chemistry illustrates how radiation chemistry contributed to this field in suggesting fruitful original concepts, in guiding and controlling specific syntheses, and in the detailed elaboration of the mechanisms of complex and long-unsolved processes, such as the dynamics of nucleation, electron transfer catalysis and photographic development. PMID:9806605

  7. Permanent excimer superstructures by supramolecular networking of metal quantum clusters

    NASA Astrophysics Data System (ADS)

    Santiago-Gonzalez, Beatriz; Monguzzi, Angelo; Azpiroz, Jon Mikel; Prato, Mirko; Erratico, Silvia; Campione, Marcello; Lorenzi, Roberto; Pedrini, Jacopo; Santambrogio, Carlo; Torrente, Yvan; De Angelis, Filippo; Meinardi, Francesco; Brovelli, Sergio

    2016-08-01

    Excimers are evanescent quasi-particles that typically form during collisional intermolecular interactions and exist exclusively for their excited-state lifetime. We exploited the distinctive structure of metal quantum clusters to fabricate permanent excimer-like colloidal superstructures made of ground-state noninteracting gold cores, held together by a network of hydrogen bonds between their capping ligands. This previously unknown aggregation state of matter, studied through spectroscopic experiments and ab initio calculations, conveys the photophysics of excimers into stable nanoparticles, which overcome the intrinsic limitation of excimers in single-particle applications—that is, their nearly zero formation probability in ultra-diluted solutions. In vitro experiments demonstrate the suitability of the superstructures as nonresonant intracellular probes and further reveal their ability to scavenge reactive oxygen species, which enhances their potential as anticytotoxic agents for biomedical applications.

  8. 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.

  9. Fluid-dynamical approach to collective modes in metal clusters

    NASA Astrophysics Data System (ADS)

    da Providência, João, Jr.; de Haro, Raphael, Jr.

    1994-01-01

    A simple variational method has recently been used to obtain the bulk-plasmon dispersion relation in a metal. In the present work we investigate the eigenmodes of the valence electrons in a metal cluster considering a semiclassical version of the method presented by Andō and Nishizaki. As a variational function we consider the Slater determinant ||φ> which is related to the Slater determinant ||φ0>, describing the ground state, by means of the unitary transformation ||φ>=e(i/ħ)S||φ0>, where S(x,p,t)=χ(x,t)+1/2[p.s(x,t)+s(x,t).p]. We use a polynomial approximation to determine the dynamical fields χ(x,t) and s(x,t). It is shown that the eigensolutions satisfy the energy weighted sum rule and the cubic energy weighted sum rule. The spectrum of excited energies, as well as transition densities and currents are obtained for the sodium, aluminum, and silver.

  10. 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.

  11. Emergence of metallicity in silver clusters in the 150 atom regime: a study of differently sized silver clusters

    NASA Astrophysics Data System (ADS)

    Chakraborty, Indranath; Erusappan, Jayanthi; Govindarajan, Anuradha; Sugi, K. S.; Udayabhaskararao, Thumu; Ghosh, Atanu; Pradeep, Thalappil

    2014-06-01

    We report the systematic appearance of a plasmon-like optical absorption feature in silver clusters protected with 2-phenylethanethiol (PET), 4-flurothiophenol (4-FTP) and (4-(t-butyl)benzenethiol (BBS) as a function of cluster size. A wide range of clusters, namely, Ag44(4-FTP)30, Ag55(PET)31, ~Ag75(PET)40, ~Ag114(PET)46, Ag152(PET)60, ~Ag202(BBS)70, ~Ag423(PET)105, and ~Ag530(PET)100 were prepared. The UV/Vis spectra show multiple features up to ~Ag114 and thereafter, from Ag152 onwards, the plasmonic feature corresponding to a single peak at ~460 nm evolves, which points to the emergence of metallicity in clusters composed of ~150 metal atoms. A minor blue shift in the plasmonic peak was observed as cluster sizes increased and merged with the spectrum of plasmonic nanoparticles of 4.8 nm diameter protected with PET. Clusters with different ligands, such as 4-FTP and BBS, also show this behavior, which suggests that the `emergence of metallicity' is independent of the functionality of the thiol ligand.We report the systematic appearance of a plasmon-like optical absorption feature in silver clusters protected with 2-phenylethanethiol (PET), 4-flurothiophenol (4-FTP) and (4-(t-butyl)benzenethiol (BBS) as a function of cluster size. A wide range of clusters, namely, Ag44(4-FTP)30, Ag55(PET)31, ~Ag75(PET)40, ~Ag114(PET)46, Ag152(PET)60, ~Ag202(BBS)70, ~Ag423(PET)105, and ~Ag530(PET)100 were prepared. The UV/Vis spectra show multiple features up to ~Ag114 and thereafter, from Ag152 onwards, the plasmonic feature corresponding to a single peak at ~460 nm evolves, which points to the emergence of metallicity in clusters composed of ~150 metal atoms. A minor blue shift in the plasmonic peak was observed as cluster sizes increased and merged with the spectrum of plasmonic nanoparticles of 4.8 nm diameter protected with PET. Clusters with different ligands, such as 4-FTP and BBS, also show this behavior, which suggests that the `emergence of metallicity' is independent of

  12. Chiral structures and tunable magnetic moments in 3d transition metal doped Pt6 clusters

    NASA Astrophysics Data System (ADS)

    Zhang, Xiu-Rong; Yang, Xing; Ding, Xun-Lei

    2012-09-01

    The structural, electronic, and magnetic properties of transition metal doped platinum clusters MPt6 (M=Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Zn) are systematically studied by using the relativistic all-electron density functional theory with the generalized gradient approximation. Most of the doped clusters show larger binding energies than the pure Pt7 cluster, which indicates that the doping of the transition metal atom can stabilize the pure platinum cluster. The results of the highest occupied molecular orbital (HOMO)—lowest unoccupied molecular orbital (LUMO) gaps suggest that the doped clusters can have higher chemical activities than the pure Pt7 cluster. The magnetism calculations demonstrate that the variation range of the magnetic moments of the MPt6 clusters is from 0 μB to 7 μB, revealing that the MPt6 clusters have potential utility in designing new spintronic nanomaterials with tunable magnetic properties.

  13. 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

  14. Metallicity determinations for globular clusters through spectrophotometry of their integrated light

    NASA Astrophysics Data System (ADS)

    Brodie, J. P.; Hanes, D. A.

    1986-01-01

    Using an appropriately weighted combination of 16 indices of absorption line strength measured in low-dispersion spectra of the integrated light of globular clusters, metallicities Fe/H are determined for thirty-six clusters in the Galaxy. The results confirm the suggestion that Zinn's (1980) scale suffers a systematic error in the region of intermediate metallicity and support an explanation in which his metallicity-indicative Q39 index has been diluted by excess ultraviolet light in clusters with anomalously rich blue horizontal branches. The methods, which involve the measurement of spectral features arising from many species, produce estimates of metallicity which are insensitive to this problem. Good agreement is found with several recent studies, but a disagreement is noted for the most metal-rich clusters studied by Frogel, Cohen, and Persson (1983). Finally, a similar method with a modified calibration is used to determine metallicities for the nuclei of six galaxies.

  15. RHAPSODY-G simulations II - Baryonic growth and metal enrichment in massive galaxy clusters

    NASA Astrophysics Data System (ADS)

    Martizzi, Davide; Hahn, Oliver; Wu, Hao-Yi; Evrard, August E.; Teyssier, Romain; Wechsler, Risa H.

    2016-04-01

    We study the evolution of the stellar component and the metallicity of both the intracluster medium and of stars in massive (Mvir ≈ 6 × 1014 M⊙/h) simulated galaxy clusters from the RHAPSODY-G suite in detail and compare them to observational results. The simulations were performed with the AMR code RAMSES and include the effect of AGN feedback at the sub-grid level. AGN feedback is required to produce realistic galaxy and cluster properties and plays a role in mixing material in the central regions and regulating star formation in the central galaxy. In both our low and high resolution runs with fiducial stellar yields, we find that stellar and ICM metallicities are a factor of two lower than in observations. We find that cool core clusters exhibit steeper metallicity gradients than non-cool core clusters, in qualitative agreement with observations. We verify that the ICM metallicities measured in the simulation can be explained by a simple "regulator" model in which the metallicity is set by a balance of stellar yield and gas accretion. It is plausible that a combination of higher resolution and higher metal yield in AMR simulation would allow the metallicity of simulated clusters to match observed values; however this hypothesis needs to be tested with future simulations. Comparison to recent literature highlights that results concerning the metallicity of clusters and cluster galaxies might depend sensitively on the scheme chosen to solve the hydrodynamics.

  16. RHAPSODY-G simulations - II. Baryonic growth and metal enrichment in massive galaxy clusters

    NASA Astrophysics Data System (ADS)

    Martizzi, Davide; Hahn, Oliver; Wu, Hao-Yi; Evrard, August E.; Teyssier, Romain; Wechsler, Risa H.

    2016-07-01

    We study the evolution of the stellar component and the metallicity of both the intracluster medium and of stars in massive (Mvir ≈ 6 × 1014 M⊙ h-1) simulated galaxy clusters from the RHAPSODY-G suite in detail and compare them to observational results. The simulations were performed with the AMR code RAMSES and include the effect of active galactic nucleus (AGN) feedback at the subgrid level. AGN feedback is required to produce realistic galaxy and cluster properties and plays a role in mixing material in the central regions and regulating star formation in the central galaxy. In both our low- and high-resolution runs with fiducial stellar yields, we find that stellar and ICM metallicities are a factor of 2 lower than in observations. We find that cool core clusters exhibit steeper metallicity gradients than non-cool core clusters, in qualitative agreement with observations. We verify that the ICM metallicities measured in the simulation can be explained by a simple `regulator' model in which the metallicity is set by a balance of stellar yield and gas accretion. It is plausible that a combination of higher resolution and higher metal yield in AMR simulation would allow the metallicity of simulated clusters to match observed values; however, this hypothesis needs to be tested with future simulations. Comparison to recent literature highlights that results concerning the metallicity of clusters and cluster galaxies might depend sensitively on the scheme chosen to solve the hydrodynamics.

  17. 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.

  18. A uniform metal distribution in the intergalactic medium of the Perseus cluster of galaxies.

    PubMed

    Werner, Norbert; Urban, Ondrej; Simionescu, Aurora; Allen, Steven W

    2013-10-31

    Most of the metals (elements heavier than helium) produced by stars in the member galaxies of clusters currently reside within the hot, X-ray-emitting intra-cluster gas. Observations of X-ray line emission from this intergalactic medium have suggested a relatively small cluster-to-cluster scatter outside the cluster centres and enrichment with iron out to large radii, leading to the idea that the metal enrichment occurred early in the history of the Universe. Models with early enrichment predict a uniform metal distribution at large radii in clusters, whereas those with late-time enrichment are expected to introduce significant spatial variations of the metallicity. To discriminate clearly between these competing models, it is essential to test for potential inhomogeneities by measuring the abundances out to large radii along multiple directions in clusters, which has not hitherto been done. Here we report a remarkably uniform iron abundance, as a function of radius and azimuth, that is statistically consistent with a constant value of ZFe = 0.306 ± 0.012 in solar units out to the edge of the nearby Perseus cluster. This homogeneous distribution requires that most of the metal enrichment of the intergalactic medium occurred before the cluster formed, probably more than ten billion years ago, during the period of maximal star formation and black hole activity. PMID:24172976

  19. Structure, dynamic and energetic of mixed transition metal clusters. A computational study of mixed clusters of silver and nickel

    NASA Astrophysics Data System (ADS)

    Hewage, J. W.; Rupika, W. L.; Amar, F. G.

    2012-11-01

    Classical molecular dynamics simulation (MD) with Sutton-Chen potential has been used to generate the minimum energy and to study the thermodynamic and dynamic properties of mixed transition metal cluster motifs of Ag n Ni(13- n) for n ≤ 13. Literature results of thirteen particle clusters of neat silver and nickel atoms were first reproduced before the successive replacement of the silver atom by nickel. Calculation was repeated for both silver-centred and nickel-centred clusters. It was found that the nickel-centred clusters were more stable than the silver-centred clusters. Heat capacities and hence the melting points of silver and nickel-centred clusters were determined by using the Histogram method. Species-centric order parameters developed by Hewage and Amar were used to understand the dynamic behaviour in the transition of silver-centred clusters to more stable nickel-centred clusters. This species-centric order parameter calculation further confirmed the stability of nickel-centred clusters over those of silver-centred species.

  20. Reverse hydrogen spillover on and hydrogenation of supported metal clusters: insights from computational model studies.

    PubMed

    Vayssilov, Georgi N; Petrova, Galina P; Shor, Elena A Ivanova; Nasluzov, Vladimir A; Shor, Alexei M; St Petkov, Petko; Rösch, Notker

    2012-05-01

    "Reverse" spillover of hydrogen from hydroxyl groups of the support onto supported transition metal clusters, forming multiply hydrogenated metal species, is an essential aspect of various catalytic systems which comprise small, highly active transition metal particles on a support with a high surface area. We review and analyze the results of our computational model studies related to reverse hydrogen spillover, interpreting available structural and spectral data for the supported species and examining the relationship between metal-support and metal-hydrogen interactions. On the examples of small clusters of late transition metals, adsorbed in zeolite cavities, we showed with computational model studies that reverse spillover of hydrogen is energetically favorable for late transition metals, except for Au. This preference is crucial for the chemical reactivity of such bifunctional catalytic systems because both functions, of metal species and of acidic sites, are strongly modified, in some cases even suppressed - due to partial oxidation of the metal cluster and the conversion of protons from acidic hydroxyl groups to hydride ligands of the metal moiety. Modeling multiple hydrogen adsorption on metal clusters allowed us to quantify how (i) the support affects the adsorption capacity of the clusters and (ii) structure and oxidation state of the metal moiety changes upon adsorption. In all models of neutral systems we found that the metal atoms are partially positively charged, compensated by a negative charge of the adsorbed hydrogen ligands and of the support. In a case study we demonstrated with calculated thermodynamic parameters how to predict the average hydrogen coverage of the transition metal cluster at a given temperature and hydrogen pressure. PMID:22353996

  1. Reactions of metal cluster anions with inorganic and organic molecules in the gas phase.

    PubMed

    Zhao, Yan-Xia; Liu, Qing-Yu; Zhang, Mei-Qi; He, Sheng-Gui

    2016-07-28

    The study of gas phase ion-molecule reactions by state-of-the-art mass spectrometric experiments in conjunction with quantum chemistry calculations offers an opportunity to clarify the elementary steps and mechanistic details of bond activation and conversion processes. In the past few decades, a considerable number of publications have been devoted to the ion-molecule reactions of metal clusters, the experimentally and theoretically tractable models for the active phase of condensed phase systems. The focus of this perspective concerns progress on activation and transformation of important inorganic and organic molecules by negatively charged metal clusters. The metal cluster anions cover bare metal clusters as well as ligated systems with oxygen, carbon, and nitrogen, among others. The following important issues have been summarized and discussed: (i) dependence of chemical reactivity and selectivity on cluster structures and sizes, metals and metal oxidation states, odd-even electron numbers, etc. and (ii) effects of doping, ligation, and pre-adsorption on the reactivity of metal clusters toward rather inert molecules. PMID:27346242

  2. LITHIUM ABUNDANCES OF THE SUPER-METAL-RICH OPEN CLUSTER NGC 6253

    SciTech Connect

    Cummings, Jeffrey D.; Deliyannis, Constantine P.; Maderak, Ryan M.; Anthony-Twarog, Barbara; Twarog, Bruce E-mail: con@astro.indiana.edu E-mail: bjat@ku.edu

    2012-11-01

    High-resolution CTIO 4 m/HYDRA spectroscopy of the super-metal-rich open cluster NGC 6253 ([Fe/H] = +0.43 {+-} 0.01) has been used to study the stellar lithium (Li) abundances near the cluster's turnoff. NGC 6253 greatly expands the range of [Fe/H] for clusters that have a Li abundance analysis. This is important for studying the complicated effects of, and potential correlations with, stellar Fe abundance on surface Li abundance. Comparisons to the younger and less-metal-rich Hyades and to the similarly aged but solar-metallicity M67 show that NGC 6253's Li abundances are qualitatively consistent with the prediction, from Standard Stellar Evolution Theory, that higher-metallicity stars have a greater Li depletion. Comparison with M67 provides evidence that the more-metal-rich NGC 6253 had a higher initial Li, which is consistent with expectations from models of Galactic Li production. NGC 6253 is also compared to the intermediate-aged NGC 3680, NGC 752, and IC 4651 open clusters. Comparison of the Li-gap positions in all six clusters shows that (1) the gap's position in T{sub eff} is independent of metallicity, but (2) higher-metallicity clusters have their gaps in higher-mass stars. In addition, the Li gap's position is shown not to evolve with age, which provides an important constraint for the non-standard depletion mechanisms that may create the Li gap.

  3. Molecular adsorption and metal-support interaction for transition-metal clusters in zeolites: NO adsorption on Pd(n) (n=1-6) clusters in mordenite.

    PubMed

    Grybos, Robert; Benco, Lubomir; Bucko, Tomas; Hafner, Jürgen

    2009-03-14

    The adsorption of NO molecules on Pd(n) clusters of varying size (n=1-6) located in the main channel of mordenite and the interaction of the metallic clusters with the zeolitic framework were investigated using ab initio density-functional calculations under periodic boundary conditions. The supported clusters are created by binding Pd(n) (2+) cations to the inner cavity of a deprotonated Al-exchanged zeolite with an Al/Si ratio of 1/11, such that a charge-neutral system is created. Compared to the highly symmetric structures of the gas-phase clusters, the clusters bound to the zeolitic framework undergo appreciable geometric distortions lowering their symmetry. The distortions are induced by strong interactions with "activated" framework oxygens located close to the charge-compensating Al/Si substitution sites, but the cluster forms also weaker bonds to "nonactivated" oxygen atoms. The interaction with the framework also affects the electronic and magnetic properties of the clusters. While in the gas phase all clusters (except the isolated Pd atom with a closed d(10) ground state) have a paramagnetic moment of 2mu(B), in the zeolite clusters with two to four atoms have zero magnetic moment, while the Pd(5) cluster has a magnetic moment of 2mu(B) and for the Pd(6) cluster, it is even enhanced to 4 mu(B) (but the magnetic energy differences relative to low-spin configurations are modest). Analysis of the magnetization densities shows that in all clusters with zero total moment (singlet ground state), there are sites with excess spin densities of opposite sign. The influence of the cluster-support interaction on the chemical properties of the clusters has been tested by the adsorption of NO molecules. The results demonstrate the interplay between the molecule-cluster and cluster-framework interactions, which can lead to an increase or decrease in the adsorption energy compared to NO on a gas-phase cluster. While on the gas-phase cluster adsorption in low

  4. Molecular adsorption and metal-support interaction for transition-metal clusters in zeolites: NO adsorption on Pdn (n=1-6) clusters in mordenite

    NASA Astrophysics Data System (ADS)

    Grybos, Robert; Benco, Lubomir; Bučko, Tomas; Hafner, Jürgen

    2009-03-01

    The adsorption of NO molecules on Pdn clusters of varying size (n =1-6) located in the main channel of mordenite and the interaction of the metallic clusters with the zeolitic framework were investigated using ab initio density-functional calculations under periodic boundary conditions. The supported clusters are created by binding Pdn2+ cations to the inner cavity of a deprotonated Al-exchanged zeolite with an Al/Si ratio of 1/11, such that a charge-neutral system is created. Compared to the highly symmetric structures of the gas-phase clusters, the clusters bound to the zeolitic framework undergo appreciable geometric distortions lowering their symmetry. The distortions are induced by strong interactions with "activated" framework oxygens located close to the charge-compensating Al/Si substitution sites, but the cluster forms also weaker bonds to "nonactivated" oxygen atoms. The interaction with the framework also affects the electronic and magnetic properties of the clusters. While in the gas phase all clusters (except the isolated Pd atom with a closed d10 ground state) have a paramagnetic moment of 2μB, in the zeolite clusters with two to four atoms have zero magnetic moment, while the Pd5 cluster has a magnetic moment of 2μB and for the Pd6 cluster, it is even enhanced to 4μB (but the magnetic energy differences relative to low-spin configurations are modest). Analysis of the magnetization densities shows that in all clusters with zero total moment (singlet ground state), there are sites with excess spin densities of opposite sign. The influence of the cluster-support interaction on the chemical properties of the clusters has been tested by the adsorption of NO molecules. The results demonstrate the interplay between the molecule-cluster and cluster-framework interactions, which can lead to an increase or decrease in the adsorption energy compared to NO on a gas-phase cluster. While on the gas-phase cluster adsorption in low-coordination sites (vertex or

  5. Theoretical research program to study transition metal trimers and embedded clusters

    NASA Technical Reports Server (NTRS)

    Walch, Stephen P.

    1987-01-01

    The results of ab-initio calculations are reported for (1) small transition metal clusters and (2) potential energy surfaces for chemical reactions important in hydrogen combustion and high temperature air chemistry.

  6. Theoretical research program to study transition metal trimers and embedded clusters

    NASA Technical Reports Server (NTRS)

    Walch, S. P.

    1984-01-01

    Small transition metal clusters were studied at a high level of approximation, including all the valence electrons in the calculation and extensive electron correlation, in order to understand the electronic structure of these small metal clusters. By comparison of dimers, trimers, and possibly higher clusters, the information obtained was used to provide insights into the electronic structure of bulk transition metals. Small metal clusters are currently of considerable experimental interest and some information is becomming available both from matrix electron spin resonance studies and from gas phase spectroscopy. Collaboration between theorists and experimentalists is thus expected to be especially profitable at this time since there is some experimental information which can serve to guide the theoretical work.

  7. 25. Steenbock symposium -- Biosynthesis and function of metal clusters for enzymes: Proceedings

    SciTech Connect

    1997-12-31

    This symposium was held June 10--14, 1997 in Madison, Wisconsin. The purpose of this conference was to provide a multidisciplinary forum for exchange of state-of-the-art information on biochemistry of enzymes that have an affinity for metal clusters. Attention is focused on the following: metal clusters involved in energy conservation and remediation; tungsten, molybdenum, and cobalt-containing enzymes; Fe proteins, and Mo-binding proteins; nickel enzymes; and nitrogenase.

  8. Mixed protein-templated luminescent metal clusters (Au and Pt) for H2O2 sensing

    PubMed Central

    2013-01-01

    A simple and cost-effective method to synthesize the luminescent noble metal clusters (Au and Pt) in chicken egg white aqueous solution at room temperature is reported. The red-emitting Au cluster is used as fluorescent probe for sensitive detection of H2O2. PMID:23601828

  9. Supersonic metal cluster beams of refractory metals: Spectral investigations of ultracold Mo2

    NASA Astrophysics Data System (ADS)

    Hopkins, J. B.; Langridge-Smith, P. R. R.; Morse, M. D.; Smalley, R. E.

    1983-02-01

    A novel technique involving pulsed laser vaporization of the bulk metal within a pulsed supersonic nozzle has been shown to successfully produce ultracold bare metal clusters of even the most refractory of metals, tungsten and molybdenum. Clusters of up to 25 atoms may be readily prepared using this technique. Mass-selective resonant two-photon ionization spectra of Mo2 produced in this fashion show that the dimer is efficiently cooled in the expansion Ttrans<6 K, Trot˜5 K, and Tvib˜325 K. We have rotationally resolved the A 1Σ+u←X 1Σ+g (0-0) band for 92Mo2 and determined the bond length in the ground and excited states to be 1.940±0.009 and 1.937±0.008 Å, respectively. This confirms and extends the analysis of Efremov et al. [J. Mol. Spectrosc. 73, 40 (1970)] who prepared 98Mo2 by flash photolysis of isotopically pure Mo(CO)6. We have also observed the (1-1), (2-2), and (3-3) sequence bands which together with the ground state data of Efremov et al. determine vibrational constants ω'e=449.0±0.2 cm-1 and ωex'e=2.3±0.2 cm-1 for the A 1Σ+u state. The lifetime of the A 1Σ+u v=0 state of Mo2 has been measured to be 18±3 ns by time-delayed two-photon ionization. The ionization potential of Mo2 is found to be less than 6.42 eV (compared to 7.10 eV for atomic Mo) indicating a substantially stronger chemical bond in Mo+2 than in Mo2. A discussion of the electronic structure of Mo2 and the implications of these findings for bonding in other transition metal dimers is also presented.

  10. Particle clustering and dielectric enhancement in percolating metal-insulator composites

    NASA Astrophysics Data System (ADS)

    Doyle, William T.

    1995-11-01

    An effective cluster model has been developed [Phys. Rev. B 42, 9319 (1990)] that treats a disordered suspension of monodisperse metal spheres as a mixture of isolated spheres and close-packed spherical clusters of spheres using the Clausius-Mossotti or Maxwell equations. The effective cluster model is adapted to such suspensions with a random intermingled cluster topology using Bruggemann's symmetrical equation. Model susceptibilities for the two cluster topologies are contrasted with one another and compared with experiments. Guillien's permittivity measurements [Ann. Phys. (Paris) Ser. 11 16, 205 (1941)] and Turner's conductivity measurements [Chem. Eng. Sci. 31, 487 (1976)] exemplify nonpercolating island topology suspensions. The permittivity measurements of Grannan, Garland, and Tanner [Phys. Rev. Lett. 46, 375 (1981)] exemplify percolating random topology clusters. The models for both cluster topologies are in excellent agreement with experiment over the entire accessible range of volume loading.

  11. The LAMOST Spectroscopic Survey of Star Clusters in M31. II. Metallicities, Ages, and Masses

    NASA Astrophysics Data System (ADS)

    Chen, Bingqiu; Liu, Xiaowei; Xiang, Maosheng; Yuan, Haibo; Huang, Yang; Shi, Jianrong; Fan, Zhou; Huo, Zhiying; Wang, Chun; Ren, Juanjuan; Tian, Zhijia; Zhang, Huawei; Liu, Gaochao; Cao, Zihuang; Zhang, Yong; Hou, Yonghui; Wang, Yuefei

    2016-08-01

    We select from Paper I a sample of 306 massive star clusters observed with the Large Sky Area Multi–Object Fibre Spectroscopic Telescope (LAMOST) in the vicinity fields of M31 and M33, and determine their metallicities, ages, and masses. Metallicities and ages are estimated by fitting the observed integrated spectra with stellar synthesis population (SSP) models with a pixel–to–pixel spectral fitting technique. Ages for most young clusters are also derived by fitting the multi–band photometric measurements with model spectral energy distributions (SEDs). The estimated cluster ages span a wide range, from several million years to the age of the universe. The numbers of clusters younger and older than 1 Gyr are, respectively, 46 and 260. With ages and metallicities determined, cluster masses are then estimated by comparing the multi–band photometric measurements with SSP model SEDs. The derived masses range from ∼ {10}3 to ∼ {10}7 M ⊙, peaking at ∼ {10}4.3 and ∼ {10}5.7 M ⊙ for young (\\lt 1 Gyr) and old (\\gt 1 Gyr) clusters, respectively. Our estimated metallicities, ages, and masses are in good agreement with available literature values. Old clusters richer than [Fe/H] ∼ ‑0.7 dex have a wide range of ages. Those poorer than [Fe/H] ∼ ‑0.7 dex seem to be composed of two groups, as previously found for Galactic globular clusters—one of the oldest ages with all values of metallicity down to ∼ -2 dex and another with metallicity increasing with decreasing age. The old clusters in the inner disk of M 31 (0–30 kpc) show a clear metallicity gradient measured at ‑0.038 ± 0.023 dex kpc‑1.

  12. The LAMOST Spectroscopic Survey of Star Clusters in M31. II. Metallicities, Ages, and Masses

    NASA Astrophysics Data System (ADS)

    Chen, Bingqiu; Liu, Xiaowei; Xiang, Maosheng; Yuan, Haibo; Huang, Yang; Shi, Jianrong; Fan, Zhou; Huo, Zhiying; Wang, Chun; Ren, Juanjuan; Tian, Zhijia; Zhang, Huawei; Liu, Gaochao; Cao, Zihuang; Zhang, Yong; Hou, Yonghui; Wang, Yuefei

    2016-08-01

    We select from Paper I a sample of 306 massive star clusters observed with the Large Sky Area Multi–Object Fibre Spectroscopic Telescope (LAMOST) in the vicinity fields of M31 and M33, and determine their metallicities, ages, and masses. Metallicities and ages are estimated by fitting the observed integrated spectra with stellar synthesis population (SSP) models with a pixel–to–pixel spectral fitting technique. Ages for most young clusters are also derived by fitting the multi–band photometric measurements with model spectral energy distributions (SEDs). The estimated cluster ages span a wide range, from several million years to the age of the universe. The numbers of clusters younger and older than 1 Gyr are, respectively, 46 and 260. With ages and metallicities determined, cluster masses are then estimated by comparing the multi–band photometric measurements with SSP model SEDs. The derived masses range from ˜ {10}3 to ˜ {10}7 M ⊙, peaking at ˜ {10}4.3 and ˜ {10}5.7 M ⊙ for young (\\lt 1 Gyr) and old (\\gt 1 Gyr) clusters, respectively. Our estimated metallicities, ages, and masses are in good agreement with available literature values. Old clusters richer than [Fe/H] ˜ ‑0.7 dex have a wide range of ages. Those poorer than [Fe/H] ˜ ‑0.7 dex seem to be composed of two groups, as previously found for Galactic globular clusters—one of the oldest ages with all values of metallicity down to ˜ -2 dex and another with metallicity increasing with decreasing age. The old clusters in the inner disk of M 31 (0–30 kpc) show a clear metallicity gradient measured at ‑0.038 ± 0.023 dex kpc‑1.

  13. One-dimensional fast migration of vacancy clusters in metals

    SciTech Connect

    Matsukawa, Yoshitaka; Zinkle, Steven J

    2007-01-01

    The migration of point defects, e.g. crystal lattice vacancies and self-interstitial atoms (SIAs), typically occurs through three-dimensional (3-D) random walk. However, when vacancies and SIAs agglomerate with like defects forming clusters, the migration mode may change. Recently, atomic-scale computer simulations using molecular dynamics (MD) codes have reported that nanometer-sized two-dimensional (2-D) clusters of SIAs exhibit one-dimensional (1-D) fast migration1-7. The 1-D migration mode transports the entire cluster containing several tens of SIAs with a mobility comparable to single SIAs3. This anisotropic migration of SIA clusters can have a significant impact on the evolution of a material fs neutron-irradiation damage microstructure, which dominates the material fs lifetime in nuclear reactor environments8-9. This is also proposed to be a key physical mechanism for the self-organization of nanometer-sized sessile vacancy cluster arrays10-13. Given these findings for SIA clusters, a fundamental question is whether the 1-D migration mode is also possible for 2-D clusters of vacancies. Preceding MD results predicted that 1-D migration of vacancy clusters is possible in body-centered cubic (bcc) iron, but not in face-centered cubic (fcc) copper2. Previous experimental studies have reported 1-D migration of SIA clusters14, but there have been no observations of 1-D vacancy cluster migration. Here we present the first experimental transmission electron microscopy (TEM) dynamic observation demonstrating the 1-D migration of vacancy clusters in fcc gold. It was found that the mobility of the vacancy clusters via the 1-D migration is much higher than single vacancies via 3-D random walk and comparable to single SIAs via 3-D random walk. Hence, the mobility of the glissile clusters is not associated with the character of their constituent point defects. Dynamic conversion of a planar vacancy loop into a 3-D stacking fault tetrahedron geometry was also observed.

  14. Metal cluster structures and properties from Born-Oppenheimer molecular dynamics

    SciTech Connect

    Calaminici, Patrizia Köster, Andreas M. Vásquez-Pérez, José Manuel Martínez, Gabriel Ulises Gamboa

    2015-01-22

    Density functional theory (DFT) Born-Oppenheimer molecular dynamics (BOMD) simulations of metal clusters are presented. The calculations have been performed with the deMon2k [1] code employing all-electron basis sets and local and non-local functionals. The capability to perform reasonable long (∼ 100 ps) first-principle BOMD simulations in order to explore potential energy landscape of metallic clusters will be presented [2,3]. The evolution of the cluster structures and properties, such as polarizability and heat capacity, with temperature is discussed.

  15. Metal etching with reactive gas cluster ion beams using pickup cell

    SciTech Connect

    Toyoda, Noriaki; Yamada, Isao

    2012-11-06

    Mixed gas cluster ion beams were formed using pickup cell for metal etching. O{sub 2} neutral clusters pick up acetic acid and formed mixed cluster beam. By using O{sub 2}-GCIB with acetic acid, enhancement of Cu etching was observed. Because of dense energy deposition by GCIB, etching of Cu proceeds by CuO formation, enhancement of chemical reaction with acetic acid and desorption of etching products. Surface roughening was not observed on poly crystalline Cu because of the small dependence of etching rate on crystal orientation. Halogen free and low-temperature metal etching with GCIB using pickup cell is possible.

  16. The old, massive, metal rich open cluster NGC 6791

    NASA Astrophysics Data System (ADS)

    Carraro, Giovanni

    2015-08-01

    NGC~6791 is a rich open cluster that attracted a lot of attention in the last decade. Recent estimates indicate that the mass is even larger, around 5000\\,$\\mathrm{M}_{\\odot}$. This is quite remarkable: the cluster is in fact 8\\,Gyr old, while the typical dissolution time for Galactic open clusters is a few Myr only. This might imply that the cluster managed to survive so long either because its original mass was much larger, or because it moved along a preferential orbit. In any case, such combination of old age and large mass is unique among Galactic open clusters, especially for clusters located in the inner regions of the Galactic disk. This is not the only special property of NGC 6791. Its abundance in iron is [Fe/H] $\\sim$ +0.40. again unique among Galactic star clusters of the same age range. Significant dispersions in various elements have been detected, that are not routinely found in Galactic open clusters. The combined UV flux of the few hot HB stars makes the cluster the closest proxy of an elliptical galaxy. This surprising result might indeed indicate that NGC 6791 was massive enough at origin to experience a strong burst of star formation and a fast enrichment.This pletora of unique properties renders NGC 6791 an extremely important object to study and understand.How and where could such a stellar system have formed? Is NGC 6791 just an open cluster? Did it form close to the bulge? How could have survived in the adverse, high-density, environment of the inner Galactic disk?These are difficult questions to answer to, of course. One of the still missing key observational evidence is whether the cluster suffered from tidal interaction, that could have significantly decreased its mass. We find such evidences, and use them as an argument to support a scenario in which the cluster formed as a massive object. We also estimate, using approximate analytic description based on available $N$-body models, how much mass NGC~6791 lost, and which was its

  17. Development of metal cluster-based energetic materials at NSWC-IHD

    NASA Astrophysics Data System (ADS)

    Lightstone, James; Stoltz, Chad; Wilson, Rebecca M.; Horn, Jillian M.; Hooper, Joe; Mayo, Dennis; Eichhorn, Bryan; Bowen, Kit H.; White, Michael G.

    2012-03-01

    Current research efforts at NSWC-IHD are utilizing gas-phase molecular beam studies, theoretical calculations, and condensed-phase production methods to identify novel metal cluster systems in which passivated metal 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 a good passivating ligand for these cluster systems. To date, small amounts of a metal-based compound with a subunit containing four aluminum atoms and four Cp* ligands has been produced and was characterized using DSC and TGA. Results indicate this cluster material is more reactive than micron- and nano-sized aluminum. However lack of stability in air precludes it from being a viable replacement for current aluminum particles. Volumetric heat of combustion of Al50Cp*12 was determined using thermodynamic data obtained from first principles calculations. The Al50 cluster is found to have a heat of combustion near 60% that of pure aluminum.

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

    DOE PAGESBeta

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

    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 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. Suchmore » 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.« less

  19. Theoretical research program to study transition metal trimers and embedded clusters

    NASA Technical Reports Server (NTRS)

    Walch, S. P.

    1985-01-01

    Small transition metal clusters at a high level of approximation i.e. including all the valence electrons in the calculation and also including extensive electron correlation were studied. Perhaps the most useful end result of these studies is the qualitative information about the electronic structure of these small metal clusters, including the nature of the bonding. The electronic structure studies of the small clusters are directly applicable to problems in catalysis. From comparison of dimers, trimers and possibly higher clusters, it is possible to extrapolate the information obtained to provide insights into the electronic structure of bulk transition metals and their interaction with other atoms and molecules at both surface and interior locations.

  20. Thermal expansion in small metal clusters and its impact on the electric polarizability

    PubMed

    Kummel; Akola; Manninen

    2000-04-24

    The thermal expansion coefficients of Na(N) clusters with 8clusters are obtained from ab initio Born-Oppenheimer local-density-approximation molecular dynamics. Thermal expansion of small metal clusters is considerably larger than that in the bulk and is size dependent. We demonstrate that the average static electric dipole polarizability of Na clusters depends linearly on the mean interatomic distance and only to a minor extent on the detailed ionic configuration when the overall shape of the electron density is enforced by electronic shell effects. Taking thermal expansion into account brings theoretical and experimental polarizabilities into quantitative agreement. PMID:11019216

  1. Sputtered metal and silicon cluster ions: collision-induced fragmentation and neutralization

    NASA Astrophysics Data System (ADS)

    Begemann, W.; Hector, R.; Liu, Y. Y.; Tiggesbäumker, J.; Meiwes-Broer, K. H.; Lutz, H. O.

    1989-03-01

    Mass separated metal and silicon cluster ion beams M{/n +, -} are produced by sputtering and undergo fragmenting and/or neutralizing collisions at different kinetic energies (100 1800 eV) in Ar and SF6. Fragment patterns induced by rare gas collisions open a way to determine ionization potentials and electron affinities of clusters. These values are compared to known experimental and theoretical data. For negatively charged clusters the absorption in gas targets is mainly due to neutralization, the cross sections varying with cluster material, number of atoms and collision partner from 10 Å2 to about 50 Å2.

  2. Introduction: advances and opportunities in cluster research. [Neutral (metal) and ionic clusters

    SciTech Connect

    Castleman, A.W. Jr.

    1983-01-01

    Examples of neutral and ionic clusters include these in the upper and lower atmosphere, interstellar grain formation, combustion, radiation physics and chemistry, surface bombardment, fission product transport in reactors, corrosion, etc. This paper is a brief overview of some recent developments in cluster research. (DLC)

  3. Inhomogeneous halo collapse and early Galactic chemical evolution - Globular cluster metallicities

    NASA Technical Reports Server (NTRS)

    Malinie, G.; Hartmann, D. H.; Mathews, G. J.

    1991-01-01

    A new solution to the observed Galactic globular cluster metallicity distribution is proposed by considering inhomogeneous collapse of a centrally condensed proto-Galaxy. In contrast to the standard one-zone model, it is shown that, for inhomogeneous models, the metallicity distribution can be reproduced without the need to decrease the nucleosynthetic yield for metal-poor stars. Chemical evolution in free fall is calculated analytically. A hybrid hydroparticle code is developed to study the effect of supernova induced pressure.

  4. Age and metallicity of star clusters in the Small Magellanic Cloud from integrated spectroscopy

    NASA Astrophysics Data System (ADS)

    Dias, Bruno; Coelho, Paula; Kerber, Leandro; Barbuy, Beatriz; Idiart, Thais

    2010-04-01

    Analysis of integrated spectra of star clusters in the Magellanic Clouds can bring important information for studies on the chemical evolution of the Clouds. The aim of the present work is to derive ages and metallicities from integrated spectra of 15 star clusters in the Small Magellanic Cloud (SMC), some of them not studied so far. Making use of a full spectrum fitting technique, we compared the integrated spectra of the sample clusters to three different sets of single stellar population models available in the literature. We derived ages and metallicities for the sample clusters employing the codes STARLIGHT and ULySS. Out of the 15 clusters in our sample, 9 are old/intermediate age clusters and 6 are young clusters. We point out the results for the newly identified as old/intermediate age clusters HW1, NGC 152, Lindsay 3 and 11. We also confirm old ages for NGC 361, NGC 419 and Kron 3, and the oldest well-known SMC cluster NGC 121.

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

    SciTech Connect

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

    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-the 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

  6. Full spectral fitting of Milky Way and M 31 globular clusters: ages and metallicities

    NASA Astrophysics Data System (ADS)

    Cezario, E.; Coelho, P. R. T.; Alves-Brito, A.; Forbes, D. A.; Brodie, J. P.

    2013-01-01

    Context. The formation and evolution of disk galaxies are long standing questions in astronomy. Understanding the properties of globular cluster systems can lead to important insights on the evolution of its host galaxy. Aims: We aim to obtain the stellar population parameters - age and metallicity - of a sample of M 31 and Galactic globular clusters. Studying their globular cluster systems is an important step towards understanding their formation and evolution in a complete way. Methods: Our analysis employs a modern pixel-to-pixel spectral fitting technique to fit observed integrated spectra to updated stellar population models. By comparing observations to models we obtain the ages and metallicities of their stellar populations. We apply this technique to a sample of 38 globular clusters in M 31 and to 41 Galactic globular clusters, used as a control sample. Results: Our sample of M 31 globular clusters spans ages from 150 Myr to the age of the Universe. Metallicities [Fe/H] range from -2.2 dex to the solar value. The age-metallicity relation obtained can be described as having two components: an old population with a flat age-[Fe/H] relation, possibly associated with the halo and/or bulge, and a second one with a roughly linear relation between age and metallicity, higher metallicities corresponding to younger ages, possibly associated with the M 31 disk. While we recover the very well known Galactic GC metallicity bimodality, our own analysis of M 31's metallicity distribution function (MDF) suggests that both GC systems cover basically the same [Fe/H] range yet M 31's MDF is not clearly bimodal. These results suggest that both galaxies experienced different star formation and accretion histories. Table 4 is available in electronic form at http://www.aanda.org

  7. Removing Cool Cores and Central Metallicity Peaks in Galaxy Clusters with Powerful Active Galactic Nucleus Outbursts

    NASA Astrophysics Data System (ADS)

    Guo, Fulai; Mathews, William G.

    2010-07-01

    Recent X-ray observations of galaxy clusters suggest that cluster populations are bimodally distributed according to central gas entropy and are separated into two distinct classes: cool core (CC) and non-cool core (NCC) clusters. While it is widely accepted that active galactic nucleus (AGN) feedback plays a key role in offsetting radiative losses and maintaining many clusters in the CC state, the origin of NCC clusters is much less clear. At the same time, a handful of extremely powerful AGN outbursts have recently been detected in clusters, with a total energy ~1061-1062 erg. Using two-dimensional hydrodynamic simulations, we show that if a large fraction of this energy is deposited near the centers of CC clusters, which is likely common due to dense cores, these AGN outbursts can completely remove CCs, transforming them to NCC clusters. Our model also has interesting implications for cluster abundance profiles, which usually show a central peak in CC systems. Our calculations indicate that during the CC to NCC transformation, AGN outbursts efficiently mix metals in cluster central regions and may even remove central abundance peaks if they are not broad enough. For CC clusters with broad central abundance peaks, AGN outbursts decrease peak abundances, but cannot effectively destroy the peaks. Our model may simultaneously explain the contradictory (possibly bimodal) results of abundance profiles in NCC clusters, some of which are nearly flat, while others have strong central peaks similar to those in CC clusters. A statistical analysis of the sizes of central abundance peaks and their redshift evolution may shed interesting insights on the origin of both types of NCC clusters and the evolution history of thermodynamics and AGN activity in clusters.

  8. Growth modes of thin films of ligand-free metal clusters

    SciTech Connect

    Dollinger, A.; Strobel, C. H.; Bleuel, H.; Marsteller, A.; Gantefoer, G.; Fairbrother, D. H.; Tang, Xin; Bowen, K. H.; Kim, Young Dok

    2015-05-21

    Size-selected Mo{sub n}{sup −}, W{sub n}{sup −}, and Fe{sub n}{sup −} cluster anions are deposited on a weakly interacting substrate (highly oriented pyrolytic graphite) and studied ex-situ using atomic force microscopy. Depending on size, three growth modes can be distinguished. Very small clusters consisting of less than 10–30 atoms behave similar to atoms and coalesce into 3-dimensional bulk-like islands. Medium sized clusters consisting of hundreds of atoms do not coalesce and follow a Stanski-Krastanov growth pattern. At low coverage, an almost perfect monolayer is formed. This is a new finding different from all previous studies on deposited metal clusters. For clusters with several thousands of atoms, the growth pattern again changes. At low coverage, the substrate is dotted with individual clusters, while at high coverage, the surface becomes extremely rough.

  9. Clusters on surface and embedded in a matrix: comparison between covalent and metallic species

    SciTech Connect

    Broyer, M.; Cottancin, E.; Lerme, J.; Palpant, B.; Pellarin, M.; Ray, C.; Vialle, J. L.; Keghelian, P.; Melinon, P.; Perez, A.; Prevel, B.; Treilleux, M.

    1997-06-20

    The free clusters obtained by the molecular beam technique exhibit original geometric structures. It appears interesting to use these clusters as elementary bricks to build new materials or cluster assembled solids. For this purpose, we use the so called Low Energy Cluster Beam Deposition (LECBD). This technique is applied to different kinds of materials. For covalent species, we observed the memory of the free clusters properties for carbon but also for silicon or silicon carbide. On the contrary for metals, the structure of the grain is the bulk structure, but the nanostructured morphology of the films is very interesting and may be controlled. These properties are illustrated for gold clusters. Their optical absorption spectra are measured and the evolution as a function of the size is discussed.

  10. Metallicity and star formation history of globular clusters

    NASA Astrophysics Data System (ADS)

    Zhang, Mei; Ma, Er

    1993-01-01

    Using population synthesis method, the star formation history in globular clusters has been studied. No single star formation mode with a constant star formation rate (SER) and an invariable initial mass function (IMF) can fit the observations of globular clusters. There are at least two stages of star formation: a pollution stage and a starburst stage. In the pollution stage, either the IMF is very peculiar (only form massive stars), or its SFR is so small that the low-mass stars form only a little. A starburst then follows to form most stars in the globular cluster. Within the framework of Fall and Rees'model, the collisions between warm clouds in the two phase medium may provide a suitable external cause to stimulate the starburst.

  11. Metallicity and star formation history of globular clusters

    NASA Astrophysics Data System (ADS)

    Zhang, Mei; Ma, Er

    1993-03-01

    Using population synthesis method, the star formation history in globular clusters has been studied. No single star formation mode with a constant star formation rate (SER) and an invariable initial mass function (IMF) can fit the observations of globular clusters. There are at least two stages of star formation: a pollution stage and a starburst stage. In the pollution stage, either the IMF is very peculiar (only form massive stars), or its SFR is so small that the low-mass stars form only a little. A starburst then follows to form most stars in the globular cluster. Within the framework of Fall and Rees' model, the collisions between warm clouds in the two phase medium may provide a suitable external cause to stimulate the starburst.

  12. Nanoscale electrodeposition of low-dimensional metal phases and clusters.

    PubMed

    Staikov, Georgi

    2016-08-01

    The present status of the problem of electrochemical formation of low-dimensional metal phases is reviewed. The progress in this field achieved in the last two decades is discussed on the basis of experimental results obtained in selected electrochemical systems with well defined single crystal substrates. The influence of crystallographic orientation and surface inhomogeneities of foreign substrates on the mechanism of formation and the atomic structure of two-dimensional (2D) metal phases in the underpotential deposition range is considered. The localized electrodeposition of metal nanoclusters on solid state surfaces applying the STM-tip as a nanoelectrode is demonstrated. PMID:27273215

  13. Dynamic screening of a localized hole during photoemission from a metal cluster

    PubMed Central

    2012-01-01

    Recent advances in attosecond spectroscopy techniques have fueled the interest in the theoretical description of electronic processes taking place in the subfemtosecond time scale. Here we study the coupled dynamic screening of a localized hole and a photoelectron emitted from a metal cluster using a semi-classical model. Electron density dynamics in the cluster is calculated with time-dependent density functional theory, and the motion of the photoemitted electron is described classically. We show that the dynamic screening of the hole by the cluster electrons affects the motion of the photoemitted electron. At the very beginning of its trajectory, the photoemitted electron interacts with the cluster electrons that pile up to screen the hole. Within our model, this gives rise to a significant reduction of the energy lost by the photoelectron. Thus, this is a velocity-dependent effect that should be accounted for when calculating the average losses suffered by photoemitted electrons in metals. PMID:22873820

  14. Low-metallicity Young Clusters in the Outer Galaxy. II. Sh 2-208

    NASA Astrophysics Data System (ADS)

    Yasui, Chikako; Kobayashi, Naoto; Saito, Masao; Izumi, Natsuko

    2016-05-01

    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 (10σ), which corresponds to a mass detection limit of ∼0.2 M⊙. 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 ∼0.5 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 (AV ∼ 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.

  15. Colorimetric recognition of different enzymology-concerning transition metals based on a hybrid cluster complex.

    PubMed

    Li, Shun-Hua; Yuan, Wen-Tao; Zheng, Hong; Xu, Jin-Gou

    2004-07-01

    A hybrid cluster complex, formed by chelating a chromogenic ligand to a [2Fe-2S] cluster, sensitively exhibited differential colorimetric responses towards Hg2+, Cd2+, Cr3+, Pb2, Sn2+, Cu2+, Zn2+, Fe3+ and Co2+ in water at physiological pH. Speciation of some of these metal elements, such as Cr(III) and Sn(IV), was also studied by UV/Vis absorption. PMID:15293390

  16. BVRI CCD photometry of the metal-poor globular cluster M68 (NGC 4590)

    SciTech Connect

    Alcaino, G.; Liller, W.; Alvarado, F.; Wenderoth, E. )

    1990-06-01

    BVRI photometry of the low metallicity globular cluster M68 (NGC 4590) was obtained with a CCD camera and the 2.2-m ESO telescope. The resulting BV color-magnitude diagrams are compared with the observations of McClure et al. (1987). The observations are also compared with theoretical isochrones, yielding a cluster age of 13 Gyr with a likely external uncertainty of 2 or 3 Gyr. 25 refs.

  17. Method of preparing size-selected metal clusters

    DOEpatents

    Elam, Jeffrey W.; Pellin, Michael J.; Stair, Peter C.

    2010-05-11

    The invention provides a method for depositing catalytic clusters on a surface, the method comprising confining the surface to a controlled atmosphere; contacting the surface with catalyst containing vapor for a first period of time; removing the vapor from the controlled atmosphere; and contacting the surface with a reducing agent for a second period of time so as to produce catalyst-containing nucleation sites.

  18. Width of the plasmon resonance in metal clusters

    NASA Astrophysics Data System (ADS)

    Montag, B.; Reinhard, P.-G.

    1995-05-01

    The width of the plasmon resonance in the clusters Na+9, Na+21, and Na+41 is investigated in the framework of the structure-averaged jellium model and compared with recent experimental data. The two leading mechanisms for the line broadening are fragmentation of the resonance into nearby 1ph states and splitting through thermal quadrupole fluctuations. The fragmentation becomes activated mainly through octupole fluctuations and it gives the dominating contribution to the width.

  19. On the interaction between perfect interstitial clusters and a vacancy in BCC, FCC and HCP metals

    SciTech Connect

    Puigvi, Mary Angels; Serra, Anna; de Diego, Nieves; Osetskiy, Yury N; Bacon, David J

    2004-01-01

    Point defects and defect clusters have been observed in metals irradiated by high-energy particles. Interactions of these defects between themselves and with existing microstructure features cause microstructure evolution and lead to changes in mechanical and physical properties of the irradiated materials. Models for prediction of radiation-induced changes should include details of reactions involving defects, and so in this paper we present the results of atomic-scale computer modelling of interactions between a cluster of self-interstitial atoms (SIAs) and a single vacancy in models of bcc, fcc and hcp metals. The vacancy is taken to lie on or within the glide prism of the cluster. This type of reaction is considered to be one of the most frequent because formation of SIA clusters, particularly glissile clusters, is commonly observed in high-energy displacement cascades in all metals. The interaction depends strongly on the dislocation nature of the cluster and therefore these interactions are different in the three crystal structures. Vacancy-SIA recombination, in particular, is inhibited by dissociation of the SIA loop on its glide prism.

  20. Synthesis and catalytic properties of metal clusters encapsulated within small-pore (SOD, GIS, ANA) zeolites.

    PubMed

    Goel, Sarika; Wu, Zhijie; Zones, Stacey I; Iglesia, Enrique

    2012-10-24

    The synthesis protocols for encapsulation of metal clusters reported here expand the diversity in catalytic chemistries made possible by the ability of microporous solids to select reactants, transition states, and products on the basis of their molecular size. We report a synthesis strategy for the encapsulation of noble metals and their oxides within SOD (Sodalite, 0.28 nm × 0.28 nm), GIS (Gismondine, 0.45 nm × 0.31 nm), and ANA (Analcime, 0.42 nm × 0.16 nm) zeolites. Encapsulation was achieved via direct hydrothermal synthesis for SOD and GIS using metal precursors stabilized by ammonia or organic amine ligands, which prevent their decomposition or precipitation as colloidal hydroxides at the conditions of hydrothermal synthesis (<380 K) and favor interactions between metal precursors and incipient aluminosilicate nuclei during self-assembly of microporous frameworks. The synthesis of ANA requires higher crystallization temperatures (~415 K) and high pH (>12), thereby causing precipitation of even ligand-stabilized metal precursors as hydroxides. As a result, encapsulation was achieved by the recrystallization of metal clusters containing GIS into ANA, which retained these metal clusters within voids throughout the GIS-ANA transformation. PMID:23016946

  1. Cage Opening of a Carborane Ligand by Metal Cluster Complexes.

    PubMed

    Adams, Richard D; Kiprotich, Joseph; Peryshkov, Dmitry V; Wong, Yuen Onn

    2016-05-01

    The reaction of Os3 (CO)10 (NCMe)2 with closo-o-C2 B10 H10 has yielded two interconvertible isomers Os3 (CO)9 (μ3 -4,5,9-C2 B10 H8 )(μ-H)2 (1 a) and Os3 (CO)9 (μ3 -3,4,8-C2 B10 H8 )(μ-H)2 (1 b) formed by the loss of the two NCMe ligands and one CO ligand from the Os3 cluster. Two BH bonds of the o-C2 B10 H10 were activated in its addition to the osmium cluster. A second triosmium cluster was added to the 1 a/1 b mixture to yield the complex Os3 (CO)9 (μ-H)2 (μ3 -4,5,9-μ3 -7,11,12-C2 B10 H7 )Os3 (CO)9 (μ-H)3 (2) that contains two triosmium triangles attached to the same carborane cage. When heated, 2 was transformed to the complex Os3 (CO)9 (μ-H)(μ3 -3,4,8-μ3 -7,11,12-C2 B10 H8 )Os3 (CO)9 (μ-H) (3) by a novel opening of the carborane cage with loss of H2 . PMID:26971388

  2. Temporal stability of magic-number metal clusters: beyond the shell closing model

    NASA Astrophysics Data System (ADS)

    Desireddy, Anil; Kumar, Santosh; Guo, Jingshu; Bolan, Michael D.; Griffith, Wendell P.; Bigioni, Terry P.

    2013-02-01

    The anomalous stability of magic-number metal clusters has been associated with closed geometric and electronic shells and the opening of HOMO-LUMO gaps. Despite this enhanced stability, magic-number clusters are known to decay and react in the condensed phase to form other products. Improving our understanding of their decay mechanisms and developing strategies to control or eliminate cluster instability is a priority, to develop a more complete theory of their stability, to avoid studying mixtures of clusters produced by the decay of purified materials, and to enable technology development. Silver clusters are sufficiently reactive to facilitate the study of the ambient temporal stability of magic-number metal clusters and to begin to understand their decay mechanisms. Here, the solution phase stability of a series of silver:glutathione (Ag:SG) clusters was studied as a function of size, pH and chemical environment. Cluster stability was found to be a non-monotonic function of size. Electrophoretic separations showed that the dominant mechanism involved the redistribution of mass toward smaller sizes, where the products were almost exclusively previously known cluster sizes. Optical absorption spectra showed that the smaller clusters evolved toward the two most stable cluster sizes. The net surface charge was found to play an important role in cluster stabilization although charge screening had no effect on stability, contrary to DLVO theory. The decay mechanism was found to involve the loss of Ag+ ions and silver glutathionates. Clusters could be stabilized by the addition of Ag+ ions and destabilized by either the addition of glutathione or the removal of Ag+ ions. Clusters were also found to be most stable in near neutral pH, where they had a net negative surface charge. These results provide new mechanistic insights into the control of post-synthesis stability and chemical decay of magic-number metal clusters, which could be used to develop design principles

  3. NONLINEAR COLOR-METALLICITY RELATIONS OF GLOBULAR CLUSTERS. V. NONLINEAR ABSORPTION-LINE INDEX VERSUS METALLICITY RELATIONS AND BIMODAL INDEX DISTRIBUTIONS OF M31 GLOBULAR CLUSTERS

    SciTech Connect

    Kim, Sooyoung; Yoon, Suk-Jin; Chung, Chul; Lee, Young-Wook; Caldwell, Nelson; Schiavon, Ricardo P.; Kang, Yongbeom; Rey, Soo-Chang

    2013-05-10

    Recent spectroscopy on the globular cluster (GC) system of M31 with unprecedented precision witnessed a clear bimodality in absorption-line index distributions of old GCs. Such division of extragalactic GCs, so far asserted mainly by photometric color bimodality, has been viewed as the presence of merely two distinct metallicity subgroups within individual galaxies and forms a critical backbone of various galaxy formation theories. Given that spectroscopy is a more detailed probe into stellar population than photometry, the discovery of index bimodality may point to the very existence of dual GC populations. However, here we show that the observed spectroscopic dichotomy of M31 GCs emerges due to the nonlinear nature of metallicity-to-index conversion and thus one does not necessarily have to invoke two separate GC subsystems. We take this as a close analogy to the recent view that metallicity-color nonlinearity is primarily responsible for observed GC color bimodality. We also demonstrate that the metallicity-sensitive magnesium line displays non-negligible metallicity-index nonlinearity and Balmer lines show rather strong nonlinearity. This gives rise to bimodal index distributions, which are routinely interpreted as bimodal metallicity distributions, not considering metallicity-index nonlinearity. Our findings give a new insight into the constitution of M31's GC system, which could change much of the current thought on the formation of GC systems and their host galaxies.

  4. Plasmon-Enhanced Multi-Ionization of Small Metal Clusters in Strong Femtosecond Laser Fields

    NASA Astrophysics Data System (ADS)

    Köller, L.; Schumacher, M.; Köhn, J.; Teuber, S.; Tiggesbäumker, J.; Meiwes-Broer, K. H.

    1999-05-01

    The multiply charging process of platinum cluster ions under intense field conditions show a strong dependence on the width of the femtosecond laser pulse. Increasing the pulse width from 140 to 600 fs while keeping the energy per pulse constant leads to an increase in the highest observed charge state z* of the ejected atoms from z* = 13 to z* = 20. This increased charging efficiency is explained by the evolution of the plasmon energy of the metal cluster upon the change in electron density during the Coulomb explosion process. Thus the time dependence of the charging of a cluster in an intense light field has been observed in real time.

  5. A study of rotating globular clusters. The case of the old, metal-poor globular cluster NGC 4372

    NASA Astrophysics Data System (ADS)

    Kacharov, N.; Bianchini, P.; Koch, A.; Frank, M. J.; Martin, N. F.; van de Ven, G.; Puzia, T. H.; McDonald, I.; Johnson, C. I.; Zijlstra, A. A.

    2014-07-01

    Context. NGC 4372 is a poorly studied old, very metal-poor globular cluster (GC) located in the inner Milky Way halo. Aims: We present the first in-depth study of the kinematic properties and derive the structural parameters of NGC 4372 based on the fit of a Plummer profile and a rotating, physical model. We explore the link between internal rotation to different cluster properties and together with similar studies of more GCs, we put these in the context of globular cluster formation and evolution. Methods: We present radial velocities for 131 cluster member stars measured from high-resolution FLAMES/GIRAFFE observations. Their membership to the GC is additionally confirmed from precise metallicity estimates. We build a velocity dispersion profile and a systemic rotation curve using this kinematic data set. Additionally, we obtain an elliptical number density profile of NGC 4372 based on optical images using a Markov chain Monte Carlo fitting algorithm. From this, we derive the cluster's half-light radius and ellipticity as rh = 3.44' ± 0.04' and ɛ = 0.08 ± 0.01. Finally, we give a physical interpretation of the observed morphological and kinematic properties of this GC by fitting an axisymmetric, differentially rotating, dynamical model. Results: Our results show that NGC 4372 has an unusually high ratio of rotation amplitude to velocity dispersion (1.2 vs. 4.5 km s-1) for its metallicity. This puts it in line, however, with two other exceptional, very metal-poor GCs: M 15 and NGC 4590. We also find a mild flattening of NGC 4372 in the direction of its rotation. Given its old age, this suggests that the flattening is indeed caused by the systemic rotation rather than tidal interactions with the Galaxy. Additionally, we estimate the dynamical mass of the GC Mdyn = 2.0 ± 0.5 × 105M⊙ based on the dynamical model, which constrains the mass-to-light ratio of NGC 4372 between 1.4 and 2.3 M⊙/L⊙, representative of an old, purely stellar population. Based on

  6. Controlled insulator-to-metal transformation in printable polymer composites with nanometal clusters

    NASA Astrophysics Data System (ADS)

    Sivaramakrishnan, Sankaran; Chia, Perq-Jon; Yeo, Yee-Chia; Chua, Lay-Lay; Ho, Peter K.-H.

    2007-02-01

    Although organic semiconductors have received the most attention, the development of compatible passive elements, such as interconnects and electrodes, is also central to plastic electronics. For this, ligand-protected metal-cluster films have been shown to anneal at low temperatures below 250∘C to highly conductive metal films, but they suffer from cracking and inadequate substrate adhesion. Here, we report printable metal-cluster-polymer nanocomposites that anneal to a controlled-percolation nanostructure without complete sintering of the metal clusters. This overcomes the previous challenges while still retaining the desired low transformation temperatures. Highly water- and alcohol-soluble gold clusters (75mgml-1) were synthesized and homogeneously dispersed into poly(3,4-ethylenedioxythiophene) to give a material with annealed d.c. conductivity tuneable between 10-4 and 105Scm-1. These composites can inject holes efficiently into all-printed polymer organic transistors. The insulator-metal transformation can also be electrically induced at 1MVcm-1, suggesting possible memory applications.

  7. Metal, Semiconductor, and Carbon Cluster Studies Including the Discovery and Characterization of Carbon -60: Buckminsterfullerene.

    NASA Astrophysics Data System (ADS)

    Heath, James Richard

    Experiments using the laser vaporization technique for production of metal clusters have been performed. The reactions of neutral metal clusters with various gases have been studied using a fast flow reactor. Dramatic reactivity variations were observed which depended on cluster size, metal, and reactant. A laser vaporization disc source has been developed for the study of semiconductor clusters. Some preliminary studies on neutral germanium and silicon clusters were performed. Their ionization potentials have been bracketed and the clusters were found to fragment by a fissioning process and to have long lived (100 nanoseconds) excited electronic states. A detailed study has been undertaken into carbon clusters. Laser synthesis of astrophysically important polyyne molecules such as H-C-(C-C)_{ rm 2n}-N has been done. Chains containing up to 22 carbon atoms are formed in a vaporized carbon and reactant gas plasma. A photophysically stable and chemically inert cluster, C_{60}, has been discovered and hypothesized to have the structure of a truncated icosahedron. All even clusters in the 60 atom size range were found to be inert to highly reactive gases, while odd clusters readily reacted. The results are consistent with a whole series (30-90 atoms) of closed cage-like structures. Closure of even clusters only is possible via the inclusion of twelve pentagons into a hexagonal network. Odd clusters show neither the photophysical nor chemical stability of the even clusters. A mechanism for the formation of spherical soot particles has been developed. Stable organometallic complexes of the formula C_{rm 2n}M (20 < n < 40 and M = La, Ba, Sr, Ca) have been laser synthesized. The dominant complex observed was C_{60}M ^+. These species are photophysically stable, chemically inert, and no C_{rm 2n}M_2^ecies were detected. The ultraviolet and visible absorption spectrum of C_{60} has been measured. Because excited electronic states are not expected to live long in a molecule

  8. 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.

  9. Phosphorus vacancy cluster model for phosphorus diffusion gettering of metals in Si

    SciTech Connect

    Chen, Renyu; Trzynadlowski, Bart; Dunham, Scott T.

    2014-02-07

    In this work, we develop models for the gettering of metals in silicon by high phosphorus concentration. We first performed ab initio calculations to determine favorable configurations of complexes involving phosphorus and transition metals (Fe, Cu, Cr, Ni, Ti, Mo, and W). Our ab initio calculations found that the P{sub 4}V cluster, a vacancy surrounded by 4 nearest-neighbor phosphorus atoms, which is the most favorable inactive P species in heavily doped Si, strongly binds metals such as Cu, Cr, Ni, and Fe. Based on the calculated binding energies, we build continuum models to describe the P deactivation and Fe gettering processes with model parameters calibrated against experimental data. In contrast to previous models assuming metal-P{sub 1}V or metal-P{sub 2}V as the gettered species, the binding of metals to P{sub 4}V satisfactorily explains the experimentally observed strong gettering behavior at high phosphorus concentrations.

  10. Polyoxometalate Cluster-Incorporated Metal-Organic Framework Hierarchical Nanotubes.

    PubMed

    Xu, Xiaobin; Chen, Shuangming; Chen, Yifeng; Sun, Hongyu; Song, Li; He, Wei; Wang, Xun

    2016-06-01

    A simple method to prepare metal-organic framework (MOF) nanotubes is developed by employing polyoxometalates (POMs) as modulators. The local structure of the MOF nanotubes is investigated combining XANES and EXAFS studies. These nanotubes show both an excellent catalytic performance in the detoxification of sulfur compounds in O2 atmosphere and a remarkable cycling stability as the anode material for lithium-ion batteries. PMID:27101564

  11. 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.

  12. Electronic structure and magnetism of transition metal doped Zn12O12 clusters: Role of defects

    NASA Astrophysics Data System (ADS)

    Ganguli, Nirmal; Dasgupta, Indra; Sanyal, Biplab

    2010-12-01

    We present a comprehensive study of the energetics and magnetic properties of ZnO clusters doped with 3d transition metals (TMs) using ab initio density functional calculations in the framework of generalized gradient approximation+Hubbard U (GGA+U) method. Our results within GGA+U for all 3d dopants except Ti indicate that antiferromagnetic interaction dominates in a neutral, defect-free cluster. Formation energies are calculated to identify the stable defects in the ZnO cluster. We have analyzed in details the role of these defects to stabilize ferromagnetism when the cluster is doped with Mn, Fe, and Co. Our calculations reveal that in the presence of charged defects the TM atoms residing at the surface of the cluster may have an unusual oxidation state, that plays an important role to render the cluster ferromagnetic. Defect induced magnetism in ZnO clusters without any TM dopants is also analyzed. These results on ZnO clusters may have significant contributions in the nanoengineering of defects to achieve desired ferromagnetic properties for spintronic applications.

  13. STAR CLUSTERS IN M33: UPDATED UBVRI PHOTOMETRY, AGES, METALLICITIES, AND MASSES

    SciTech Connect

    Fan, Zhou; De Grijs, Richard E-mail: grijs@pku.edu.cn

    2014-04-01

    The photometric characterization of M33 star clusters is far from complete. In this paper, we present homogeneous UBVRI photometry of 708 star clusters and cluster candidates in M33 based on archival images from the Local Group Galaxies Survey, which covers 0.8 deg{sup 2} along the galaxy's major axis. Our photometry includes 387, 563, 616, 580, and 478 objects in the UBVRI bands, respectively, of which 276, 405, 430, 457, and 363 do not have previously published UBVRI photometry. Our photometry is consistent with previous measurements (where available) in all filters. We adopted Sloan Digital Sky Survey ugriz photometry for complementary purposes, as well as Two Micron All Sky Survey near-infrared JHK photometry where available. We fitted the spectral-energy distributions of 671 star clusters and candidates to derive their ages, metallicities, and masses based on the updated PARSEC simple stellar populations synthesis models. The results of our χ{sup 2} minimization routines show that only 205 of the 671 clusters (31%) are older than 2 Gyr, which represents a much smaller fraction of the cluster population than that in M31 (56%), suggesting that M33 is dominated by young star clusters (<1 Gyr). We investigate the mass distributions of the star clusters—both open and globular clusters—in M33, M31, the Milky Way, and the Large Magellanic Cloud. Their mean values are log (M {sub cl}/M {sub ☉}) = 4.25, 5.43, 2.72, and 4.18, respectively. The fraction of open to globular clusters is highest in the Milky Way and lowest in M31. Our comparisons of the cluster ages, masses, and metallicities show that our results are basically in agreement with previous studies (where objects in common are available); differences can be traced back to differences in the models adopted, the fitting methods used, and stochastic sampling effects.

  14. Asymmetric partitioning of metals among cluster anions and cations generated via laser ablation of mixed aluminum/Group 6 transition metal targets.

    PubMed

    Waller, Sarah E; Mann, Jennifer E; Jarrold, Caroline Chick

    2013-02-28

    While high-power laser ablation of metal alloys indiscriminately produces gas-phase atomic ions in proportion to the abundance of the various metals in the alloy, gas-phase ions produced by moderate-power laser ablation sources coupled with molecular beams are formed by more complicated mechanisms. A mass spectrometric study that directly compares the mass distributions of cluster anions and cations generated from laser ablation of pure aluminum, an aluminum/molybdenum mixed target, and an aluminum/tungsten mixed target is detailed. Mass spectra of anionic species generated from the mixed targets showed that both tungsten and molybdenum were in higher abundance in the negatively charged species than in the target material. Mass spectra of the cationic species showed primarily Al(+) and aluminum oxide and hydroxide cluster cations. No molybdenum- or tungsten-containing cluster cations were definitively assigned. The asymmetric distribution of aluminum and Group 6 transition metals in cation and anion cluster composition is attributed to the low ionization energy of atomic aluminum and aluminum suboxide clusters. In addition, the propensity of both molybdenum and tungsten to form metal oxide cluster anions under the same conditions that favor metallic aluminum cluster anions is attributed to differences in the optical properties of the surface oxide that is present in the metal powders used to prepare the ablation targets. Mechanisms of mixed metal oxide clusters are considered. PMID:23413829

  15. Carbonyl clusters of transition metals on oxide supports as heterogeneous catalysts for hydrocarbon synthesis

    SciTech Connect

    Kuznetsov, B.N.; Koval`chuk, V.I.

    1995-05-01

    The methods of preparation of heterogeneous catalysts by immobilization of carbonyl clusters of transition metals on oxide supports, as well as the study of the state of supported compounds and their catalytic properties in CO hydrogenation and olefin hydroformulation are briefly reviewed.

  16. Optical response and gas sequestration properties of metal cluster supported graphene nanoflakes.

    PubMed

    Chakraborty, Debdutta; Chattaraj, Pratim Kumar

    2016-07-28

    The possibility of obtaining metal cluster (M3O(+), M = Li, Na, K) supported pristine, B-doped and BN-doped graphene nanoflakes (GR, BGR and BNGR, respectively) has been investigated by carrying out density functional theory (DFT) based calculations. Thermochemical analysis reveals the good stability of M3O(+)@GR/BGR/BNGR moieties. The dynamic stability of M3O(+)@GR/BGR/BNGR moieties is confirmed through an atom-centered density matrix propagation simulation at 298 K up to 500 fs. Orbital and electrostatic interactions play pivotal roles in stabilizing the metal-cluster supported graphene nanoflakes. The metal clusters lower the Fermi levels of the host nanoflakes and enable them to exhibit reasonably good optical response properties such as polarizability and static first hyperpolarizability. In particular, Na3O(+)/K3O(+)@BGR complexes exhibit very large first hyperpolarizability values at the static field limit. All the M3O(+)@BGR/BNGR moieties demonstrate broadband optical absorption encompassing the ultraviolet, visible as well as infrared domains. The metal-cluster supported graphene nanoflakes, in general, can sequestrate polar molecules, viz. CO, NO and CH3OH, in a thermodynamically more favorable way than GR, BGR and BNGR. In the adsorbed state, the CO, NO and CH3OH molecules, in general, attain an 'active' state as compared to their free counterparts. PMID:27346831

  17. A high-nuclearity metal-cyanide cluster [Mo6Cu14] with photomagnetic properties.

    PubMed

    Bridonneau, N; Chamoreau, L-M; Gontard, G; Cantin, J-L; von Bardeleben, J; Marvaud, V

    2016-06-21

    A high-nuclearity metal-cyanide cluster [Mo6Cu14] has been prepared and its photomagnetic properties investigated. The photoswitchable magnetic phenomenon observed is thermally reversible (T≈ 230 K). In the field of photomagnetism, [Mo6Cu14] represents a unique example of a nanocage and the highest nuclearity observed so far. PMID:27174703

  18. Glass formation and cluster evolution in the rapidly solidified monatomic metallic liquid Ta under high pressure

    NASA Astrophysics Data System (ADS)

    Jiang, Dejun; Wen, Dadong; Tian, Zean; Liu, Rangsu

    2016-12-01

    Molecular dynamics (MD) simulations have been performed to examine the glass formation and cluster evolution during the rapid solidification of monatomic metallic liquid Ta under high pressure. The atomic structures in the systems are characterized by the radical distribution function (RDF), Honeycutt-Anderson (H-A) bond-type index method and cluster-type index method (CTIM). It is observed that the defective icosahedra play the critical role in the formation of Ta monatomic metallic glasses (MGs) rather than (12 0 12 0) perfect icosahedra, which have been identified as the basic local atomic units in many multi-component MGs. With the increase of pressure P, the fraction of icosahedral type clusters decreases remarkably in Ta MGs, while the fraction of bcc type clusters rises evidently. The evolution of vitrification degree (DSRO or DMRO) of the rapidly cooled metal Ta system further reveals that a higher pressure P is disadvantageous to the formation of Ta monatomic MGs. The weaker glass forming ability (GFA) of liquid metal Ta obtained under higher pressure P can be contributed to the decrease of DSRO or DMRO which is induced by increasing high pressure P to some extent.

  19. BVRI CCD photometry of the metal-poor globular cluster NGC 4372

    SciTech Connect

    Alcaino, G.; Liller, W.; Alvarado, F.; Wenderoth, E. )

    1991-07-01

    BVRI CCD photometry is presented in two overlapping fields in the metal-poor globular cluster NGC 4372. The observations extend approximately 2 mag below the main-sequence turnoff to V about 21. By comparing the color-magnitude diagram (CMD) with those of clusters with similar metallicities, it is found that E(B-V) = 0.50 {plus minus} 0.03, and (m-M)v = 14.75 {plus minus} 0.06. Comparison with theoretical isochrones leads to a value E(B-V) = 0.53 {plus minus} 0.03. Comparison of the CMD with that of bright stars published by other authors yields a value for Delta V(TO-HB) = 3.3 {plus minus} 0.3. The weighted mean value of the age of the cluster, derived from the four colors, is 15 {plus minus} 4 Gyr (estimated external uncertainty). 17 refs.

  20. TOWARD THE GENERAL RED GIANT BRANCH SLOPE-METALLICITY-AGE CALIBRATION. I. METALLICITIES, AGES, AND KINEMATICS FOR EIGHT LARGE MAGELLANIC CLOUD CLUSTERS

    SciTech Connect

    Sharma, Saurabh; Borissova, J.; Kurtev, R.; Ivanov, V. D.; Geisler, D. E-mail: jura.borissova@uv.cl E-mail: vivanov@eso.org

    2010-03-15

    In this paper, we discuss the properties of color-magnitude diagrams, age, metallicity, and radial velocities of eight massive Large Magellanic Cloud (LMC) clusters using data taken from the FORS2 multiobject spectrograph at the 8.2 m Very Large Telescope/Unit Telescope 1. The strong near-infrared Ca II triplet lines of red giant branch stars obtained from the high signal-to-noise ratio spectra are used to determine the metallicity and radial velocity of cluster members. We report for the first time spectroscopically determined metallicity values for four clusters based on the mean [Fe/H] value of {approx}10 cluster members each. We found two concentrations in the distribution of ages of the target clusters. Six have ages between 0.8 Gyr and 2.2 Gyr and the other two, NGC 1754 and NGC 1786, are very old. The metallicity of the six intermediate-age clusters, with a mean age of 1.5 Gyr, is -0.49 with a scatter of only 0.04. This tight distribution suggests that a close encounter between the LMC and Small Magellanic Cloud may have caused not only the restart of cluster formation in the LMC but also the generation of the central bar. The metallicity for the two old clusters is similar to that of the other old, metal-poor LMC clusters. We find that the LMC cluster system exhibits disk-like rotation with no clusters appearing to have halo kinematics and there is no evidence of a metallicity gradient in the LMC, in contrast with the stellar population of the Milky Way and M33, where the metallicity decreases as galactocentric distance increases. The LMC's stellar bar may be the factor responsible for the dilution of any kind of gradient in the LMC.

  1. 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.

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

    SciTech Connect

    Smirnov, B. M.

    2015-10-15

    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.

  3. On the Nature of Bonding in Parallel Spins in Monovalent Metal Clusters.

    PubMed

    Danovich, David; Shaik, Sason

    2016-05-27

    As we approach the Lewis model centennial, it may be timely to discuss novel bonding motifs. Accordingly, this review discusses no-pair ferromagnetic (NPFM) bonds that hold together monovalent metallic atoms using exclusively parallel spins. Thus, without any traditional electron-pair bonds, the bonding energy per atom in these clusters can reach 20 kcal mol(-1). This review describes the origins of NPFM bonding using a valence bond (VB) analysis, which shows that this bonding motif arises from bound triplet electron pairs that are delocalized over all the close neighbors of a given atom in the cluster. The VB model accounts for the tendency of NPFM clusters to assume polyhedral shapes with rather high symmetry and for the very steep rise of the bonding energy per atom. The advent of NPFM clusters offers new horizons in chemistry of highly magnetic species sensitive to magnetic and electric fields. PMID:27070320

  4. 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

    2016-08-01

    We investigated the stellar density substructures around four metal-poor globular clusters (NGC 6266, NGC 6626, NGC 6642, and NGC 6723) in the Galactic bulge. Wide-field near-infrared (JHK s ) imaging data were obtained from WFCAM of UKIRT telescope. Field stars contamination around the globular clusters was reduced by using a statistical weighted filtering algorithm. Tidal stripping stellar substructures in the form of tidal tail (NGC 6266 and NGC 6626) or small density lobes/chunk (NGC 6642 and NGC 6723) were found around the four globular clusters in the two-dimensional density contour maps. We also find the overdensity features, which deviate from the theoretical models, in the outer region of radial density profiles. The observed results imply that the four globular clusters have experienced a strong tidal force or the bulge/disk shock effect of the Galaxy.

  5. Cluster ion beam assisted fabrication of metallic nanostructures for plasmonic applications

    NASA Astrophysics Data System (ADS)

    Saleem, Iram; Tilakaratne, Buddhi P.; Li, Yang; Bao, Jiming; Wijesundera, Dharshana N.; Chu, Wei-Kan

    2016-08-01

    We report a high-throughput, single-step method for fabricating rippled plasmonic nanostructure arrays via self-assembly induced by oblique angle cluster ion beam irradiation of metal surfaces. This approach does not require lithographic or chemical processes and has the prominent advantage of possible large surface area coverage and applicability to different starting materials. The polarization dependent plasmonic property of the gold nano-ripple is due to their one dimension structure. The localized plasmon resonance frequency of synthesized nano-ripple arrays is tunable by changing nano-ripple dimensions that can be engineered by changing the cluster ion beam irradiation parameters. In this specific case presented, using 30 keV Ar-gas cluster ion beam, we fabricate gold nano-ripple arrays that show localized plasmon resonance in the visible range through near IR range, tunable by varying cluster ion irradiation fluence.

  6. On the Nature of Bonding in Parallel Spins in Monovalent Metal Clusters

    NASA Astrophysics Data System (ADS)

    Danovich, David; Shaik, Sason

    2016-05-01

    As we approach the Lewis model centennial, it may be timely to discuss novel bonding motifs. Accordingly, this review discusses no-pair ferromagnetic (NPFM) bonds that hold together monovalent metallic atoms using exclusively parallel spins. Thus, without any traditional electron-pair bonds, the bonding energy per atom in these clusters can reach 20 kcal mol-1. This review describes the origins of NPFM bonding using a valence bond (VB) analysis, which shows that this bonding motif arises from bound triplet electron pairs that are delocalized over all the close neighbors of a given atom in the cluster. The VB model accounts for the tendency of NPFM clusters to assume polyhedral shapes with rather high symmetry and for the very steep rise of the bonding energy per atom. The advent of NPFM clusters offers new horizons in chemistry of highly magnetic species sensitive to magnetic and electric fields.

  7. Evolution of long-lived globular cluster stars. II. Sodium abundance variations on the asymptotic giant branch as a function of globular cluster age and metallicity

    NASA Astrophysics Data System (ADS)

    Charbonnel, Corinne; Chantereau, William

    2016-02-01

    Context. Long-lived stars in globular clusters exhibit chemical peculiarities with respect to their halo counterparts. In particular, sodium-enriched stars are identified as belonging to a second stellar population born from cluster material contaminated by the hydrogen-burning ashes of a first stellar population. Their presence and numbers in different locations of the colour-magnitude diagram provide important constraints on the self-enrichment scenarios. In particular, the ratio of Na-poor to Na-rich stars on the asymptotic giant branch (AGB) has recently been found to vary strongly from cluster to cluster (NGC 6752, 47 Tuc, and NGC 2808), while it is relatively constant on the red giant branch (RGB). Aims: We investigate the impact of both age and metallicity on the theoretical sodium spread along the AGB within the framework of the fast rotating massive star (FRMS) scenario for globular cluster self-enrichment. Methods: We computed evolution models of low-mass stars for four different metallicities ([Fe/H] = -2.2, -1.75, -1.15, -0.5) assuming the initial helium-sodium abundance correlation for second population stars derived from the FRMS models and using mass loss prescriptions on the RGB with two realistic values of the free parameter in the Reimers formula. Results: Based on this grid of models we derive the theoretical critical initial mass for a star born with a given helium, sodium, and metal content that determines whether that star will climb or not the AGB. This allows us to predict the maximum sodium content expected on the AGB for globular clusters as a function of both their metallicity and age. We find that (1) at a given metallicity, younger clusters are expected to host AGB stars exhibiting a larger sodium spread than older clusters and (2) at a given age, higher sodium dispersion along the AGB is predicted in the most metal-poor globular clusters than in the metal-rich ones. We also confirm the strong impact of the mass loss rate in the earlier

  8. 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.

  9. A Transition Metal Complex (Venus Flytrap Cluster) for Radioimmunodetection and Radioimmunotherapy

    NASA Astrophysics Data System (ADS)

    Paxton, Raymond J.; Beatty, Barbara G.; Hawthorne, M. Frederick; Varadarajan, Aravamuthan; Williams, Lawrence E.; Curtis, Frederick L.; Knobler, Carolyn B.; Beatty, J. David; Shiveley, John E.

    1991-04-01

    A novel transition metal complex, Venus flytrap cluster (VFC), is described for the preparation of radiolabeled antibodies. VFC contained 57Co, which was held tightly between the faces of two covalently bridged carborane ligands by cluster bonding of the metal with appropriate ligand orbitals. Anti-carcinoembryonic antigen monoclonal antibody T84.66 was conjugated to 57Co-VFC with full retention of immunological activity. Biodistribution studies in nude mice bearing carcinoembryonic antigen-producing tumors showed excellent tumor localization of 57Co-VFC-T84.66. The accumulation of radionuclide in normal liver was low and independent of dose, which may reflect the stability of the radionuclide complex. These results presage the use of VFC systems for binding transition metals that are clinically useful for radio-immunodiagnosis and radioimmunotherapy.

  10. A transition metal complex (Venus flytrap cluster) for radioimmunodetection and radioimmunotherapy

    SciTech Connect

    Paxton, R.J.; Curtis, F.L.; Shively, J.E. ); Beatty, B.G.; Williams, L.E.; Beatty, J.D. ); Hawthorne, M.F.; Varadarajan, A.; Knobler, C.B. )

    1991-04-15

    A novel transition metal complex, Venus flytrap cluster (VFC), is described for the preparation of radiolabeled antibodies. VFC contained {sup 57}Co, which was held tightly between the faces of two covalently bridged carborane ligands by cluster bonding of the metal with appropriate ligand orbitals. Anti-carcinoembryonic antigen monoclonal antibody T84,66 was conjugated to {sup 57}Co-VFC with full retention of immunological activity. Biodistribution studies in nude mice bearing carcinoembryonic antigen-producing tumors showed excellent tumor localization of {sup 57}Co-VFC-T84.66. The accumulation of radionuclide in normal liver was low and independent of dose, which may reflect the stability of the radionuclide complex. These results presage the use of VFC systems for binding transition metals that are clinically useful for radioimmunodiagnosis and radioimmunotherapy.

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

    SciTech Connect

    Chun, Sang-Hyun; Kang, Minhee; Jung, DooSeok; Sohn, Young-Jong

    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 stellar 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.

  12. ENVIRONMENTAL EFFECTS ON THE METAL ENRICHMENT OF LOW-MASS GALAXIES IN NEARBY CLUSTERS

    SciTech Connect

    Petropoulou, V.; Vilchez, J.; Iglesias-Paramo, J.

    2012-04-20

    In this paper, we study the chemical history of low-mass star-forming (SF) galaxies in the local universe clusters Coma, A1367, A779, and A634. The aim of this work is to search for the imprint of the environment on the chemical evolution of these galaxies. Galaxy chemical evolution is linked to the star formation history, as well as to the gas interchange with the environment, and low-mass galaxies are well known to be vulnerable systems to environmental processes affecting both these parameters. For our study we have used spectra from the SDSS-III DR8. We have examined the spectroscopic properties of SF galaxies of stellar masses 10{sup 8}-10{sup 10} M{sub Sun }, located from the core to the cluster's outskirts. The gas-phase O/H and N/O chemical abundances have been derived using the latest empirical calibrations. We have examined the mass-metallicity relation of cluster galaxies, finding well-defined sequences. The slope of these sequences, for galaxies in low-mass clusters and galaxies at large cluster-centric distances, follows the predictions of recent hydrodynamic models. A flattening of this slope has been observed for galaxies located in the core of the two more massive clusters of the sample, principally in Coma, suggesting that the imprint of the cluster environment on the chemical evolution of SF galaxies should be sensitive to both the galaxy mass and the host cluster mass. The H I gas content of Coma and A1367 galaxies indicates that low-mass SF galaxies, located at the core of these clusters, have been severely affected by ram-pressure stripping (RPS). The observed mass-dependent enhancement of the metal content of low-mass galaxies in dense environments seems plausible, according to hydrodynamic simulations. This enhanced metal enrichment could be produced by the combination of effects such as wind reaccretion, due to pressure confinement by the intracluster medium (ICM), and the truncation of gas infall, as a result of the RPS. Thus, the

  13. Spectroscopic age and metallicity for a sample of Globular Clusters from Stellar Population Models

    NASA Astrophysics Data System (ADS)

    Stock, M. J.; Calderón, P.

    2009-05-01

    We present spectroscopic age and metallicity predictions for a sample of 20 Globular Clusters in the massive E0 galaxy NGC 1407 (data from Cenarro et al. 2007, AJ, 134, 391) and for the Galacic Globular Clusters data from the Library of Integrated Spectra of Galactic Globular Clusters (GGC's) from Schiavon et al. (2005, ApJS, 160, 163) including the widely studied 47 Tuc cluster. Using index-index plots we compared model Single Stellar Populations (SSP's) spectra to the integrated spectra of both samples of Globular Clusters using high resolution line strength indices (Stock, in prep.) and the syntethic SSP's models from P. Coelho (2007, private comm.) as well as the CB07 solar models. For the GC's in NGC1407, the predictions from the syntethic models's with [α /Fe]=0.4 are in good agreement with the results from Cenarro et al. (2007, AJ, 134, 391), taking into account that the dispersion is partially due to the fact that the mean [α/Fe] ratio of the sample is ≈ 0.3 dex, resulting in younger ages and lower metallicities (Thomas et al. 2003, A&A, 401, 429). We observe a bimodal distribution of the Fe4383+ index which is in turn an indicator of metallicity, also seen in Cenarro et al. (2005). The CB07 models predict ages that are widely spread over the plot yielding ages greater than 14 Gyrs. The metallicity derived from these models are very low for almost all the objects (Z < 0.008). The distribution of the GGC's on the syntethic model grid shows a trend in the sense that metal poor clusters are younger than metal rich ones, but this effect might not be real (de Angeli et al. 2005, AJ, 130, 116). For 47 Tuc we estimate an age of ≈ 10 Gyr, and metallicity Z < 0.011 (<[Fe/H]= -0.5) which are both comparable with the values reported in the literature (Carretta et al. 2000; Liu & Chaboyer 2000, ApJ, 544, 818; Schiavon et al. 2002, ApJ, 580, 873; Gratton et al. 2003, A&A, 408, 529).

  14. The changes in small metal cluster size with adsorption Be13Xn, X = H, O, S, Cl and F

    NASA Technical Reports Server (NTRS)

    Bauschlicher, C. W., Jr.

    1985-01-01

    The Be-Be and Be-adsorbate distances are optimized for small Be13Xn clusters,s assuming only two independent degrees of freedom. Results for chemisorption into the three-fold hollows are quite similar to those found for small metal clusters on supports. It is predicted that Cl and F will have the same effect on the metal-metal bond lengths, and so will O and S.

  15. Discovery of Extended Blue Horizontal Branches in Two Metal-rich Globular Clusters

    NASA Astrophysics Data System (ADS)

    Rich, R. Michael; Sosin, Craig; Djorgovski, S. George; Piotto, Giampaolo; King, Ivan R.; Renzini, Alvio; Phinney, E. Sterl; Dorman, Ben; Liebert, James; Meylan, Georges

    1997-07-01

    We have used WFPC2 to construct B, V color-magnitude diagrams of four metal-rich globular clusters, NGC 104 (47 Tuc), NGC 5927, NGC 6388, and NGC 6441. All four clusters have well populated red horizontal branches (RHB), as expected for their metallicity. However, NGC 6388 and 6441 also exhibit a prominent blue horizontal-branch (BHB) extension, including stars reaching as faint in V as the turnoff luminosity. This discovery demonstrates directly for the first time that a major population of hot horizontal-branch (HB) stars can exist in old, metal-rich systems. This may have important implications for the interpretation of the integrated spectra of elliptical galaxies. The cause of the phenomenon remains uncertain. We examine the possibility that NGC 6388 and 6441 are older than the other clusters, but a simple difference in age may not be sufficient to produce the observed distributions along the HB. The high central densities in NGC 6388 and 6441 suggest that the existence of the BHB tails might be caused by stellar interactions in the dense cores of these clusters, which we calculate to have two of the highest collision rates among globular clusters in the Galaxy. Tidal collisions might act in various ways to enhance loss of envelope mass and therefore populate the blue side of the HB. However, the relative frequency of tidal collisions does not seem large enough (compared to that of the clusters with pure RHBs) to account for such a drastic difference in HB morphology. While a combination of an age difference and dynamical interactions may help, prima facie the lack of a radial gradient in the BHB/RHB star ratio seems to argue against dynamical effects playing a role. Based on observations with the NASA/ESA Hubble Space Telescope, obtained at the Space Telescope Science Institute, which is operated by AURA, Inc., under NASA contract NAS 5-26555.

  16. On the lithium dip in the metal poor open cluster NGC 2243

    SciTech Connect

    François, P.; Pasquini, L.; Palsa, R.; Biazzo, K.; Bonifacio, P.

    2014-05-02

    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{sub ⊙}, 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.

  17. 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.

  18. First-principles studies on graphene-supported transition metal clusters

    SciTech Connect

    Sahoo, Sanjubala Khanna, Shiv N.; Gruner, Markus E.; Entel, Peter

    2014-08-21

    Theoretical studies on the structure, stability, and magnetic properties of icosahedral TM{sub 13} (TM = Fe, Co, Ni) clusters, deposited on pristine (defect free) and defective graphene sheet as well as graphene flakes, have been carried out within a gradient corrected density functional framework. The defects considered in our study include a carbon vacancy for the graphene sheet and a five-membered and a seven-membered ring structures for graphene flakes (finite graphene chunks). It is observed that the presence of defect in the substrate has a profound influence on the electronic structure and magnetic properties of graphene-transition metal complexes, thereby increasing the binding strength of the TM cluster on to the graphene substrate. Among TM{sub 13} clusters, Co{sub 13} is absorbed relatively more strongly on pristine and defective graphene as compared to Fe{sub 13} and Ni{sub 13} clusters. The adsorbed clusters show reduced magnetic moment compared to the free clusters.

  19. Selective self-assembly of molecular clusters with designed sizes on metal surfaces

    NASA Astrophysics Data System (ADS)

    Wang, Jun; Li, Qing; Fuentes-Cabrera, Miguel; Sumpter, Bobby G.; Baddorf, Arthur P.; Pan, Minghu

    2014-03-01

    The self-assembly of ``magic'' molecular clusters on various substrates provides a new arena for studies of surface nanocatalysis and molecular electronics. Here we present the self-assembly of phenylacetylene molecules on Cu(100) by a combined low-temperature STM and in-depth density functional theory investigation. We observe the molecules form distinct tetramer clusters on Cu(100) at 40 K. Each cluster has a four-fold symmetry and consists of four molecules. A delicate balance of intramolecular and dipole-dipole interactions between clusters maintains this magic tetramer configuration on Cu(100). The strong interaction between the molecules and the copper surface creates an anchor at each adsorption site. Through comparison with our previous observed hexamer (six-molecule) clusters on Au(111), we conclude that the epitaxial relationship between the molecules and metal surfaces is crucial in defining magic numbers of surface-supported molecular clusters under weak intermolecular interaction. This research was conducted at the Center for Nanophase Materials Sciences, which is sponsored at Oak Ridge National Laboratory by the Scientific User Facilities Division, Office of Basic Energy Sciences, U.S. Department of Energy.

  20. Trends in methanol decomposition on transition metal alloy clusters from scaling and Brønsted–Evans–Polanyi relationships

    SciTech Connect

    Mehmood, Faisal; Rankin, Rees B.; Greeley, Jeffrey; Curtiss, Larry A.

    2012-05-15

    A combination of first principles Density Functional Theory calculations and thermochemical scaling relationships are employed to estimate the thermochemistry and kinetics of methanol decomposition on unsupported subnanometer metal clusters. The approach uses binding energies of various atomic and molecular species, determined on the pure metal clusters, to develop scaling relationships that are then further used to estimate the methanol decomposition thermodynamics for a series of pure and bimetallic clusters with four atoms per cluster. Additionally, activation energy barriers are estimated from Brønsted–Evans–Polanyi plots relating transition and final state energies on these clusters. The energetic results are combined with a simple, microkinetically-inspired rate expression to estimate reaction rates as a function of important catalytic descriptors, including the carbon and atomic oxygen binding energies to the clusters. Finally, based on these analyses, several alloy clusters are identified as promising candidates for the methanol decomposition reaction.

  1. Theoretical Investigations into Self-Organized Ordered Metallic Semi-Clusters Arrays on Metallic Substrate

    PubMed Central

    2010-01-01

    Using the energy minimization calculations based on an interfacial potential and a first-principles total energy method, respectively, we show that (2 × 2)/(3 × 3) Pb/Cu(111) system is a stable structure among all the [(n − 1) × (n − 1)]/(n × n) Pb/Cu(111) (n = 2, 3,…, 12) structures. The electronic structure calculations indicate that self-organized ordered Pb semi-clusters arrays are formed on the first Pb monolayer of (2 × 2)/(3 × 3) Pb/Cu(111), which is due to a strain-release effect induced by the inherent misfits. The Pb semi-clusters structure can generate selective adsorption of atoms of semiconductor materials (e.g., Ge) around the semi-clusters, therefore, can be used as a template for the growth of nanoscale structures with a very short periodic length (7.67 Å). PMID:20672088

  2. Electronic interactions and charge transfers of metal atoms and clusters on oxide surfaces.

    PubMed

    Pacchioni, Gianfranco

    2013-02-14

    Understanding the interaction of small metal clusters and isolated atoms with oxide surfaces is crucial in order to rationalize the properties of heterogeneous catalysts composed of sub-nanometer metal particles dispersed on an oxide support. The interaction with the oxide surface can significantly alter the original properties of the metal deposit. In particular, the occurrence and the direction of charge transfer at the metal/oxide interface determine the chemical activity of the supported catalyst. The charge transfer depends on a number of factors like the nature of the oxide (reducible or non-reducible), the surface exposed, the presence of defects, the nature of the supported metal, etc. In this article we describe the most important conceptual aspects of the electronic metal-support interaction, a phenomenon related to the direct modification of the metal nano-particle determined by the formation of chemical bonds at the interface with the oxide. For metal nano-particles with a size of about 1 nm or below these effects become dominant although difficult to identify experimentally. PMID:23287900

  3. Model studies in catalysis with uhv-deposited metal particles and clusters

    NASA Technical Reports Server (NTRS)

    Poppa, H.

    1984-01-01

    Small supported metal particles have become a popular area of intense research interest, and important contributions to the considered problems are being made from the fields of uhv technology, thin film physics surface science, and surface and thin film instrumentation. Attention is given to insulating supports, particulate metal deposits and their properties, metal/support interactions and gas exposures, and integrated experimental approaches. It is concluded that major contributions to the field of model catalysis should be forthcoming in the near future from uhv-based methods of research. Catalysis and catalysis-related problem areas expected to benefit from advanced model studies include catalyst preparation processing, sintering mechanisms for metals and alloys, separation of initial and final state effects for supported clusters, and the influence of particle and/or support morphologies.

  4. Structurally Well-Defined Sigmoidal Gold Clusters: Probing the Correlation between Metal Atom Arrangement and Chiroptical Response.

    PubMed

    He, Xin; Wang, Yuechao; Jiang, Hong; Zhao, Liang

    2016-05-01

    Asymmetric arrangement of metal atoms is crucial for understanding the chirality origin of chiral metal nanoclusters and facilitating the design and development of new chiral catalysts and chiroptical devices. Here, we describe the construction of four asymmetric gold and gold-silver clusters by chirality transfer from diimido ligands. The acquired metal clusters show strong circular dichroism (CD) response with large anisotropy factors of up to 6 × 10(-3), larger than the values of most reported chiral gold nanoclusters. Regardless of the same absolute configuration of the applied three diimido ligands, sigmoidal and reverse-sigmoidal arrangements of gold atoms both can be achieved, which resultantly produce an opposite Cotton effect within a specific absorption range. On the basis of the detailed structural characterization via X-ray crystallography and contrast experiments, the chirality contribution of the imido ligand, the asymmetrically arranged metal cluster, and the chiral arrangement of aromatic rings of phosphine ligands have been qualitatively evaluated. Time-dependent DFT calculations reveal that the chiroptical property of the acquired metal clusters is mainly influenced by the asymmetrically arranged metal atoms. Correlation of asymmetric arrangements of metal atoms in clusters with their chiroptical response provides a viable means of fabricating a designable chiral surface of metal nanoclusters and opens a broader prospect for chiral cluster application. PMID:27070415

  5. Fuzzy hierarchical cross-clustering of data from abandoned mine site contaminated with heavy metals

    NASA Astrophysics Data System (ADS)

    Pourjabbar, A.; Sârbu, C.; Kostarelos, K.; Einax, J. W.; Büchel, G.

    2014-11-01

    The characteristics of pore water and slate samples are critically analyzed using fuzzy hierarchical cross-clustering statistical techniques. The main aim of this study was to investigate the source of contamination near an abandoned uranium mine in Germany. The mining activities were abandoned in 1990 the site was closed, and the surrounding area was remediated. However, heavy metal contamination is still detectable in water, soil and plants today. Hence, investigating the source of the current contamination is an important task. In order to achieve the goal, results from chemical analysis of both pore water samples and leachates from slate samples were initially analyzed using hard (classical) hierarchical clustering algorithms that did not provide meaningful results. By using two fuzzy clustering algorithms, Fuzzy Divisive Hierarchical Clustering (FDHC) and Fuzzy Hierarchical Cross-Clustering (FHCC), a relationship between the leachate from Ordovician-Silurian slate samples (10 samples collected from the test site and the surrounding area) and pore water samples (53 samples collected from 3 locations within the test site at 3 depths over the course of 4 years) was identified. The leachate data formed a cluster which was statistically similar to the cluster formed by the pore water samples collected from two of three locations. In addition, the fuzzy cross-clustering approach allowed for the identification of the characteristics (qualitative and quantitative) responsible for the observed similarities between all the samples. We conclude that the fuzzy algorithms were a better tool for the analysis and interpretation of geological/hydrogeological data where the data sets have an inherent vagueness/uncertainty.

  6. The metallicity distribution function of globular clusters systems through near-infrared photometry

    NASA Astrophysics Data System (ADS)

    Okon, Waldemar M. M.

    New, deep, wide-field photometry in the K -band obtained with the Canada- France-Hawaii Telescope Infrared Camera (CFHT-IR) is used in combination with archival V and I -band data from the Hubble Space Telescope Wide Field Planetary Camera 2 (HST-WFPC2) to study the globular cluster systems (GCSs) of eight elliptical galaxies of various luminosities. These include the Leo Group galaxies NGC 3377 and 3379, Virgo Galaxy Cluster galaxies M 60, M 86, M 89, as well as the giant elliptical M 87. Two other galaxies, NGC 2768 in Ursa Major and NGC 3608 in Leo are also studied. Combining the new CFHT-IR data with archival HST-WFPC2 data, V - K colours, which are significantly more sensitive to metallicity than the commonly used V - I colour indices, are derived. The main properties of the GCSs of these galaxies that are studied here are the V - K colour distribution functions, metallicity distribution functions, abundance distribution functions, V - K vs V - I colour-colour diagrams and cumulative age distributions. The metallicities are derived by transforming the V - K colours using an existing empirical calibration between colour and metallicity. Four galaxies showed a bimodal CDF. The bias-corrected mean colour and metallicity for the GCSs were found to be < V - K > 2.61 ± 0.32 and - 0.88 ± 0.33 dex respectively. From the abundance distributions and the application of a simple chem ical evolution model, it was found that the average yield for the metal-poor clusters for these GCSs is 0.0033 ± 0.0016, and for the metal-rich 0.0132 ± 0.0059, or about four times higher. The average value lies in between the yields of the Milky Way and M 31 GCSs. The age information is obtained with the aid of colour-colour diagrams and theoretical isochrones from simple stellar population (SSP) models. Several of the GCSs studied here (most notably M 60 and M 87) show evidence for intermediate-age clusters in the metal-rich regime. In addition, artificial colour-colour diagrams

  7. AGES AND METALLICITIES OF CLUSTER GALAXIES IN A779 USING MODIFIED STROeMGREN PHOTOMETRY

    SciTech Connect

    Sreedhar, Yuvraj Harsha; Rakos, Karl D.; Hensler, Gerhard; Zeilinger, Werner W.; Odell, Andrew P.

    2012-03-01

    In the quest for the formation and evolution of galaxy clusters, Rakos and co-workers introduced a spectrophotometric method using modified Stroemgren photometry, but with the considerable debate toward the project's abilities, we re-introduce the system by testing for the repeatability of the modified Stroemgren colors and compare them with the Stroemgren colors, and check for the reproducibility of the ages and metallicities (using the Principle Component Analysis (PCA) technique and the GALEV models) for the six common galaxies in all three A779 data sets. As a result, a fair agreement between two filter systems was found to produce similar colors (with a precision of 0.09 mag in (uz - vz), 0.02 mag in (bz - yz), and 0.03 mag in (vz - vz)) and the generated ages and metallicities are also similar (with an uncertainty of 0.36 Gyr and 0.04 dex from PCA and 0.44 Gyr and 0.2 dex using the GALEV models). We infer that the technique is able to relieve the age-metallicity degeneracy by separating the age effects from the metallicity effects, but it is still unable to completely eliminate it. We further extend this paper to re-study the evolution of galaxies in the low mass, dynamically poor A779 cluster (as it was not elaborately analyzed by Rakos and co-workers in their previous work) by correlating the luminosity (mass), density, and radial distance with the estimated age, metallicity, and the star formation history. Our results distinctly show the bimodality of the young, low-mass, metal-poor population with a mean age of 6.7 Gyr ({+-} 0.5 Gyr) and the old, high-mass, metal-rich galaxies with a mean age of 9 Gyr ({+-} 0.5 Gyr). The method also observes the color evolution of the blue cluster galaxies to red (Butcher-Oemler phenomenon), and the downsizing phenomenon. Our analysis shows that modified Stroemgren photometry is very well suited for studying low- and intermediate-z clusters, as it is capable of observing deeper with better spatial resolution at

  8. The transformation of organic amines by transition metal cluster compounds. Progress report, 1993--1994

    SciTech Connect

    Adams, R.D.

    1994-01-01

    In the recent year, the authors extended investigations into insertion reactions by investigating the insertion of dicarboxylate acetylene into the metal-metal bond of Re{sub 2}(CO){sub 9}(NCMe). Secondly, the authors considered the ring opening reactions of the cyclic thioethers: tetrahydrothiophene and thiacyclohexane when complexed to Os{sub 3}(CO){sub 10}(NCMe){sub 2}. In a third effort, various osmium complexes of cyclobutynes were synthesized and the subsequent reactivity probed. Finally, energy storage (via absorption of UV-visible photons) in osmium cluster compounds was investigated.

  9. Tunable two types of Fano resonances in metal-dielectric core-shell nanoparticle clusters

    NASA Astrophysics Data System (ADS)

    Yang, Zhong-Jian; Wang, Qu-Quan; Lin, Hai-Qing

    2013-09-01

    We demonstrate that two types of Fano resonances could be observed in metal-dielectric core-shell nanoparticle heptamer clusters. The first kind of Fano resonance is caused by the coupling between electric dipolar plasmon modes. It still remains with high refractive index shells even though metal cores are separated by them. The second one is caused by the interference between scattering electromagnetic modes of dielectric shell and modified plasmon modes. The energy and line shape of these Fano resonances are highly tunable with shell index and particle geometry, which could find applications in nanophotonics.

  10. VizieR Online Data Catalog: Metallicity of the γ Vel cluster (Spina+, 2014)

    NASA Astrophysics Data System (ADS)

    Spina, L.; Randich, S.; Palla, F.; Sacco, G. G.; Magrini, L.; Franciosini, E.; Morbidelli, L.; Prisinzano, L.; Alfaro, E. J.; Biazzo, K.; Frasca, A.; Gonzalez Hernandez, J. I.; Sousa, S. G.; Adibekyan, V.; Delgado-Mena, E.; Montes, D.; Tabernero, H.; Klutsch, A.; Gilmore, G.; Feltzing, S.; Jeffries, R. D.; Micela, G.; Vallenari, A.; Bensby, T.; Bragaglia, A.; Flaccomio, E.; Koposov, S.; Lanzafame, A. C.; Pancino, E.; Recio-Blanco, A.; Smiljanic, R.; Costado, M. T.; Damiani, F.; Hill, V.; Hourihane, A.; Jofre, P.; de Laverny, P.; Masseron, T.; Worley, C.

    2014-05-01

    Atmospheric parameters, radial velocities, lithium equivalent widths are products of the Gaia-ESO Survey that were used for our membership analysis of the 48 UVES targets observed in the Gamma Velorum fields. Also photometry from Jeffries et al. (2009MNRAS.393..538J) has been used. Iron abundances of these stars have been used to determine the metal content of the cluster. We also discussed the metallicity derived through the iron abundances of the 208 cluster members targeted with GIRAFFE and identified by Jeffries et al. (2014A&A...563A..94J). Stellar parameters of 39 stars targeted by both UVES and GIRAFFE have been used to check the quality of the data. (4 data files).

  11. Electrospray Ionization Mass Spectrometry: From Cluster Ions to Toxic metal Ions in Biology

    SciTech Connect

    Lentz, Nicholas B.

    2007-01-01

    This dissertation focused on using electrospray ionization mass spectrometry to study cluster ions and toxic metal ions in biology. In Chapter 2, it was shown that primary, secondary and quarternary amines exhibit different clustering characteristics under identical instrument conditions. Carbon chain length also played a role in cluster ion formation. In Chapters 3 and 4, the effects of solvent types/ratios and various instrumental parameters on cluster ion formation were examined. It was found that instrument interface design also plays a critical role in the cluster ion distribution seen in the mass spectrum. In Chapter 5, ESI-MS was used to investigate toxic metal binding to the [Gln11]-amyloid β-protein fragment (1-16). Pb and Cd bound stronger than Zn, even in the presence of excess Zn. Hg bound weaker than Zn. There are endless options for future work on cluster ions. Any molecule that is poorly ionized in positive ion mode can potentially show an increase in ionization efficiency if an appropriate anion is used to produce a net negative charge. It is possible that drug protein or drug/DNA complexes can also be stabilized by adding counter-ions. This would preserve the solution characteristics of the complex in the gas phase. Once in the gas phase, CID could determine the drug binding location on the biomolecule. There are many research projects regarding toxic metals in biology that have yet to be investigated or even discovered. This is an area of research with an almost endless future because of the changing dynamics of biological systems. What is deemed safe today may show toxic effects in the future. Evolutionary changes in protein structures may render them more susceptible to toxic metal binding. As the understanding of toxicity evolves, so does the demand for new toxic metal research. New instrumentation designs and software make it possible to perform research that could not be done in the past. What was undetectable yesterday will

  12. Geometric and electronic structure of mixed metal-semiconductor clusters from global optimization.-

    NASA Astrophysics Data System (ADS)

    Hagelberg, Frank; Wu, Jianhua

    2006-03-01

    In addition to pure metal and semiconductor clusters, hybrid species that contain both types of constituents occur at the metal-semiconductor interface. Thus, clusters of the form Cu(x)Si(y) were detected by mass spectrometry [1]. In this contribution, the geometric and energetic features of Me(m)Si(7-m) (Me=Cu and Li) clusters are discussed. The choice of these systems is motivated by the structural similarity of the pure Si(7), Li(7), and Cu(7) systems which all stabilize in D(5h) symmetry. On the other hand, Li and Cu, representing the alkali group (IA) and the noble metal group (IB) of the periodic system, are expected to display strongly differing behavior when integrated into a Si(n) cluster, resulting in different ground state geometries for the cases Me = Li and Me = Cu. Addressing this problem by means of geometry optimization requires, in view of the large number of possible atomic permutations for Me(m)Si(7-m) with 0 < m < 7, the use of a global search algorithm. Equilibrium geometries are obtained by simulated annealing within the Nose' thermostat frame. It is observed that Cu(m)Si(7-m) clusters with m < 6 tend towards ground state geometries derived from the D(5h) prototype. For Li(m)Si(7-m), the Li(m) subsystem is found to adsorb on the framework of the Si(7-m) dianion. [1] J.J. Scherer, J.B. Pau, C.P. Collier, A. O'Keefe, and R.J. Saykally, J. Chem. Phys. 103, 9187 (1995).

  13. Spectroscopic Metallicities for Fornax Ultracompact Dwarf Galaxies, Globular Clusters, and Nucleated Dwarf Elliptical Galaxies

    NASA Astrophysics Data System (ADS)

    Mieske, S.; Hilker, M.; Infante, L.; Jordán, A.

    2006-05-01

    Various formation channels for the puzzling ultracompact dwarf galaxies (UCDs) have been proposed in the last few years. To better judge some of the competing scenarios, we present spectroscopic [Fe/H] estimates for a sample of 26 compact objects in the central region of the Fornax Cluster, covering the magnitude range of UCDs and bright globular clusters (18 magmetallicity distribution of compact objects at MV~=-11 mag (~=3×106 Msolar): for MV<-11 mag the mean metallicity is [Fe/H]=-0.62+/-0.05 dex, 0.56+/-0.15 dex higher than the value of -1.18+/-0.15 dex found for MV>-11 mag. This metallicity break is accompanied by a change in the size-luminosity relation for compact objects, as deduced from Hubble Space Telescope imaging: for MV<-11 mag, rh scales with luminosity, while for MV>-11 mag, rh is almost luminosity-independent. In our study we therefore assume a limiting absolute magnitude of MV=-11 mag between UCDs and globular clusters. The mean metallicity of five Fornax nucleated dwarf elliptical galaxy (dE,N) nuclei included in our study is about 0.8 dex lower than that of the UCDs, a difference significant at the 4.5 σ level. This difference is marginally higher than expected from a comparison of their (V-I) colors, indicating that UCDs are younger than or at most coeval to dE,N nuclei. Because of the large metallicity discrepancy between UCDs and nuclei, we disfavor the hypothesis that most of the Fornax UCDs are the remnant nuclei of tidally stripped dE,Ns. Our metallicity estimates for UCDs are closer to but slightly below those derived for young massive clusters (YMCs) of comparable masses. We therefore favor a scenario in which most UCDs in Fornax are successors of merged YMCs produced in the course of violent galaxy-galaxy mergers. It is noted that, in contrast, the properties of Virgo UCDs are more consistent with the stripping scenario, suggesting that different UCD formation channels may

  14. Influence of group 10 metals on the growth and subsequent Coulomb explosion of small silicon clusters under strong light pulses.

    PubMed

    Ross, Matt W; Castleman, A W

    2013-03-18

    Growth and ionization patterns of small silicon clusters are studied using ultrafast pulses centered at 624 nm by varying the metal electron source for cluster formation using group 10 transition metals. The silicon-cluster size was observed to change as the electron source was varied from Pdcluster growth in the palladium system is attributed to the higher work function of palladium metal, producing less collisions of the laser-induced plasma with the silane. This shows that changing the metal electron source while holding the laser intensity constant affects the degree of dehydrogenation of SiH4 due to the number of collisions in the cluster source. The saturation intensities of each atomic charge state of silicon, resulting from Coulomb explosion of pure silicon clusters, formed with each metal are measured and compared to those calculated by using semi-classical tunneling theory assuming sequential ionization. The ion signal of silicon atomic charge states produced when using palladium as electron source for cluster formation shows a greater degree of ionization enhancement than that observed for the nickel and platinum systems. This is reflected by the smaller-size clusters formed in the palladium system. Based on a plot of the ion signal as a function of laser intensity compared to the simulated ion signal from tunneling theory, the ionization enhancement of silicon high-charge states is found to increase by varying the electron source from Ni

  15. CLUSTER CHEMISTRY

    SciTech Connect

    Muetterties, Earl L.

    1980-05-01

    Metal cluster chemistry is one of the most rapidly developing areas of inorganic and organometallic chemistry. Prior to 1960 only a few metal clusters were well characterized. However, shortly after the early development of boron cluster chemistry, the field of metal cluster chemistry began to grow at a very rapid rate and a structural and a qualitative theoretical understanding of clusters came quickly. Analyzed here is the chemistry and the general significance of clusters with particular emphasis on the cluster research within my group. The importance of coordinately unsaturated, very reactive metal clusters is the major subject of discussion.

  16. The transformation of organic amines by transition metal cluster compounds: Progress report

    SciTech Connect

    Adams, R.D.

    1994-11-01

    Research during the current award period has covered several related topics which have emerged and grown as a consequence of the various discoveries that have been made during this award period. They have been divided into the following subsections for clarity and emphasis: The activation of tertiary amines by osmium cluster complexes; CH bond activation and ring opening of a nitrogen containing strained ring heterocycle by an osmium cluster complex; Ring opening of cyclic thioethers; cyclooligomerization of Thietanes; Studies of the cyclobutyne ligand; Insertion of an alkynes into metal-metal bonds; and Energy storage in metal clusters. A summary of the results of these studies is given in the following sections of this report. These studies have resulted in 50 scientific publications over the last three years and details of their studies beyond that given in the following sections can be found in those reports. All of these reports are listed in the final section of this report by the author`s names, title and journal citation.

  17. Classification and identification of metal-accumulating plant species by cluster analysis.

    PubMed

    Yang, Wenhao; Li, He; Zhang, Taoxiang; Sen, Lin; Ni, Wuzhong

    2014-09-01

    Identification and classification of metal-accumulating plant species is essential for phytoextraction. Cluster analysis is used for classifying individuals based on measured characteristics. In this study, classification of plant species for metal accumulation was conducted using cluster analysis based on a practical survey. Forty plant samples belonging to 21 species were collected from an ancient silver-mining site. Five groups such as hyperaccumulator, potential hyperaccumulator, accumulator, potential accumulator, and normal accumulating plant were graded. For Cd accumulation, the ancient silver-mining ecotype of Sedum alfredii was treated as a Cd hyperaccumulator, and the others were normal Cd-accumulating plants. For Zn accumulation, S. alfredii was considered as a potential Zn hyperaccumulator, Conyza canadensis and Artemisia lavandulaefolia were Zn accumulators, and the others were normal Zn-accumulating plants. For Pb accumulation, S. alfredii and Elatostema lineolatum were potential Pb hyperaccumulators, Rubus hunanensis, Ajuga decumbens, and Erigeron annuus were Pb accumulators, C. canadensis and A. lavandulaefolia were potential Pb accumulators, and the others were normal Pb-accumulating plants. Plant species with the potential for phytoextraction were identified such as S. alfredii for Cd and Zn, C. canadensis and A. lavandulaefolia for Zn and Pb, and E. lineolatum, R. hunanensis, A. decumbens, and E. annuus for Pb. Cluster analysis is effective in the classification of plant species for metal accumulation and identification of potential species for phytoextraction. PMID:24888623

  18. Magnetic properties of bimetallic clusters composed of Gd and transition metals

    NASA Astrophysics Data System (ADS)

    Mukherjee, Prajna; Gupta, Bikash C.; Jena, Puru

    2016-02-01

    Gadolinium, a rare earth metal, is ferromagnetic, while Mn, a transition metal atom, is antiferromagnetic in the bulk phase. Clusters of these elements, however, share some common properties; both exhibit ferrimagnetic behavior and maintain magnetic moments close to their free atomic value. Using density functional theory and generalized gradient approximation for exchange and correlation, we have studied the magnetic properties of bimetallic clusters composed of Gd and Mn to see if they show unusual behavior. The coupling between Gd and Mn spins is found to be antiferromagnetic, while that between Mn atoms is ferromagnetic. Moreover, the bonding between Gd and Mn atoms is stronger than that between the Gd atoms or Mn atoms, thus enabling the possibility of creating more stable magnetic particles. A systematic study of the magnetic and binding properties of clusters composed of Gd atom and other transition metal atoms such as V, Sc, Ti, Cr, Fe, and Co is also carried out to probe the effect of 3d-orbital occupation on magnetic coupling.

  19. Heterometallic Triiron-Oxo/Hydroxo Clusters: Effect of Redox-Inactive Metals

    PubMed Central

    Herbert, David E.; Lionetti, Davide; Rittle, Jonathan; Agapie, Theodor

    2014-01-01

    A series of tetranuclear oxo/hydroxo clusters comprised of three Fe centers and a redox-inactive metal (M) of various charge is reported. Crystallographic studies show an unprecedented Fe3M(μ4-O)(μ2-OH) core that remains intact upon changing M or the oxidation state of iron. Electrochemical studies reveal that the reduction potentials (E1/2) span a window of 500 mV and depend upon the Lewis acidity of M. Using the pKa of the redox-inactive metal aqua complex as a measure of Lewis acidity, these compounds display a linear dependence between E1/2 and acidity with a slope of ca. 70 mV per pKa unit. The current study of [Fe3MO(OH)] and previous ones of [Mn3MOn] (n = 2, 4) moieties support the generality of the above relationship between the reduction potentials of heterometallic oxido clusters and the Lewis acidity of incorporated cations, as applied to clusters of different redox-active metals. PMID:24304416

  20. ANISOTROPIC METAL-ENRICHED OUTFLOWS DRIVEN BY ACTIVE GALACTIC NUCLEI IN CLUSTERS OF GALAXIES

    SciTech Connect

    Kirkpatrick, C. C.; McNamara, B. R.; Cavagnolo, K. W.

    2011-04-20

    We present an analysis of the spatial distribution of metal-rich gas in 10 galaxy clusters using deep observations from the Chandra X-ray Observatory. The brightest cluster galaxies (BCGs) have experienced recent active galactic nucleus activity in the forms of bright radio emission, cavities, and shock fronts embedded in the hot atmospheres. The heavy elements are distributed anisotropically and are aligned with the large-scale radio and cavity axes. They are apparently being transported from the halo of the BCG into the intracluster medium along large-scale outflows driven by the radio jets. The radial ranges of the metal-enriched outflows are found to scale with jet power as R{sub Fe} {proportional_to} P {sup 0.42}{sub jet}, with a scatter of only 0.5 dex. The heavy elements are transported beyond the extent of the inner cavities in all clusters, suggesting that this is a long-lasting effect sustained over multiple generations of outbursts. Black holes in BCGs will likely have difficulty ejecting metal-enriched gas beyond 1 Mpc unless their masses substantially exceed 10{sup 9} M{sub sun}.

  1. Nonlinear Color-Metallicity Relations of Globular Clusters. III. On the Discrepancy in Metallicity between Globular Cluster Systems and Their Parent Elliptical Galaxies

    NASA Astrophysics Data System (ADS)

    Yoon, Suk-Jin; Lee, Sang-Yoon; Blakeslee, John P.; Peng, Eric W.; Sohn, Sangmo T.; Cho, Jaeil; Kim, Hak-Sub; Chung, Chul; Kim, Sooyoung; Lee, Young-Wook

    2011-12-01

    One of the conundrums in extragalactic astronomy is the discrepancy in observed metallicity distribution functions (MDFs) between the two prime stellar components of early-type galaxies—globular clusters (GCs) and halo field stars. This is generally taken as evidence of highly decoupled evolutionary histories between GC systems and their parent galaxies. Here we show, however, that new developments in linking the observed GC colors to their intrinsic metallicities suggest nonlinear color-to-metallicity conversions, which translate observed color distributions into strongly peaked, unimodal MDFs with broad metal-poor tails. Remarkably, the inferred GC MDFs are similar to the MDFs of resolved field stars in nearby elliptical galaxies and those produced by chemical evolution models of galaxies. The GC MDF shape, characterized by a sharp peak with a metal-poor tail, indicates a virtually continuous chemical enrichment with a relatively short timescale. The characteristic shape emerges across three orders of magnitude in the host galaxy mass, suggesting a universal process of chemical enrichment among various GC systems. Given that GCs are bluer than field stars within the same galaxy, it is plausible that the chemical enrichment processes of GCs ceased somewhat earlier than that of the field stellar population, and if so, GCs preferentially trace the major, vigorous mode of star formation events in galactic formation. We further suggest a possible systematic age difference among GC systems, in that the GC systems in more luminous galaxies are older. This is consistent with the downsizing paradigm whereby stars of brighter galaxies, on average, formed earlier than those of dimmer galaxies; this additionally supports the similar nature shared by GCs and field stars. Although the sample used in this study (the Hubble Space Telescope Advanced Camera for Surveys/Wide Field Channel, WFPC2, and WFC3 photometry for the GC systems in the Virgo galaxy cluster) confines our

  2. NONLINEAR COLOR-METALLICITY RELATIONS OF GLOBULAR CLUSTERS. III. ON THE DISCREPANCY IN METALLICITY BETWEEN GLOBULAR CLUSTER SYSTEMS AND THEIR PARENT ELLIPTICAL GALAXIES

    SciTech Connect

    Yoon, Suk-Jin; Lee, Sang-Yoon; Cho, Jaeil; Kim, Hak-Sub; Chung, Chul; Kim, Sooyoung; Lee, Young-Wook; Blakeslee, John P.; Peng, Eric W.; Sohn, Sangmo T.

    2011-12-20

    One of the conundrums in extragalactic astronomy is the discrepancy in observed metallicity distribution functions (MDFs) between the two prime stellar components of early-type galaxies-globular clusters (GCs) and halo field stars. This is generally taken as evidence of highly decoupled evolutionary histories between GC systems and their parent galaxies. Here we show, however, that new developments in linking the observed GC colors to their intrinsic metallicities suggest nonlinear color-to-metallicity conversions, which translate observed color distributions into strongly peaked, unimodal MDFs with broad metal-poor tails. Remarkably, the inferred GC MDFs are similar to the MDFs of resolved field stars in nearby elliptical galaxies and those produced by chemical evolution models of galaxies. The GC MDF shape, characterized by a sharp peak with a metal-poor tail, indicates a virtually continuous chemical enrichment with a relatively short timescale. The characteristic shape emerges across three orders of magnitude in the host galaxy mass, suggesting a universal process of chemical enrichment among various GC systems. Given that GCs are bluer than field stars within the same galaxy, it is plausible that the chemical enrichment processes of GCs ceased somewhat earlier than that of the field stellar population, and if so, GCs preferentially trace the major, vigorous mode of star formation events in galactic formation. We further suggest a possible systematic age difference among GC systems, in that the GC systems in more luminous galaxies are older. This is consistent with the downsizing paradigm whereby stars of brighter galaxies, on average, formed earlier than those of dimmer galaxies; this additionally supports the similar nature shared by GCs and field stars. Although the sample used in this study (the Hubble Space Telescope Advanced Camera for Surveys/Wide Field Channel, WFPC2, and WFC3 photometry for the GC systems in the Virgo galaxy cluster) confines our

  3. 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

  4. The grape cluster, metal particle 63344,1. [in lunar coarse fines

    NASA Technical Reports Server (NTRS)

    Goldstein, J. I.; Axon, H. J.; Agrell, S. O.

    1975-01-01

    The grape cluster metal particle 63344,1 found in lunar coarse fines is examined using the scanning electron microscope (SEM), electron microprobe, and an optical microscope. This metal particle is approximately 0.5 cm in its largest dimension and consists of hundreds of metallic globules welded together to form a structure somewhat like a bunch of grapes. Electron microprobe analysis for Fe, Ni, Co, P, and S in the metal was carried out using wavelength dispersive detectors. No primary solidification structure is observed in the globules, and the particle is slow cooled from the solidification temperature (nearly 1300 C) taking days to probably months to reach 600 C. Two mechanisms for the formation of globules are proposed. One mechanism involves the primary impact of an iron meteorite which produces a metallic liquid and vapor phase. The second mechanism involves the formation of a liquid pool of metal after impact of an iron meteorite projectile followed by a secondary impact in the liquid metal pool.

  5. THE SLUGGS SURVEY: NGC 3115, A CRITICAL TEST CASE FOR METALLICITY BIMODALITY IN GLOBULAR CLUSTER SYSTEMS

    SciTech Connect

    Brodie, Jean P.; Conroy, Charlie; Arnold, Jacob A.; Romanowsky, Aaron J.; Usher, Christopher; Forbes, Duncan A.; Strader, Jay

    2012-11-10

    Due to its proximity (9 Mpc) and the strongly bimodal color distribution of its spectroscopically well-sampled globular cluster (GC) system, the early-type galaxy NGC 3115 provides one of the best available tests of whether the color bimodality widely observed in GC systems generally reflects a true metallicity bimodality. Color bimodality has alternatively been attributed to a strongly nonlinear color-metallicity relation reflecting the influence of hot horizontal-branch stars. Here, we couple Subaru Suprime-Cam gi photometry with Keck/DEIMOS spectroscopy to accurately measure GC colors and a CaT index that measures the Ca II triplet. We find the NGC 3115 GC system to be unambiguously bimodal in both color and the CaT index. Using simple stellar population models, we show that the CaT index is essentially unaffected by variations in horizontal-branch morphology over the range of metallicities relevant to GC systems (and is thus a robust indicator of metallicity) and confirm bimodality in the metallicity distribution. We assess the existing evidence for and against multiple metallicity subpopulations in early- and late-type galaxies and conclude that metallicity bi/multimodality is common. We briefly discuss how this fundamental characteristic links directly to the star formation and assembly histories of galaxies.

  6. Atmospheric parameters and metallicities for 2191 stars in the globular cluster M4

    SciTech Connect

    Malavolta, Luca; Piotto, Giampaolo; Nascimbeni, Valerio; Sneden, Christopher; Milone, Antonino P.; Bedin, Luigi R. E-mail: giampaolo.piotto@unipd.it E-mail: luigi.bedin@oapd.inaf.it E-mail: milone@mso.anu.edu.au

    2014-02-01

    We report new metallicities for stars of Galactic globular cluster M4 using the largest number of stars ever observed at high spectral resolution in any cluster. We analyzed 7250 spectra for 2771 cluster stars gathered with the Very Large Telescope (VLT) FLAMES+GIRAFFE spectrograph at VLT. These medium-resolution spectra cover a small wavelength range, and often have very low signal-to-noise ratios. We approached this data set by reconsidering the whole method of abundance analysis of large stellar samples from beginning to end. We developed a new algorithm that automatically determines the atmospheric parameters of a star. Nearly all of the data preparation steps for spectroscopic analyses are processed on the syntheses, not the observed spectra. For 322 red giant branch (RGB) stars with V ≤ 14.7, we obtain a nearly constant metallicity, ([Fe/H]) = –1.07 (σ = 0.02). No difference in the metallicity at the level of 0.01 dex is observed between the two RGB sequences identified by Monelli et al. For 1869 subgiant and main-sequence stars with V > 14.7, we obtain ([Fe/H]) = –1.16 (σ = 0.09) after fixing the microturbulent velocity. These values are consistent with previous studies that have performed detailed analyses of brighter RGB stars at higher spectroscopic resolution and wavelength coverage. It is not clear if the small mean metallicity difference between brighter and fainter M4 members is real or is the result of the low signal-to-noise characteristics of the fainter stars. The strength of our approach is shown by recovering a metallicity close to a single value for more than 2000 stars, using a data set that is non-optimal for atmospheric analyses. This technique is particularly suitable for noisy data taken in difficult observing conditions.

  7. Atmospheric Parameters and Metallicities for 2191 Stars in the Globular Cluster M4

    NASA Astrophysics Data System (ADS)

    Malavolta, Luca; Sneden, Christopher; Piotto, Giampaolo; Milone, Antonino P.; Bedin, Luigi R.; Nascimbeni, Valerio

    2014-02-01

    We report new metallicities for stars of Galactic globular cluster M4 using the largest number of stars ever observed at high spectral resolution in any cluster. We analyzed 7250 spectra for 2771 cluster stars gathered with the Very Large Telescope (VLT) FLAMES+GIRAFFE spectrograph at VLT. These medium-resolution spectra cover a small wavelength range, and often have very low signal-to-noise ratios. We approached this data set by reconsidering the whole method of abundance analysis of large stellar samples from beginning to end. We developed a new algorithm that automatically determines the atmospheric parameters of a star. Nearly all of the data preparation steps for spectroscopic analyses are processed on the syntheses, not the observed spectra. For 322 red giant branch (RGB) stars with V <= 14.7, we obtain a nearly constant metallicity, lang[Fe/H]rang = -1.07 (σ = 0.02). No difference in the metallicity at the level of 0.01 dex is observed between the two RGB sequences identified by Monelli et al. For 1869 subgiant and main-sequence stars with V > 14.7, we obtain lang[Fe/H]rang = -1.16 (σ = 0.09) after fixing the microturbulent velocity. These values are consistent with previous studies that have performed detailed analyses of brighter RGB stars at higher spectroscopic resolution and wavelength coverage. It is not clear if the small mean metallicity difference between brighter and fainter M4 members is real or is the result of the low signal-to-noise characteristics of the fainter stars. The strength of our approach is shown by recovering a metallicity close to a single value for more than 2000 stars, using a data set that is non-optimal for atmospheric analyses. This technique is particularly suitable for noisy data taken in difficult observing conditions.

  8. A very deep Chandra view of metals, sloshing and feedback in the Centaurus cluster of galaxies

    NASA Astrophysics Data System (ADS)

    Sanders, J. S.; Fabian, A. C.; Taylor, G. B.; Russell, H. R.; Blundell, K. M.; Canning, R. E. A.; Hlavacek-Larrondo, J.; Walker, S. A.; Grimes, C. K.

    2016-03-01

    We examine deep Chandra X-ray observations of the Centaurus cluster of galaxies, Abell 3526. Applying a gradient magnitude filter reveals a wealth of structure, from filamentary soft emission on 100 pc (0.5 arcsec) scales close to the nucleus to features 10 s of kpc in size at larger radii. The cluster contains multiple high-metallicity regions with sharp edges. Relative to an azimuthal average, the deviations of metallicity and surface brightness are correlated, and the temperature is inversely correlated, as expected if the larger scale asymmetries in the cluster are dominated by sloshing motions. Around the western cold front are a series of ˜7 kpc `notches', suggestive of Kelvin-Helmholtz instabilities. The cold front width varies from 4 kpc down to close to the electron mean free path. Inside the front are multiple metallicity blobs on scales of 5-10 kpc, which could have been uplifted by AGN activity, also explaining the central metallicity drop and flat inner metallicity profile. Close to the nucleus are multiple shocks, including a 1.9-kpc-radius inner shell-like structure and a weak 1.1-1.4 Mach number shock around the central cavities. Within a 10 kpc radius are nine depressions in surface brightness, several of which appear to be associated with radio emission. The shocks and cavities imply that the nucleus has been repeatedly active on 5-10 Myr time-scales, indicating a tight balance between heating and cooling. We confirm the presence of a series of linear quasi-periodic structures. If they are sound waves, the ˜5 kpc spacing implies a period of 6 Myr, similar to the ages of the shocks and cavities. Alternatively, these structures may be Kelvin-Helmholtz instabilities, their associated turbulence or amplified magnetic field layers.

  9. Mono- and Dinuclear Macrocyclic Calcium Complexes as Platforms for Mixed-Metal Complexes and Clusters.

    PubMed

    Connolly, Emma A; Leeland, James W; Love, Jason B

    2016-01-19

    Mono- and dinuclear calcium complexes of the Schiff-base macrocycles H4L have been prepared and characterized spectroscopically and crystallographically. In the formation of Ca(THF)2(H2L(1)), Ca2(THF)2(μ-THF)(L(1)), and Ca2(THF)4(L(2)), the ligand framework adopts a bowl-shaped conformation instead of the conventional wedge, Pacman-shaped structure as seen with the anthracenyl-hinged complex Ca2(py)5(L(3)). The mononuclear calcium complex Ca(THF)2(H2L(1)) reacts with various equivalents of LiN(SiMe3)2 to form calcium/alkali metal clusters and dinuclear transition metal complexes when reacted subsequently with transition metal salts. The dinuclear calcium complex Ca2(THF)2(μ-THF)(L(1)), when reacted with various equivalents of NaOH, is shown to act as a platform for the formation of calcium/alkali metal hydroxide clusters, displaying alternate wedged and bowl-shaped conformations. PMID:26709870

  10. Globular Cluster Systems in Giant Ellipticals: The Mass/Metallicity Relation

    NASA Astrophysics Data System (ADS)

    Harris, William E.

    2009-07-01

    Data from the Hubble Space Telescope taken with the Advanced Camera for Surveys/WFC camera have been used to investigate the globular cluster (GC) populations around six giant elliptical galaxies that are ~40 Mpc distant. From these six fields, imaged in B and I, a total of more than 15,000 candidate GCs have been measured, of which 8000 or more are high-probability GCs. The data reach a limiting magnitude near MI sime -8, about 0.4 mag fainter than the GC luminosity function turnover point, and thus thoroughly cover the bright half of the GC population. Most of the individual GCs on these images are marginally resolved nonstellar objects, so King-model profiles convolved with the stellar point-spread functions are used to measure their individual total magnitudes, colors, and linear effective radii. The classic bimodal form of the GC color-magnitude distribution shows up unambiguously in all the galaxies, allowing an accurate definition of the mean colors along each of the two sequences as a function of magnitude (the mass/metallicity relation or MMR). The blue, metal-poor cluster sequence shows a clearly defined but nonlinear MMR: in this particular photometric data set the mean GC color changes smoothly from a near-vertical sequence at low luminosity (MI gsim -9.5) to an increasingly redward slope at higher luminosity. By contrast, the red, metal-rich sequence shows little trace of an MMR and is nearly vertical at all luminosities. The form and slope of the MMR along either sequence do not depend strongly on either cluster size rh or galactocentric distance R gc. All the observed features of the present data agree with the interpretation that the MMR is created primarily by GC self-enrichment, along the lines of the quantitative model of Bailin & Harris. During the protocluster formation stage, the more massive GCs are better able to hold back the enriched products of the earliest supernovae and to seed the lower-mass stars still in formation. The "threshold

  11. Variable Stars in the Unusual, Metal-Rich Globular Cluster NGC-6441

    NASA Technical Reports Server (NTRS)

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

    2001-01-01

    We have undertaken a search for variable stars in the metal-rich globular cluster NGC 6441 using time-series BV photometry. The total number of variables found near NGC 6441 has been increased to approx. 104, with 48 new variables being found in this survey. A significant number of the variables are RR Lyrae stars (approx. 46), most of which are probable cluster members. As was noted by Layden et al. (1999), the periods of the fundamental mode RR Lyrae are unusually long compared to field stars of similar metallicity. The existence of these long period RRab stars is consistent with Sweigart & Catelan's (1998) prediction that the horizontal branch of NGC 6441 is unusually bright. This result implies that the metallicity-luminosity relationship for RR Lyrae stars is not universal. We discuss the difficulty in determining the Oosterhoff classification of NGC 6441 due to the unusual nature of its RR Lyrae. A number of ab-type RR Lyrae are found to be both brighter and redder than the other probable RRab found along the horizontal branch, which may be a result of blending with stars of redder color. A smaller than usual gap is found between the shortest period fundamental mode and the longest period first-overtone mode RR Lyrae. We determine the reddening of the cluster to be E(B - V) = 0.51 +/- 0.02 mag, with substantial differential reddening across the face of the cluster. The mean V magnitude of the RR Lyrae is found to be 17.51 +/- 0.02 resulting in a distance of 10.4 to 11.9 kpc, for a range of assumed values of < M(sub V)> for RR Lyrae stars. The possibility that stars in NGC 6441 may span a range in [Fe/H] is also discussed.

  12. Atomic Resolution of the Structure of a Metal Support Interface: Triosmium Clusters on MgO (110)

    SciTech Connect

    Browning, Nigel D.; Chi, Miaofang; Gates, Bruce C.; kulkarni, Apoorva; Ortalan, Volkan

    2010-01-01

    Aberration-corrected STEM images of MgO-supported triosmium clusters show that the osmium atoms reside atop magnesium atoms. On the basis of the results, structural models of the clusters that include the metal-support interaction are derived.

  13. THE METALLICITY BIMODALITY OF GLOBULAR CLUSTER SYSTEMS: A TEST OF GALAXY ASSEMBLY AND OF THE EVOLUTION OF THE GALAXY MASS-METALLICITY RELATION

    SciTech Connect

    Tonini, Chiara

    2013-01-01

    We build a theoretical model to study the origin of the globular cluster metallicity bimodality in the hierarchical galaxy assembly scenario. The model is based on empirical relations such as the galaxy mass-metallicity relation [O/H]-M {sub star} as a function of redshift, and on the observed galaxy stellar mass function up to redshift z {approx} 4. We make use of the theoretical merger rates as a function of mass and redshift from the Millennium simulation to build galaxy merger trees. We derive a new galaxy [Fe/H]-M {sub star} relation as a function of redshift, and by assuming that globular clusters share the metallicity of their original parent galaxy at the time of their formation, we populate the merger tree with globular clusters. We perform a series of Monte Carlo simulations of the galaxy hierarchical assembly, and study the properties of the final globular cluster population as a function of galaxy mass, assembly and star formation history, and under different assumptions for the evolution of the galaxy mass-metallicity relation. The main results and predictions of the model are the following. (1) The hierarchical clustering scenario naturally predicts a metallicity bimodality in the galaxy globular cluster population, where the metal-rich subpopulation is composed of globular clusters formed in the galaxy main progenitor around redshift z {approx} 2, and the metal-poor subpopulation is composed of clusters accreted from satellites, and formed at redshifts z {approx} 3-4. (2) The model reproduces the observed relations by Peng et al. for the metallicities of the metal-rich and metal-poor globular cluster subpopulations as a function of galaxy mass; the positions of the metal-poor and metal-rich peaks depend exclusively on the evolution of the galaxy mass-metallicity relation and the [O/Fe], both of which can be constrained by this method. In particular, we find that the galaxy [O/Fe] evolves linearly with redshift from a value of {approx}0.5 at redshift

  14. Structure and Function of Non-Native Metal Clusters in Human Arginase I

    PubMed Central

    D’Antonio, Edward L.; Hai, Yang; Christianson, David W.

    2012-01-01

    Various binuclear metal ion clusters and complexes have been reconstituted in crystalline human arginase I by removing the Mn2+2-cluster of the wild-type enzyme with metal chelators and subsequently soaking the crystalline apoenzyme in buffer solutions containing NiCl2 or ZnCl2. X-ray crystal structures of these metal ion variants are correlated with catalytic activity measurements that reveal differences resulting from metal ion substitution. Additionally, treatment of crystalline Mn2+2-human arginase I with Zn2+ reveals for the first time the structural basis for inhibition by Zn2+, which forms a carboxylate-histidine-Zn2+ triad with H141 and E277. The imidazole side chain of H141 is known to be hyper-reactive and its chemical modification or mutagenesis is known to similarly compromise catalysis. The reactive substrate analogue 2(S)-amino-6-boronohexanoic acid (ABH) binds as a tetrahedral boronate anion to Mn2+2, Co2+2, Ni2+2, and Zn2+2 clusters in human arginase I, and it can be stabilized by a third inhibitory Zn2+ ion coordinated by H141. Since ABH binds as an analogue of the tetrahedral intermediate and its flanking transition states in catalysis, this implies that the various metallosubstituted enzymes are capable of some level of catalysis with an actual substrate. Accordingly, we establish the following trend for turnover number (kcat) and catalytic efficiency (kcat/KM): Mn2+ > Ni2+ ≈ Co2+ ≫ Zn2+. Therefore, Mn2+ is required for optimal catalysis by human arginase I. PMID:23061982

  15. Which Ab Initio Wave Function Methods Are Adequate for Quantitative Calculations of the Energies of Biradicals? The Performance of Coupled-Cluster and Multi-Reference Methods Along a Single-Bond Dissociation Coordinate

    SciTech Connect

    Yang, Ke; Jalan, Amrit; Green, William H.; Truhlar, Donald G.

    2013-01-08

    We examine the accuracy of single-reference and multireference correlated wave function methods for predicting accurate energies and potential energy curves of biradicals. The biradicals considered are intermediate species along the bond dissociation coordinates for breaking the F-F bond in F2, the O-O bond in H2O2, and the C-C bond in CH3CH3. We apply a host of single-reference and multireference approximations in a consistent way to the same cases to provide a better assessment of their relative accuracies than was previously possible. The most accurate method studied is coupled cluster theory with all connected excitations through quadruples, CCSDTQ. Without explicit quadruple excitations, the most accurate potential energy curves are obtained by the single-reference RCCSDt method, followed, in order of decreasing accuracy, by UCCSDT, RCCSDT, UCCSDt, seven multireference methods, including perturbation theory, configuration interaction, and coupled-cluster methods (with MRCI+Q being the best and Mk-MR-CCSD the least accurate), four CCSD(T) methods, and then CCSD.

  16. Photoelectron Spectroscopy of Transition Metal Hydride Cluster Anions and Their Roles in Hydrogenation Reactions

    NASA Astrophysics Data System (ADS)

    Zhang, Xinxing; Bowen, Kit

    The interaction between transition metals and hydrogen has been an intriguing research topic for such applications as hydrogen storage and catalysis of hydrogenation and dehydrogenation. Special bonding features between TM and hydrogen are interesting not only because they are scarcely reported but also because they could help to discover and understand the nature of chemical bonding. Very recently, we discovered a PtZnH5- cluster which possessed an unprecedented planar pentagonal coordination between the H5- moiety and Pt, and exhibited special σ-aromaticity. The H5-kernel as a whole can be viewed as a η5-H5 ligand for Pt. As the second example, an H2 molecule was found to act as a ligand in the PdH3-cluster, in which two H atoms form a η2-H2 type of ligation to Pd. These transition metal hydride clusters were considered to be good hydrogen sources for hydrogenation. The reactions between PtHn- and CO2 were investigated. We observed formate in the final product H2Pt(HCO2)- .

  17. Heterometallic triiron-oxo/hydroxo clusters: effect of redox-inactive metals.

    PubMed

    Herbert, David E; Lionetti, Davide; Rittle, Jonathan; Agapie, Theodor

    2013-12-26

    A series of tetranuclear oxo/hydroxo clusters comprised of three Fe centers and a redox-inactive metal (M) of various charge is reported. Crystallographic studies show an unprecedented Fe3M(μ4-O)(μ2-OH) core that remains intact upon changing M or the oxidation state of iron. Electrochemical studies reveal that the reduction potentials (E1/2) span a window of 500 mV and depend upon the Lewis acidity of M. Using the pKa of the M-aqua complex as a measure of Lewis acidity, these compounds display a linear dependence between E1/2 and acidity, with a slope of ∼70 mV per pKa unit. The current study of [Fe3MO(OH)] and previous ones of [Mn3MOn] (n = 2,4) moieties support the generality of the above relationship between the reduction potentials of heterometallic oxido clusters and the Lewis acidity of incorporated cations, as applied to clusters of different redox-active metals. PMID:24304416

  18. Collective-field-corrected strong field approximation for laser-irradiated metal clusters

    NASA Astrophysics Data System (ADS)

    Keil, Th; Bauer, D.

    2014-06-01

    The strong field approximation (SFA) formulated in terms of so-called ‘quantum orbits’ led to much insight into intense-laser driven ionization dynamics. In plain SFA, the emitted electron is treated as a free electron in the laser field alone. However, with improving experimental techniques and more advanced numerical simulations, it becomes more and more obvious that the plain SFA misses interesting effects even on a qualitative level. Examples are holographic side lobes, the low-energy structure, radial patterns in photoelectron spectra at low kinetic energies and strongly rotated angular distributions. For this reason, increasing efforts have been recently devoted to Coulomb corrections of the SFA. In the current paper, we follow a similar line but consider ionization of metal clusters. It is known that photoelectrons from clusters can be much more energetic than those emitted from atoms or small molecules, especially if the Mie resonance of the expanding cluster is evoked. We develop a SFA that takes the collective field inside the cluster via the simple rigid-sphere model into account. Our approach is based on field-corrected quantum orbits so that the acceleration process (or any other spectral feature of interest) can be investigated in detail.

  19. Scalable properties of metal clusters: A comparative study of modern exchange-correlation functionals

    NASA Astrophysics Data System (ADS)

    Koitz, Ralph; Soini, Thomas M.; Genest, Alexander; Trickey, S. B.; Rösch, Notker

    2012-07-01

    The performance of eight generalized gradient approximation exchange-correlation (xc) functionals is assessed by a series of scalar relativistic all-electron calculations on octahedral palladium model clusters Pdn with n = 13, 19, 38, 55, 79, 147 and the analogous clusters Aun (for n up through 79). For these model systems, we determined the cohesive energies and average bond lengths of the optimized octahedral structures. We extrapolate these values to the bulk limits and compare with the corresponding experimental values. While the well-established functionals BP, PBE, and PW91 are the most accurate at predicting energies, the more recent forms PBEsol, VMTsol, and VT{84}sol significantly improve the accuracy of geometries. The observed trends are largely similar for both Pd and Au. In the same spirit, we also studied the scalability of the ionization potentials and electron affinities of the Pd clusters, and extrapolated those quantities to estimates of the work function. Overall, the xc functionals can be classified into four distinct groups according to the accuracy of the computed parameters. These results allow a judicious selection of xc approximations for treating transition metal clusters.

  20. Main sequence of the metal-poor globular cluster M30 (NGC 7099)

    SciTech Connect

    Alcaino, G.; Liller, W.

    1980-10-01

    We present photographic photometry for 673 stars in the metal-poor globular cluster M30 (NGC 7099). The Racine wedge was used with the CTIO 1-m Yale telescope (..delta..m=3/sup m/.60), the CTIO 4-m telescope (..delta..m=6/sup m/.83), and the ESO 3.6-m telescope (..delta..m=4/sup m/.12) to extend the photoelectric limit from Vapprox. =16.3 to Vapprox. =20.4. For the main-sequence turn-off, we have determined its position to lie at V=18.4 +- 0.1 (m.e.) and B-V=0.49 +- 0.03 (m.e.). From these values, we calculate the intrinsic values M/sub v/ =3.87 and (B-V)/sub 0/=0.47. For the cluster as a whole, we derive a distance modulus (m-M)/sub V/=14.53 +- 0.15 and reddening E(B-V)=0.02 +- 0.02. Using the models of Iben and Rood (Astrophys. J. 159, 605 (1970)) and the isochrones of Demarque and McClure ((1977), in Evolution of Galaxies and Stellar Populations, edited by B. Tinsley and R. B. Larson (Yale University Observatory, New Haven), p. 199), we deduce the cluster's age to be 14.5( +- 4.0) x 10/sup 9/ yr. The large uncertainty in this value emphasizes the dire need for more work on cluster evolution.

  1. Supernovae contributions to metals in intra-cluster medium observed with Suzaku

    NASA Astrophysics Data System (ADS)

    Sato, Kosuke; Tokoi, Kazuyo; Matsushita, Kyoko; Ishisaki, Yoshitaka; Yamasaki, Noriko Y.; Ishida, Manabu; Ohashi, Takaya

    2008-05-01

    We studied the properties of the intra-cluster medium (ICM) in two clusters of galaxies (AWM 7 and Abell 1060) and two groups (HCG 62 and NGC 507) observed with the 5th Japanese X-ray astronomical satellite, Suzaku. We measured for the first time precise cumulative ICM metal masses and distributions for various elements, such as O, Ne, Mg, Si, S, Fe, within 0.1 and ~0.3 r180. Because of the good XIS sensitivity to emission lines, especially below 2 keV, we directly measured O and Mg line intensities and obtained abundances. Comparing our results with supernova nucleosynthesis models, the number ratio of Type II (SNe II) to Type Ia (SNe Ia) is estimated to be ~3.5, assuming the metal mass in the ICM is represented by the sum of products synthesized in SNe Ia and SNe II. Normalized by the K-band luminosities of present galaxies, and including the metals in stars, the integrated number of past SNe II explosions is estimated to be close to or somewhat higher than the star formation rate determined from Hubble Deep Field observations.

  2. Depth resolution improvement in secondary ion mass spectrometry analysis using metal cluster complex ion bombardment

    SciTech Connect

    Tomita, M.; Kinno, T.; Koike, M.; Tanaka, H.; Takeno, S.; Fujiwara, Y.; Kondou, K.; Teranishi, Y.; Nonaka, H.; Fujimoto, T.; Kurokawa, A.; Ichimura, S.

    2006-07-31

    Secondary ion mass spectrometry analyses were carried out using a metal cluster complex ion of Ir{sub 4}(CO){sub 7}{sup +} as a primary ion beam. Depth resolution was evaluated as a function of primary ion species, energy, and incident angle. The depth resolution obtained using cluster ion bombardment was considerably better than that obtained by oxygen ion bombardment under the same experimental condition due to reduction of atomic mixing in the depth. The authors obtained a depth resolution of {approx}1 nm under 5 keV, 45 deg. condition. Depth resolution was degraded by ion-bombardment-induced surface roughness at 5 keV with higher incident angles.

  3. Defect clusters formed from large collision cascades in fcc metals irradiated with spallation neutrons

    NASA Astrophysics Data System (ADS)

    Satoh, Y.; Matsuda, Y.; Yoshiie, T.; Kawai, M.; Matsumura, H.; Iwase, H.; Abe, H.; Kim, S. W.; Matsunaga, T.

    2013-11-01

    Fcc pure metals were irradiated with spallation neutrons (energies up to 500 MeV) at room temperature to a neutron fluence of 1 × 1018 n m-2 at KENS, High Energy Accelerator Research Organization (KEK). Defect clusters induced by large collision cascades were examined using transmission electron microscopy (TEM). In Au, large groups of defects included more than 10 clusters, and the damage zone extended over 50 nm, which was larger than that induced by fusion neutron irradiation (<20 nm). Although small stacking fault tetrahedra (SFT) are formed in subcascades by fission and fusion neutron irradiation, dislocation loops were also observed in the present experiments. Large dislocation loops (>10 nm) were identified as vacancy type by the conventional inside-outside contrast method. Because of the low neutron fluence, spatial overlapping of collision cascades was ignored. Large vacancy loops are formed through cooperative reactions among subcascades in a single collision cascade with large recoil energy.

  4. Niobium Cluster Compounds with Transition Metals: K 2Mn[Nb 6Cl 18

    NASA Astrophysics Data System (ADS)

    Sitar, Jennifer; Lachgar, Abdessadek; Womelsdorf, Hermann; Meyer, H.-Jürgen

    1996-03-01

    A new quaternary niobium cluster chloride, K2Mn[Nb6Cl18], has been synthesized in a sealed quartz tube from stoichiometric amounts of NbCl5, niobium metal, KCl, and MnCl2at 720°C. The structure, as determined by single-crystal X-ray diffraction, is rhombohedral, space groupR3 (No. 148) withZ= 3 and has lattice parametersa= 914.01 (4) pm,c= 2522.9 (2) pm (hexagonal setting). The structure refinement based onF2yielded wR2 = 0.040. (For comparison, a refinement based onFvalues yieldedR1 = 0.016). The structure contains isolated [Nb6Cl18]4-clusters, separated by K+and Mn2+cations, being located in an anticubeoctahedral and octahedral chloride coordination environment, respectively.

  5. Smoothing metallic glasses without introducing crystallization by gas cluster ion beam

    SciTech Connect

    Shao, Lin; Chen, Di; Myers, Michael; Wang, Jing; Tilakaratne, Buddhi; Wijesundera, Dharshana; Chu, Wei-Kan; Xie, Guoqiang; Zare, Arezoo; Lucca, Don A.

    2013-03-11

    We show that 30 keV Ar cluster ion bombardment of Ni{sub 52.5}Nb{sub 10}Zr{sub 15}Ti{sub 15}Pt{sub 7.5} metallic glass (MG) can remove surface mountain-like features and reduce the root mean square surface roughness from 12 nm to 0.7 nm. X-ray diffraction analysis reveals no crystallization after cluster ion irradiation. Molecular dynamics simulations show that, although damage cascades lead to local melting, the subsequent quenching rate is a few orders of magnitude higher than the critical cooling rate for MG formation, thus the melted zone retains its amorphous nature down to room temperature. These findings can be applied to obtain ultra-smooth MGs without introducing crystallization.

  6. 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

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

    SciTech Connect

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

    2015-06-15

    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 with 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.

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

    SciTech Connect

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

    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 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.

  9. Constraining Stellar Population Models. I. Age, Metallicity and Abundance Pattern Compilation for Galactic Globular Clusters

    NASA Astrophysics Data System (ADS)

    Roediger, Joel C.; Courteau, Stéphane; Graves, Genevieve; Schiavon, Ricardo P.

    2014-01-01

    We present an extensive literature compilation of age, metallicity, and chemical abundance pattern information for the 41 Galactic globular clusters (GGCs) studied by Schiavon et al. Our compilation constitutes a notable improvement over previous similar work, particularly in terms of chemical abundances. Its primary purpose is to enable detailed evaluations of and refinements to stellar population synthesis models designed to recover the above information for unresolved stellar systems based on their integrated spectra. However, since the Schiavon sample spans a wide range of the known GGC parameter space, our compilation may also benefit investigations related to a variety of astrophysical endeavors, such as the early formation of the Milky Way, the chemical evolution of GGCs, and stellar evolution and nucleosynthesis. For instance, we confirm with our compiled data that the GGC system has a bimodal metallicity distribution and is uniformly enhanced in the α elements. When paired with the ages of our clusters, we find evidence that supports a scenario whereby the Milky Way obtained its globular clusters through two channels: in situ formation and accretion of satellite galaxies. The distributions of C, N, O, and Na abundances and the dispersions thereof per cluster corroborate the known fact that all GGCs studied so far with respect to multiple stellar populations have been found to harbor them. Finally, using data on individual stars, we verify that stellar atmospheres become progressively polluted by CN(O)-processed material after they leave the main sequence. We also uncover evidence which suggests that the α elements Mg and Ca may originate from more than one nucleosynthetic production site. We estimate that our compilation incorporates all relevant analyses from the literature up to mid-2012. As an aid to investigators in the fields named above, we provide detailed electronic tables of the data upon which our work is based at http

  10. Microplasma synthesis of sub-5 nm metal clusters: A novel platform for study and discovery

    NASA Astrophysics Data System (ADS)

    Sankaran, R. Mohan

    2013-09-01

    Homogeneous, gas-phase nucleation of particles in reactive plasmas is well known. Dust formation in chemical vapor deposition (CVD) processes is undesired and can lead to deleterious effects on device fabrication and performance. Recently, plasma systems have been developed to purposefully synthesize nanoparticles for technological applications. The advantage of plasmas over other chemical methods include the high purity, uniformity of particle size, and the possibility of accessing unique chemistries through the non-equilibrium environment. In this talk, I will present our contribution to this rapidly emerging field: the development of a new class of atmospheric-pressure, low-temperature microplasma systems that enables the synthesis of unagglomerated, sub-5 nm particles in a single step. The synthesis of clusters in this size range is of current interest for the study and discovery of novel nanomaterials. To illustrate this point, two examples will be presented. One, clusters of Ni, Fe, and other metals are produced from their corresponding organometallic precursors. Alloys with precisely controlled compositions are also obtained by tuning the relative amount of the precursors in the plasma phase. The availability of metal clusters with well-defined size and composition has allowed us to systematically study carbon nanotube nucleation and growth, and relate the properties of the catalyst to the as-grown tube diameter and chirality. Two, we have carried out studies of carbon cluster formation and observed the presence of diamond-phase carbon. The nucleation of diamond at near ambient conditions supports theoretical predictions of the stability of sp3 diamond over sp2 carbon and suggests a potential route for their existence in the cosmos. NSF Award No. CBET-0746821 and AFOSR Award No. FA9550-10-1-0160.

  11. METAL FORMING AND FABRICATION CLUSTER--AN INVESTIGATION AND DEVELOPMENT OF THE CLUSTER CONCEPT AS A PROGRAM IN VOCATIONAL EDUCATION AT THE SECONDARY LEVEL.

    ERIC Educational Resources Information Center

    MALEY, DONALD

    THIS COURSE OUTLINE ON METAL FORMING AND FABRICATION IS PART OF THE FINAL REPORT ON "CLUSTER CONCEPT" COURSES IN VOCATIONAL EDUCATION FOR SECONDARY EDUCATION (ED 010 301). EACH JOB ENTRY TASK WAS ANALYZED FOR HUMAN REQUIREMENTS (COMMUNICATION,MEASUREMENT, MATHEMATICS, SCIENCE, SKILLS, AND INFORMATION) NECESSARY TO PERFORMANCE OF THE TASK. THE TASK…

  12. Voltage clustering in redox-active ligand complexes: mitigating electronic communication through choice of metal ion.

    PubMed

    Zarkesh, Ryan A; Ichimura, Andrew S; Monson, Todd C; Tomson, Neil C; Anstey, Mitchell R

    2016-06-14

    The redox-active bis(imino)acenapthene (BIAN) ligand was used to synthesize homoleptic aluminum, chromium, and gallium complexes of the general formula (BIAN)3M. The resulting compounds were characterized using X-ray crystallography, NMR, EPR, magnetic susceptibility and cyclic voltammetry measurements and modeled using both DFT and ab initio wavefunction calculations to compare the orbital contributions of main group elements and transition metals in ligand-based redox events. Complexes of this type have the potential to improve the energy density and electrolyte stability of grid-scale energy storage technologies, such as redox flow batteries, through thermodynamically-clustered redox events. PMID:26998892

  13. Voltage clustering in redox-active ligand complexes: mitigating electronic communication through choice of metal ion

    DOE PAGESBeta

    Zarkesh, Ryan A.; Ichimura, Andrew S.; Monson, Todd C.; Tomson, Neil C.; Anstey, Mitchell R.

    2016-02-01

    We used the redox-active bis(imino)acenapthene (BIAN) ligand to synthesize homoleptic aluminum, chromium, and gallium complexes of the general formula (BIAN)3M. The resulting compounds were characterized using X-ray crystallography, NMR, EPR, magnetic susceptibility and cyclic voltammetry measurements and modeled using both DFT and ab initio wavefunction calculations to compare the orbital contributions of main group elements and transition metals in ligand-based redox events. Ultimately, complexes of this type have the potential to improve the energy density and electrolyte stability of grid-scale energy storage technologies, such as redox flow batteries, through thermodynamically-clustered redox events.

  14. Investigating the Synthesis of Ligated Metal Clusters in Solution Using a Flow Reactor and Electrospray Ionization Mass Spectrometry

    SciTech Connect

    Olivares, Astrid M.; Laskin, Julia; Johnson, Grant E.

    2014-09-18

    The scalable synthesis of subnanometer metal clusters containing an exact number of atoms is of interest due to the highly size-dependent catalytic, electronic and optical properties of these species. While significant research has been conducted on the batch preparation of clusters through reduction synthesis in solution, the processes of metal complex reduction as well as cluster nucleation, growth and post-reduction etching are still not well understood. Herein, we demonstrate a temperature-controlled flow reactor for studying cluster formation in solution at well-defined conditions. Employing this technique methanol solutions of a chloro(triphenylphosphine)gold precursor, 1,4-bis(diphenylphosphino)butane capping ligand and borane-tert-butylamine reducing agent were combined in a mixing tee and introduced into a heated capillary with an adjustable length. In this manner, the temperature dependence of the relative abundance of different ionic reactants, intermediates and products synthesized in real time was characterized using online mass spectrometry. A wide distribution of doubly and triply charged cationic gold clusters was observed as well as smaller singly charged metal-ligand complexes. The results demonstrate that temperature plays a crucial role in determining the relative population of cationic gold clusters and, in general, that higher temperature promotes the formation of doubly charged clusters and singly charged metal-ligand complexes while hindering the growth of triply charged clusters. Moreover, the distribution of clusters observed at elevated temperatures is found to be consistent with that obtained at longer reaction times at room temperature, thereby demonstrating that heating may be used to access cluster distributions characteristic of different stages of reduction synthesis in solution.

  15. CO{sub 2} reduction by group 6 transition metal suboxide cluster anions

    SciTech Connect

    Hossain, Ekram; Rothgeb, David W.; Jarrold, Caroline Chick

    2010-07-14

    Reactions between small group 6 transition metal suboxide clusters, M{sub x}O{sub y}{sup -} (M={sup 98}Mo or {sup 186}W; x=1-4; y{<=}3x) and both CO{sub 2} and CO were studied in gas phase using mass spectrometric analysis of high-pressure, fast flow reaction products. Both Mo{sub 2}O{sub y}{sup -} and W{sub 2}O{sub y}{sup -} show evidence of sequential oxidation by CO{sub 2} of the form, M{sub 2}O{sub y}{sup -}+CO{sub 2}{yields}M{sub 2}O{sub y+1}{sup -}+CO for the more reduced species. Similar evidence is observed for the trimetallic clusters, although Mo{sub 3}O{sub 6}{sup -} appears uniquely unreactive. Lower mass resolution in the M{sub 4}O{sub y}{sup -} range precludes definitive product mass assignments, but intensity patterns suggest the continued trend of sequential oxidation of the more reduced end of the M{sub 4}O{sub y}{sup -} oxide series. Based on thermodynamic arguments, cluster oxidation by CO{sub 2} is possible if D{sub 0}(O-Mo{sub x}O{sub y}{sup -})>5.45 eV. Although simple bond energy analysis suggests that tungsten oxides may be more reactive toward CO{sub 2} compared to molybdenum oxides, this is not born out experimentally, suggesting that the activation barrier for the reduction of CO{sub 2} by tungsten suboxide clusters is very high compared to analogous molybdenum suboxide clusters. In reactions with CO, suboxides of both metal-based oxides show CO addition, with the product distribution being more diverse for Mo{sub x}O{sub y}{sup -} than for W{sub x}O{sub y}{sup -}. No evidence of cluster reduction by CO is observed.

  16. Destructive Clustering of Metal Nanoparticles in Chalcogenide and Oxide Glassy Matrices

    NASA Astrophysics Data System (ADS)

    Shpotyuk, M. V.; Shpotyuk, O. I.; Cebulski, J.; Kozyukhin, S.

    2016-01-01

    The energetic χ-criterion is developed to parameterize difference in the origin of high-order optical non-linearity associated with metallic atoms (Cu, Ag, Au) embedded destructively in oxide- and chalcogenide glasses. Within this approach, it is unambiguously proved that covalent-bonded networks of soft semiconductor chalcogenides exemplified by binary As(Ge)-S(Se) glasses differ essentially from those typical for hard dielectric oxides like vitreous silica by impossibility to accommodate pure agglomerates of metallic nanoparticles. In an excellence according to known experimental data, it is suggested that destructive clustering of nanoparticles is possible in Cu-, Ag-, and Au-ion-implanted dielectric oxide glass media, possessing a strongly negative χ-criterion. Some recent speculations trying to ascribe equally this ability to soft chalcogenide glasses despite an obvious difference in the corresponding bond dissociation energies have been disclosed and criticized as inconclusive.

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

    NASA Technical Reports Server (NTRS)

    Kahn, L. R.

    1981-01-01

    The application of ab initio quantum mechanical approaches in the study of metal atom clusters requires simplifying techniques that do not compromise the reliability of the calculations. Various aspects of the implementation of the effective core potential (ECP) technique for the removal of the metal atom core electrons from the calculation were examined. The ECP molecular integral formulae were modified to bring out the shell characteristics as a first step towards fulfilling the increasing need to speed up the computation of the ECP integrals. Work on the relationships among the derivatives of the molecular integrals that extends some of the techniques pioneered by Komornicki for the calculation of the gradients of the electronic energy was completed and a formulation of the ECP approach that quite naturally unifies the various state-of-the-art "shape- and Hamiltonian-consistent" techniques was discovered.

  18. Destructive Clustering of Metal Nanoparticles in Chalcogenide and Oxide Glassy Matrices.

    PubMed

    Shpotyuk, M V; Shpotyuk, O I; Cebulski, J; Kozyukhin, S

    2016-12-01

    The energetic χ-criterion is developed to parameterize difference in the origin of high-order optical non-linearity associated with metallic atoms (Cu, Ag, Au) embedded destructively in oxide- and chalcogenide glasses. Within this approach, it is unambiguously proved that covalent-bonded networks of soft semiconductor chalcogenides exemplified by binary As(Ge)-S(Se) glasses differ essentially from those typical for hard dielectric oxides like vitreous silica by impossibility to accommodate pure agglomerates of metallic nanoparticles. In an excellence according to known experimental data, it is suggested that destructive clustering of nanoparticles is possible in Cu-, Ag-, and Au-ion-implanted dielectric oxide glass media, possessing a strongly negative χ-criterion. Some recent speculations trying to ascribe equally this ability to soft chalcogenide glasses despite an obvious difference in the corresponding bond dissociation energies have been disclosed and criticized as inconclusive. PMID:26787053

  19. A comment on the metal abundance of the globular cluster M71

    NASA Astrophysics Data System (ADS)

    Bell, R. A.; Gustafsson, B.

    1982-04-01

    A new estimate of the metal abundance of the globular cluster M71 is derived based on the echelle spectra obtained by Cohen (1980) for four M71 red giants and the application of synthetic colors to the interpretation of available photometry. The colors used are the DDO colors of Bell and Gustafsson (1978), and colors for the Searle and Zinn (1978) system computed from the same synthetic spectra as the DDO colors. Photometric data yield a value for the metal abundance of M71 of about -0.6, whereas a reanalysis of Cohen's data yields a value of about -0.9 or less. Possible explanations for the discrepancy are suggested, and future studies which may serve to determine the correct explanation are pointed out.

  20. Ab Initio Molecular Dynamics of Dimerization and Clustering in Alkali Metal Vapors.

    PubMed

    Chaban, Vitaly V; Prezhdo, Oleg V

    2016-06-30

    Alkali metals are known to form dimers, trimers, and tetramers in their vapors. The mechanism and regularities of this phenomenon characterize the chemical behavior of the first group elements. We report ab initio molecular dynamics (AIMD) simulations of the alkali metal vapors and characterize their structural properties, including radial distribution functions and atomic cluster size distributions. AIMD confirms formation of Men, where n ranges from 2 to 4. High pressure sharply favors larger structures, whereas high temperature decreases their fraction. Heavier alkali metals maintain somewhat larger fractions of Me2, Me3, and Me4, relative to isolated atoms. A single atom is the most frequently observed structure in vapors, irrespective of the element and temperature. Due to technical difficulties of working with high temperatures and pressures in experiments, AIMD is the most affordable method of research. It provides valuable understanding of the chemical behavior of Li, Na, K, Rb, and Cs, which can lead to development of new chemical reactions involving these metals. PMID:27294399

  1. PRIMORDIAL r-PROCESS DISPERSION IN METAL-POOR GLOBULAR CLUSTERS

    SciTech Connect

    Roederer, Ian U.

    2011-05-01

    Heavy elements, those produced by neutron-capture reactions, have traditionally shown no star-to-star dispersion in all but a handful of metal-poor globular clusters (GCs). Recent detections of low [Pb/Eu] ratios or upper limits in several metal-poor GCs indicate that the heavy elements in these GCs were produced exclusively by an r-process. Re-examining GC heavy element abundances from the literature, we find unmistakable correlations between the [La/Fe] and [Eu/Fe] ratios in four metal-poor GCs (M5, M15, M92, and NGC 3201), only two of which were known previously. This indicates that the total r-process abundances vary from star to star (by factors of 2-6) relative to Fe within each GC. We also identify potential dispersion in two other GCs (M3 and M13). Several GCs (M12, M80, and NGC 6752) show no evidence of r-process dispersion. The r-process dispersion is not correlated with the well-known light element dispersion, indicating that it was present in the gas throughout the duration of star formation. The observations available at present suggest that star-to-star r-process dispersion within metal-poor GCs may be a common but not ubiquitous phenomenon that is neither predicted by nor accounted for in current models of GC formation and evolution.

  2. A new method for measuring metallicities of young super star clusters

    SciTech Connect

    Gazak, J. Zachary; Kudritzki, Rolf; Bresolin, Fabio; Davies, Ben; Bastian, Nate; Bergemann, Maria; Plez, Bertrand; Evans, Chris; Patrick, Lee; Schinnerer, Eva

    2014-06-01

    We demonstrate how the metallicities of young super star clusters (SSC) can be measured using novel spectroscopic techniques in the J-band. The near-infrared flux of SSCs older than ∼6 Myr is dominated by tens to hundreds of red supergiant stars. Our technique is designed to harness the integrated light of that population and produces accurate metallicities for new observations in galaxies above (M83) and below (NGC 6946) solar metallicity. In M83 we find [Z] = +0.28 ± 0.14 dex using a moderate resolution (R ∼ 3500) J-band spectrum and in NGC 6496 we report [Z] = -0.32 ± 0.20 dex from a low resolution spectrum of R ∼ 1800. Recently commissioned low resolution multiplexed spectrographs on the Very Large Telescope (KMOS) and Keck (MOSFIRE) will allow accurate measurements of SSC metallicities across the disks of star-forming galaxies up to distances of 70 Mpc with single night observation campaigns using the method presented in this paper.

  3. Metal distribution in sloshing galaxy clusters: the case of A496

    NASA Astrophysics Data System (ADS)

    Ghizzardi, Simona; De Grandi, Sabrina; Molendi, Silvano

    2014-10-01

    We report results from a detailed study of the sloshing gas in the core of A496. We detected the low-temperature/entropy spiral feature found in several cores. We also found that conduction between the gas in the spiral and the ambient medium must be suppressed by more than one order of magnitude compared with the Spitzer conductivity. Intriguingly, while the gas in the spiral pattern features a higher metal abundance than the surrounding medium, it follows the relation of entropy vs metal abundance defined by gas outside the spiral. The most plausible explanation for this behavior is that the low-entropy metal-rich plasma that is lifted up through the cluster atmosphere by sloshing suffers little heating or mixing with the ambient medium. While sloshing appears to be capable of lifting up significant amount of gas, the limited heat exchange and mixing between gas within and outside the spiral implies that this mechanism is not at all effective in 1) permanently redistributing metals within the core region and 2) heating up the coolest and densest gas, thereby providing little or no contribution to the staving off of catastrophic cooling in cool cores. Appendices are available in electronic form at http://www.aanda.org

  4. Electronic structures and water reactivity of mixed metal sulfide cluster anions

    SciTech Connect

    Saha, Arjun; Raghavachari, Krishnan

    2014-08-21

    The electronic structures and chemical reactivity of the mixed metal sulfide cluster anion (MoWS{sub 4}{sup −}) have been investigated with density functional theory. Our study reveals the presence of two almost isoenergetic structural isomers, both containing two bridging sulfur atoms in a quartet state. However, the arrangement of the terminal sulfur atoms is different in the two isomers. In one isomer, the two metals are in the same oxidation state (each attached to one terminal S). In the second isomer, the two metals are in different oxidation states (with W in the higher oxidation state attached to both terminal S). The reactivity of water with the two lowest energy isomers has also been studied, with an emphasis on pathways leading to H{sub 2} release. The reactive behavior of the two isomers is different though the overall barriers in both systems are small. The origin of the differences are analyzed and discussed. The reaction pathways and barriers are compared with the corresponding behavior of monometallic sulfides (Mo{sub 2}S{sub 4}{sup −} and W{sub 2}S{sub 4}{sup −}) as well as mixed metal oxides (MoWO{sub 4}{sup −})

  5. First principle investigation of the magnetic properties of transition metal doped (ZnS)n (n=1-16) clusters

    NASA Astrophysics Data System (ADS)

    Kaur, Navjot; Singh, Kanchan L.; Sharma, Hitesh

    2015-08-01

    The magnetic properties of (ZnS)n clusters (n = 1 - 16) due to 3d transition metals have been investigated using spin polarized density functional theory. The transition metals are more stable at Zn site than at the S site in (ZnS)n clusters. The binding energy of (ZnS)n clusters increases significantly on doping with transition metal indicating enhanced structural stability of the doped (ZnS)n clusters. All 3d transition metals induced magnetic moment of order 5μB-1μB per atom in all (ZnS)n clusters. The magnetic moment is mainly localized on the TM dopant. The magnetic moment increases gradually with the increase in number of electrons in 3d orbital which is in accordance with Hund's rule till Mn and decreases thereafter. All 3d TMs retain their atomic magnetic moment in ZnS clusters of all sizes. Ti, V, Cr and Mn interact anti-ferromagnetically with the surrounding S and Zn, whereas Sc, Fe, Co, Ni and Cu interact with ferromagnetic interactions.

  6. The helium abundance in the metal-poor globular clusters M30 and NGC 6397

    SciTech Connect

    Mucciarelli, A.; Lovisi, L.; Lanzoni, B.; Ferraro, F. R.

    2014-05-01

    We present the helium abundance of the two metal-poor clusters M30 and NGC 6397. Helium estimates have been obtained by using the high-resolution spectrograph FLAMES at the European Southern Observatory Very Large Telescope and by measuring the He I line at 4471 Å in 24 and 35 horizontal branch (HB) stars in M30 and NGC 6397, respectively. This sample represents the largest data set of He abundances collected so far in metal-poor clusters. The He mass fraction turns out to be Y = 0.252 ± 0.003 (σ = 0.021) for M30 and Y = 0.241 ± 0.004 (σ = 0.023) for NGC 6397. These values are fully compatible with the cosmological abundance, thus suggesting that the HB stars are not strongly enriched in He. The small spread of the Y distributions are compatible with those expected from the observed main sequence splitting. Finally, we find a hint of a weak anticorrelation between Y and [O/Fe] in NGC 6397 in agreement with the prediction that O-poor stars are formed by (He-enriched) gas polluted by the products of hot proton-capture reactions.

  7. 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.

  8. 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.

  9. Effect of clustering on the surface plasmon band in thin films of metallic nanoparticles

    NASA Astrophysics Data System (ADS)

    Pereira, Rui M. S.; Borges, Joel; Peres, Filipa C. R.; Pereira, Paulo A. S.; Smirnov, Georgi V.; Vaz, Filipe; Cavaleiro, Albano; Vasilevskiy, Mikhail I.

    2015-01-01

    We theoretically investigate the optical response of ensembles of polarizable metallic nanoparticles (NPs) that form (1) submonolayer films of particles adsorbed on a dielectric substrate, considered as two-dimensional (2-D) systems, and (2) thin three-dimensional (3-D) films, where NPs are embedded in a dielectric matrix. For system (1), the effect of NPs' distance to the substrate is taken into account. In both cases, we find that short-range clustering leads to a broadening and a spectral shift of the absorption band related to the surface plasmon resonance (SPR) in individual NPs. We show that the clustering can help in achieving spectrally broad SPR bands, especially if NPs aggregate into fractal clusters, which can be interesting for some applications such as surface-enhanced Raman scattering. In particular, submonolayer films on NPs generated using the diffusion-limited aggregation algorithm produce sizable and spectrally broad absorption, which can be tuned to the visible range by choosing an appropriate capping and/or substrate material. Calculated results for thin 3-D films are compared with experimental data obtained for Au/TiO2 nanocomposite layers produced by reactive cosputtering.

  10. A comparative topological study of different metal-metal and metal-ligand interactions in polynuclear organometallic clusters

    SciTech Connect

    Van der Maelen, Juan F.; García-Granda, Santiago

    2015-01-22

    The existence and characterization of a bond between the Zn atoms in the recently synthesized complex [Zn{sub 2}(η{sup 5}−C{sub 5}Me{sub 5}){sub 2}] (I), as well as between two of the three Ru atoms in [Ru{sub 3}(μ−H){sub 2}(μ{sub 3}−MeImCH)(CO{sub 9}] (Me{sub 2}Im = 1,3-dimethylimidazolin-2-ylidene) (II), are firmly based on low temperature X-ray synchrotron diffraction experiments. The multipolar refinement of the experimental electron densities and their topological analyses by means of the Atoms in Molecules (AIM) theory reveal the details of the Zn-Zn and Ru-Ru bonds, such as their open-shell intermediate character. The results are consistent with a typical metal-metal single σ bond for the former, whereas a delocalized kind of bond involving 5c-6e is present in the latter. In addition, experimental results are compared with theoretical ab initio calculations of the DFT (density functional theory) and MP2 (Mo/ller-Plesset perturbation theory) electron densities, giving a coherent view of the bonding in both complexes. Many other topological properties of both compounds are also studied, in particular the different metal-ligand interactions.

  11. Fluorescent probes for tracking the transfer of iron-sulfur cluster and other metal cofactors in biosynthetic reaction pathways.

    PubMed

    Vranish, James N; Russell, William K; Yu, Lusa E; Cox, Rachael M; Russell, David H; Barondeau, David P

    2015-01-14

    Iron-sulfur (Fe-S) clusters are protein cofactors that are constructed and delivered to target proteins by elaborate biosynthetic machinery. Mechanistic insights into these processes have been limited by the lack of sensitive probes for tracking Fe-S cluster synthesis and transfer reactions. Here we present fusion protein- and intein-based fluorescent labeling strategies that can probe Fe-S cluster binding. The fluorescence is sensitive to different cluster types ([2Fe-2S] and [4Fe-4S] clusters), ligand environments ([2Fe-2S] clusters on Rieske, ferredoxin (Fdx), and glutaredoxin), and cluster oxidation states. The power of this approach is highlighted with an extreme example in which the kinetics of Fe-S cluster transfer reactions are monitored between two Fdx molecules that have identical Fe-S spectroscopic properties. This exchange reaction between labeled and unlabeled Fdx is catalyzed by dithiothreitol (DTT), a result that was confirmed by mass spectrometry. DTT likely functions in a ligand substitution reaction that generates a [2Fe-2S]-DTT species, which can transfer the cluster to either labeled or unlabeled Fdx. The ability to monitor this challenging cluster exchange reaction indicates that real-time Fe-S cluster incorporation can be tracked for a specific labeled protein in multicomponent assays that include several unlabeled Fe-S binding proteins or other chromophores. Such advanced kinetic experiments are required to untangle the intricate networks of transfer pathways and the factors affecting flux through branch points. High sensitivity and suitability with high-throughput methodology are additional benefits of this approach. We anticipate that this cluster detection methodology will transform the study of Fe-S cluster pathways and potentially other metal cofactor biosynthetic pathways. PMID:25478817

  12. Surface modes of big clusters and resonances in generalized LC-model of metal-dielectric nanocomposites

    NASA Astrophysics Data System (ADS)

    Olekhno, N. A.; Beltukov, Y. M.; Parshin, D. A.

    2015-12-01

    Random impedance networks with inductive L and capacitive C bonds have been widely addressed in a literature to describe properties of disordered metal-dielectric nanocomposites. In this paper we show that networks with single bonds in the form of parallel oscillatory LC-circuits and capacitances C are more appropriate model for metal-dielectric composite in optical frequency range. Resonant spectrum of such networks demonstrates absence of resonances at frequencies higher than the plasma frequency of metal ωp. Eigenmodes of big ordered clusters are studied. Their resonances are shown to be surface modes having the form of multipoles of various order. It is in agreement with theory of surface plasmons in metallic nanowires. The idea for metal-metal and metal-semiconductor nanocomposites with different plasma frequencies is put forward.

  13. Modeling of cluster organization in metal-doped oxide glasses irradiated by a train of femtosecond laser pulses

    NASA Astrophysics Data System (ADS)

    Smetanina, Evgeniya; Chimier, Benoit; Petit, Yannick; Varkentina, Nadezda; Fargin, Evelyne; Hirsch, Lionel; Cardinal, Thierry; Canioni, Lionel; Duchateau, Guillaume

    2016-01-01

    The formation of silver cluster structures at submicrometer spatial scales under the irradiation by high-power femtosecond laser pulses with high repetition rate was observed in various glasses containing silver ions. In order to account for the formation of these structures in metal-doped glasses, we present a theoretical model for the organization of noble metallic clusters induced by a train of femtosecond laser pulses. The model includes photoionization and laser heating of the sample, diffusion, kinetic reactions, and dissociation of metallic species. This model was applied to reproduce the formation of cluster structures in silver-doped phosphate glass. The parameters of the silver structures were obtained numerically under various incident pulse intensities and number of pulses. Numerical modeling shows that the involved microscopic physical and chemical processes naturally lead to the emergence of a silver cluster organization, together with charge migration and subsequent trapping giving rise to a strong static electric field buried in the irradiated area as experimentally observed. Based on this modeling, a theoretical basis is provided for the design of new metallic cluster structures with nanoscale size.

  14. Ferromagnetism and suppression of metallic clusters in Fe implanted ZnO -- a phenomenon related to defects?

    SciTech Connect

    Arenholz, Elke; Zhou, S.; Potzger, K.; Talut, G.; Reuther, H.; Kuepper, K.; Grenzer, J.; Xu, Q.; Mucklich, A.; Helm, M.; Fassbender, J.; Arenholz, E.

    2008-03-12

    We investigated ZnO(0001) single crystals annealed in high vacuum with respect to their magnetic properties and cluster formation tendency after implant-doping with Fe. While metallic Fe cluster formation is suppressed, no evidence for the relevance of the Fe magnetic moment to the observed ferromagnetism was found. The latter along with the cluster suppression is discussed with respect to defects in the ZnO host matrix, since the crystalline quality of the substrates was lowered due to the preparation as observed by x-ray diffraction.

  15. Noble metal alloy clusters in the gas phase derived from protein templates: unusual recognition of palladium by gold.

    PubMed

    Baksi, Ananya; Pradeep, T

    2013-12-21

    Matrix assisted laser desorption ionization of a mixture of gold and palladium adducts of the protein lysozyme (Lyz) produces naked alloy clusters of the type Au24Pd(+) in the gas phase. While a lysozyme-Au adduct forms Au18(+), Au25(+), Au38(+) and Au102(+) ions in the gas phase, lysozyme-Pd alone does not form any analogous cluster. Addition of various transition metal ions (Ag(+), Pt(2+), Pd(2+), Cu(2+), Fe(2+), Ni(2+) and Cr(3+)) in the adducts contributes to drastic changes in the mass spectrum, but only palladium forms alloys in the gas phase. Besides alloy formation, palladium enhances the formation of specific single component clusters such as Au38(+). While other metal ions like Cu(2+) help forming Au25(+) selectively, Fe(2+) catalyzes the formation of Au25(+) over all other clusters. Gas phase cluster formation occurs from protein adducts where Au is in the 1+ state while Pd is in the 2+ state. The creation of alloys in the gas phase is not affected whether a physical mixture of Au and Pd adducts or a Au and Pd co-adduct is used as the precursor. The formation of Au cores and AuPd alloy cores of the kind comparable to monolayer protected clusters implies that naked clusters themselves may be nucleated in solution. PMID:24146135

  16. Assessment of PM10 and heavy metals concentration in a Ceramic Cluster (NE Spain)

    NASA Astrophysics Data System (ADS)

    Belen Vicente, Ana; Pardo, Francisco; Sanfeliu, Teofilo; Bech, Joan

    2013-04-01

    Environmental pollution control is one of the most important goals in pollution risk assessment today. The aim of this study is conducting a retrospective view of the evolution of particulate matter (PM10) and heavy metals (As, Cd, Ni and Pb) at different localities in the Spanish cluster ceramic in the period between January 2007 and December 2011. The study area is in the province of Castellón. This province is a strategical area in the framework of European Union Pollution control. Approximately 80% of European ceramic tiles and ceramic frits manufacturers are concentrated in two areas, forming the so-called "Ceramics Clusters"; one is in Modena (Italy) and the other in Castellón (Spain). In this kind of areas, there are a lot of pollutants from this industry that represent an important contribution to soil contamination so it is necessary to control the air quality in them. These atmospheric particles are deposited in the ground through both dry and wet deposition. Soil is a major sink for heavy metals released into the environment. The level of pollution of soils by heavy metals depends on the retention capacity of the soil, especially on physical-chemical properties (mineralogy, grain size, organic matter) affecting soil particle surfaces and also on the chemical properties of the metal. The most direct consequences on the ground of air pollutants are acidification, salinization and the pollutions that can cause heavy metals as components of suspended particulate matter. For this purpose the levels of PM10 in ambient air and the corresponding annual and weekly trend were calculated. The results of the study show that the PM10 and heavy metals concentrations are below the limit values recommended by European Union Legislation for the protection of human health and ecosystems in the study period. There is an important reduction of them from 2009 in all control stations due to the economic crisis. References Moral, R., Gilkes, R.J., Jordán, M.M., 2005

  17. Cluster Ion Beam Induced Nano Metallic Rippled Structures for Localized Surface Plasmon Resonance (LSPR) Based Sensors

    NASA Astrophysics Data System (ADS)

    Saleem, Iram; Tilakaratne, Buddhi; He, Yanzhi; Nzumbe, Epie; Wijesundera, Dharshana; Chen, Quark; Chu, Wei-Kan

    2015-03-01

    Localized surface plasmon resonance (LSPR) based bio sensors have a high sensitivity and exploit a label free real time analytical detection mechanism. We have produced plasmonic nano-structured substrates by cluster ion beam irradiation of thin gold films and have studied their effectiveness as potential plasmonic sensors. By adsorbing a mono-layer of thiolated organic compounds on the surface of these substrates we identified the shift in the LSPR peaks triggered by the change of dielectric function in the neighborhood of the structures. These plasmonic nano-metallic structures can be utilized to observe the change of LSPR resonance frequency due to adsorption, re-adsorption and reactions taking place on the surface that can potentially be mapped to reaction mechanics

  18. Quantum Monte Carlo study of charged transition-metal organometallic cluster systems

    NASA Astrophysics Data System (ADS)

    Tokar, Kamil; Derian, Rene; Stich, Ivan

    2015-03-01

    Using accurate fixed-node quantum Monte Carlo (QMC) methods we study 1D clusters formed by transition metal atoms separated by benzene molecules (TMBz), both positively and negatively charged. TMBz are among the most important π-bonded organometallics, which, however, often require charged states for experimental studies. We have performed a systematic study of ground-sate spin multiplets, ionization potentials, electron affinities, and dissociation energies of vanadium-benzene cationic and anionic half- and full-sandwiches. By comparison of QMC and DFT results, we find a very strong impact of electronic correlation on properties of these systems, such as dissociation energies, where ~1 eV energy corrections are found. In particular, the anions are unstable at the DFT level and are stabilized only at the QMC level after sophisticated optimization of the trial wavefunction. Supported by APVV-0207-11 and VEGA (2/0007/12) projects.

  19. INSIGHTS INTO PRE-ENRICHMENT OF STAR CLUSTERS AND SELF-ENRICHMENT OF DWARF GALAXIES FROM THEIR INTRINSIC METALLICITY DISPERSIONS

    SciTech Connect

    Leaman, Ryan

    2012-12-01

    Star clusters are known to have smaller intrinsic metallicity spreads than dwarf galaxies due to their shorter star formation timescales. Here we use individual spectroscopic [Fe/H] measurements of stars in 19 Local Group dwarf galaxies, 13 Galactic open clusters, and 49 globular clusters to show that star cluster and dwarf galaxy linear metallicity distributions are binomial in form, with all objects showing strong correlations between their mean linear metallicity Z-bar and intrinsic spread in metallicity {sigma}(Z){sup 2}. A plot of {sigma}(Z){sup 2} versus Z-bar shows that the correlated relationships are offset for the dwarf galaxies from the star clusters. The common binomial nature of these linear metallicity distributions can be explained with a simple inhomogeneous chemical evolution model, where the star cluster and dwarf galaxy behavior in the {sigma}(Z){sup 2}- Z-bar diagram is reproduced in terms of the number of enrichment events, covering fraction, and intrinsic size of the enriched regions. The inhomogeneity of the self-enrichment sets the slope for the observed dwarf galaxy {sigma}(Z){sup 2}- Z-bar correlation. The offset of the star cluster sequence from that of the dwarf galaxies is due to pre-enrichment, and the slope of the star cluster sequence represents the remnant signature of the self-enriched history of their host galaxies. The offset can be used to separate star clusters from dwarf galaxies without a priori knowledge of their luminosity or dynamical mass. The application of the inhomogeneous model to the {sigma}(Z){sup 2}- Z-bar relationship provides a numerical formalism to connect the self-enrichment and pre-enrichment between star clusters and dwarf galaxies using physically motivated chemical enrichment parameters. Therefore we suggest that the {sigma}(Z){sup 2}- Z-bar relationship can provide insight into what drives the efficiency of star formation and chemical evolution in galaxies, and is an important prediction for galaxy

  20. Structure Determination of Noble Metal Clusters by Trapped Ion Electron Diffraction

    NASA Astrophysics Data System (ADS)

    Schooss, Detlef

    2006-03-01

    The structures of noble metal cluster ions have been studied by the recently developed technique of trapped ion electron diffraction (TIED)^1. In brief, cluster ions are generated by a magnetron sputter source and injected into a cooled (95 K) quadrupole ion trap. After mass selection and thermalization, the trapped ions are irradiated with a 40 keV electron beam. The resulting diffraction pattern is integrated with a CCD detector. The assignment of the structural motif is done via a comparison of the experimental and simulated scattering function, calculated from density functional theory structure calculations. The structures of mass selected silver cluster cations Ag19^+, Ag38^+, Ag55^+, Ag59^+, Ag75^+ and Ag79^+ have been investigated^2. The resulting experimental data are best described by structures based on the icosahedral motif, while closed packed structures could be ruled out. Additionally, we present a comparison of the structures of Cu20^+/-, Ag20^+/- and Au20^+/-. Our findings show unambiguously that the structure of Au20^- is predominantly given by a tetrahedron in agreement with the results of L.S. Wang et al.^3 In contrast, structures of Ag20^- and Cu20^- based on the icosahedral motif agree best with the experimental data. Small structural differences between the charge states are observed. The possibilities and limitations of the TIED method are discussed. (1) M. Maier-Borst, D. B. Cameron, M. Rokni, and J. H. Parks, Physical Review A 59 (5), R3162 (1999); S. Krückeberg, D. Schooss, M. Maier-Borst, and J. H. Parks, Physical Review Letters 85 (21), 4494 (2000). (2) D. Schooss, M.N. Blom, B. v. Issendorff, J. H. Parks, and M.M. Kappes, Nano Letters 5 (10), 1972 (2005). (3) J. Li, X. Li, H. J. Zhai, and L. S. Wang, Science 299, 864 (2003)

  1. Equilibrium properties of transition-metal ion-argon clusters via simulated annealing

    NASA Technical Reports Server (NTRS)

    Asher, Robert L.; Micha, David A.; Brucat, Philip J.

    1992-01-01

    The geometrical structures of M(+) (Ar)n ions, with n = 1-14, have been studied by the minimization of a many-body potential surface with a simulated annealing procedure. The minimization method is justified for finite systems through the use of an information theory approach. It is carried out for eight potential-energy surfaces constructed with two- and three-body terms parametrized from experimental data and ab initio results. The potentials should be representative of clusters of argon atoms with first-row transition-metal monocations of varying size. The calculated geometries for M(+) = Co(+) and V(+) possess radial shells with small (ca. 4-8) first-shell coordination number. The inclusion of an ion-induced-dipole-ion-induced-dipole interaction between argon atoms raises the energy and generally lowers the symmetry of the cluster by promoting incomplete shell closure. Rotational constants as well as electric dipole and quadrupole moments are quoted for the Co(+) (Ar)n and V(+) (Ar)n predicted structures.

  2. C-H Bond Activation by Early Transition Metal Carbide Cluster Anion MoC3 (-).

    PubMed

    Li, Zi-Yu; Hu, Lianrui; Liu, Qing-Yu; Ning, Chuan-Gang; Chen, Hui; He, Sheng-Gui; Yao, Jiannian

    2015-12-01

    Although early transition metal (ETM) carbides can activate CH bonds in condensed-phase systems, the electronic-level mechanism is unclear. Atomic clusters are ideal model systems for understanding the mechanisms of bond activation. For the first time, CH activation of a simple alkane (ethane) by an ETM carbide cluster anion (MoC3 (-) ) under thermal-collision conditions has been identified by using high-resolution mass spectrometry, photoelectron imaging spectroscopy, and high-level quantum chemical calculations. Dehydrogenation and ethene elimination were observed in the reaction of MoC3 (-) with C2 H6 . The CH activation follows a mechanism of oxidative addition that is much more favorable in the carbon-stabilized low-spin ground electronic state than in the high-spin excited state. The reaction efficiency between the MoC3 (-) anion and C2 H6 is low (0.23±0.05) %. A comparison between the anionic and a highly efficient cationic reaction system (Pt(+) +C2 H6 ) was made. It turned out that the potential-energy surfaces for the entrance channels of the anionic and cationic reaction systems can be very different. PMID:26490554

  3. Oxide- and zeolite-supported molecular metal complexes and clusters: physical characterization and determination of structure, bonding, and metal oxidation state.

    PubMed

    Fierro-Gonzalez, Juan C; Kuba, Stefan; Hao, Yalin; Gates, Bruce C

    2006-07-13

    This article is a review of the physical characterization of well-defined site-isolated molecular metal complexes and metal clusters supported on metal oxides and zeolites. These surface species are of interest primarily as catalysts; as a consequence of their relatively uniform structures, they can be characterized much more precisely than traditional supported catalysts. The properties discussed in this review include metal nuclearity, oxidation state, and ligand environment, as well as metal-support interactions. These properties are determined by complementary techniques, including transmission electron microscopy; X-ray absorption, infrared, Raman, and NMR spectroscopies; and density functional theory. The strengths and limitations of these techniques are assessed in the context of results characterizing samples that have been investigated thoroughly and with multiple techniques. The depth of understanding of well-defined metal complexes and metal clusters on supports is approaching that attainable for molecular analogues in solution. The results provide a foundation for understanding the more complex materials that are typical of industrial catalysts. PMID:16821852

  4. 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.

  5. An extended basis set {ital ab} {ital initio} study of alkali metal cation--water clusters

    SciTech Connect

    Feller, D.; Glendening, E.D.; Woon, D.E.; Feyereisen, M.W.

    1995-09-01

    Ionic clusters comprised of a single alkali metal cation and up to eight water molecules were studied at the Hartree--Fock and correlated levels of theory using the correlation consistent sequence of basis sets. Estimates of the degree of convergence in the computed properties with respect to the complete basis set limit were facilitated by the underlying systematic manner in which the correlation consistent sets approach completeness. In favorable cases, improved property values could be obtained by fitting finite basis set results with a simple analytical expression in order to extrapolate to the complete basis set limit. The sensitivity of structures and binding energies were analyzed with regard to the inclusion of valence and core-valence correlation recovery at the MP2, MP4, and CCSD(T) levels of theory. The replacement of metal core electrons and the introduction of relativistic contributions via effective core potentials was compared to corresponding all-electron results. {copyright} {ital 1995} {ital American} {ital Institute} {ital of} {ital Physics}.

  6. 21 CFR 1404.900 - Adequate evidence.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 9 2010-04-01 2010-04-01 false Adequate evidence. 1404.900 Section 1404.900 Food and Drugs OFFICE OF NATIONAL DRUG CONTROL POLICY GOVERNMENTWIDE DEBARMENT AND SUSPENSION (NONPROCUREMENT) Definitions § 1404.900 Adequate evidence. Adequate evidence means information sufficient to support the reasonable belief that a particular...

  7. 29 CFR 98.900 - Adequate evidence.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 29 Labor 1 2010-07-01 2010-07-01 true Adequate evidence. 98.900 Section 98.900 Labor Office of the Secretary of Labor GOVERNMENTWIDE DEBARMENT AND SUSPENSION (NONPROCUREMENT) Definitions § 98.900 Adequate evidence. Adequate evidence means information sufficient to support the reasonable belief that a...

  8. STROeMGREN PHOTOMETRY OF GALACTIC GLOBULAR CLUSTERS. II. METALLICITY DISTRIBUTION OF RED GIANTS IN omega CENTAURI

    SciTech Connect

    Calamida, A.; Hilker, M.; Bono, G. E-mail: mhilker@eso.or

    2009-12-01

    We present new intermediate-band Stroemgren photometry based on more than 300 u, v, b, y images of the Galactic globular cluster omega Cen. Optical data were supplemented with new multiband near-infrared (NIR) photometry (350 J, H, K{sub s} images). The final optical-NIR catalog covers a region of more than 20 x 20 arcmin squared across the cluster center. We use different optical-NIR color-color planes together with proper-motion data available in the literature to identify candidate cluster red-giant (RG) stars. By adopting different Stroemgren metallicity indices, we estimate the photometric metallicity for approx4000 RGs, the largest sample ever collected. The metallicity distributions show multiple peaks ([Fe/H]{sub phot} = -1.73 +- 0.08, -1.29 +- 0.03, -1.05 +- 0.02, -0.80 +- 0.04, -0.42 +- 0.12, and -0.07 +- 0.08 dex) and a sharp cutoff in the metal-poor (MP) tail ([Fe/H]{sub phot} approx< -2 dex) that agree quite well with spectroscopic measurements. We identify four distinct subpopulations, namely, MP ([Fe/H] <= -1.49), metal-intermediate (MI; -1.49 < [Fe/H] <= -0.93), metal-rich (MR; -0.95 < [Fe/H] <= -0.15), and solar metallicity ([Fe/H] approx 0). The last group includes only a small fraction of stars (approx8% +- 5%) and should be confirmed spectroscopically. Moreover, using the difference in metallicity based on different photometric indices, we find that the 19% +- 1% of RGs are candidate CN-strong stars. This fraction agrees quite well with recent spectroscopic estimates and could imply a large fraction of binary stars. The Stroemgren metallicity indices display a robust correlation with alpha-elements ([Ca+Si/H]) when moving from the MI to the MR regime ([Fe/H] approx> -1.7 dex).

  9. A metal-organic framework constructed using a flexible tripodal ligand and tetranuclear copper cluster for sensing small molecules.

    PubMed

    Hou, Chaoyi; Bai, Yue-Ling; Bao, XiaoLi; Xu, Liangzhen; Lin, Rong-Guang; Zhu, Shourong; Fang, Jianhui; Xu, Jiaqiang

    2015-05-01

    A new porous metal-organic framework (MOF) {[Cu4(OH)2(tci)2(bpy)2]·11H2O} (1) based on a tetranuclear copper cluster with intracluster antiferromagnetic interactions was synthesized. Quartz crystal microbalance (QCM) sensor studies reveal sensitive and selective sensing for small molecules. PMID:25857286

  10. Nonlinear optical properties of the inorganic metal cluster MO2Ag4S8(PPh3)4

    NASA Astrophysics Data System (ADS)

    Xia, Tie J.; Dogariu, Aristide C.; Mansour, Kamjou; Hagan, David J.; Said, Ali A.; Van Stryland, Eric W.; Shi, Shu

    1996-10-01

    We describe a series of experiments on solutions of the inorganic metal cluster molecules Mo2Ag4S8(PPh3)4 and compare them with data on a suspension of carbon particles in liquid (ink). The optical limiting behavior is measured using both single picosecond 532 nm pulses and nanosecond long trains of these picosecond pulses. Both materials show reduced transmittance for increasing fluence (energy per unit area). We also perform picosecond time-resolved pump-probe measurements. We find that the observed pump-probe data is nearly identical for the metal cluster solution and the carbon particle suspension (CBS), and we conclude that the nonlinear mechanisms are the same for the two materials. Our previous studies have shown that the nonlinear losses are due to scattering and absorption by microplasmas formed after thermionic emission from heated particles of carbon or inorganic clusters.

  11. WIYN Open Cluster Study. LXIII. Abundances in the Super-metal-rich Open Cluster NGC 6253 from Hydra Spectroscopy of the 7774 Å Oxygen Triplet Region

    NASA Astrophysics Data System (ADS)

    Maderak, Ryan M.; Deliyannis, Constantine P.; Anthony-Twarog, Barbara J.; Twarog, Bruce A.; Cummings, Jeffery D.; King, Jeremy R.; Steiman-Cameron, Thomas Y.

    2015-04-01

    We present a spectroscopic abundance analysis of the old, super-metal-rich open cluster NGC 6253, with emphasis on its O abundance. High-dispersion, 7774 Å O i triplet region spectra of 47 stars were obtained using Hydra II on the CTIO Blanco 4 m. Radial velocity analysis confirms 39 stars consistent with single star membership, primarily at the turnoff. Thirty-six of these are included in our abundance analysis. Our differential analysis relative to the Sun yields primarily scaled-solar values, with weighted cluster averages of [O/H] = +0.440 ± 0.020, [Fe/H] = +0.445 ± 0.014, [Al/H] = +0.487 ± 0.020, [Si/H] = +0.504 ± 0.018, and [Ni/H] = +0.702 ± 0.018 (where the errors are {{σ }μ }). We discuss possible origins for the three known super-metal-rich clusters based upon their abundance patterns, Galactic locations, and space motions. The abundance patterns of NGC 6253 are very similar to those of NGC 6791 and NGC 6583. With the possible exception of oxygen, the abundances of these clusters are all close to scaled-solar, and they are similar to patterns seen in metal-rich disk dwarfs and giants. However, they also seem to differ from those of metal-rich bulge stars. We demonstrate that NGC 6253 is unusually oxygen rich (in [O/H]) for its 3.3 Gyr age. While we find [O/Fe] to be scaled-solar for NGC 6253, the more recently reported values for NGC 6791 show a large variation, from values close to scaled-solar down to values at least a factor of two below scaled-solar. We discuss the possibility that the scaled-solar [O/Fe] abundances of NGC 6253 and NGC 6791 might reflect a flattening of the Galactic [O/Fe] versus [Fe/H] relationship. This possibility may be consistent with disk star abundance data, which show an apparent “floor” at [O/Fe] ˜ -0.1 for [Fe/H] \\gt 0, and with chemical evolution model results, which may predict such a flattening due to a decrease in supernova Fe yields at super-solar-metallicities. Orbit solutions for NGC 6791 allow that it

  12. Quantitative Z-Contrast Imaging of Supported Metal Complexes and Clusters - A Gateway to Understanding Catalysis on the Atomic Scale

    SciTech Connect

    Browning, Nigel D.; Aydin, C.; Lu, Jing; Kulkarni, Apoorva; Okamoto, Norihiko L.; Ortalan, V.; Reed, Bryan W.; Uzun, Alper; Gates, Bruce C.

    2013-09-01

    Z-contrast imaging in an aberration-corrected scanning transmission electron microscope can be used to observe and quantify the sizes, shapes, and compositions of the metal frames in supported mono-, bi-, and multimetallic metal clusters and can even detect the metal atoms in single-metal-atom complexes, as well as providing direct structural information characterizing the metal-support interface. Herein, we assess the major experimental challenges associated with obtaining atomic resolution Z-contrast images of the materials that are highly beam-sensitive, that is, the clusters readily migrate and sinter on support surfaces, and the support itself can drastically change in structure if the experiment is not properly controlled. Calibrated and quantified Z-contrast images are used in conjunction with exsitu analytical measurements and larger-scale characterization methods such as extended X-ray absorption fine structure spectroscopy to generate an atomic-scale understanding of supported catalysts and their function. Examples of the application of these methods include the characterization of a wide range of sizes and compositions of supported clusters, primarily those incorporating Ir, Os, and Au, on highly crystalline supports (zeolites and MgO).

  13. Does C-C bonding proceed during exposure of adequate metal surfaces to CH{sub 4}? Reply to {open_quotes}Comment by Z. Hlavathy, Z. Paal, and P. Tetenyi{close_quotes}

    SciTech Connect

    Amaraiglio, A.; Pareja, P.; Amariglio, H.

    1997-02-01

    The comments, results, and reflections presented by Hlavathy and co-workers in their Letter aim at demonstrating that C-C bonding between CH{sub x} adspecies, formed upon exposure of Pt to CH{sub 4}, can proceed as well during the exposure itself as during further exposure to H{sub 2}. This possibility was implicitly put forward because they thought that a tight parallelism exists between the interactions of CH{sub 4} and CO with a metal surface, provided that the exposure to CH{sub 4} is carried out at a high enough temperature (450{degrees}C). In both cases these authors assumed that three kinds of carbon, C{sub {alpha}}, C{sub {beta}}, and C{sub {gamma}}, can be formed, C{sub {alpha}} being the main species responsible for the production of CH{sub 4} and of the C{sub 2}, alkanes obtained when the metal was further contacted with H{sub 2} at 100{degrees}C. As they argued that C{sub {alpha}} (also named carbidic carbon) has only metal atoms in its first coordination shell, they were implicitly led it that C-C bonding must take place during the hydrogenation step. The authors have not denied this possibility, but they have suggested that different situations can result from exposures to CH{sub 4} conducted at temperatures much lower than those used by Koerts et al.. 13 refs.

  14. Carbonyl substitution chemistry of some trimetallic transition metal cluster complexes with polyfunctional ligands

    SciTech Connect

    Byrne, Lindsay T.; Hondow, Nicole S.; Koutsantonis, George A.; Skelton, Brian W.; Torabi, A. Asgar; White, Allan H.; Wild, S. Bruce

    2008-11-03

    The trimetallic clusters [Ru{sub 3}(CO){sub 10}(dppm)], [Ru{sub 3}(CO){sub 12}] and [RuCo{sub 2}(CO){sub 11}] react with a number of multifunctional secondary phosphine and tertiary arsine ligands to give products consequent on carbonyl substitution and, in the case of the secondary phosphines, PH activation. The reaction with the unresolved mixed P/S donor, 1-phenylphosphino-2-thio(ethane), HSCH{sub 2}CH{sub 2}PHPh ({double_bond}LH{sub 2}), gave two products under various conditions which have been characterized by spectroscopic and crystallographic means. These two complexes [Ru{sub 3}({mu}dppm)(H)(CO){sub 7}(LH)] and [Ru{sub 3}({mu}-dppm)(H)(CO){sub 8}(LH)Ru{sub 3}({mu}-dppm)(CO){sub 9}], show the versatility of the ligand, with it chelating in the former and bridging two Ru{sub 3} units in the latter. The stereogenic centres in the molecules gave rise to complicated spectroscopic data which are consistent with the presence of diastereoisomers. In the case of [Ru{sub 3}(CO){sub 12}] the reaction with LH{sub 2} gave a poor yield of a tetranuclear butterfly cluster, [Ru{sub 4}(CO){sub 10}(L){sub 2}], in which two of the ligands bridge opposite hinge wingtip bonds of the cluster. A related ligand, HSCH{sub 2}CH{sub 2}AsMe(C{sub 6}H{sub 4}CH{sub 2}OMe), reacted with [RuCo{sub 2}(CO){sub 11}] to give a low yield of the heterobimetallic Ru-Co adduct, [RuCo(CO){sub 6}(SCH{sub 2}CH{sub 2}AsMe(C{sub 6}H{sub 4}CH{sub 2}OMe))], which appears to be the only one of its type so far structurally characterized. The secondary phosphine, HPMe(C{sub 6}H{sub 4}(CH{sub 2}OMe)) and its oxide HP(O)Me(C{sub 6}H{sub 4}(CH{sub 2}OMe)) also react with the cluster [Ru{sub 3}(CO){sub 10}(dppm)] to give carbonyl substitution products, [Ru{sub 3}(CO){sub 5}(dppm)({mu}{sub 2}-PMe(C{sub 6}H{sub 4}CH{sub 2}OMe)){sub 4}], and [Ru{sub 3}H(CO){sub 7}(dppm)({mu}{sub 2},{eta}{sup 1}P({double_bond}O)Me(C{sub 6}H{sub 4}CH{sub 2}OMe))]. The former consists of an open Ru{sub 3} triangle with four

  15. Light-element Abundance Variations at Low Metallicity: The Globular Cluster NGC 5466

    NASA Astrophysics Data System (ADS)

    Shetrone, Matthew; Martell, Sarah L.; Wilkerson, Rachel; Adams, Joshua; Siegel, Michael H.; Smith, Graeme H.; Bond, Howard E.

    2010-10-01

    We present low-resolution (R sime850) spectra for 67 asymptotic giant branch (AGB), horizontal branch, and red giant branch (RGB) stars in the low-metallicity globular cluster NGC 5466, taken with the VIRUS-P integral-field spectrograph at the 2.7 m Harlan J. Smith telescope at McDonald Observatory. Sixty-six stars are confirmed, and one rejected, as cluster members based on radial velocity, which we measure to an accuracy of 16 km s-1 via template-matching techniques. CN and CH band strengths have been measured for 29 RGB and AGB stars in NGC 5466, and the band-strength indices measured from VIRUS-P data show close agreement with those measured from Keck/LRIS spectra previously taken for five of our target stars. We also determine carbon abundances from comparisons with synthetic spectra. The RGB stars in our data set cover a range in absolute V magnitude from +2 to -3, which permits us to study the rate of carbon depletion on the giant branch as well as the point of its onset. The data show a clear decline in carbon abundance with rising luminosity above the luminosity function "bump" on the giant branch, and also a subdued range in CN band strength, suggesting ongoing internal mixing in individual stars but minor or no primordial star-to-star variation in light-element abundances. Based in part on data obtained at the W. M. Keck Observatory, which is operated as a scientific partnership among the California Institute of Technology, the University of California, and the National Aeronautics and Space Administration. The Observatory was made possible by the generous financial support of the W. M. Keck Foundation.

  16. A study into the role of surface capping on energy transfer in metal cluster-semiconductor nanocomposites

    NASA Astrophysics Data System (ADS)

    Bain, Dipankar; Paramanik, Bipattaran; Sadhu, Suparna; Patra, Amitava

    2015-12-01

    Metal cluster-semiconductor nanocomposite materials remain a frontier area of research for the development of optoelectronic, photovoltaic and light harvesting devices because metal nanoclusters and semiconductor QDs are promising candidates for photon harvesting. Here, we have designed well defined metal cluster-semiconductor nanostructures using different surface capped negatively charged Au25 nanoclusters (Au NCs) and positively charged cysteamine capped CdTe quantum dots using electrostatic interactions. The main focus of this article is to address the impact of surface capping agents on the photophysical properties of Au cluster-CdTe QD hybrid nanocomposites. Steady state and time resolved spectroscopic studies reveal that photoluminescence quenching, radiative and nonradiative rate, and energy transfer between Au nanoclusters and CdTe QDs have been influenced by the nature of the capping agent. We have calculated the energy transfer related parameters such as the overlap integral, distance between donor and acceptor, Förster distance, efficiency of energy transfer and rate of energy transfer from CdTe QDs to three different Au NCs. Photoluminescence quenching varies from 73% to 43% when changing the capping agents from bovine serum albumin (BSA) to glutathione (GSH). The efficiency of the energy transfer from CdTe QDs to BSA-capped Au NCs is found to be 83%, for Cys-capped Au NCs it was 46% and for GSH-capped Au NCs it was 35%. The efficiency depends on the number of Au clusters attached per QD. This reveals that the nature of capping ligands plays a crucial role in the energy transfer phenomena from CdTe QDs to Au NCs. Interesting findings reveal that the efficient energy transfer in metal cluster-semiconductor nanocomposites may open up new possibilities in designing artificial light harvesting systems for future applications.Metal cluster-semiconductor nanocomposite materials remain a frontier area of research for the development of optoelectronic

  17. The extreme chemistry of multiple stellar populations in the metal-poor globular cluster NGC 4833

    NASA Astrophysics Data System (ADS)

    Carretta, E.; Bragaglia, A.; Gratton, R. G.; D'Orazi, V.; Lucatello, S.; Momany, Y.; Sollima, A.; Bellazzini, M.; Catanzaro, G.; Leone, F.

    2014-04-01

    Our FLAMES survey of Na-O anticorrelation in globular clusters (GCs) is extended to NGC 4833, a metal-poor GC with a long blue tail on the horizontal branch (HB). We present the abundance analysis for a large sample of 78 red giants based on UVES and GIRAFFE spectra acquired at the ESO-VLT. We derived abundances of Na, O, Mg, Al, Si, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Ba, La, and Nd. This is the first extensive study of this cluster from high resolution spectroscopy. On the scale of our survey, the metallicity of NGC 4833 is [Fe/H] = -2.015 ± 0.004 ± 0.084 dex (rms = 0.014 dex) from 12 stars observed with UVES, where the first error is from statistics and the second one refers to the systematic effects. The iron abundance in NGC 4833 is homogeneous at better than 6%. On the other hand, the light elements involved in proton-capture reactions at high temperature show the large star-to-star variations observed in almost all GCs studied so far. The Na-O anticorrelation in NGC 4833 is quite extended, as expected from the high temperatures reached by stars on the HB, and NGC 4833 contains a conspicuous fraction of stars with extreme [O/Na] ratios. More striking is the finding that large star-to-star variations are also seen for Mg, which spans a range of more than 0.5 dex in this GC. Depletions in Mg are correlated to the abundances of O and anti-correlated with Na, Al, and Si abundances. This pattern suggests the action of nuclear processing at unusually high temperatures, producing the extreme chemistry observed in the stellar generations of NGC 4833. These extreme changes are also seen in giants of the much more massive GCs M 54 and ω Cen, and our conclusion is that NGC 4833 has probably lost a conspicuous fraction of its original mass due to bulge shocking, as also indicated by its orbit. Based on observations collected at ESO telescopes under programmes 083.D-0208 and 68.D-0265.Full Tables 2, 6-11 are only available at the CDS via anonymous ftp to http

  18. Manganese-centered tubular boron cluster - MnB16 (-): A new class of transition-metal molecules.

    PubMed

    Jian, Tian; Li, Wan-Lu; Popov, Ivan A; Lopez, Gary V; Chen, Xin; Boldyrev, Alexander I; Li, Jun; Wang, Lai-Sheng

    2016-04-21

    We report the observation of a manganese-centered tubular boron cluster (MnB16 (-)), which is characterized by photoelectron spectroscopy and ab initio calculations. The relatively simple pattern of the photoelectron spectrum indicates the cluster to be highly symmetric. Ab initio calculations show that MnB16 (-) has a Mn-centered tubular structure with C4v symmetry due to first-order Jahn-Teller effect, while neutral MnB16 reduces to C2v symmetry due to second-order Jahn-Teller effect. In MnB16 (-), two unpaired electrons are observed, one on the Mn 3dz(2) orbital and another on the B16 tube, making it an unusual biradical. Strong covalent bonding is found between the Mn 3d orbitals and the B16 tube, which helps to stabilize the tubular structure. The current result suggests that there may exist a whole class of metal-stabilized tubular boron clusters. These metal-doped boron clusters provide a new bonding modality for transition metals, as well as a new avenue to design boron-based nanomaterials. PMID:27389223

  19. Manganese-centered tubular boron cluster - MnB16-: A new class of transition-metal molecules

    NASA Astrophysics Data System (ADS)

    Jian, Tian; Li, Wan-Lu; Popov, Ivan A.; Lopez, Gary V.; Chen, Xin; Boldyrev, Alexander I.; Li, Jun; Wang, Lai-Sheng

    2016-04-01

    We report the observation of a manganese-centered tubular boron cluster (MnB16-), which is characterized by photoelectron spectroscopy and ab initio calculations. The relatively simple pattern of the photoelectron spectrum indicates the cluster to be highly symmetric. Ab initio calculations show that MnB16- has a Mn-centered tubular structure with C4v symmetry due to first-order Jahn-Teller effect, while neutral MnB16 reduces to C2v symmetry due to second-order Jahn-Teller effect. In MnB16-, two unpaired electrons are observed, one on the Mn 3dz2 orbital and another on the B16 tube, making it an unusual biradical. Strong covalent bonding is found between the Mn 3d orbitals and the B16 tube, which helps to stabilize the tubular structure. The current result suggests that there may exist a whole class of metal-stabilized tubular boron clusters. These metal-doped boron clusters provide a new bonding modality for transition metals, as well as a new avenue to design boron-based nanomaterials.

  20. A study into the role of surface capping on energy transfer in metal cluster-semiconductor nanocomposites.

    PubMed

    Bain, Dipankar; Paramanik, Bipattaran; Sadhu, Suparna; Patra, Amitava

    2015-12-28

    Metal cluster-semiconductor nanocomposite materials remain a frontier area of research for the development of optoelectronic, photovoltaic and light harvesting devices because metal nanoclusters and semiconductor QDs are promising candidates for photon harvesting. Here, we have designed well defined metal cluster-semiconductor nanostructures using different surface capped negatively charged Au25 nanoclusters (Au NCs) and positively charged cysteamine capped CdTe quantum dots using electrostatic interactions. The main focus of this article is to address the impact of surface capping agents on the photophysical properties of Au cluster-CdTe QD hybrid nanocomposites. Steady state and time resolved spectroscopic studies reveal that photoluminescence quenching, radiative and nonradiative rate, and energy transfer between Au nanoclusters and CdTe QDs have been influenced by the nature of the capping agent. We have calculated the energy transfer related parameters such as the overlap integral, distance between donor and acceptor, Förster distance, efficiency of energy transfer and rate of energy transfer from CdTe QDs to three different Au NCs. Photoluminescence quenching varies from 73% to 43% when changing the capping agents from bovine serum albumin (BSA) to glutathione (GSH). The efficiency of the energy transfer from CdTe QDs to BSA-capped Au NCs is found to be 83%, for Cys-capped Au NCs it was 46% and for GSH-capped Au NCs it was 35%. The efficiency depends on the number of Au clusters attached per QD. This reveals that the nature of capping ligands plays a crucial role in the energy transfer phenomena from CdTe QDs to Au NCs. Interesting findings reveal that the efficient energy transfer in metal cluster-semiconductor nanocomposites may open up new possibilities in designing artificial light harvesting systems for future applications. PMID:26603192

  1. Noble metal alloy clusters in the gas phase derived from protein templates: unusual recognition of palladium by gold

    NASA Astrophysics Data System (ADS)

    Baksi, Ananya; Pradeep, T.

    2013-11-01

    Matrix assisted laser desorption ionization of a mixture of gold and palladium adducts of the protein lysozyme (Lyz) produces naked alloy clusters of the type Au24Pd+ in the gas phase. While a lysozyme-Au adduct forms Au18+, Au25+, Au38+ and Au102+ ions in the gas phase, lysozyme-Pd alone does not form any analogous cluster. Addition of various transition metal ions (Ag+, Pt2+, Pd2+, Cu2+, Fe2+, Ni2+ and Cr3+) in the adducts contributes to drastic changes in the mass spectrum, but only palladium forms alloys in the gas phase. Besides alloy formation, palladium enhances the formation of specific single component clusters such as Au38+. While other metal ions like Cu2+ help forming Au25+ selectively, Fe2+ catalyzes the formation of Au25+ over all other clusters. Gas phase cluster formation occurs from protein adducts where Au is in the 1+ state while Pd is in the 2+ state. The creation of alloys in the gas phase is not affected whether a physical mixture of Au and Pd adducts or a Au and Pd co-adduct is used as the precursor. The formation of Au cores and AuPd alloy cores of the kind comparable to monolayer protected clusters implies that naked clusters themselves may be nucleated in solution.Matrix assisted laser desorption ionization of a mixture of gold and palladium adducts of the protein lysozyme (Lyz) produces naked alloy clusters of the type Au24Pd+ in the gas phase. While a lysozyme-Au adduct forms Au18+, Au25+, Au38+ and Au102+ ions in the gas phase, lysozyme-Pd alone does not form any analogous cluster. Addition of various transition metal ions (Ag+, Pt2+, Pd2+, Cu2+, Fe2+, Ni2+ and Cr3+) in the adducts contributes to drastic changes in the mass spectrum, but only palladium forms alloys in the gas phase. Besides alloy formation, palladium enhances the formation of specific single component clusters such as Au38+. While other metal ions like Cu2+ help forming Au25+ selectively, Fe2+ catalyzes the formation of Au25+ over all other clusters. Gas phase cluster

  2. A DIFFERENTIAL CHEMICAL ELEMENT ANALYSIS OF THE METAL-POOR GLOBULAR CLUSTER NGC 6397

    SciTech Connect

    Koch, Andreas; McWilliam, Andrew E-mail: andy@obs.carnegiescience.edu

    2011-08-15

    We present chemical abundances in three red giants and two turnoff (TO) stars in the metal-poor Galactic globular cluster (GC) NGC 6397 based on spectroscopy obtained with the Magellan Inamori Kyocera Echelle high-resolution spectrograph on the Magellan 6.5 m Clay telescope. Our results are based on a line-by-line differential abundance analysis relative to the well-studied red giant Arcturus and the Galactic halo field star Hip 66815. At a mean of -2.10 {+-} 0.02 (stat.) {+-}0.07 (sys.), the differential iron abundance is in good agreement with other studies in the literature based on gf-values. As in previous differential works we find a distinct departure from ionization equilibrium in that the abundances of Fe I and Fe II differ by {approx}0.1 dex, with opposite signs for the red giant branch (RGB) and TO stars. The {alpha}-element ratios are enhanced to 0.4 (RGB) and 0.3 dex (TO), respectively, and we also confirm strong variations in the O, Na, and Al/Fe abundance ratios. Accordingly, the light-element abundance patterns in one of the red giants can be attributed to pollution by an early generation of massive Type II supernovae. TO and RGB abundances are not significantly different, with the possible exception of Mg and Ti, which are, however, amplified by the patterns in one TO star additionally belonging to this early generation of GC stars. We discuss interrelations of these light elements as a function of the GC metallicity.

  3. First-principles simulation of light propagation and exciton dynamics in metal cluster nanostructures

    NASA Astrophysics Data System (ADS)

    Lisinetskaya, Polina G.; Röhr, Merle I. S.; Mitrić, Roland

    2016-06-01

    We present a theoretical approach for the simulation of the electric field and exciton propagation in ordered arrays constructed of molecular-sized noble metal clusters bound to organic polymer templates. In order to describe the electronic coupling between individual constituents of the nanostructure we use the ab initio parameterized transition charge method which is more accurate than the usual dipole-dipole coupling. The electronic population dynamics in the nanostructure under an external laser pulse excitation is simulated by numerical integration of the time-dependent Schrödinger equation employing the fully coupled Hamiltonian. The solution of the TDSE gives rise to time-dependent partial point charges for each subunit of the nanostructure, and the spatio-temporal electric field distribution is evaluated by means of classical electrodynamics methods. The time-dependent partial charges are determined based on the stationary partial and transition charges obtained in the framework of the TDDFT. In order to treat large plasmonic nanostructures constructed of many constituents, the approximate self-consistent iterative approach presented in (Lisinetskaya and Mitrić in Phys Rev B 89:035433, 2014) is modified to include the transition-charge-based interaction. The developed methods are used to study the optical response and exciton dynamics of {Ag}3+ and porphyrin-Ag4 dimers. Subsequently, the spatio-temporal electric field distribution in a ring constructed of ten porphyrin-Ag4 subunits under the action of circularly polarized laser pulse is simulated. The presented methodology provides a theoretical basis for the investigation of coupled light-exciton propagation in nanoarchitectures built from molecular size metal nanoclusters in which quantum confinement effects are important.

  4. First-principles simulation of light propagation and exciton dynamics in metal cluster nanostructures

    NASA Astrophysics Data System (ADS)

    Lisinetskaya, Polina G.; Röhr, Merle I. S.; Mitrić, Roland

    2016-06-01

    We present a theoretical approach for the simulation of the electric field and exciton propagation in ordered arrays constructed of molecular-sized noble metal clusters bound to organic polymer templates. In order to describe the electronic coupling between individual constituents of the nanostructure we use the ab initio parameterized transition charge method which is more accurate than the usual dipole-dipole coupling. The electronic population dynamics in the nanostructure under an external laser pulse excitation is simulated by numerical integration of the time-dependent Schrödinger equation employing the fully coupled Hamiltonian. The solution of the TDSE gives rise to time-dependent partial point charges for each subunit of the nanostructure, and the spatio-temporal electric field distribution is evaluated by means of classical electrodynamics methods. The time-dependent partial charges are determined based on the stationary partial and transition charges obtained in the framework of the TDDFT. In order to treat large plasmonic nanostructures constructed of many constituents, the approximate self-consistent iterative approach presented in (Lisinetskaya and Mitrić in Phys Rev B 89:035433, 2014) is modified to include the transition-charge-based interaction. The developed methods are used to study the optical response and exciton dynamics of Ag3+ and porphyrin-Ag4 dimers. Subsequently, the spatio-temporal electric field distribution in a ring constructed of ten porphyrin-Ag4 subunits under the action of circularly polarized laser pulse is simulated. The presented methodology provides a theoretical basis for the investigation of coupled light-exciton propagation in nanoarchitectures built from molecular size metal nanoclusters in which quantum confinement effects are important.

  5. Age-metallicity relation and chemical evolution of the LMC from UVES spectra of Globular Cluster giants

    NASA Astrophysics Data System (ADS)

    Hill, V.; François, P.; Spite, M.; Primas, F.; Spite, F.

    2000-12-01

    We report on the first high-resolution spectroscopy of 10 giants in LMC Globular Clusters in a wide age range, obtained with the newly commissioned spectrograph UVES at VLT UT2. These observations are used to derive oxygen and iron content of these clusters, and the abundances are then used to cast a more precise view, not only on the age-metallicity relation in the LMC, but also on the chemical evolution of this dwarf irregular galaxy. Based on observations made at the ESO Telescopes in Chile

  6. FORMATION OF METAL-POOR GLOBULAR CLUSTERS IN Ly{alpha} EMITTING GALAXIES IN THE EARLY UNIVERSE

    SciTech Connect

    Elmegreen, Bruce G.; Malhotra, Sangeeta; Rhoads, James

    2012-09-20

    The size, mass, luminosity, and space density of Ly{alpha} emitting (LAE) galaxies observed at intermediate to high redshift agree with expectations for the properties of galaxies that formed metal-poor halo globular clusters (GCs). The low metallicity of these clusters is the result of their formation in low-mass galaxies. Metal-poor GCs could enter spiral galaxies along with their dwarf galaxy hosts, unlike metal-rich GCs, which form in the spirals themselves. Considering an initial GC mass larger than the current mass to account for multiple stellar populations, and considering the additional clusters that are likely to form with massive clusters, we estimate that each GC with a mass today greater than 2 Multiplication-Sign 10{sup 5} M{sub Sun} was likely to have formed among a total stellar mass {approx}> 3 Multiplication-Sign 10{sup 7} M{sub Sun }, a molecular mass {approx}> 10{sup 9} M{sub Sun }, and 10{sup 7} to 10{sup 9} M{sub Sun} of older stars, depending on the relative gas fraction. The star formation rate would have been several M{sub Sun} yr{sup -1} lasting for {approx}10{sup 7} yr, and the Ly{alpha} luminosity would have been {approx}> 10{sup 42} erg s{sup -1}. Integrating the LAE galaxy luminosity function above this minimum, considering the average escape probability for Ly{alpha} photons (25%), and then dividing by the probability that a dwarf galaxy is observed in the LAE phase (0.4%), we find agreement between the comoving space density of LAEs and the average space density of metal-poor GCs today. The local galaxy WLM, with its early starburst and old GC, could be an LAE remnant that did not get into a galaxy halo because of its remote location.

  7. Electronic Structure of Transition Metal Clusters, Actinide Complexes and Their Reactivities

    SciTech Connect

    Krishnan Balasubramanian

    2009-07-18

    methods with all-electron Douglas-Kroll relativistic methods. We have the capabilities for computing full CI extrapolations including spin-orbit effects and several one-electron properties and electron density maps including spin-orbit effects. We are continuously collaborating with several experimental groups around the country and at National Labs to carry out computational studies on the DOE-BES funded projects. The past work in the last 3 years was primarily motivated and driven by the concurrent or recent experimental studies on these systems. We were thus significantly benefited by coordinating our computational efforts with experimental studies. The interaction between theory and experiment has resulted in some unique and exciting opportunities. For example, for the very first time ever, the upper spin-orbit component of a heavy trimer such as Au{sub 3} was experimentally observed as a result of our accurate computational study on the upper electronic states of gold trimer. Likewise for the first time AuH{sub 2} could be observed and interpreted clearly due to our computed potential energy surfaces that revealed the existence of a large barrier to convert the isolated AuH{sub 2} back to Au and H{sub 2}. We have also worked on yet to be observed systems and have made predictions for future experiments. We have computed the spectroscopic and thermodynamic properties of transition metal carbides transition metal clusters and compared our electronic states to the anion photodetachment spectra of Lai Sheng Wang. Prof Mike Morse and coworkers(funded also by DOE-BES) and Prof Stimle and coworkers(also funded by DOE-BES) are working on the spectroscopic properties of transition metal carbides and nitrides. Our predictions on the excited states of transition metal clusters such as Hf{sub 3}, Nb{sub 2}{sup +} etc., have been confirmed experimentally by Prof. Lombardi and coworkers using resonance Raman spectroscopy. We have also been studying larger complexes critical to the

  8. Variable stars in metal-rich globular clusters. IV. Long-period variables in NGC 6496

    SciTech Connect

    Abbas, Mohamad A.; Layden, Andrew C.; Guldenschuh, Katherine A.; Reichart, D. E.; Ivarsen, K. M.; Haislip, J. B.; Nysewander, M. C.; LaCluyze, A. P.; Welch, Douglas L. E-mail: laydena@bgsu.edu

    2015-02-01

    We present VI-band photometry for stars in the metal-rich globular cluster NGC 6496. Our time-series data were cadenced to search for long-period variables (LPVs) over a span of nearly two years, and our variability search yielded the discovery of 13 new variable stars, of which 6 are LPVs, 2 are suspected LPVs, and 5 are short-period eclipsing binaries. An additional star was found in the ASAS database, and we clarify its type and period. We argue that all of the eclipsing binaries are field stars, while five to six of the LPVs are members of NGC 6496. We compare the period–luminosity distribution of these LPVs with those of LPVs in the Large Magellanic Cloud and 47 Tucanae, and with theoretical pulsation models. We also present a VI color–magnitude diagram, display the evolutionary states of the variables, and match isochrones to determine a reddening of E(B−V)= 0.21±0.02 mag and apparent distance modulus of 15.60±0.15 mag.

  9. Tribological coatings for complex mechanical elements produced by supersonic cluster beam deposition of metal dichalcogenide nanoparticles

    NASA Astrophysics Data System (ADS)

    Piazzoni, C.; Buttery, M.; Hampson, M. R.; Roberts, E. W.; Ducati, C.; Lenardi, C.; Cavaliere, F.; Piseri, P.; Milani, P.

    2015-07-01

    Fullerene-like MoS2 and WS2 nanoparticles can be used as building blocks for the fabrication of fluid and solid lubricants. Metal dichalcogenide films have a very low friction coefficient in vacuum, therefore they have mostly been used as solid lubricants in space and vacuum applications. Unfortunately, their use is significantly hampered by the fact that in the presence of humidity, oxygen and moisture, the low-friction properties of these materials rapidly degrade due to oxidation. The use of closed-cage MoS2 and WS2 nanoparticles may eliminate this problem, although the fabrication of lubricant thin films starting from dichalcogenide nanoparticles is, to date, a difficult task. Here we demonstrate the use of supersonic cluster beam deposition for the coating of complex mechanical elements (angular contact ball bearings) with nanostructured MoS2 and WS2 thin films. We report structural and tribological characterization of the coatings in view of the optimization of tribological performances for aerospace applications.

  10. Computer simulation structure and vibrations of small metal cluster on the Cu (111) surface

    SciTech Connect

    Borisova, Svetlana D. Rusina, Galina G.

    2015-10-27

    Vibrational properties of the small tetrahedral cluster of Co on the Cu (111) surface are studied by using tight-binding second moment approximation interatomic interaction potentials. It was shown that interaction of the clusters with substrate leads to arising of frustrated translation and frustrated rotation in-plane polarized vibrational modes localized on the cluster atoms. The Co{sub 4} cluster on the surface the high frequency modes remain strongly localized and mixed with the nearest neighbor atoms vibrations.

  11. 34 CFR 85.900 - Adequate evidence.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ...) Definitions § 85.900 Adequate evidence. Adequate evidence means information sufficient to support the reasonable belief that a particular act or omission has occurred. Authority: E.O. 12549 (3 CFR, 1986 Comp., p. 189); E.O 12689 (3 CFR, 1989 Comp., p. 235); 20 U.S.C. 1082, 1094, 1221e-3 and 3474; and Sec....

  12. 29 CFR 452.110 - Adequate safeguards.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 29 Labor 2 2010-07-01 2010-07-01 false Adequate safeguards. 452.110 Section 452.110 Labor... DISCLOSURE ACT OF 1959 Election Procedures; Rights of Members § 452.110 Adequate safeguards. (a) In addition to the election safeguards discussed in this part, the Act contains a general mandate in section...

  13. 29 CFR 452.110 - Adequate safeguards.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 29 Labor 2 2011-07-01 2011-07-01 false Adequate safeguards. 452.110 Section 452.110 Labor... DISCLOSURE ACT OF 1959 Election Procedures; Rights of Members § 452.110 Adequate safeguards. (a) In addition to the election safeguards discussed in this part, the Act contains a general mandate in section...

  14. How chain plasmons govern the optical response in strongly interacting self-assembled metallic clusters of nanoparticles.

    PubMed

    Esteban, Ruben; Taylor, Richard W; Baumberg, Jeremy J; Aizpurua, Javier

    2012-06-19

    Self-assembled clusters of metallic nanoparticles separated by nanometric gaps generate strong plasmonic modes that support both intense and localized near fields. These find use in many ultrasensitive chemical and biological sensing applications through surface enhanced Raman scattering (SERS). The inability to control at the nanoscale the structure of the clusters on which the optical response crucially depends, has led to the development of general descriptions to model the various morphologies fabricated. Here, we use rigorous electrodynamic calculations to study clusters formed by a hundred nanospheres that are separated by ∼1 nm distance, set by the dimensions of the macrocyclic molecular linker employed experimentally. Three-dimensional (3D) cluster structures of moderate compactness are of special interest since they resemble self-assembled clusters grown under typical diffusion-limited aggregation conditions. We find very good agreement between the simulated and measured far-field extinction spectra, supporting the equivalence of the assumed and experimental morphologies. From these results we argue that the main features of the optical response of two- and three-dimensional clusters can be understood in terms of the excitation of simple units composed of different length resonant chains. Notably, we observe a qualitative difference between short- and long-chain modes in both spectral response and spatial distribution: dimer and short-chain modes are observed in the periphery of the cluster at higher energies, whereas inside the structure longer chain excitation occurs at lower energies. We study in detail different configurations of isolated one-dimensional chains as prototypical building blocks for large clusters, showing that the optical response of the chains is robust to disorder. This study provides an intuitive understanding of the behavior of very complex aggregates and may be generalized to other types of aggregates and systems formed by large

  15. Design and Formation of a Large, Tetrahedral, Metal-ligand Cluster Using 1,1'-Binaphthyl Ligands

    SciTech Connect

    Biros, Shannon M.; Yeh, Robert M.; Raymond, Kenneth N.

    2008-03-13

    Many chemists have been fascinated with the development of discrete supramolecular structures that encapsulate guest molecules. These structures can be assembled through covalent or hydrogen bonds, electrostatic or metal-ligand interactions. These host structures have provided valuable insight into the forces involved in small molecule recognition. Our work has focused on the design and study of metal-ligand clusters of varying sizes. The naphthalene [M{sub 4}L{sub 6}]{sup 12-} cluster 1, shown in Figure 1, has demonstrated diastereoselective guest binding and chiral induction properties as well as the ability to catalyze reactions carried out inside the cavity in an enzyme-like manner. However, the size of the cavity (ca. 300-500 {angstrom}{sup 3}) has often limited the scope of substrates for these transformations.

  16. Measurement of sub-2 nm clusters of pristine and composite metal oxides during nanomaterial synthesis in flame aerosol reactors.

    PubMed

    Fang, Jiaxi; Wang, Yang; Attoui, Michel; Chadha, Tandeep S; Ray, Jessica R; Wang, Wei-Ning; Jun, Young-Shin; Biswas, Pratim

    2014-08-01

    Measuring stable clusters to understand particle inception will aid the synthesis of well-controlled nanoparticles via gas-phase aerosol routes. Using a Half Mini differential mobility analyzer, the presence of monomers, dimers, trimers, and tetramers was detected for the first time in a flame aerosol reactor during the synthesis of pristine TiO2 and TiO2/SiO2 nanocomposites. Atomic force microscopy confirmed the presence and the size of sub-2 nm clusters. The detection of these clusters elucidated the initial stages of particle formation during combustion synthesis and supported previous hypotheses that collisional growth from stable monomers of metal oxides is the first step of particle growth. PMID:24968004

  17. Structure and magnetic exchange in heterometallic 3d-3d transition metal triethanolamine clusters.

    PubMed

    Langley, Stuart K; Chilton, Nicholas F; Moubaraki, Boujemaa; Murray, Keith S

    2012-01-21

    Synthetic methods are described that have resulted in the formation of seven heterometallic complexes, all of which contain partially deprotonated forms of the ligand triethanolamine (teaH(3)). These compounds are [Mn(III)(4)Co(III)(2)Co(II)(2)O(2)(teaH(2))(2)(teaH)(0.82)(dea)(3.18)(O(2)CMe)(2)(OMe)(2)](BF(4))(2)(O(2)CMe)(2)·3.18MeOH·H(2)O (1), [Mn(II)(2)Mn(III)(2)Co(III)(2)(teaH)(4)(OMe)(2)(acac)(4)](NO(3))(2)·2MeOH (2), [Mn(III)(2)Ni(II)(4)(teaH)(4)(O(2)CMe)(6)]·2MeCN (3), [Mn(III)(2)Co(II)(2)(teaH)(2)(sal)(2)(acac)(2)(MeOH)(2)]·2MeOH (4), [Mn(II)(2)Fe(III)(2)(teaH)(2)(paa)(4)](NO(3))(2)·2MeOH·CH(2)Cl(2) (5), [Mn(II)Mn(III)(2)Co(III)(2)O(teaH)(2)(dea)(Iso)(OMe)(F)(2)(Phen)(2)](BF(4))(NO(3))·3MeOH (6) and [Mn(II)(2)Mn(III)Co(III)(2)(OH)(teaH)(3)(teaH(2))(acac)(3)](NO(3))(2)·3CH(2)Cl(2) (7). All of the compounds contain manganese, combined with 3d transition metal ions such as Fe, Co and Ni. The crystal structures are described and examples of 'rods', tetranuclear 'butterfly' and 'triangular' Mn(3) cluster motifs, flanked in some cases by diamagnetic cobalt(III) centres, are presented. Detailed DC and AC magnetic susceptibility and magnetization studies, combined with spin Hamiltonian analysis, have yielded J values and identified the spin ground states. In most cases, the energies of the low-lying excited states have also been obtained. The features of note include the 'inverse butterfly' spin arrangement in 2, 4 and 5. A S = 5/2 ground state occurs, for the first time, in the Mn(III)(2)Mn(II) triangular moiety within 6, the many other reported [Mn(3)O](6+) examples having S = ½ or 3/2 ground states. Compound 7 provides the first example of a Mn(II)(2)Mn(III) triangle, here within a pentanuclear Mn(3)Co(2) cluster. PMID:22113523

  18. FORMATION OF COMPACT STELLAR CLUSTERS BY HIGH-REDSHIFT GALAXY OUTFLOWS. II. EFFECT OF TURBULENCE AND METAL-LINE COOLING

    SciTech Connect

    Gray, William J.; Scannapieco, Evan

    2011-06-01

    In the primordial universe, low-mass structures with virial temperatures less than 10{sup 4} K were unable to cool by atomic line transitions, leading to a strong suppression of star formation. On the other hand, these 'minihalos' were highly prone to triggered star formation by interactions from nearby galaxy outflows. In Gray and Scannapieco, we explored the impact of nonequilibrium chemistry on these interactions. Here we turn our attention to the role of metals, carrying out a series of high-resolution three-dimensional adaptive mesh refinement simulations that include both metal cooling and a subgrid turbulent mixing model. Despite the presence of an additional coolant, we again find that outflow-minihalo interactions produce a distribution of dense, massive stellar clusters. We also find that these clusters are evenly enriched with metals to a final abundance of Z {approx} 10{sup -2} Z{sub sun}. As in our previous simulations, all of these properties suggest that these interactions may have given rise to present-day halo globular clusters.

  19. DERIVING METALLICITIES FROM THE INTEGRATED SPECTRA OF EXTRAGALACTIC GLOBULAR CLUSTERS USING THE NEAR-INFRARED CALCIUM TRIPLET

    SciTech Connect

    Foster, Caroline; Forbes, Duncan A.; Proctor, Robert N.; Spitler, Lee R.; Strader, Jay; Brodie, Jean P.

    2010-04-15

    The Ca II triplet (CaT) feature in the near-infrared has been employed as a metallicity indicator for individual stars as well as integrated light of Galactic globular clusters (GCs) and galaxies with varying degrees of success, and sometimes puzzling results. Using the DEIMOS multi-object spectrograph on Keck we obtain a sample of 144 integrated light spectra of GCs around the brightest group galaxy NGC 1407 to test whether the CaT index can be used as a metallicity indicator for extragalactic GCs. Different sets of single stellar population models make different predictions for the behavior of the CaT as a function of metallicity. In this work, the metallicities of the GCs around NGC 1407 are obtained from CaT index values using an empirical conversion. The measured CaT/metallicity distributions show unexpected features, the most remarkable being that the brightest red and blue GCs have similar CaT values despite their large difference in mean color. Suggested explanations for this behavior in the NGC 1407 GC system are (1) the CaT may be affected by a population of hot blue stars, (2) the CaT may saturate earlier than predicted by the models, and/or (3) color may not trace metallicity linearly. Until these possibilities are understood, the use of the CaT as a metallicity indicator for the integrated spectra of extragalactic GCs will remain problematic.

  20. Optimal control of light propagation and exciton transfer in arrays of molecular-like noble-metal clusters

    NASA Astrophysics Data System (ADS)

    Lisinetskaya, Polina G.; Mitrić, Roland

    2015-03-01

    We demonstrate theoretically the possibility of optimal control of light propagation and exciton transfer in arrays constructed of subnanometer sized noble-metal clusters by using phase-shaped laser pulses and analyze the mechanism underlying this process. The theoretical approach for simulation of light propagation in the arrays is based on the numerical solution of the coupled time-dependent Schrödinger equation and the classical electric field propagation in an iterative self-consistent manner. The electronic eigenstates of individual clusters and the dipole couplings are obtained from ab initio TDDFT calculations. The total electric field is propagated along the array by coupling an external excitation electric field with the electric fields produced by all clusters. A genetic algorithm is used to determine optimal pulse shapes which drive the excitation in a desired direction. The described theoretical approach is applied to control the light propagation and exciton transfer dynamics into a T-shaped structure built of seven Ag8 clusters. We demonstrate that a selective switching of light localization is possible in ˜5 nm sized cluster arrays which might serve as a building block for plasmonic devices with an ultrafast operation regime.

  1. Na-O anticorrelation and HB. VIII. Proton-capture elements and metallicities in 17 globular clusters from UVES spectra

    NASA Astrophysics Data System (ADS)

    Carretta, E.; Bragaglia, A.; Gratton, R.; Lucatello, S.

    2009-10-01

    We present homogeneous abundance determinations for iron and some of the elements involved in the proton-capture reactions (O, Na, Mg, Al, and Si) for 202 red giants in 17 Galactic globular clusters (GCs) from the analysis of high-resolution UVES spectra obtained with the FLAMES facility at the ESO VLT2 telescope. Our programme clusters span almost the whole range of the metallicity distribution of GCs and were selected to sample the widest range of global parameters (horizontal-branch morphology, masses, concentration, etc.). In this paper we focus on the discussion of the Na-O and Mg-Al anticorrelations and related issues. Our study finds clear Na and O star-to-star abundance variations, exceeding those expected from the error in the analysis, in all clusters. Variations in Al are present in all but a few GCs. Finally, a spread in abundances of Mg and Si are also present in a few clusters. Mg is slightly less overabundant and Si slightly more overabundant in the most Al-rich stars. The correlation between Si and Al abundances is a signature of production of 28Si leaking from the Mg-Al cycle in a few clusters. The cross sections required for the proper reactions to take over in the cycle point to temperatures in excess of about 65 million K for the favoured site of production. We used a dilution model to infer the total range of Al abundances starting from the Na and Al abundances in the FLAMES-UVES spectra, and the Na abundance distributions found from analysis of the much larger set of stars for which FLAMES-GIRAFFE spectra were available. We found that the maximum amount of additional Al produced by first-generation polluters contributing to the composition of the second-generation stars in each cluster is closely correlated with the same combination of metallicity and cluster luminosity that reproduced the minimum O-abundances found from GIRAFFE spectra. We then suggest that the high temperatures required for the Mg-Al cycle are only reached in the most

  2. 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

  3. A mechanistic insight into metal-cluster π-envelopment: a dual binding mode involving bent and planar ligand-conformers.

    PubMed

    Masai, Kohei; Shirato, Katsunori; Yamamoto, Koji; Kurashige, Yuki; Murahashi, Tetsuro

    2016-05-11

    Metal clusters are effectively stabilized by bridging π-coordination of planar π-conjugated unsaturated hydrocarbons. However, the mechanism of π-envelopment of a metal cluster has been elusive. By employing 1,2-bis(4-aryl-1,3-butadienyl)benzene as the π-conjugated ligand, we found that the π-envelopment of a Pd4 cluster proceeded in a stepwise manner, where the sp(2)-carbon ligands initially envelop the Pd4 cluster through a bent binding mode, and then isomerized to a thermodynamically more stable planar mode under mild heating or visible light irradiation. The involvement of a bent binding mode indicates the kinetically preferred coordination at the axial coordination site trans to a metal-metal bond. PMID:27093889

  4. Americans Getting Adequate Water Daily, CDC Finds

    MedlinePlus

    ... medlineplus/news/fullstory_158510.html Americans Getting Adequate Water Daily, CDC Finds Men take in an average ... new government report finds most are getting enough water each day. The data, from the U.S. National ...

  5. Americans Getting Adequate Water Daily, CDC Finds

    MedlinePlus

    ... gov/news/fullstory_158510.html Americans Getting Adequate Water Daily, CDC Finds Men take in an average ... new government report finds most are getting enough water each day. The data, from the U.S. National ...

  6. Oscillatory behavior in the size dependence of cluster mobility on metal surfaces: Rh on Rh(100)

    SciTech Connect

    Kellogg, G.L. )

    1994-09-26

    The mobility of Rh clusters containing two to twelve atoms adsorbed on the Rh(100) plane is examined by field ion microscopy. The activation energy of surface diffusion exhibits an interesting, oscillatory behavior as a function of cluster size. Compact geometric structures (squares and rectangles) have a consistently higher activation energy than structures with extra atoms at the periphery. The atomic-level mechanism involved in cluster diffusion is inferred from a comparison of the measured activation energies to previous theoretical calculations.

  7. THE OPEN CLUSTER CHEMICAL ANALYSIS AND MAPPING SURVEY: LOCAL GALACTIC METALLICITY GRADIENT WITH APOGEE USING SDSS DR10

    SciTech Connect

    Frinchaboy, Peter M.; Thompson, Benjamin; Jackson, Kelly M. E-mail: b.a.thompson1@tcu.edu; and others

    2013-11-01

    The Open Cluster Chemical Analysis and Mapping (OCCAM) survey aims to produce a comprehensive, uniform, infrared-based data set for hundreds of open clusters, and constrain key Galactic dynamical and chemical parameters from this sample. This first contribution from the OCCAM survey presents analysis of 141 members stars in 28 open clusters with high-resolution metallicities derived from a large uniform sample collected as part of the Sloan Digital Sky Survey III/Apache Point Observatory Galactic Evolution Experiment. This sample includes the first high-resolution metallicity measurements for 22 open clusters. With this largest ever uniformly observed sample of open cluster stars we investigate the Galactic disk gradients of both [M/H] and [α/M]. We find basically no gradient in [α/M] across 7.9 kpc ≤ R {sub GC} ≤ 14.5 kpc, but [M/H] does show a gradient for R {sub GC} < 10 kpc and a significant flattening beyond R {sub GC} = 10 kpc. In particular, whereas fitting a single linear trend yields an [M/H] gradient of –0.09 ± 0.03 dex kpc{sup –1}—similar to previously measure gradients inside 13 kpc—by independently fitting inside and outside 10 kpc separately we find a significantly steeper gradient near the Sun (7.9 ≤ R {sub GC} ≤ 10) than previously found (–0.20 ± 0.08 dex kpc{sup –1}) and a nearly flat trend beyond 10 kpc (–0.02 ± 0.09 dex kpc{sup –1})

  8. Globular cluster ages determined from the Oosterhoff period-metallicity effect using oxygen-enhanced isochrones. III

    NASA Astrophysics Data System (ADS)

    Sandage, Allan

    1993-08-01

    The new brighter calibration of absolute luminosities of RR Lyrae stars by about 0.25 mag as a function of metallicity via the Oosterhoff period effect gives a revised age of the Galactic globular cluster system as 14 Gyr when used with the oxygen-enhanced main-sequence termination models of Bergbush and VandenBerg (1992). There is no correlation of cluster age with metallicity. The presence or absence of age differences between any two clusters is neither proof nor disproof of the Eggen-Lynden Bell-Sandage model of the formation of the Galaxy by collapse. If there were different density regimes within the initial density fluctuation that was the protogalaxy, then there has been a hierarchy of collapse times for the various parts of the present Galaxy. The age of the universe is 15 Gyr, based on the age of the Galaxy at 14 Gyr, to which 1 Gyr is added for the gestation time of the galaxies. The ratio of this age to the inverse Hubble constant with H(0) about 45 km/s Mpc, based on a recent concordant determination using supernovae of type Ia, is close to the critical value of 2/3 required if the deceleration is caused by a mean density just equal to that needed for closure. For the first time, these new data give the possibility that Omega = 1 from this timing test.

  9. Hydrogen storage on metal oxide model clusters using density-functional methods and reliable van der Waals corrections.

    PubMed

    Gebhardt, Julian; Viñes, Francesc; Bleiziffer, Patrick; Hieringer, Wolfgang; Görling, Andreas

    2014-03-21

    We investigate the capability of low-coordinated sites on small model clusters to act as active centers for hydrogen storage. A set of small magic clusters with the formula (XY)6 (X = Mg, Ba, Be, Zn, Cd, Na, Li, B and Y = O, Se, S, F, I, N) and a "drumlike" hexagonal shape showing a low coordination number of three was screened. Oxide clusters turned out to be the most promising candidates for hydrogen storage. For these ionic compounds we explored the suitability of different van der Waals (vdW) corrections to density-functional calculations by comparing the respective H2 physisorption profile to highly accurate CCSD(T) (Coupled Cluster Singles Doubles with perturbative Triples) calculations. The Grimme D3 vdW correction in combination with the Perdew-Burke-Ernzerhof exchange-correlation functional was found to be the best approach compared to CCSD(T) hydrogen physisorption profiles and is, therefore, suited to study these and other light metal oxide systems. H2 adsorption on sites of oxide model clusters is found to meet the adsorption energy criteria for H2 storage, with bond strengths ranging from 0.15 to 0.21 eV. Energy profiles and estimates of kinetic constants for the H2 splitting reaction reveal that H2 is likely to be adsorbed molecularly on sites of (MgO)6, (BaO)6, and (BeO)6 clusters, suggesting a rapid H2 uptake/release at operating temperatures and moderate pressures. The small mass of beryllium and magnesium makes such systems appealing for meeting the gravimetric criterion for H2 storage. PMID:24499810

  10. Coulomb frustration of the multiphoton ionization of metallic clusters under intense EUV FEL evidenced by ion spectrometry

    NASA Astrophysics Data System (ADS)

    Mazza, T.; Devetta, M.; Milani, P.; Motomura, K.; Liu, X.-J.; Fukuzawa, H.; Yamada, A.; Okunishi, M.; Nagaya, K.; Iwayama, H.; Sugishima, A.; Mizoguchi, Y.; Saito, N.; Coreno, M.; Fennel, Th; Nagasono, M.; Tono, K.; Togashi, T.; Kimura, H.; Senba, Y.; Ohashi, H.; Yabashi, M.; Ishikawa, T.; Yao, M.; Ueda, K.; Piseri, P.

    2015-12-01

    Free electron laser light sources delivering high intensity pulses of short wavelength radiation are opening novel possibilities for the investigation of matter at the nanoscale and for the discovery and understanding of new physical processes occurring at the exotic transient states they make accessible. Strong ionization of atomic constituents of a nano-sized sample is a representative example of such processes and the understanding of ionization dynamics is crucial for a realistic description of the experiments. We report here on multiple ionization experiments on free clusters of titanium, a high cohesive energy metal. The time of flight ion spectra reveal a saturation of the cluster ionization at ∼1016 photons per pulse per cm2. Our results also show a clear lack of any explosion process, opposite to what is observed for a rare-gas cluster under similar conditions. A simple and generalized multi-step ionization model including Coulomb frustration of the photoemission process effectively reproduces with a good agreement the main features of the experimental observation and points to an interpretation of the data involving a substantial energy deposition into the cluster through electronic system heating upon scattering events within photoemission.

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

    NASA Astrophysics Data System (ADS)

    Holmlid, Leif; Kotzias, Bernhard

    2016-04-01

    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 H2N(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 H4(0) and H3(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 H2N(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.

  12. Gas-generated thermal oxidation of a coordination cluster for an anion-doped mesoporous metal oxide

    PubMed Central

    Hirai, Kenji; Isobe, Shigehito; Sada, Kazuki

    2015-01-01

    Central in material design of metal oxides is the increase of surface area and control of intrinsic electronic and optical properties, because of potential applications for energy storage, photocatalysis and photovoltaics. Here, we disclose a facile method, inspired by geochemical process, which gives rise to mesoporous anion-doped metal oxides. As a model system, we demonstrate that simple calcination of a multinuclear coordination cluster results in synchronic chemical reactions: thermal oxidation of Ti8O10(4-aminobenzoate)12 and generation of gases including amino-group fragments. The gas generation during the thermal oxidation of Ti8O10(4-aminobenzoate)12 creates mesoporosity in TiO2. Concurrently, nitrogen atoms contained in the gases are doped into TiO2, thus leading to the formation of mesoporous N-doped TiO2. The mesoporous N-doped TiO2 can be easily synthesized by calcination of the multinuclear coordination cluster, but shows better photocatalytic activity than the one prepared by a conventional sol-gel method. Owing to an intrinsic designability of coordination compounds, this facile synthetic will be applicable to a wide range of metal oxides and anion dopants. PMID:26681104

  13. Gas-generated thermal oxidation of a coordination cluster for an anion-doped mesoporous metal oxide.

    PubMed

    Hirai, Kenji; Isobe, Shigehito; Sada, Kazuki

    2015-01-01

    Central in material design of metal oxides is the increase of surface area and control of intrinsic electronic and optical properties, because of potential applications for energy storage, photocatalysis and photovoltaics. Here, we disclose a facile method, inspired by geochemical process, which gives rise to mesoporous anion-doped metal oxides. As a model system, we demonstrate that simple calcination of a multinuclear coordination cluster results in synchronic chemical reactions: thermal oxidation of Ti8O10(4-aminobenzoate)12 and generation of gases including amino-group fragments. The gas generation during the thermal oxidation of Ti8O10(4-aminobenzoate)12 creates mesoporosity in TiO2. Concurrently, nitrogen atoms contained in the gases are doped into TiO2, thus leading to the formation of mesoporous N-doped TiO2. The mesoporous N-doped TiO2 can be easily synthesized by calcination of the multinuclear coordination cluster, but shows better photocatalytic activity than the one prepared by a conventional sol-gel method. Owing to an intrinsic designability of coordination compounds, this facile synthetic will be applicable to a wide range of metal oxides and anion dopants. PMID:26681104

  14. Charge Transfer and Dissociation in Collisions of Metal Clusters with Atoms

    NASA Astrophysics Data System (ADS)

    Bréchignac, C.; Cahuzac, Ph.; Concina, B.; Leygnier, J.; Ruiz, L. F.; Zarour, B.; Hervieux, P. A.; Hanssen, J.; Politis, M. F.; Martín, F.

    2002-10-01

    We present a combined theoretical and experimental study of charge transfer and dissociation in collisions of slow Li2+31 clusters with Cs atoms. We provide a direct quantitative comparison between theory and experiment and show that good agreement is found only when the exact experimental time of flight and initial cluster temperature are taken into account in the theoretical modeling. We demonstrate the validity of the simple physical image that consists in explaining evaporation as resulting from a collisional energy deposit due to cluster electronic excitation during charge transfer.

  15. Synergistic assembly of heavy metal clusters and luminescent organic bridging ligands in metal-organic frameworks for highly efficient X-ray scintillation.

    PubMed

    Wang, Cheng; Volotskova, Olga; Lu, Kuangda; Ahmad, Moiz; Sun, Conroy; Xing, Lei; Lin, Wenbin

    2014-04-30

    We have designed two metal-organic frameworks (MOFs) to efficiently convert X-ray to visible-light luminescence. The MOFs are constructed from M6(μ3-O)4(μ3-OH)4(carboxylate)12 (M = Hf or Zr) secondary building units (SBUs) and anthracene-based dicarboxylate bridging ligands. The high atomic number of Zr and Hf in the SBUs serves as effective X-ray antenna by absorbing X-ray photons and converting them to fast electrons through the photoelectric effect. The generated electrons then excite multiple anthracene-based emitters in the MOF through inelastic scattering, leading to efficient generation of detectable photons in the visible spectrum. The MOF materials thus serve as efficient X-ray scintillators via synergistic X-ray absorption by the metal-cluster SBUs and optical emission by the bridging ligands. PMID:24730683

  16. Asbestos/NESHAP adequately wet guidance

    SciTech Connect

    Shafer, R.; Throwe, S.; Salgado, O.; Garlow, C.; Hoerath, E.

    1990-12-01

    The Asbestos NESHAP requires facility owners and/or operators involved in demolition and renovation activities to control emissions of particulate asbestos to the outside air because no safe concentration of airborne asbestos has ever been established. The primary method used to control asbestos emissions is to adequately wet the Asbestos Containing Material (ACM) with a wetting agent prior to, during and after demolition/renovation activities. The purpose of the document is to provide guidance to asbestos inspectors and the regulated community on how to determine if friable ACM is adequately wet as required by the Asbestos NESHAP.

  17. Health risk assessment of heavy metals in soils and vegetables from wastewater irrigated area, Beijing-Tianjin city cluster, China.

    PubMed

    Wang, Yanchun; Qiao, Min; Liu, Yunxia; Zhu, Yongguan

    2012-01-01

    The possible health risks of heavy metals contamination to local population through food chain were evaluated in Beijing and Tianjin city cluster, China, where have a long history of sewage irrigation. The transfer factors (TF) for heavy metals from soil to vegetables for six elements including Cu, Zn, Pb, Cr, As and Cd were calculated and the pollution load indexes (PLI) were also assessed. Results indicate that only Cd exceeded the maximum acceptable limit in these sites. So far, the heavy metal concentrations in soils and vegetables were all below the permissible limits set by the Ministry of Environmental Protection of China and World Health Organization. The transfer factors of six heavy metals showed the trend as Cd > Zn > Cu > Pb > As > Cr, which were dependent on the vegetable species. The estimated dietary intakes of Cu, Zn, Pb, Cr, As and Cd were far below the tolerable limits and the target hazard quotient (THQ) values were less than 1, which suggested that the health risks of heavy metals exposure through consuming vegetables were generally assumed to be safe. PMID:22894104

  18. Structural, electronic, and magnetic properties of 3D metal trioxide and tetraoxide superhalogen cluster-doped monolayer BN

    NASA Astrophysics Data System (ADS)

    Meng, Jingjing; Li, Dan; Niu, Yuan; Zhao, Hongmin; Liang, Chunjun; He, Zhiqun

    2016-07-01

    The structural, electronic, and magnetic properties of monolayer BN doped with 3D metal trioxide and tetraoxide superhalogen clusters are investigated using first-principle calculations. TMO3(4)-doped monolayer BN exhibits a low negative formation energy, whereas TM atoms embedded in monolayer BN show a high positive formation energy. TMO3(4) clusters are embedded more easily in monolayer BN than TM atoms. Compared with TMO3-doped structures, TMO4-doped structures have a higher structural stability because of their higher binding energies. Given their low negative formation energies, TMO4-doped structures are more favored for specific applications than TMO3-doped structures and TM atom-doped structures. Large magnetic moments per supercell and significant ferromagnetic couplings between a TM atom and neighboring B and N atoms on the BN layer were observed in all TMO4-doped structures, except for TiO4-doped structures.

  19. Dodecanuclear 3d/4f-metal clusters with a 'Star of David' topology: single-molecule magnetism and magnetocaloric properties.

    PubMed

    Alexandropoulos, Dimitris I; Cunha-Silva, Luís; Lorusso, Giulia; Evangelisti, Marco; Tang, Jinkui; Stamatatos, Theocharis C

    2016-01-28

    A family of interwoven molecular inorganic knots, shaped like the 'Star of David', was prepared by the employment of naphthalene-2,3-diol in 3d/4f-metal cluster chemistry; the isoskeletal dodecanuclear compounds exhibit slow relaxation of the magnetization and magnetocaloric properties, depending on the metal ion. PMID:26666673

  20. Detailed chemical abundances in NGC 5824: another metal-poor globular cluster with internal heavy element abundance variations

    NASA Astrophysics Data System (ADS)

    Roederer, Ian U.; Mateo, Mario; Bailey, John I.; Spencer, Meghin; Crane, Jeffrey D.; Shectman, Stephen A.

    2016-01-01

    We present radial velocities, stellar parameters, and detailed abundances of 39 elements derived from high-resolution spectroscopic observations of red giant stars in the luminous, metal-poor globular cluster NGC 5824. We observe 26 stars in NGC 5824 using the Michigan/Magellan Fiber System (M2FS) and two stars using the Magellan Inamori Kyocera Echelle spectrograph. We derive a mean metallicity of [Fe/H] = -1.94 ± 0.02 (statistical) ±0.10 (systematic). The metallicity dispersion of this sample of stars, 0.08 dex, is in agreement with previous work and does not exceed the expected observational errors. Previous work suggested an internal metallicity spread only when fainter samples of stars were considered, so we cannot exclude the possibility of an intrinsic metallicity dispersion in NGC 5824. The M2FS spectra reveal a large internal dispersion in [Mg/Fe], 0.28 dex, which is found in a few other luminous, metal-poor clusters. [Mg/Fe] is correlated with [O/Fe] and anticorrelated with [Na/Fe] and [Al/Fe]. There is no evidence for internal dispersion among the other α- or Fe-group abundance ratios. 25 of the 26 stars exhibit a n-capture enrichment pattern dominated by r-process nucleosynthesis (<[Eu/Fe]> = +0.11 ± 0.12; <[Ba/Eu]> = -0.66 ± 0.05). Only one star shows evidence of substantial s-process enhancement ([Ba/Fe] = +0.56 ± 0.12; [Ba/Eu] = +0.38 ± 0.14), but this star does not exhibit other characteristics associated with s-process enhancement via mass transfer from a binary companion. The Pb and other heavy elements produced by the s-process suggest a time-scale of no more than a few hundred Myr for star formation and chemical enrichment, like the complex globular clusters M2, M22, and NGC 5286.

  1. 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

  2. Adequate supervision for children and adolescents.

    PubMed

    Anderst, James; Moffatt, Mary

    2014-11-01

    Primary care providers (PCPs) have the opportunity to improve child health and well-being by addressing supervision issues before an injury or exposure has occurred and/or after an injury or exposure has occurred. Appropriate anticipatory guidance on supervision at well-child visits can improve supervision of children, and may prevent future harm. Adequate supervision varies based on the child's development and maturity, and the risks in the child's environment. Consideration should be given to issues as wide ranging as swimming pools, falls, dating violence, and social media. By considering the likelihood of harm and the severity of the potential harm, caregivers may provide adequate supervision by minimizing risks to the child while still allowing the child to take "small" risks as needed for healthy development. Caregivers should initially focus on direct (visual, auditory, and proximity) supervision of the young child. Gradually, supervision needs to be adjusted as the child develops, emphasizing a safe environment and safe social interactions, with graduated independence. PCPs may foster adequate supervision by providing concrete guidance to caregivers. In addition to preventing injury, supervision includes fostering a safe, stable, and nurturing relationship with every child. PCPs should be familiar with age/developmentally based supervision risks, adequate supervision based on those risks, characteristics of neglectful supervision based on age/development, and ways to encourage appropriate supervision throughout childhood. PMID:25369578

  3. Small Rural Schools CAN Have Adequate Curriculums.

    ERIC Educational Resources Information Center

    Loustaunau, Martha

    The small rural school's foremost and largest problem is providing an adequate curriculum for students in a changing world. Often the small district cannot or is not willing to pay the per-pupil cost of curriculum specialists, specialized courses using expensive equipment no more than one period a day, and remodeled rooms to accommodate new…

  4. Funding the Formula Adequately in Oklahoma

    ERIC Educational Resources Information Center

    Hancock, Kenneth

    2015-01-01

    This report is a longevity, simulational study that looks at how the ratio of state support to local support effects the number of school districts that breaks the common school's funding formula which in turns effects the equity of distribution to the common schools. After nearly two decades of adequately supporting the funding formula, Oklahoma…

  5. ROLE OF C AND P SITES ON THE CHEMICAL ACTIVITY OF METAL CARBIDE AND PHOSPHIDES: FROM CLUSTERS TO SINGLE-CRYSTAL SURFACES

    SciTech Connect

    RODRIGUEZ,J.A.; VINES, F.; LIU, P.; ILLAS, F.

    2007-07-01

    Transition metal carbides and phosphides have shown tremendous potential as highly active catalysts. At a microscopic level, it is not well understood how these new catalysts work. Their high activity is usually attributed to ligand or/and ensemble effects. Here, we review recent studies that examine the chemical activity of metal carbide and phosphides as a function of size, from clusters to extended surfaces, and metal/carbon or metal/phosphorous ratio. These studies reveal that the C and P sites in these compounds cannot be considered as simple spectators. They moderate the reactivity of the metal centers and provide bonding sites for adsorbates.

  6. Searching for variable stars in the cores of five metal-rich globular clusters using EMCCD observations

    NASA Astrophysics Data System (ADS)

    Skottfelt, J.; Bramich, D. M.; Figuera Jaimes, R.; Jørgensen, U. G.; Kains, N.; Arellano Ferro, A.; Alsubai, K. A.; Bozza, V.; Calchi Novati, S.; Ciceri, S.; D'Ago, G.; Dominik, M.; Galianni, P.; Gu, S.-H.; Harpsøe, K. B. W.; Haugbølle, T.; Hinse, T. C.; Hundertmark, M.; Juncher, D.; Korhonen, H.; Liebig, C.; Mancini, L.; Popovas, A.; Rabus, M.; Rahvar, S.; Scarpetta, G.; Schmidt, R. W.; Snodgrass, C.; Southworth, J.; Starkey, D.; Street, R. A.; Surdej, J.; Wang, X.-B.; Wertz (The Mindstep Consortium), O.

    2015-01-01

    Aims: In this paper, we present the analysis of time-series observations from 2013 and 2014 of five metal-rich ([Fe/H] > -1) globular clusters: NGC 6388, NGC 6441, NGC 6528, NGC 6638, and NGC 6652. The data have been used to perform a census of the variable stars in the central parts of these clusters. Methods: The observations were made with the electron-multiplying charge-couple device (EMCCD) camera at the Danish 1.54 m Telescope at La Silla, Chile, and they were analysed using difference image analysis to obtain high-precision light curves of the variable stars. Results: It was possible to identify and classify all of the previously known or suspected variable stars in the central regions of the five clusters. Furthermore, we were able to identify and, in most cases, classify 48, 49, 7, 8, and 2 previously unknown variables in NGC 6388, NGC 6441, NGC 6528, NGC 6638, and NGC 6652, respectively. Especially interesting is the case of NGC 6441, for which the variable star population of about 150 stars has been thoroughly examined by previous studies, including a Hubble Space Telescope study. In this paper we are able to present 49 new variable stars for this cluster, of which one (possibly two) are RR Lyrae stars, two are W Virginis stars, and the rest are long-period semi-regular or irregular variables on the red giant branch. We have also detected the first double-mode RR Lyrae in the cluster. Based on data collected by MiNDSTEp with the Danish 1.54 m telescope.The light curves presented in this paper (full Table 3) 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/573/A103

  7. GLOBULAR CLUSTERS IN THE OUTER GALACTIC HALO: NEW HUBBLE SPACE TELESCOPE/ADVANCED CAMERA FOR SURVEYS IMAGING OF SIX GLOBULAR CLUSTERS AND THE GALACTIC GLOBULAR CLUSTER AGE-METALLICITY RELATION

    SciTech Connect

    Dotter, Aaron; Anderson, Jay; Sarajedini, Ata

    2011-09-01

    Color-magnitude diagrams (CMDs) derived from Hubble Space Telescope (HST) Advanced Camera for Surveys F606W, F814W photometry of six globular clusters (GCs) are presented. The six GCs form two loose groupings in Galactocentric distance (R{sub GC}): IC 4499, NGC 6426, and Ruprecht 106 at {approx}15-20 kpc and NGC 7006, Palomar 15, and Pyxis at {approx}40 kpc. The CMDs allow the ages to be estimated from the main-sequence turnoff in every case. In addition, the age of Palomar 5 (R{sub GC} {approx} 18 kpc) is estimated using archival HST Wide Field Planetary Camera 2 V, I photometry. The age analysis reveals the following: IC 4499, Ruprecht 106, and Pyxis are 1-2 Gyr younger than inner halo GCs with similar metallicities; NGC 7006 and Palomar 5 are marginally younger than their inner halo counterparts; NGC 6426 and Palomar 15, the two most metal-poor GCs in the sample, are coeval with all the other metal-poor GCs within the uncertainties. Combined with our previous efforts, the current sample provides strong evidence that the Galactic GC age-metallicity relation consists of two distinct branches. One suggests a rapid chemical enrichment in the inner Galaxy while the other suggests prolonged GC formation in the outer halo. The latter is consistent with the outer halo GCs forming in dwarf galaxies and later being accreted by the Milky Way.

  8. Design and Implementation of Noble Metal Nanoparticle Cluster Arrays for Plasmon Enhanced Biosensing

    PubMed Central

    Yan, Bo; Boriskina, Svetlana V.; Reinhard, Björn M.

    2011-01-01

    Nanoparticle Cluster Arrays (NCAs) are a class of electromagnetic materials that comprise chemically defined nanoparticles assembled into clusters of defined size in an extended deterministic arrangement. NCAs are fabricated through integration of chemically synthesized building blocks into predefined patterns using a hybrid top-down/bottom-up fabrication approach that overcomes some of the limitations of conventional top-down fabrication methods with regard to minimum available feature size and structural complexity. NCAs can sustain near-field interactions between nanoparticles within individual clusters as well as between entire neighboring clusters. The availability of near-field interactions on multiple length scales - together with the ability to further enhance the coupled plasmon modes through photonic modes in carefully designed array morphologies - leads to a multiscale cascade electromagnetic field enhancement throughout the array. This feature article introduces the design and fabrication fundamentals of NCAs and characterizes the electromagnetic coupling mechanisms in the arrays. Furthermore, it reviews how the optical properties of NCAs can be tuned through the size and shape of the nanoparticle building blocks and the geometry, size, and separation of the assembled clusters. NCAs have potential applications in many different areas; this feature article focuses on plasmon enhanced biosensing and surface enhanced Raman spectroscopy (SERS), in particular. PMID:22299057

  9. High performance organic photovoltaics with plasmonic-coupled metal nanoparticle clusters.

    PubMed

    Park, Hyung Il; Lee, Seunghoon; Lee, Ju Min; Nam, Soo Ah; Jeon, Taewoo; Han, Sang Woo; Kim, Sang Ouk

    2014-10-28

    Performance enhancement of organic photovoltaics using plasmonic nanoparticles has been limited without interparticle plasmon coupling. We demonstrate high performance organic photovoltaics employing gold nanoparticle clusters with controlled morphology as a plasmonic component. Near-field coupling at the interparticle gaps of nanoparticle clusters gives rise to strong enhancement in localized electromagnetic field, which led to the significant improvement of exciton generation and dissociation in the active layer of organic solar cells. A power conversion efficiency of 9.48% is attained by employing gold nanoparticle clusters at the bottom of the organic active layer. This is one of the highest efficiency values reported thus far for the single active layer organic photovoltaics. PMID:25299878

  10. Stability and structure of metal clusters - Be(13) and Be(55)

    NASA Technical Reports Server (NTRS)

    Pettersson, Lars G. M.; Bauschlicher, Charles W., Jr.

    1986-01-01

    Face-centered cubic (fcc) and hexagonally close-packed (hcp) structures are compared for Be(13) and Be(55) clusters. Both Be(13) and Be(55) prefer the fcc structure over the bulk hcp structure, but the energy difference per atom decreases for Be(55) relative to Be(13). The binding energy per atom, 1.3 eV for Be(55) and 0.8-0.9 eV for Be(13), reflects the greater total number of bonds in the larger cluster rather than a difference in bonding. The energies per bond are much more similar, in the range of 0.30-0.34 eV for both clusters. The size of the p-basis set used influences both stability and ionization potentials strongly.

  11. Plasmon-Enhanced Electron Acceleration in Intense Laser Metal-Cluster Interactions

    SciTech Connect

    Fennel, Th.; Doeppner, T.; Passig, J.; Schaal, Ch.; Tiggesbaeumker, J.; Meiwes-Broer, K.-H.

    2007-04-06

    We have measured the energy and angular-resolved electron emission from medium-sized silver clusters (N{approx_equal}500-2000) exposed to dual laser pulses of moderate intensity (I{approx}10{sup 13-14} W/cm{sup 2}). When the second pulse excites the plasmon resonantly, we observe enhanced emission along the laser polarization axis. The asymmetry of the electron spectrum is strongly increasing with electron energy. Semiclassical simulations reveal the following mechanism: Electrons bound in highly excited states can leave, return to, and traverse the cluster. Those electrons that return at zero plasmon deflection and traverse the cluster during a favorable plasmon half-cycle can experience maximum acceleration by the evolving polarization field. As a result of these constraints energetic electrons are emitted in direction of the laser polarization axis in subcycle bursts.

  12. ASCA Measurements of Metallicity and Temperature Distributions in Three Clusters: A4059, MKW 3s, and 2A 0335+096

    NASA Astrophysics Data System (ADS)

    Kikuchi, Ken'ichi; Furusho, Tae; Ezawa, Hajime; Yamasaki, Noriko Y.; Ohashi, Takaya; Fukazawa, Yasushi; Ikebe, Yasushi

    1999-06-01

    We present ASCA results on the distributions of the metallicity and temperature in 3 bright near-by clusters: A4059, MKW 3s, and 2A 0335+096. A significant gradient in the metal abundance is detected in A4059, while other clusters suggest similar gradients with low significance. These features together with recent results on AWM 7 and Perseus clusters suggest that metals injected in the ICM are not effectively mixed in the cluster space. An analysis of the GIS data, without explicitly including the cooling flow model, shows no substantial temperature drop at large radii (at half the virial radii) for the 3 systems. This is contrary to the recent results for 30 clusters by Markevitch et al. (1998, ApJ 503, 77), who assume rather strong cooling flows. The gas mass fraction of these clusters is 10-15% within 1 Mpc, which suggests that a baryonic fraction of about 20%, including the stellar mass, is a common level in galaxy groups and clusters.

  13. NO adsorption and dissociation on palladium clusters: The importance of charged state and metal doping

    NASA Astrophysics Data System (ADS)

    Gao, Yang; Zhang, Li Mei; Kong, Chun Cai; Yang, Zhi Mao; Chen, Yong Mei

    2016-08-01

    The NO adsorption and dissociation on neutral, charged and Ni-doped Pd13 clusters were studied by using density functional calculations. Our results revealed that NO always prefers to adsorb on the hollow site rather than the top or bridge sites. However, the charge state and Ni doping remarkably influence NO adsorption energy, dissociation barrier and reaction energy. The reaction on Pd13- has the lowest energy barrier and largest reaction energy. The Hirshfeld charge analysis discloses that the origin of the catalytic activity difference is the charge transfer from clusters to NO in the metastable NO adsorption state.

  14. Overcoming statistical error and bias in quantum Monte Carlo: Application to metal-doped helium clusters

    NASA Astrophysics Data System (ADS)

    Warren, Gary Lee, Jr.

    2005-11-01

    Quantum Monte Carlo (QMC) methods are a class of powerful computer simulation techniques for solving the many-body Schrodinger equation. These techniques deliver essentially exact results and boast favorable computational scaling with system size. Calculations provide a full quantum mechanical treatment and may be carried to arbitrary precision. These characteristics make QMC a promising choice for the investigation of doped helium clusters, where quantum effects are substantial. Stochastic in nature, QMC methods are susceptible to statistical bias and error, which must be carefully controlled. Moreover, the relationship between the finite sampling error and the statistical uncertainty in observables has never been systematically investigated. Estimates of arbitrary observables are often substandard and can be plagued by statistical uncertainties an order of magnitude or greater than those for corresponding estimates of the energy. In this work, we present an analysis of how finite populations, importance sampling, and dimensionality affect the statistical uncertainties in QMC estimates of arbitrary observables. We find that the uncertainty depends exponentially on the dimensionality of the system, independent of the observable or nature of the system. This provides insight into the minimal population sizes and importance sampling requirements necessary to obtain useful QMC estimates of properties in high-dimensional systems. With this understanding, we develop new, more robust energy optimization procedures for cluster wavefunctions. We also implement a high quality eight parameter ansatz for the investigation of both pure and doped helium cluster systems. Compared to exact DMC results, the optimized wavefunctions recover over 90% of the total energy for clusters of size n ≤ 20. Finally, we apply this knowledge directly to the study of the solvation behavior of neutral calcium and magnesium impurities in helium nanodroplets. Diffusion Monte Carlo calculations

  15. Atomic-scale dynamics of a model glass-forming metallic liquid: Dynamical crossover, dynamical decoupling, and dynamical clustering

    NASA Astrophysics Data System (ADS)

    Jaiswal, Abhishek; Egami, Takeshi; Zhang, Yang

    2015-04-01

    The phase behavior of multicomponent metallic liquids is exceedingly complex because of the convoluted many-body and many-elemental interactions. Herein, we present systematic studies of the dynamical aspects of a model ternary metallic liquid Cu40Zr51Al9 using molecular dynamics simulations with embedded atom method. We observed a dynamical crossover from Arrhenius to super-Arrhenius behavior in the transport properties (self diffusion coefficient, self relaxation time, and shear viscosity) bordered at Tx˜1300 K. Unlike in many molecular and macromolecular liquids, this crossover phenomenon occurs well above the melting point of the system (Tm˜900 K) in the equilibrium liquid state; and the crossover temperature Tx is roughly twice of the glass-transition temperature of the system (Tg). Below Tx, we found the elemental dynamics decoupled and the Stokes-Einstein relation broke down, indicating the onset of heterogeneous spatially correlated dynamics in the system mediated by dynamic communications among local configurational excitations. To directly characterize and visualize the correlated dynamics, we employed a nonparametric, unsupervised machine learning technique and identified dynamical clusters of atoms with similar atomic mobility. The revealed average dynamical cluster size shows an accelerated increase below Tx and mimics the trend observed in other ensemble averaged quantities that are commonly used to quantify the spatially heterogeneous dynamics such as the non-Gaussian parameter α2 and the four-point correlation function χ4.

  16. Theoretical monomer/cluster model of a polymer/metal interface: poly(methacrylonitrile) on a nickel surface

    NASA Astrophysics Data System (ADS)

    Bureau, Christophe; Defranceschi, Mireille; Delhalle, Joseph; Deniau, Guy; Tanguy, Jean; Lecayon, Gérard

    1994-05-01

    A low-energy contribution at 283.6 eV noted in the C1s region of the XPS spectrum of thin films of poly(methacrylonitrile) obtained via cathodic electropolymerization of 2-methyl-2-propenenitrile on nickel surfaces and recent electrochemical impedance measurements are strongly indicative of a chemical bond formed between the first monomer and metallic atoms during the grafting step of the reaction. A model of a carbon/nickel surface bond comprising a saturated monomer of 2-methyl-2-propenenitrile bound to nickel clusters (Ni 3 and Ni 7) is designed to mimic the final state of the reaction of cathodic electropolymerization. Hartree-Fock calculations are performed to obtain optimized geometry parameters. An evaluation of the chemical shift obtained on the XPS spectrum is made by computing the C1s ionization potentials via Koopmans' theorem. In addition, the analysis of the electronic redistribution upon chemisorption brings valuable insights on the precise nature of chemisorption sites as well as on the validity of a cluster/monomer approach to render the present polymer/metal interface.

  17. Atomic-scale dynamics of a model glass-forming metallic liquid: Dynamical crossover, dynamical decoupling, and dynamical clustering

    DOE PAGESBeta

    Jaiswal, Abhishek; Egami, Takeshi; Zhang, Yang

    2015-04-01

    The phase behavior of multi-component metallic liquids is exceedingly complex because of the convoluted many-body and many-elemental interactions. Herein, we present systematic studies of the dynamic aspects of such a model ternary metallic liquid Cu40Zr51Al9 using molecular dynamics simulation with embedded atom method. We observed a dynamical crossover from Arrhenius to super-Arrhenius behavior in the transport properties (diffusion coefficient, relaxation times, and shear viscosity) bordered at Tx ~1300K. Unlike in many molecular and macromolecular liquids, this crossover phenomenon occurs in the equilibrium liquid state well above the melting temperature of the system (Tm ~ 900K), and the crossover temperature ismore » roughly twice of the glass-transition temperature (Tg). Below Tx, we found the elemental dynamics decoupled and the Stokes-Einstein relation broke down, indicating the onset of heterogeneous spatially correlated dynamics in the system mediated by dynamic communications among local configurational excitations. To directly characterize and visualize the correlated dynamics, we employed a non-parametric, unsupervised machine learning technique and identified dynamical clusters of atoms with similar atomic mobility. The revealed average dynamical cluster size shows an accelerated increase below Tx and mimics the trend observed in other ensemble averaged quantities that are commonly used to quantify the spatially heterogeneous dynamics such as the non-Gaussian parameter and the four-point correlation function.« less

  18. Structural skeleton of preferentially interpenetrated clusters and correlation with shear localization in Mg-Cu-Ni ternary metallic glasses.

    PubMed

    Wang, Q; Li, J H; Liu, J B; Liu, B X

    2014-09-28

    Inherent hierarchical structure and its effect on shear localization were clarified for ternary Mg-Cu-Ni metallic glasses via molecular dynamics studies based on a newly constructed n-body potential for the system. Assisted by a proposed index to detect the medium-range correlation heterogeneity, it was found that the Cu/Ni-centered icosahedra and specific Mg-centered clusters exhibit a strong preference to interconnect, leading to the formation, over an extended scale, of a percolated network that serves as structural skeleton in the glassy matrix. In constituting the skeleton network, the clusters mainly integrate in an interpenetrating mode, while the noninterpenetrating linkages provide additional reinforcements, jointly consolidating the structural and energetic stability of the skeleton. Furthermore, by monitoring the structural evolution upon compressive deformation, it was revealed that the gradual collapse of the skeleton network is intimately correlated to the mechanical response of metallic glasses and acts as a structural signature of the initiation and propagation of shear bands. PMID:25110190

  19. Magnetism of 3{ital d} transition-metal monolayers and two-dimensional Cr clusters deposited on Fe(001)

    SciTech Connect

    Pizzagalli, L.; Stoeffler, D.; Gautier, F.

    1996-11-01

    We study the magnetic properties of transition-metal monolayers (ML) and Cr clusters deposited on Fe(001). We use a self-consistent tight-binding model and the recursion technique in order to get the most stable magnetic state for each atomic configuration. The magnetism is taken into account in the mean-field approximation. We show that for a Cr ML the {ital p}(2{times}2) magnetic solution is lower in energy than all the others. We find that monolayers of V, Ni, and Co are ferromagnetic {ital p}(1{times}1) on Fe(001) whereas the Mn ML are {ital c}(2{times}2) antiferromagnetic. We study also the magnetic transition occurring for Cr clusters, for an increasing Cr atoms number, from ferromagnetic to the {ital p}(2{times}2) order. The results of these calculations are in agreement with those of an Ising model whose parameters are determined. Such an Ising model predicts with a good accuracy the most stable state and the first excited states for each cluster shape. {copyright} {ital 1996 The American Physical Society.}

  20. The Clusters AgeS Experiment (CASE). Analysis of the Detached Eclipsing Binary V15 in the Metal-Rich Open Cluster NGC 6253

    NASA Astrophysics Data System (ADS)

    Rozyczka, M.; Kaluzny, J.; Thompson, I. B.; Dotter, A.; Pych, W.; Narloch, W.

    2014-09-01

    We present the first detailed analysis of the detached eclipsing binary V15 in the super-metal rich open cluster NGC 6253. We obtain the following absolute parameters: Mp=1.303±0.006 MSun, Rp=1.71±0.03 RSun, Lp=2.98±0.10 LSun for the primary, and Ms=1.225±0.006 MSun, Rs=1.44±0.02 RSun, Ls=2.13±0.06 LSun for the secondary. Based on Dartmouth isochrones, the age of NGC 6253 is estimated to be 3.80-4.25 Gyr from the mass-radius diagram and 3.9-4.6 Gyr from color-magnitude diagram fitting. Both of these estimates are significantly higher than those reported so far. The derived apparent distance modulus of 11.65 mag agrees well with the range of 10.9-12.2 mag derived by other authors; however our estimated reddening (0.113 mag) is lower than the lowest published value (0.15 mag). We confirm earlier observations that model atmospheres are not accurate enough to account for the whole CMD of the cluster, with the largest discrepancies appearing on the subgiant and giant branches. Although age estimation from the mass-radius diagram is a relatively safe, distance- and reddening-independent procedure, our results should be verified by photometric and spectroscopic observations of additional detached eclipsing binaries which we have discovered, at least two of which are proper-motion members of NGC 6253.

  1. Mössbauer characterization of the metal clusters in Azotobacter vinelandii nitrogenase VFe protein.

    PubMed

    Ravi, N; Moore, V; Lloyd, S G; Hales, B J; Huynh, B H

    1994-08-19

    The VFe protein of alternative nitrogenase, isolated from Azotobacter vinelandii, strain LS15 and designated as Av1', has been investigated by Mössbauer spectroscopy. The Mössbauer spectrum of the dithionite-reduced Av1', recorded at 4.2 K with a 60-millitesla magnetic field applied parallel to the gamma-beam, is a superposition of three spectral components: 1) a complex spectrum (the M component) with magnetic hyperfine structures attributed to the paramagnetic FeV cofactor, 2) a component (the P component) consisting of three quadrupole doublets identifiable as the Fe2+, D, and S doublets similar to those observed for the P cluster pairs in MoFe proteins, and 3) a minor (4% of total absorption) quadrupole doublet attributable to adventitiously bound iron. The observed 4.2-K parameters for the Fe2+ (delta EQ = 2.99 mm/s and delta = 0.64 mm/s), D (delta EQ = 0.75 mm/s and delta = 0.63 mm/s), and S (delta EQ = 1.2 mm/s and delta = 0.65 mm/s) iron sites and their temperature dependence are very similar to those observed for the P cluster pairs in the conventional MoFe proteins. Similar to those of the MoFe protein, strong field spectra indicate that these doublets are associated with a diamagnetic system. Their percent absorption intensities (Fe(2+)/D/S = 13.0:32.2:6.8) determined at 4.2 K after the removal of the contributions from the adventitiously bound iron are comparable to those of the P cluster pairs in MoFe proteins. These observations established that Av1' also contains P cluster pairs that are identical, in both composition and quantity, to those of the MoFe proteins; i.e. each molecule contains two P cluster pairs and each pair is formed by two Fe2+, five D, and one S iron sites. Considering that 52% absorption of the P component corresponding to two 8Fe clusters, the remaining 48% absorption determined for the M component is consistent with two 7Fe-containing FeV cofactors/molecule of Av1'. The fact that both P cluster pairs are found in the

  2. A Possible Solution for the M/L–[Fe/H] Relation of Globular Clusters in M3. I. A Metallicity- and Density-dependent Top-heavy IMF

    NASA Astrophysics Data System (ADS)

    Zonoozi, A. H.; Haghi, H.; Kroupa, P.

    2016-07-01

    The observed mass-to-light (M/L) ratios of a large sample of globular clusters (GCs) in M31 show an inverse trend with metallicity compared to what is expected from simple stellar population (SSP) models with an invariant canonical stellar initial mass function (IMF), in the sense that the observed M/L ratios decrease with increasing metallicity. We show that when incorporating the effect of dynamical evolution the SSP models with a canonical IMF cannot explain the decreasing M/L ratios with increasing metallicity for the M31 GCs. The recently derived top-heavy IMF as a function of metallicity and embedded cluster density is proposed to explain the lower-than-expected M/L ratios of metal-rich GCs. We find that the SSP models with a top-heavy IMF, retaining a metallicity- and cluster-mass-dependent fraction of the remnants within the clusters, and taking standard dynamical evolution into account, can successfully explain the observed M/L–[Fe/H] relation of M31 GCs. Thus we propose that the kinematic data of GCs can be used to constrain the top-heaviness of the IMF in GCs.

  3. Theoretical study on the encapsulation of Pd3-based transition metal clusters inside boron nitride nanotubes.

    PubMed

    Wang, Qing; Liu, Yue-jie; Zhao, Jing-xiang

    2013-03-01

    Chemical functionalization of the boron nitride nanotube (BNNT) allows a wider flexibility in engineering its electronic and magnetic properties as well as chemical reactivity, thus making it have potential applications in many fields. In the present work, the encapsulation of 13 different Pd(3)M (M = Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Pd, Pt, and Au) clusters inside the (10, 0) BNNT has been studied by performing comprehensive density functional theory (DFT) calculations. Particular attention is paid to searching for the stable configurations, calculating the corresponding binding energies, and evaluating the effects of the encapsulation of Pd(3)M cluster on the electronic and magnetic properties of BNNT. The results indicate that all the studied Pd(3)M clusters can be stably encapsulated inside the (10, 0) BNNT, with binding energies ranging from -0.96 (for Pd(3)Sc) to -5.31 eV (for Pd(3)V). Moreover, due to a certain amount of charge transfer from Pd(3)M clusters to BNNT, certain impurity states are induced within the band gap of pristine BNNT, leading to the reduction of the band gap in various ways. Most Pd(3)M@BNNT nanocomposites exhibit nonzero magnetic moments, which mainly originate from the contribution of the Pd(3)M clusters. In particular, the adsorption of O(2) molecule on BNNT is greatly enhanced due to Pd(3)M encapsulation. The elongation of O-O bonds of the adsorbed O(2) molecules indicates that Pd(3)M@BNNT could be used to fabricate the oxidative catalysis. PMID:23149764

  4. Radial velocities and metallicities from infrared Ca ii triplet spectroscopy of open clusters. II. Berkeley 23, King 1, NGC 559, NGC 6603, and NGC 7245

    NASA Astrophysics Data System (ADS)

    Carrera, R.; Casamiquela, L.; Ospina, N.; Balaguer-Núñez, L.; Jordi, C.; Monteagudo, L.

    2015-06-01

    Context. Open clusters are key to studying the formation and evolution of the Galactic disc. However, there is a deficiency of radial velocity and chemical abundance determinations for open clusters in the literature. Aims: We intend to increase the number of determinations of radial velocities and metallicities from spectroscopy for open clusters. Methods: We acquired medium-resolution spectra (R ~ 8000) in the infrared region Ca ii triplet lines (~8500 Å) for several stars in five open clusters with the long-slit IDS spectrograph on the 2.5 m Isaac Newton Telescope (Roque de los Muchachos Observatory, Spain). Radial velocities were obtained by cross-correlation fitting techniques. The relationships available in the literature between the strength of infrared Ca ii lines and metallicity were also used to derive the metallicity for each cluster. Results: We obtain ⟨Vr⟩ = 48.6 ± 3.4, -58.4 ± 6.8, 26.0 ± 4.3, and -65.3 ± 3.2 km s-1 for Berkeley 23, NGC 559, NGC 6603, and NGC 7245, respectively. We found [ Fe/H ] = -0.25 ± 0.14 and -0.15 ± 0.18 for NGC 559 and NGC 7245, respectively. Berkeley 23 has low metallicity, [ Fe/H ] = -0.42 ± 0.13, which is similar to other open clusters in the outskirts of the Galactic disc. In contrast, we derived high metallicity ([ Fe/H ] = +0.43 ± 0.15) for NGC 6603, which places this system among the most metal-rich known open clusters. To our knowledge, this is the first determination of radial velocities and metallicities from spectroscopy for these clusters, except NGC 6603, for which radial velocities had been previously determined. We have also analysed ten stars in the line of sight to King 1. Because of the large dispersion obtained in both radial velocity and metallicity, we cannot be sure that we have sampled true cluster members. Based on observations made with the 2.5 m Isaac Newton Telescope operated on the island of La Palma by the Isaac Newton Group in the Spanish Observatorio del Roque de los Muchachos of the

  5. THE EVOLUTION OF THE INTRACLUSTER MEDIUM METALLICITY IN SUNYAEV ZEL’DOVICH-SELECTED GALAXY CLUSTERS AT 0 > z > 1.5

    DOE PAGESBeta

    McDonald, M.; Bulbul, E.; Haan, T. de; Miller, E. D.; Benson, B. A.; Bleem, L. E.; Brodwin, M.; Carlstrom, J. E.; Chiu, I.; Forman, W. R.; et al

    2016-07-27

    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

  6. The Evolution of the Intracluster Medium Metallicity in Sunyaev Zel’dovich-selected Galaxy Clusters at 0 > z > 1.5

    NASA Astrophysics Data System (ADS)

    McDonald, M.; Bulbul, E.; de Haan, T.; Miller, E. D.; Benson, B. A.; Bleem, L. E.; Brodwin, M.; Carlstrom, J. E.; Chiu, I.; Forman, W. R.; Hlavacek-Larrondo, J.; Garmire, G. P.; Gupta, N.; Mohr, J. J.; Reichardt, C. L.; Saro, A.; Stalder, B.; Stark, A. A.; Vieira, J. D.

    2016-08-01

    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 of < Z> =0.23+/- 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.

  7. The Evolution of the Intracluster Medium Metallicity in Sunyaev Zel’dovich-selected Galaxy Clusters at 0 > z > 1.5

    NASA Astrophysics Data System (ADS)

    McDonald, M.; Bulbul, E.; de Haan, T.; Miller, E. D.; Benson, B. A.; Bleem, L. E.; Brodwin, M.; Carlstrom, J. E.; Chiu, I.; Forman, W. R.; Hlavacek-Larrondo, J.; Garmire, G. P.; Gupta, N.; Mohr, J. J.; Reichardt, C. L.; Saro, A.; Stalder, B.; Stark, A. A.; Vieira, J. D.

    2016-08-01

    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 of < Z> =0.23+/- 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.

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

    DOE PAGESBeta

    McDonald, M.; Bulbul, E.; Haan, T. de; Miller, E. D.; Benson, B. A.; Bleem, L. E.; Brodwin, M.; Carlstrom, J. E.; Chiu, I.; Forman, W. R.; et al

    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

  9. Cluster harvesting by successive reduction of a metal halide with a nonconventional reduction agent: a benefit for the exploration of metal-rich halide systems.

    PubMed

    Ströbele, Markus; Mos, Agnieszka; Meyer, Hans-Jürgen

    2013-06-17

    The preparation of thermally labile compounds is a great temptation in chemistry which requires a careful selection of reaction media and reaction conditions. With a new scanning technique denoted here as Cluster Harvesting, a whole series of metal halide compounds is detected by differential thermal analysis (DTA) in fused silica tubes and structurally characterized by X-ray powder diffraction. Experiments of the reduction of tungsten hexahalides with elemental antimony and iron are presented. A cascade of six compounds is identified during the reduction with antimony, and five compounds or phases are monitored following the reduction with iron. The crystal structure of Fe2W2Cl10 is reported, and two other phases in the Fe-W-Cl system are discussed. PMID:23718691

  10. Ceci N'est Pas a globular cluster: the metallicity distribution of the stellar system Terzan 5

    SciTech Connect

    Massari, D.; Mucciarelli, A.; Ferraro, F. R.; Lanzoni, B.; Dalessandro, E.; Lovisi, L.; Rich, R. M.; Reitzel, D.; Valenti, E.; Ibata, R.

    2014-11-01

    We present new determinations of the iron abundance for 220 stars belonging to the stellar system Terzan 5 in the Galactic bulge. The spectra have been acquired with FLAMES at the Very Large Telescope of the European Southern Observatory and DEIMOS at the Keck II Telescope. This is by far the largest spectroscopic sample of stars ever observed in this stellar system. From this data set, a subsample of targets with spectra unaffected by TiO bands was extracted and statistically decontaminated from field stars. Once combined with 34 additional stars previously published by our group, a total sample of 135 member stars covering the entire radial extent of the system has been used to determine the metallicity distribution function of Terzan 5. The iron distribution clearly shows three peaks: a super-solar component at [Fe/H] ≅ 0.25 dex, accounting for ∼29% of the sample, a dominant sub-solar population at [Fe/H] ≅ –0.30 dex, corresponding to ∼62% of the total, and a minor (6%) metal-poor component at [Fe/H] ≅ –0.8 dex. Such a broad, multi-modal metallicity distribution demonstrates that Terzan 5 is not a genuine globular cluster but the remnant of a much more complex stellar system.

  11. Structure and role of metal clusters in a metal-organic coordination network determined by density functional theory

    NASA Astrophysics Data System (ADS)

    Svane, K. L.; Linderoth, T. R.; Hammer, B.

    2016-02-01

    We present a comprehensive theoretical investigation of the structures formed by self-assembly of tetrahydroxybenzene (THB)-derivatives on Cu(111). The THB molecule is known to dehydrogenate completely during annealing, forming a reactive radical which assembles into a close-packed structure or a porous metal-coordinated network depending on the coverage of the system. Here, we present details on how the structures are determined by density functional theory calculations, using scanning tunneling microscopy-derived information on the periodicity. The porous network is based on adatom trimers. By analysing the charge distribution of the structure, it is found that this unusual coordination motif is preferred because it simultaneously provides a good coordination of all oxygen atoms and allows for the formation of a two-dimensional network on the surface.

  12. Controllable Encapsulation of "Clean" Metal Clusters within MOFs through Kinetic Modulation: Towards Advanced Heterogeneous Nanocatalysts.

    PubMed

    Liu, Hongli; Chang, Lina; Bai, Cuihua; Chen, Liyu; Luque, Rafael; Li, Yingwei

    2016-04-11

    Surfactant-free tiny Pt clusters were successfully encapsulated within MOFs with controllable size and spatial distribution by a novel kinetically modulated one-step strategy. Our synthesis relies on the rational manipulation of the reduction rate of Pt ions and/or the growth rate of MOFs by using H2 as assistant reducing agent and/or acetic acid as MOF-formation modulator. The as-prepared Pt@MOF core-shell composites exhibited exceedingly high activity and excellent selectivity in the oxidation of alcohols as a result of the ultrafine "clean" Pt clusters, as well as interesting molecular-sieving effects derived from the outer platinum-free MOF shell. PMID:26970412

  13. Unusual cluster shapes and directional bonding of an fcc metal: Pt/Pt(111).

    PubMed

    Schmid, Michael; Garhofer, Andreas; Redinger, Josef; Wimmer, Florian; Scheiber, Philipp; Varga, Peter

    2011-07-01

    Small clusters of Pt adatoms grown on Pt(111) exhibit a preference for the formation of linear chains, which cannot be explained by simple diffusion-limited aggregation. Density functional theory calculations show that short chains are energetically favorable to more compact configurations due to strong directional bonding by d(z)(2)-like orbitals, explaining the stability of the chains. The formation of the chains is governed by substrate distortions, leading to funneling towards the chain ends. PMID:21797553

  14. 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

  15. 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…

  16. Theoretical differential Raman scattering cross-sections of totally-symmetric vibrational modes of free pyridine and pyridine-metal cluster complexes

    NASA Astrophysics Data System (ADS)

    Wu, D. Y.; Hayashi, M.; Lin, S. H.; Tian, Z. Q.

    2004-01-01

    The differential Raman scattering cross-sections of totally-symmetric vibrational modes for pyridine and pyridine-metal clusters have been calculated by using ab initio and density functional methods. The results are compared with experimental data and a good agreement is obtained. In particular, we can theoretically reproduce the significant changes in the relative Raman intensities of the ν12 mode in pyridine-metal cluster complexes. We focus on two mechanisms for these Raman intensities changes: (1) the chemical interaction between the pyridine and the metal clusters; and (2) the charge transfer mechanism. For the pyridine-silver cluster complexes, we find that due to the weak bonding, the chemical interaction does not influence the relative intensities of the Raman peaks of the ν1 and ν12 modes. However, in the case where the copper or the gold clusters are attached to pyridine, the intensity of the band of the ν12 mode is weakened significantly. We also find that the charge transfer mechanism increases the asymmetry of the bands of the ν1 and ν12 modes on all three metals.

  17. Cluster formation at metal surfaces under bombardment with SFm+ (m = 1, …, 5) and Ar+ projectiles

    NASA Astrophysics Data System (ADS)

    Ghalab, S.; Wucher, A.

    2004-11-01

    We investigate the formation of ionic and neutral clusters emitted from a polycrystalline indium surface under bombardment with SFm+ (m = 1, …, 5) and Ar+ projectile ions at 10 keV impact energy. Mass spectra of secondary ions and sputtered neutral particles are recorded under otherwise identical conditions. The neutral species are post-ionized prior to mass analysis by means of single photon-ionization using an intense UV laser at a wavelength of 193 nm. It is found that the measured secondary ion signals increase much more than those of the corresponding neutral particles if SFm+ projectiles are used instead of Ar+ ions, indicating that the ionization probability under bombardment with SFm+ is enhanced by a chemical matrix effect induced by fluorine incorporation into the surface. Interestingly, the largest values of the ionization probability are observed for SF3+ projectiles. The total sputtering yield is found to be larger for SFm+ compared to Ar+ projectiles and to increase linearly with increasing m. Both findings are shown to be understandable in the framework of linear cascade sputtering theory. The partial sputtering yields of Inn clusters exhibit a stronger enhancement than the sputtered monomers, the magnitude of the effect increasing with increasing cluster size and projectile nuclearity.

  18. Luminescent quantum clusters of gold in bulk by albumin-induced core etching of nanoparticles: metal ion sensing, metal-enhanced luminescence, and biolabeling.

    PubMed

    Habeeb Muhammed, Madathumpady Abubaker; Verma, Pramod Kumar; Pal, Samir Kumar; Retnakumari, Archana; Koyakutty, Manzoor; Nair, Shantikumar; Pradeep, Thalappil

    2010-09-01

    The synthesis of a luminescent quantum cluster (QC) of gold with a quantum yield of approximately 4 % is reported. It was synthesized in gram quantities by the core etching of mercaptosuccinic acid protected gold nanoparticles by bovine serum albumin (BSA), abbreviated as Au(QC)@BSA. The cluster was characterized and a core of Au(38) was assigned tentatively from mass spectrometric analysis. Luminescence of the QC is exploited as a "turn-off" sensor for Cu(2+) ions and a "turn-on" sensor for glutathione detection. Metal-enhanced luminescence (MEL) of this QC in the presence of silver nanoparticles is demonstrated and a ninefold maximum enhancement is seen. This is the first report of the observation of MEL from QCs. Folic acid conjugated Au(QC)@BSA was found to be internalized to a significant extent by oral carcinoma KB cells through folic acid mediated endocytosis. The inherent luminescence of the internalized Au(QC)@BSA was used in cell imaging. PMID:20623564

  19. Spectroscopic study of globular clusters in the halo of M31 with the Xinglong 2.16 m telescope II: dynamics, metallicity and age

    NASA Astrophysics Data System (ADS)

    Fan, Zhou; Huang, Ya-Fang; Li, Jin-Zeng; Zhou, Xu; Ma, Jun; Zhao, Yong-Heng

    2012-07-01

    In Paper I, we performed spectroscopic observations on 11 confirmed globular clusters (GCs) in M31 with the Xinglong 2.16 m telescope. We mainly focused on the fitting method and the metallicity gradient for the M31 GC sample. Here, we analyze and further discuss the dynamics, metallicity and age, and their distributions, as well as the relationships between these parameters. In our work, eight more confirmed GCs in the halo of M31 were observed, most of which lack previous spectroscopic information. These star clusters are located far from the galactic center at a projected radius of ~ 14 to ~ 117 kpc, which is more spatially extended than that in the previous work. Firstly, we measured the Lick absorption-line indices and the radial velocities. Then the ages and metallicity values of [Fe/H] and [α/Fe] were fitted by comparing the observed spectral feature indices and the Single Stellar Population model of Thomas et al. in the Cassisi and Padova stellar evolutionary tracks, respectively. Our results show that most of the star clusters in our sample are older than 10 Gyr except B290, which is ~ 5.5 Gyr, and most of them are metal-poor with metallicity [Fe/H] < -1, suggesting that these clusters were born at the early stage of the galaxy's formation. We find that the metallicity gradient for the outer halo clusters with rp > 25 kpc may have an insignificant slope of -0.005 ± 0.005 dex kpc-1 and if the outliers G001 and H11 are excluded, the slope does not change significantly, with a value of -0.002 ± 0.003 dex kpc-1. We also find that the metallicity is not a function of age for the GCs with age < 7 Gyr, but for the old GCs with age > 7 Gyr, there seems to be a trend that the older ones have lower metallicity. Additionally, we plot metallicity distributions with the largest sample of M31 GCs so far and show the bimodality is not significant, and the number of metal-poor and metal-rich groups becomes comparable. The spatial distributions show that the metal

  20. Expansion flow and cluster distributions originating from ultrafast-laser-induced fragmentation of thin metal films: A molecular-dynamics study

    SciTech Connect

    Upadhyay, Arun K.; Urbassek, Herbert M.

    2006-01-15

    Using molecular-dynamics simulation, we study the fragmentation patterns of ultrathin metal films as a function of the initial energization. The energization is assumed to occur instantaneously. Above the threshold for fragmentation, a homogeneous expansion of the exploding film is observed, in which a mixture of clusters of all sizes is found. The internal temperature of the clusters is constant, independent of space, time, and cluster size. The cluster size distribution can be characterized for small energizations as a biexponential distribution, but is better represented for larger energizations by a power law in cluster size m,{proportional_to}m{sup -{alpha}}, with an exponent {alpha} congruent with 2.8-3.1.

  1. Metal telluride clusters composed of niobocene carbonyl, telluride, and cobalt carbonyl units: syntheses, structures, and reactivity

    PubMed

    Brunner; Lucas; Monzon; Mugnier; Nuber; Stubenhofer; Stuckl; Wachter; Wanninger; Zabel

    2000-02-01

    Abstract: The reaction of [Cp#2NbTe2H] (1#; Cp# = Cp* (C5Me5) or Cp(x) (C5Me4Et)) with two equivalents of [Co2(CO)8] gives a series of cobalt carbonyl telluride clusters that contain different types of niobocene carbonyl fragments. At 0 degrees C, [Cp#2NbTe2CO3(CO)7] (2#) and [Co4Te2(CO)10] (3) are formed which disappear at higher temperatures: in boiling toluene a mixture of [cat2][Co9Te6(CO)8] (5#) (cat= [Cp#2Nb(CO)2]+) and [cat2][Co11Te7(CO)10] (6#) is formed along with [cat][Co(CO)4] (4#). Complexes 6# transform into [cat][Co11Te7(CO)10] (7#) upon interaction with HPF6 or wet SiO2. The molecular structures of 2(Cp(x)), 4(Cp(x)), 5(Cp*), 6(Cp*) and 7(Cp*) have been determined by X-ray crystallography. The structure of the neutral 2(Cp(x)) consists of a [Co3(CO)6Te2] bipyramid which is connected to a [(C5Me4Et)2Nb(CO)] fragment through a mu4-Te bridge. The ionic structures of 4(Cp(x)), 5(Cp*), 6(Cp*) and 7(Cp*) each contain one (4, 7) or two (5, 6) [Cp#2Nb(CO)2]+ cations. Apart from 4, the anionic counterparts each contain an interstitial Co atom and are hexacapped cubic cluster anions [Co9Te6(CO)8]2- (5) or heptacapped pentagonal prismatic cluster anions [Co11Te7(CO)10]n- (n=2: [6]2- , n=1: [7]-), respectively. Electrochemical studies established a reversible electron transfer between the anionic clusters [Co11,Te7(CO)10]- and [Co11Te7(CO)10]2in 6# and 7# and provided evidence for the existence of species containing [Co11Te7(CO),0] and [Co11Te7(CO)0]3-. The electronic structures of the new clusters and their relative stabilities are examined by means of DFT calculations. PMID:10747416

  2. A versatile hard-soft N/S-ligand for metal coordination and cluster formation.

    PubMed

    Benson, Callum G M; Plajer, Alex J; García-Rodríguez, Raúl; Bond, Andrew D; Singh, Sanjay; Gade, Lutz H; Wright, Dominic S

    2016-08-11

    Deprotonation of the thialdiphosphazane [S[double bond, length as m-dash]PH(μ-N(t)Bu)]2 with a range of metal-bases gives the stable dianion [S-P(μ-N(t)Bu)]2(2-), which is valence-isoelectronic with the widely-used [RN-P(μ-NR)]2(2-) ligand. Structural studies show that the new ligand has adaptable hard-soft character with respect to the coordinated metal centre and that its multidentate nature can be exploited to construct large cage architectures. PMID:27405360

  3. Clear Evidence for the Presence of Second-generation Asymptotic Giant Branch Stars in Metal-poor Galactic Globular Clusters

    NASA Astrophysics Data System (ADS)

    García-Hernández, D. A.; Mészáros, Sz.; Monelli, M.; Cassisi, S.; Stetson, P. B.; Zamora, O.; Shetrone, M.; Lucatello, S.

    2015-12-01

    Galactic globular clusters (GCs) are known to host multiple stellar populations: a first generation (FG) with a chemical pattern typical of halo field stars and a second generation (SG) enriched in Na and Al and depleted in O and Mg. Both stellar generations are found at different evolutionary stages (e.g., the main-sequence turnoff, the subgiant branch, and the red giant branch (RGB)). The non detection of SG asymptotic giant branch (AGB) stars in several metal-poor ([Fe/H] < -1) GCs suggests that not all SG stars ascend the AGB phase, and that failed AGB stars may be very common in metal-poor GCs. This observation represents a serious problem for stellar evolution and GC formation/evolution theories. We report fourteen SG-AGB stars in four metal-poor GCs (M13, M5, M3, and M2) with different observational properties: horizontal branch (HB) morphology, metallicity, and age. By combining the H-band Al abundances obtained by the Apache Point Observatory Galactic Evolution Experiment survey with ground-based optical photometry, we identify SG Al-rich AGB stars in these four GCs and show that Al-rich RGB/AGB GC stars should be Na-rich. Our observations provide strong support for present, standard stellar models, i.e., without including a strong mass-loss efficiency, for low-mass HB stars. In fact, current empirical evidence is in agreement with the predicted distribution of FG and SG stars during the He-burning stages based on these standard stellar models.

  4. The XLF of LMXBs in the fields of early-type galaxies, their metal-rich, and metal-poor globular clusters

    NASA Astrophysics Data System (ADS)

    Peacock, Mark; Zepf, Steve E.

    2016-04-01

    The X-ray luminosity function (XLF) of extragalactic low mass X-ray binaries (LMXBs) can provide insights into their nature and origin. We present an analysis of seven early-type galaxies. These galaxies have deep Chandra observations, which detect X-ray sources down to 1037erg/s, and HST optical mosaics that enable the classification of these sources into field LMXBs, globular cluster (GC) LMXBs, and contaminating sources. At all luminosities, we find that the number of field LMXBs per stellar mass is similar in these galaxies. This sample therefore suggests that the GC specific frequency may not influence the field LMXB population. It also suggests that other parameters, such as the stellar IMF, are either similar across the galaxy sample or vary in a way that does not effect the LMXB population. The XLF of the field and GC LMXBs are significantly different (p-value of 3x10-6), with the latter having a flatter XLF. The XLFs of the metal-rich and metal-poor GC LMXBs are similar, although larger samples will be needed to provide sharper tests in the future.

  5. Yields from low metallicity, intermediate mass AGB stars:. Their role for the CNO and lithium abundances in Globular Cluster stars

    NASA Astrophysics Data System (ADS)

    Ventura, P.; D'Antona, F.; Mazzitelli, I.

    2002-10-01

    We present the results of extensive computation of the Thermal Pulse phase AGB evolution of stars of metallicities in mass fraction 2 x 10-4 <= Z <= 0.01, for those masses in the range 2.5 <= M/Msun <= 6, which suffer the Hot Bottom Burning (HBB) phase. The evolution is fully computed, by assuming a mass loss rate consistent with the observations of the Magellanic Clouds lithium-rich stars, and modelling convection with the Full Spectrum of Turbulence model by Canuto and Mazzitelli. The results are discussed in the framework of their importance for the evolution of proto-Globular Clusters, whose spectra show that the stars are very probably formed from matter contaminated by the ejecta of these stars, or have accreted it after formation. The main results we find are the following: 1) for metallicities Z <= 10-3, masses above ~ 4 Msun suffer complete CNO cycling in HBB, so that they show at the surface the result of this process, and the oxygen abundance is reduced; 2) most models suffer the third dredge up. Although carbon is processed to nitrogen by HBB, the oxygen burning is so strong in the lowest metallicities (2 x 10-4) that carbon becomes more abundant than oxygen: in other words, low-metallicity intermediate mass stars may show up as carbon stars due to the drastic oxygen burning; 3) if Globular Cluster stars are contaminated by matter processed through these phases, we must expect a non negligible helium enhancement in their composition: from a Big Bang abundance Y=0.24, e.g., we might expect an abundance Y=0.28. This may have no practical consequences if pollution concerns only the external parts of the stars, but is very important if the stars formed as a whole from a helium rich environment. 4) The lithium yields, although not important for galactic chemical evolution, are very interestingly close to the initial Big Bang abundance: processing by HBB is the only way in which we can obtain substantial amounts of gas which have gone through full CNO burning

  6. VizieR Online Data Catalog: On the metallicity of open clusters. III. (Netopil+, 2016)

    NASA Astrophysics Data System (ADS)

    Netopil, M.; Paunzen, E.; Heiter, U.; Soubiran, C.

    2016-03-01

    In Paper II (Heiter et al., Paper II 2014A&A...561A..93H) we have evaluated available spectroscopic iron abundance determinations of open cluster stars and presented mean values for 78 open clusters. The results are based on high-resolution data (R>=25000) with high signal-to-noise ratios (S/N>=50). Furthermore, quality criteria were introduced by adopting only [Fe/H] measurements of stars with Teff=4400-6500K and logg>=2.0dex. We have to note that the mean iron abundance for Berkeley 29, listed in Paper II, also incorporates some measurements based upon lower S/N data. In the present paper we therefore list the correct values for the higher and lower quality data. Since publication of Paper II, some new studies were made (Boesgaard et al., 2013ApJ...775...58B; Bocek Topcu et al., 2015, Cat. J/MNRAS/446/3562; Carraro et al., 2014A&A...568A..86C; Donati et al., 2015, Cat. J/MNRAS/446/1411; Magrini et al.. 2014A&A...563A..44M, 2015A&A...580A..85M; Molenda-Zakowicz et al., 2014MNRAS.445.2446M; Monaco et al., 2014A&A...564L...6M; Reddy et al., 2015MNRAS.450.4301R), which we examined the same way as described in Paper II. This adds ten open clusters to our list (Berkeley 81, NGC 1342, NGC 1662, NGC 1912, NGC 2354, NGC 4337, NGC 4815, NGC 6811, Trumpler 5, and Trumpler 20) and supplementary data for NGC 752, NGC 2447, NGC 2632, and NGC 6705. (1 data file).

  7. The emergence of nonbulk properties in supported metal clusters: negative thermal expansion and atomic disorder in Pt nanoclusters supported on gamma-Al2O3.

    PubMed

    Sanchez, Sergio I; Menard, Laurent D; Bram, Ariella; Kang, Joo H; Small, Matthew W; Nuzzo, Ralph G; Frenkel, Anatoly I

    2009-05-27

    The structural dynamics-cluster size and adsorbate-dependent thermal behaviors of the metal-metal (M-M) bond distances and interatomic order-of Pt nanoclusters supported on a gamma-Al(2)O(3) are described. Data from scanning transmission electron microscopy (STEM) and X-ray absorption spectroscopy (XAS) studies reveal that these materials possess a dramatically nonbulklike nature. Under an inert atmosphere small, subnanometer Pt/gamma-Al(2)O(3) clusters exhibit marked relaxations of the M-M bond distances, negative thermal expansion (NTE) with an average linear thermal expansion coefficient alpha = (-2.4 +/- 0.4) x 10(-5) K(-1), large static disorder and dynamical bond (interatomic) disorder that is poorly modeled within the constraints of classical theory. The data further demonstrate a significant temperature-dependence to the electronic structure of the Pt clusters, thereby suggesting the necessity of an active model to describe the cluster/support interactions mediating the cluster's dynamical structure. The quantitative dependences of these nonbulklike behaviors on cluster size (0.9 to 2.9 nm), ambient atmosphere (He, 4% H(2) in He or 20% O(2) in He) and support identity (gamma-Al(2)O(3) or carbon black) are systematically investigated. We show that the nonbulk structural, electronic and dynamical perturbations are most dramatically evidenced for the smallest clusters. The adsorption of hydrogen on the clusters leads to an increase of the Pt-Pt bondlengths (due to a lifting of the surface relaxation) and significant attenuation of the disorder present in the system. Oxidation of these same clusters has the opposite effect, leading to an increase in Pt-Pt bond strain and subsequent enhancement in nonbulklike thermal properties. The structural and electronic properties of Pt nanoclusters supported on carbon black contrast markedly with those of the Pt/gamma-Al(2)O(3) samples in that neither NTE nor comparable levels of atomic disorder are observed. The Pt

  8. Atomic-scale dynamics of a model glass-forming metallic liquid: Dynamical crossover, dynamical decoupling, and dynamical clustering

    SciTech Connect

    Jaiswal, Abhishek; Egami, Takeshi; Zhang, Yang

    2015-04-01

    The phase behavior of multi-component metallic liquids is exceedingly complex because of the convoluted many-body and many-elemental interactions. Herein, we present systematic studies of the dynamic aspects of such a model ternary metallic liquid Cu40Zr51Al9 using molecular dynamics simulation with embedded atom method. We observed a dynamical crossover from Arrhenius to super-Arrhenius behavior in the transport properties (diffusion coefficient, relaxation times, and shear viscosity) bordered at Tx ~1300K. Unlike in many molecular and macromolecular liquids, this crossover phenomenon occurs in the equilibrium liquid state well above the melting temperature of the system (Tm ~ 900K), and the crossover temperature is roughly twice of the glass-transition temperature (Tg). Below Tx, we found the elemental dynamics decoupled and the Stokes-Einstein relation broke down, indicating the onset of heterogeneous spatially correlated dynamics in the system mediated by dynamic communications among local configurational excitations. To directly characterize and visualize the correlated dynamics, we employed a non-parametric, unsupervised machine learning technique and identified dynamical clusters of atoms with similar atomic mobility. The revealed average dynamical cluster size shows an accelerated increase below Tx and mimics the trend observed in other ensemble averaged quantities that are commonly used to quantify the spatially heterogeneous dynamics such as the non-Gaussian parameter and the four-point correlation function.

  9. Comparing Local and High-z X-ray Galaxy Clusters: Properties of the Gas Mass Fraction, Metallicity, and Entropy

    NASA Astrophysics Data System (ADS)

    Ettori, S.; Tozzi, P.; Rosati, P.

    We summarize here some of the results on the properties of the X-ray emitting plasma in galaxy clusters at high redshift that we present and discuss in a series of papers (Ettori, Tozzi & Rosati 2003a; Tozzi et al. 2003; Rosati et al. 2003; Ettori et al. 2003b). In particular, we report on (1) how the gas mass fraction measured in galaxy clusters at z>0.7 is used to put significant constraints on the cosmological parameters in a independent and complementary way with respect to the power spectrum of the observed anisotropies in the Cosmic Microwave Background and the magnitude-redshift relation for distant type Ia supernovae (Ettori et al. 2003a), (2) what is the measured metallicity of the intracluster medium at redshift between 0.3 and 1.3 (Tozzi et al. 2003, Rosati et al. 2003), (3) how the observed entropy values in the cores of these high-z systems compare with local estimates (Ettori et al. 2003b).

  10. Modeling the Noble Metal/TiO2 (110) Interface with Hybrid DFT Functionals: A Periodic Electrostatic Embedded Cluster Model Study

    SciTech Connect

    Ammal, Salai Cheettu; Heyden, Andreas

    2010-10-26

    The interaction of Aun and Ptn (n=2,3) clusters with the stoichiometric and partially reduced rutile TiO2 (110) surfaces has been investigated using periodic slab and periodic electrostatic embedded cluster models. Compared to Au clusters, Pt clusters interact strongly with both stoichiometric and reduced TiO2 (110) surfaces and are able to enhance the reducibility of the TiO2 (110) surface, i.e., reduce the oxygen vacancy formation energy. The focus of this study is the effect of Hartree–Fock exchange on the description of the strength of chemical bonds at the interface of Au/Pt clusters and the TiO2 (110) surface. Hartree–Fock exchange helps describing the changes in the electronic structures due to metal cluster adsorption as well as their effect on the reducibility of the TiO2 surface. Finally, the performance of periodic embedded cluster models has been assessed by calculating the Pt adsorption and oxygen vacancy formation energies. Cluster models, together with hybrid PBE0 functional, are able to efficiently compute reasonable electronic structures of the reduced TiO2 surface and predict charge localization at surface oxygen vacancies, in agreement with the experimental data, that significantly affect computed adsorption and reaction energies.

  11. High-resolution abundance analysis of red giants in the metal-poor bulge globular cluster HP 1

    NASA Astrophysics Data System (ADS)

    Barbuy, B.; Cantelli, E.; Vemado, A.; Ernandes, H.; Ortolani, S.; Saviane, I.; Bica, E.; Minniti, D.; Dias, B.; Momany, Y.; Hill, V.; Zoccali, M.; Siqueira-Mello, C.

    2016-06-01

    Context. The globular cluster HP 1 is projected at only 3.̊33 from the Galactic center. Together with its distance, this makes it one of the most central globular clusters in the Milky Way. It has a blue horizontal branch (BHB) and a metallicity of [Fe/H] ≈ -1.0. This means that it probably is one of the oldest objects in the Galaxy. Abundance ratios can reveal the nucleosynthesis pattern of the first stars as well as the early chemical enrichment and early formation of stellar populations. Aims: High-resolution spectra obtained for six stars were analyzed to derive the abundances of the light elements C, N, O, Na, and Al, the alpha-elements Mg, Si, Ca, and Ti, and the heavy elements Sr, Y, Zr, Ba, La, and Eu. Methods: High-resolution spectra of six red giants that are confirmed members of the bulge globular cluster HP 1 were obtained with the 8 m VLT UT2-Kueyen telescope with the UVES spectrograph in FLAMES-UVES configuration. The spectroscopic parameter derivation was based on the excitation and ionization equilibrium of Fe i and Fe ii. Results: We confirm a mean metallicity of [Fe/H] = -1.06 ± 0.10, by adding the two stars that were previously analyzed in HP 1. The alpha-elements O and Mg are enhanced by about +0.3 ≲ [O,Mg/Fe] ≲ +0.5 dex, Si is moderately enhanced with +0.15 ≲ [Si/Fe] ≲ +0.35 dex, while Ca and Ti show lower values of -0.04 ≲ [Ca,Ti/Fe] ≲ +0.28 dex. The r-element Eu is also enhanced with [Eu/Fe] ≈ +0.4, which together with O and Mg is indicative of early enrichment by type II supernovae. Na and Al are low, but it is unclear if Na-O are anticorrelated. The heavy elements are moderately enhanced, with -0.20 < [La/Fe] < +0.43 dex and 0.0 < [Ba/Fe] < +0.75 dex, which is compatible with r-process formation. The spread in Y, Zr, Ba, and La abundances, on the other hand, appears to be compatible with the spinstar scenario or other additional mechanisms such as the weak r-process. Observations collected at the European Southern

  12. 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.

  13. MASS-TO-LIGHT RATIOS FOR M31 GLOBULAR CLUSTERS: AGE DATING AND A SURPRISING METALLICITY TREND

    SciTech Connect

    Strader, Jay; Huchra, John P.; Smith, Graeme H.; Brodie, Jean P.

    2009-08-15

    We have obtained velocity dispersions from Keck high-resolution integrated spectroscopy of 10 M31 globular clusters (GCs), including three candidate intermediate-age GCs. We show that these candidates have the same V-band mass-to-light (M/L{sub V} ) ratios as the other GCs, implying that they are likely to be old. We also find a trend of derived velocity dispersion with wavelength, but cannot distinguish between a systematic error and a physical effect. Our new measurements are combined with photometric and spectroscopic data from the literature in a re-analysis of all M31 GC M/L{sub V} values. In a combined sample of 27 GCs, we show that the metal-rich GCs have lower M/L{sub V} than the metal-poor GCs, in conflict with predictions from stellar population models. Fragmentary data for other galaxies support this observation. The M31 GC fundamental plane is extremely tight, and we follow up an earlier suggestion by Djorgovski to show that the fundamental plane can be used to estimate accurate distances (potentially 10% or better)

  14. Anion Photoelectron Spectroscopy of Mo-V Binary Transition Metal Suboxide Clusters

    NASA Astrophysics Data System (ADS)

    Jarrold, Caroline Chick; Mann, Jennifer E.; Waller, Sarah E.; Rothgeb, David W.

    2010-06-01

    Vibrationally-resolved photoelectron spectra of molybdenum vanadium oxo cluster anions with 2 to 5 oxygen atoms and measured using 2.33 eV, 3.49 eV and 4.66 eV photon energies generally exhibit broad and overlapping electronic states. The adiabatic electron affinities for the series are 1.68(3) eV, 1.73(3) eV, 2.89(1) eV, and 3.4(1) eV for two through five oxygen atoms, respectively. Vibrational structure observed in the spectra can be reconciled with the lowest energy structural isomers of the anions determined in DFT calculations: The lowest energy isomers have low symmetry, with the Mo center in a higher oxidation state than the V center, and high spin states are favored.

  15. Is a vegetarian diet adequate for children.

    PubMed

    Hackett, A; Nathan, I; Burgess, L

    1998-01-01

    The number of people who avoid eating meat is growing, especially among young people. Benefits to health from a vegetarian diet have been reported in adults but it is not clear to what extent these benefits are due to diet or to other aspects of lifestyles. In children concern has been expressed concerning the adequacy of vegetarian diets especially with regard to growth. The risks/benefits seem to be related to the degree of restriction of he diet; anaemia is probably both the main and the most serious risk but this also applies to omnivores. Vegan diets are more likely to be associated with malnutrition, especially if the diets are the result of authoritarian dogma. Overall, lacto-ovo-vegetarian children consume diets closer to recommendations than omnivores and their pre-pubertal growth is at least as good. The simplest strategy when becoming vegetarian may involve reliance on vegetarian convenience foods which are not necessarily superior in nutritional composition. The vegetarian sector of the food industry could do more to produce foods closer to recommendations. Vegetarian diets can be, but are not necessarily, adequate for children, providing vigilance is maintained, particularly to ensure variety. Identical comments apply to omnivorous diets. Three threats to the diet of children are too much reliance on convenience foods, lack of variety and lack of exercise. PMID:9670174

  16. Open-Framework Oxysulfide Based on the Supertetrahedral [In4Sn16O10S34](12-) Cluster and Efficient Sequestration of Heavy Metals.

    PubMed

    Zhang, Xian-Ming; Sarma, Debajit; Wu, Ya-Qin; Wang, Li; Ning, Zhi-Xue; Zhang, Fu-Qiang; Kanatzidis, Mercouri G

    2016-05-01

    The new ion-exchange oxy-sulfide material has a three-dimensional open framework comprising the pseudo-T4 supertetrahedral [In4Sn16O10S34](12-) cluster. This material has large pores and is a fast ion exchanger. It exhibits high selectivity in sequestering heavy metal ions from aqueous solutions including solutions containing heavy concentrations of sodium, calcium, ammonium, magnesium, zinc, carbonate, phosphate, and acetate ions. Moreover, the ion-exchange efficiency in competitive ion-exchange experiments involving mixtures of metal ions is significantly higher than for solutions of single metal ions. PMID:27082786

  17. Ceci N'est Pas a Globular Cluster: The Metallicity Distribution of the Stellar System Terzan 5

    NASA Astrophysics Data System (ADS)

    Massari, D.; Mucciarelli, A.; Ferraro, F. R.; Origlia, L.; Rich, R. M.; Lanzoni, B.; Dalessandro, E.; Valenti, E.; Ibata, R.; Lovisi, L.; Bellazzini, M.; Reitzel, D.

    2014-11-01

    We present new determinations of the iron abundance for 220 stars belonging to the stellar system Terzan 5 in the Galactic bulge. The spectra have been acquired with FLAMES at the Very Large Telescope of the European Southern Observatory and DEIMOS at the Keck II Telescope. This is by far the largest spectroscopic sample of stars ever observed in this stellar system. From this data set, a subsample of targets with spectra unaffected by TiO bands was extracted and statistically decontaminated from field stars. Once combined with 34 additional stars previously published by our group, a total sample of 135 member stars covering the entire radial extent of the system has been used to determine the metallicity distribution function of Terzan 5. The iron distribution clearly shows three peaks: a super-solar component at [Fe/H] ~= 0.25 dex, accounting for ~29% of the sample, a dominant sub-solar population at [Fe/H] ~= -0.30 dex, corresponding to ~62% of the total, and a minor (6%) metal-poor component at [Fe/H] ~= -0.8 dex. Such a broad, multi-modal metallicity distribution demonstrates that Terzan 5 is not a genuine globular cluster but the remnant of a much more complex stellar system. Based on FLAMES observations performed at the European Southern Observatory, proposal numbers 087.D-0716(B), 087.D-0748(A), and 283.D-5027(A), and at the W. M. Keck Observatory. Keck is operated as a scientific partnership among the California Institute of Technology, the University of California, and the National Aeronautics and Space Administration. The Observatory was made possible by the generous financial support of the W. M. Keck Foundation.

  18. Scanning tunneling microscopy study: From clean surface to surfaces adsorbed with atom/cluster or metallic island

    NASA Astrophysics Data System (ADS)

    Zhang, Xieqiu

    2007-12-01

    Nanostructures, namely materials in the nanometer or sub-nanometer scales, can possess completely diRTMerent properties from their bulk counterparts. Due to the potential applications in different disciplines, the study of nanostructures has attracted extensive attention worldwide in recent years. Metal nanostructures grown on semiconductor substrates are a special group of nanostructures. Since these nanostructures can be prepared in ultrahigh vacuum with high controllability, one can use low-temperature scanning tunneling microscopy (STM) to obtain information in situ on both the structural and electronic properties of these nanostructures simultaneously. In this thesis, I will present the growth behavior of metal or semiconductor nanostructures at the initial stage and the novel electronic properties of some of these nanostructures. The study of single Ge atoms adsorbed on the Si(111)-7x7 surface shows that different deposition temperatures result in diRTMerent adsorption structures. We find Ge substitution for the Si adatoms during high temperature growth and simple Ge adsorption above the Si atoms during low temperature growth. Small Ag clusters, formed on the Si(111)-7x7 surface at controlled coverages, show a strong rectification effect, which is an indication of the initial stage of Schottky barrier formation and possibly the smallest Schottky diode. On the surfaces of heavily n-doped and p-doped Si substrates, although the 7x7 is metallic at room temperature, an energy gap opens at low temperatures. This energy gap is correlated well with the electronic localization induced by the doping impurities. For Pb nanoislands, a pseudogap was discovered at temperatures higher than the superconducting transition temperature. The strength of the pseudogap depends on the lateral size and temperature, which is speculated to originate from the weak electronic localization induced by structural disorder.

  19. Star formation in the first galaxies - III. Formation, evolution, and characteristics of the first metal-enriched stellar cluster

    NASA Astrophysics Data System (ADS)

    Safranek-Shrader, Chalence; Montgomery, Michael H.; Milosavljević, Miloš; Bromm, Volker

    2016-01-01

    We simulate the formation of a low-metallicity (10-2 Z⊙) stellar cluster at redshift z ˜ 14. Beginning with cosmological initial conditions, the simulation utilizes adaptive mesh refinement and sink particles to follow the collapse and evolution of gas past the opacity limit for fragmentation, thus resolving the formation of individual protostellar cores. A time- and location-dependent protostellar radiation field, which heats the gas by absorption on dust, is computed by integration of protostellar evolutionary tracks. The simulation also includes a robust non-equilibrium chemical network that self-consistently treats gas thermodynamics and dust-gas coupling. The system is evolved for 18 kyr after the first protostellar source has formed. In this time span, 30 sink particles representing protostellar cores form with a total mass of 81 M⊙. Their masses range from ˜0.1 to 14.4 M⊙ with a median mass ˜0.5-1 M⊙. Massive protostars grow by competitive accretion while lower mass protostars are stunted in growth by close encounters and many-body ejections. In the regime explored here, the characteristic mass scale is determined by the cosmic microwave background temperature floor and the onset of efficient dust-gas coupling. It seems unlikely that host galaxies of the first bursts of metal-enriched star formation will be detectable with the James Webb Space Telescope or other next-generation infrared observatories. Instead, the most promising access route to the dawn of cosmic star formation may lie in the scrutiny of metal-poor, ancient stellar populations in the Galactic neighbourhood. The observable targets corresponding to the system simulated here are ultra-faint dwarf satellite galaxies such as Boötes II and Willman I.

  20. Solvent Effects on the Dynamic Polarizability and Raman Response of Molecule-Metal Oxide Hybrid Clusters.

    PubMed

    Orozco-Gonzalez, Yoelvis; Tarakeshwar, Pilarisetty; Canuto, Sylvio; Mujica, Vladimiro

    2016-08-18

    Currently, there is considerable interest in the properties of semiconducting metal oxide nanoparticle substrates because of their utility in surface-enhanced Raman scattering, dye-sensitized solar cells, and photocatalysis. While the enhancement of Raman activities of molecules adsorbed on these nanoparticles is due to a large increase in the polarizability, because of charge transfer from the molecule to the semiconducting nanoparticle, little is known about the factors responsible for modulating the polarizability, particularly the influence of the solvent. Consequently, we have carried out Monte Carlo simulations of several hybrids to study the solvent effect on the dynamic polarizabilities and electronic spectra. Our results indicate that the presence of the solvent induces a shift and an increase in the polarization response that is dependent on the identity of the hybrid. The observed enhancement can be attributed to both the resonant character of the excitation and the participation of the solvent in the charge redistribution. The methodology employed in this work could be very valuable in both identifying and developing metal oxides as novel molecular sensors. PMID:27145884

  1. Reducing the Cost and Preserving the Reactivity in Noble-Metal-Based Catalysts: Oxidation of CO by Pt and Al-Pt Alloy Clusters Supported on Graphene.

    PubMed

    Koizumi, Kenichi; Nobusada, Katsuyuki; Boero, Mauro

    2016-04-01

    The oxidation mechanisms of CO to CO2 on graphene-supported Pt and Pt-Al alloy clusters are elucidated by reactive dynamical simulations. The general mechanism evidenced is a Langmuir-Hinshelwood (LH) pathway in which O2 is adsorbed on the cluster prior to the CO oxidation. The adsorbed O2 dissociates into two atomic oxygen atoms thus promoting the CO oxidation. Auxiliary simulations on alloy clusters in which other metals (Al, Co, Cr, Cu, Fe, Ni) replace a Pt atom have pointed to the aluminum doped cluster as a special case. In the nanoalloy, the reaction mechanism for CO oxidation is still a LH pathway with an activation barrier sufficiently low to be overcome at room temperature, thus preserving the catalyst efficiency. This provides a generalizable strategy for the design of efficient, yet sustainable, Pt-based catalysts at reduced cost. PMID:26878836

  2. Ferromagnetic Cluster Glass Phase Embedded in a Paramagnetic and Metallic Host in Non-Uniform Magnetic System CaRu1-xScxO3

    NASA Astrophysics Data System (ADS)

    Yamamoto, Takafumi D.; Kotani, Atsuhiro; Nakajima, Hiroshi; Okazaki, Ryuji; Taniguchi, Hiroki; Mori, Shigeo; Terasaki, Ichiro

    2016-03-01

    We have investigated both static and dynamic magnetic properties of polycrystalline CaRu1-xScxO3 system in order to clarify the role of Sc ions as a disorder for magnetic ordering. We have observed typical features of a ferromagnetic cluster glass state below around 40 K: (i) a broad, frequency-dependent peak in the ac magnetic susceptibility, (ii) a slow relaxation of the magnetization, and (iii) a continuous increase in the dc magnetic susceptibility in field cooling process. The composition dependence of characteristic parameters for the cluster glass state suggests that chemical segregation can hardly explain the clustering mechanism. We propose a possible picture that the ferromagnetic clusters are distributed uniformly and form the glassy state embedded in the paramagnetic and metallic host of CaRuO3.

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

    SciTech Connect

    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 ilustran 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.

  4. Atomistic mechanisms of intermittent plasticity in metals: dislocation avalanches and defect cluster pinning.

    PubMed

    Niiyama, Tomoaki; Shimokawa, Tomotsugu

    2015-02-01

    Intermittent plastic deformation in crystals with power-law behaviors has been reported in previous experimental studies. The power-law behavior is reminiscent of self-organized criticality, and mesoscopic models have been proposed that describe this behavior in crystals. In this paper, we show that intermittent plasticity in metals under tensile deformation can be observed in molecular dynamics models, using embedded atom method potentials for Ni, Cu, and Al. Power-law behaviors of stress drop and waiting time of plastic deformation events are observed. It is shown that power-law behavior is due to dislocation avalanche motions in Cu and Ni. A different mechanism of dislocation pinning is found in Al. These different stress relaxation mechanisms give different power-law exponents. We propose a probabilistic model to describe the novel dislocation motion in Al and analytically deduce the power-law behavior. PMID:25768512

  5. High-Resolution Identification of Chemical States in Individual Metal Clusters in an Insulating Amorphous Polymer.

    PubMed

    Kubo, Yugo; Mizoguchi, Akira; Fujita, Jun-Ichi

    2016-05-17

    The effectivity of cryo-scanning transmission electron microscopy-electron energy loss spectroscopy was demonstrated for nanoscale analysis of the cross-section of the Cu/polyimide interface. The nanoscale Cu/Cu2O/CuO layer structure at the interface was clearly observed for the first time. In addition, a Cu atom was identified, embedded in the polyimide matrix, and the average valence of diffusing Cu atoms or nanoclusters was determined using (cryo-)scanning transmission electron microscopy-electron energy loss spectroscopy. On the basis of these results, we have proposed a mechanism for the diffusion of Cu atoms in polyimide. To the best of our knowledge, this is the first report of the observation of a metal atom embedded in an insulating amorphous polymer. PMID:27104743

  6. A metallothionein containing a zinc finger within a four-metal cluster protects a bacterium from zinc toxicity

    PubMed Central

    Blindauer, Claudia A.; Harrison, Mark D.; Parkinson, John A.; Robinson, Andrea K.; Cavet, Jennifer S.; Robinson, Nigel J.; Sadler, Peter J.

    2001-01-01

    Zinc is essential for many cellular processes, including DNA synthesis, transcription, and translation, but excess can be toxic. A zinc-induced gene, smtA, is required for normal zinc-tolerance in the cyanobacterium Synechococcus PCC 7942. Here we report that the protein SmtA contains a cleft lined with Cys-sulfur and His-imidazole ligands that binds four zinc ions in a Zn4Cys9His2 cluster. The thiolate sulfurs of five Cys ligands provide bridges between the two ZnCys4 and two ZnCys3His sites, giving two fused six-membered rings with distorted boat conformations. The inorganic core strongly resembles the Zn4Cys11 cluster of mammalian metallothionein, despite different amino acid sequences, a different linear order of the ligands, and presence of histidine ligands. Also, SmtA contains elements of secondary structure not found in metallothioneins. One of the two Cys4-coordinated zinc ions in SmtA readily exchanges with exogenous metal (111Cd), whereas the other is inert. The thiolate sulfur ligands bound to zinc in this site are buried within the protein. Regions of β-strand and α-helix surround the inert site to form a zinc finger resembling the zinc fingers in GATA and LIM-domain proteins. Eukaryotic zinc fingers interact specifically with other proteins or DNA and an analogous interaction can therefore be anticipated for prokaryotic zinc fingers. SmtA now provides structural proof for the existence of zinc fingers in prokaryotes, and sequences related to the zinc finger motif can be identified in several bacterial genomes. PMID:11493688

  7. Hybrid magnetic nanoparticle/nanogold clusters and their distance-dependent metal-enhanced fluorescence effect via DNA hybridization

    NASA Astrophysics Data System (ADS)

    GuThese Authors Contributed Equally To This Study., Xuefan; Wu, Youshen; Zhang, Lingze; Liu, Yongchun; Li, Yan; Yan, Yongli; Wu, Daocheng

    2014-07-01

    To improve the metal-enhanced fluorescence (MEF) effect of nanogolds (AuNPs) and accurately detect specific DNA sequences via DNA hybridization, novel hybrid magnetic nanoparticles/nanogold clusters (HMNCs) were designed based on finite-difference time-domain simulation results and prepared by using Fe3O4 and nanogolds. The nanogolds outside the HMNC were then conjugated with thiol-terminated DNA molecules, thus DNA modified-HMNCs (DNA-HMNCs) were obtained. The size distributions of these nanostructures were measured by a Malvern size analyzer, and their morphology was observed via transmission electron microscopy (TEM). The ultraviolet (UV)-visible (vis) absorption spectra of the samples were recorded with a UV-2600 spectrophotometer. Fluorescence spectra and the MEF effect were recorded using a spectrophotofluorometer, and lifetimes were determined using a time-correlated single photon counting apparatus. The prepared HMNCs were stable in aqueous solutions and had an average diameter of 87 +/- 3.2 nm, with six to eight AuNPs around a single Fe3O4 nanoparticle. Fluorescein isothiocyanate (FITC) tagged DNA-HMNC conjugates exhibited a significant MEF effect and could accurately detect specific DNA sequences after DNA hybridization. This result indicates their various potential applications in sensors and biomedical fields.To improve the metal-enhanced fluorescence (MEF) effect of nanogolds (AuNPs) and accurately detect specific DNA sequences via DNA hybridization, novel hybrid magnetic nanoparticles/nanogold clusters (HMNCs) were designed based on finite-difference time-domain simulation results and prepared by using Fe3O4 and nanogolds. The nanogolds outside the HMNC were then conjugated with thiol-terminated DNA molecules, thus DNA modified-HMNCs (DNA-HMNCs) were obtained. The size distributions of these nanostructures were measured by a Malvern size analyzer, and their morphology was observed via transmission electron microscopy (TEM). The ultraviolet (UV

  8. Thermochromic and mechanochromic luminescence umpolung in isostructural metal-organic frameworks based on Cu6I6 clusters.

    PubMed

    Deshmukh, Mahesh S; Yadav, Ashok; Pant, Rakesh; Boomishankar, Ramamoorthy

    2015-02-16

    Two isostructural metal-organic framework (MOF) materials, namely, {[MeSi((3)Py)3]6(Cu6I6)}n (1) and {[ MeSi((3)Qy)3]6(Cu6I6)}n (2), featuring Cu6I6 clusters were synthesized from tridentate arylsilane ligands of the type MeSi((3)Py)3 ((3)Py = 3-pyridyl) and MeSi((3)Qy)3 ((3)Qy = 3-quinolyl), respectively. While the MOF 1 displays the usual thermochromism associated with traditional Cu4I4Py4 clusters, the MOF 2 shows (3)XLCT/(3)MLCT emission due to the Cu6I6 cluster core at both 298 and 77 K, albeit with some marginal variations in its emission wavelengths. Interestingly, an unusual reversal in the mechanochromic luminescent behavior was observed for these isostructural MOFs at 298 K wherein a pronounced blue-shifted high energy emission for 1 (from orange to yellowish-orange) and a red-shifted low-energy emission for 2 (from green to orange) were obtained upon grinding these samples. This is primarily due to the variations in their cuprophilic interactions as 1 displays shorter Cu···Cu distances (2.745(1) Å) in comparison with those present in 2 (3.148(0) Å). As a result, the ground sample of 2 exhibits a prominent red shift in luminescence owing to the reduction of its Cu···Cu distances to an unknown value closer to the sum of van der Waals radii between two Cu(I) atoms (2.80 Å). However, the blue-shifted emission in 1 is presumably attributed to the rise in its lowest unoccupied molecular orbital energy levels caused by changes in the secondary packing forces. Furthermore, the absorption and emission characteristics of 1 and 2 were substantiated by time-dependent density functional theory calculations on their discrete-model compounds. In addition, the syntheses, reactivity studies, and photophysical properties of two one-dimensional MOFs, namely, {[MeSi((3)Qy)3]2(Cu2I2)}n (3) and {[MeSi((3)Qy)3](CuI)}n (4), having dimeric Cu2I2 and monomeric CuI moieties, respectively, were examined. PMID:25602737

  9. DFT based study of transition metal nano-clusters for electrochemical NH3 production.

    PubMed

    Howalt, J G; Bligaard, T; Rossmeisl, J; Vegge, T

    2013-05-28

    Theoretical studies of the possibility of producing ammonia electrochemically at ambient temperature and pressure without direct N2 dissociation are presented. Density functional theory calculations were used in combination with the computational standard hydrogen electrode to calculate the free energy profile for the reduction of N2 admolecules and N adatoms on transition metal nanoclusters in contact with an acidic electrolyte. This work has established linear scaling relations for the dissociative reaction intermediates NH, NH2, and NH3. In addition, linear scaling relations for the associative reaction intermediates N2H, N2H2, and N2H3 have been determined. Furthermore, correlations between the adsorption energies of N, N2, and H have been established. These scaling relations and the free energy corrections are used to establish volcanoes describing the onset potential for electrochemical ammonia production and hence describe the potential determining steps for the electrochemical ammonia production. The competing hydrogen evolution reaction has also been analyzed for comparison. PMID:23598667

  10. Observation of triply charged metal ion clusters by electrospray and laser spray

    PubMed

    Kojima; Kudaka; Sato; Asakawa; Akiyama; Kawashima; Hiraoka

    1999-01-01

    Studies of the gas phase ion chemistry of triply charged metal ions, M(3+) = Sc(3+), Y(3+), La(3+), Ce(3+), and Yb(3+), were made by electrospray and laser spray. Triply charged ion ligand complexes, M(3+)(ligand)(n) were produced in the gas phase by electrospray and laser spray for the following ligands; glucose; sucrose; raffinose; cyclodextrin; ginsenoside Rb(1); dimethyl sulfoxide (DMSO) and hexamethylphosphoramide (HMPA). The ion evaporation mechanism must be invoked to explain the transfer of more surface active ions (e.g., NH(4)(+)(H(2)O)(n)) in solution to the gas phase, while the transfer of low surface active ions (e.g., La(3+)(sucrose)(n)) may be explained by the charged residue model. In general, the laser spray gives stronger ion signals than electrospray for aqueous and water/methanol solutions. The laser spray is found to be more suitable for the observation of ions with larger solvation energies (e.g., Sc(3+)(DMSO)(n)). These results may be due to the enrichment of the sample concentration by the selective vaporization of the volatile solvent on the tip of the stainless steel capillary and also to the finer droplet formation caused by the laser irradiation. Copyright 1999 John Wiley & Sons, Ltd. PMID:10523765

  11. Localization-Delocalization in Bridged Mixed-Valence Metal Clusters: Vibronic PKS Model Revisited.

    PubMed

    Palii, A; Tsukerblat, B; Clemente-Juan, J M; Aldoshin, S M

    2015-09-24

    Here we describe a new vibronic model of mixed valence (MV) dimer inspired by the conventional Piepho, Krausz, and Schatz (PKS) approach. We attempted to partially lift the main restriction of the PKS model dealing with the vibronically independent moieties of a MV molecule. The refined version of the PKS model in which the bridging ligands are included deals with the three main interactions: electron transfer (integral t0) related to the high-symmetric ligand configuration, on-site vibronic coupling (parameter υ) arising from the modulation of the crystal field on the metal sites by the breathing displacements of their nearest ligand surroundings, and intercenter vibronic coupling (parameter ζ) describing the dependence of the electron transfer on ligand positions in the course of their breathing movement. We apply the modified model to the analysis of the adiabatic potentials and electronic density distributions in the minima of their lower sheets for the cases of one-electron MV dimer with long and short bridges and for the two-electron MV dimer exhibiting a valence disproportionation effect. The inclusion of the intercenter interaction in addition to the conventional PKS coupling is shown to produce a strong effect on the degree of localization in MV dimers and, in particular, on the assignments to the Robin and Day classes and on the conditions of stabilization of valence disproportionated states in bielectron transfer systems. PMID:26305153

  12. Influence of electronic stopping on sputtering induced by cluster impact on metallic targets

    SciTech Connect

    Sandoval, Luis; Urbassek, Herbert M.

    2009-04-01

    Using molecular-dynamics simulation, we model the sputtering of a Au (111) crystallite induced by the impact of Au{sub 13} projectiles with total energies up to 500 keV. Due to the uncertainty of the electronic stopping of Au moving in particular at small velocities, we performed several simulations, in which the electronic stopping parameters are systematically changed. Our results demonstrate the dominating influence of the cut-off energy E{sub c}, below which the high-velocity electronic stopping of atoms is switched off in the simulation. If E{sub c} is smaller than roughly one half the cohesive energy of the target, sputtering ceases after a few ps; the spike contribution to sputtering (also called phase explosion or gas-flow contribution) is entirely quenched and the sputtering yield is up to an order of magnitude smaller than when electronic stopping is taken into account only at higher atom energies. Our results demonstrate the importance of a careful modeling of electronic stopping in simulations of spike sputtering from metals.

  13. High resolution CCD spectra of stars in globular clusters. Part 2: Metals and CNO in M71

    NASA Technical Reports Server (NTRS)

    Leep, E. M.; Oke, J. B.; Wallerstein, G.

    1986-01-01

    Palomar coude CCD spectra of resolution 0.3 and 0.6 has been used to redetermine abundances in five stars of the relatively metal rich globular cluster M71. The (Fe/H) value is restricted to the limits of -0.6 to -1.0. The largest source of uncertainty is a systematic difference in f-values between those derived via the Holweger-Muller (1974) solar model and the Bell et al. (1976) solar model. If we use absolute f-values measured by the Oxford group (Blackwell et al. 1982) we find Fe/H to lie in the range of -0.6 to -0.75, i.e., as given by using the Bell et al. solar model. The relative abundances of the light elements, i.e., Na through Ca and probably including Ti show an average excess relative to iron of 0.4 dex. The effect of this difference on metal indices derived from broad- and narrow- band photometry is discussed. For three stars we find O/H = -0.6 using absolute f-values. For CN an analysis of individual rotational lines of the 2-0 band of the red system yields lines in the (C/H,N/H) plane that are consistent with either an original C/Fe = N/Fe = 0 or a modest increase in N relative to C due to CN burning and mixing. A search for C-13N was not successful and an uncertain lower limit of C-12/C-13 near 10 was obtained.

  14. "Ligands-with-Benefits": Naphthalene-Substituted Schiff Bases Yielding New Ni(II) Metal Clusters with Ferromagnetic and Emissive Properties and Undergoing Exciting Transformations.

    PubMed

    Perlepe, Panagiota S; Cunha-Silva, Luís; Gagnon, Kevin J; Teat, Simon J; Lampropoulos, Christos; Escuer, Albert; Stamatatos, Theocharis C

    2016-02-01

    The initial employment of the fluorescent bridging ligand N-naphthalidene-2-amino-5-chlorobenzoic acid (nacbH2) in metal cluster chemistry has led to new Ni12 (1) and Ni5 (2) clusters with wheel-like and molecular-chain topologies, respectively. The doubly-deprotonated nacb(2-) ligands were found to adopt four different coordination modes within 1 and 2. The nature of the ligand has also allowed unexpected organic transformations to occur and ferromagnetic and emission behaviors to emerge. The combined work demonstrates the ability of some "ligands-with-benefits" to yield beautiful structures with exciting topologies and interesting physicochemical properties. PMID:26788587

  15. Multiple Metal-rich Sub-populations in Galaxies: the Star Formation/Assembly History of Galaxies Probed by Globular Clusters

    NASA Astrophysics Data System (ADS)

    Kissler-Patig, Markus

    Extragalactic globular clusters are used since a decade to probe the star formation and assembly history of nearby galaxies. In the early 90's, Zepf & Ashman (1993, MNRAS 264, 611) showed that several galaxies host at least two sub-populations of globular clusters. This fact was reinforced by subsequent studies (e. g. Gebhardt & Kissler-Patig 1999, AJ 118, 1526; Kundu 1999, PhD thesis), and many following studies dealt with the interpretation of the two main sub-populations (e. g. Kissler-Patig 2000, Reviews in Modern Astronomy, Vol. 13, p. 13 for a recent review) and their implications for galaxy formation scenarios. The nature of the metal-poor sub-populations is slowly understood as being a very uniform population in the nearby universe and most probably having formed in small fragments at the very beginning of galaxy formation and assembly. The nature of the metal-rich sub-populations is still hotly debated. It remains unclear whether its origin it mostly due to major mergers, whether it formed in situ during a monolithic bulge collapse, or whether it was accreted or cannibalized. The key to the answer lies in a more detailed analysis of the metal-rich sub-population. Is it itself composed by several sub-components? And can these sub-components tell us which mechanism dominated? First studies of extragalactic globular clusters in the optical and near-infrared show that the metal-rich sub-population might indeed be composed of several components. If confirmed, it would point to a significant contribution of hierarchical-like processes (accretion or mergers) to the metal-rich cluster and stellar component of galaxies.

  16. A structure-based analysis of the vibrational spectra of nitrosyl ligands in transition-metal coordination complexes and clusters

    NASA Astrophysics Data System (ADS)

    De La Cruz, Carlos; Sheppard, Norman

    2011-01-01

    The vibrational spectra of nitrogen monoxide or nitric oxide (NO) bonded to one or to several transition-metal (M) atom(s) in coordination and cluster compounds are analyzed in relation to the various types of such structures identified by diffraction methods. These structures are classified in: (a) terminal (linear and bent) nitrosyls, [M(σ-NO)] or [M(NO)]; (b) twofold nitrosyl bridges, [M 2(μ 2-NO)]; (c) threefold nitrosyl bridges, [M 3(μ 3-NO)]; (d) σ/π-dihaptonitrosyls or " side-on" nitrosyls; and (e) isonitrosyls (oxygen-bonded nitrosyls). Typical ranges for the values of internuclear N-O and M-N bond-distances and M-N-O bond-angles for linear nitrosyls are: 1.14-1.20 Å/1.60-1.90 Å/180-160° and for bent nitrosyls are 1.16-1.22 Å/1.80-2.00 Å/140-110°. The [M 2(μ 2-NO)] bridges have been divided into those that contain one or several metal-metal bonds and those without a formal metal/metal bond (M⋯M). Typical ranges for the M-M, N-O, M-N bond distances and M-N-M bond angles for the normal twofold NO bridges are: 2.30-3.00 Å/1.18-1.22 Å/1.80-2.00 Å/90-70°, whereas for the analogous ranges of the long twofold NO bridges these are 3.10-3.40 Å/1.20-1.24 Å/1.90-2.10 Å/130-110°. In both situations the N-O vector is approximately at right angle to the M-M (or M⋯M) vector within the experimental error; i.e. the NO group is symmetrical bonded to the two metal atoms. In contrast the threefold NO bridges can be symmetrically or unsymmetrically bonded to an M 3-plane of a cluster compound. Characteristic values for the N-O and M-N bond-distances of these NO bridges are: 1.24-1.28 Å/1.80-1.90 Å, respectively. As few dihaptonitrosyl and isonitrosyl complexes are known, the structural features of these are discussed on an individual basis. The very extensive vibrational spectroscopy literature considered gives emphasis to the data from linearly bonded NO ligands in stable closed-shell metal complexes; i.e. those which are consistent with the

  17. A structure-based analysis of the vibrational spectra of nitrosyl ligands in transition-metal coordination complexes and clusters.

    PubMed

    De La Cruz, Carlos; Sheppard, Norman

    2011-01-01

    The vibrational spectra of nitrogen monoxide or nitric oxide (NO) bonded to one or to several transition-metal (M) atom(s) in coordination and cluster compounds are analyzed in relation to the various types of such structures identified by diffraction methods. These structures are classified in: (a) terminal (linear and bent) nitrosyls, [M(σ-NO)] or [M(NO)]; (b) twofold nitrosyl bridges, [M2(μ2-NO)]; (c) threefold nitrosyl bridges, [M3(μ3-NO)]; (d) σ/π-dihaptonitrosyls or "side-on" nitrosyls; and (e) isonitrosyls (oxygen-bonded nitrosyls). Typical ranges for the values of internuclear N-O and M-N bond-distances and M-N-O bond-angles for linear nitrosyls are: 1.14-1.20 Å/1.60-1.90 Å/180-160° and for bent nitrosyls are 1.16-1.22 Å/1.80-2.00 Å/140-110°. The [M2(μ2-NO)] bridges have been divided into those that contain one or several metal-metal bonds and those without a formal metal/metal bond (M⋯M). Typical ranges for the M-M, N-O, M-N bond distances and M-N-M bond angles for the normal twofold NO bridges are: 2.30-3.00 Å/1.18-1.22 Å/1.80-2.00 Å/90-70°, whereas for the analogous ranges of the long twofold NO bridges these are 3.10-3.40 Å/1.20-1.24 Å/1.90-2.10 Å/130-110°. In both situations the N-O vector is approximately at right angle to the M-M (or M⋯M) vector within the experimental error; i.e. the NO group is symmetrical bonded to the two metal atoms. In contrast the threefold NO bridges can be symmetrically or unsymmetrically bonded to an M3-plane of a cluster compound. Characteristic values for the N-O and M-N bond-distances of these NO bridges are: 1.24-1.28 Å/1.80-1.90 Å, respectively. As few dihaptonitrosyl and isonitrosyl complexes are known, the structural features of these are discussed on an individual basis. The very extensive vibrational spectroscopy literature considered gives emphasis to the data from linearly bonded NO ligands in stable closed-shell metal complexes; i.e. those which are consistent with the

  18. DISCOVERY OF A SUPER-Li-RICH TURNOFF STAR IN THE METAL-POOR GLOBULAR CLUSTER NGC 6397

    SciTech Connect

    Koch, Andreas; Lind, Karin; Michael Rich, R.

    2011-09-10

    We report on the discovery of a super-Li-rich turnoff (TO) star in the old (12 Gyr), metal-poor ([Fe/H] = -2.1 dex) globular cluster (GC) NGC 6397, based on high-resolution MIKE/Magellan spectra. This star shows an unusually high lithium abundance of A(Li){sub NLTE} = 4.03 {+-} 0.06 {+-} 0.14 dex (or, 4.21, accounting for possible contamination from a binary companion) that lies above the canonical Li-plateau by a factor of 100. This is the highest Li enhancement found in a Galactic GC dwarf star to date. We discuss several enhancement mechanisms, but none can unambiguously explain such a high overabundance. The spectrum of the star shows a possible indication of binarity, but its line strengths and chemical element abundance ratios are fully compatible with other TO stars in this GC, seemingly ruling out mass transfer from an asymptotic giant branch companion as origin of the high A(Li). A possible cause is an interaction with a red giant that has undergone cool bottom processing.

  19. The integrated calcium II triplet as a metallicity indicator: comparisons with high-resolution [Fe/H] in M31 globular clusters

    NASA Astrophysics Data System (ADS)

    Sakari, Charli M.; Wallerstein, George

    2016-02-01

    Medium resolution (R = 4000-9000) spectra of the near infrared Ca II lines (at 8498, 8542, and 8662 Å) in M31 globular cluster (GC) integrated light spectra are presented. In individual stars the Ca II triplet (CaT) traces stellar metallicity; this paper compares integrated CaT strengths to well determined, high-precision [Fe/H] values from high-resolution integrated light spectra. The target GCs cover a wide range in metallicity (from [Fe/H] ˜ -2.1 to -0.2). While most are older than ˜10 Gyr, some may be of intermediate age (2-6 Gyr). A handful (3-6) have detailed abundances (e.g. low [Ca/Fe]) that indicate they may have been accreted from dwarf galaxies. Using various measurements and definitions of CaT strength, it is confirmed that for GCs with [Fe/H] ≲ -0.4 and older than ˜2 Gyr the integrated CaT traces cluster [Fe/H] to within ˜0.2 dex, independent of age. CaT lines in metal-rich GCs are very sensitive to nearby atomic lines (and TiO molecular lines in the most metal-rich GCs), largely due to line blanketing in continuum regions. The [Ca/Fe] ratio has a mild effect on the integrated CaT strength in metal poor GCs. The integrated CaT can therefore be safely used to determine rough metallicities for distant, unresolved clusters, provided that attention is paid to the limits of the measurement techniques.

  20. Cluster model of amorphized particles formation by plasma spraying of metallic powder

    NASA Astrophysics Data System (ADS)

    Barakhtin, Boris K.; Nesterova, E. V.

    1999-05-01

    Multifunctional coatings from materials with amorphized microcrystalline or nano-phase structure cause a considerable scientific and practical interest. With their help it is to manufacture heat resistant neutralizers of harmful ejections, to produce ecologically clean sources of electric current, to design electromagnetic protective shields and to fabricate a lot of other technical products. The variety of application and a unique complex of operating characteristics (ductility, strength, magnetic and chemical properties) are governed by the basic peculiarity of material in amorphized state - its thermodynamic instability. In comparison with traditional thermodynamically equilibrium metallic alloys, the kinetics of structure changes in amorphous materials is quite different. Thus, it is suggested, that they have peculiar defects (phasonics) which are not typical of materials in crystalline state, they have no translational symmetry and elementary cells. In the process of coatings forming with non-equilibrium structure states can be realized in them, which are characterized by a fluctuation type of origin, entropy export, appearance of space or temporary symmetry uncertainty of the transition direction 'order $ARLR disorder' in bifurcation points. The aforesaid explains a great scientific (not only practical) interest in the structure study of disordered medium. Functional coatings with amorphized, nano- and microcrystalline structure components formed on copper substrate by plasma spraying of dispersed (to 50 mcm) Ni-Al powder. According to the constitutional diagram it was expected to obtain a mixture from equilibrium intermetallide phases NiAl3 + Ni2Al3. The experimental results and investigations performed by X-ray structure, X-ray spectrum and electron microscopy techniques have shown it is possible to obtain phases of variable composition (Ni)m(Al)n with Ni content from 25 to 75 vol.%, including NiAl. It turned out that in the process of spraying the

  1. 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.

  2. Direct optical resolution of the enantiomers of novel chiral tetrahedral metal clusters by HPLC on a cellulose tris-(3,5-dimethylphenylcarbamate) stationary phase.

    PubMed

    Li, Wenzhi; Zhang, Weiqiang; Zhao, Quanyi; Li, Yongmin; Ma, Chunlin; Chen, Liren; Yin, Yuanqi

    2004-03-01

    The enantioseparation of seven novel chiral transition metal tetrahedral clusters has been achieved for the first time on cellulose derivatized with tris(3,5-dimethylphenylcarbamate) (CDMPC) as chiral stationary phase (CSP) and hexane containing different alcohols as modifiers as mobile phases. The effect of mobile-phase composition on enantioselectivity was studied, and the effect of structural variation of the solutes on their enantioseparation was also investigated. It was found that both the metal in the tetrahedral core and the ligand coordinated to the atom in the tetrahedral core had significant effects on the chromatographic behavior of the analytes. PMID:14735279

  3. The horizontal-branch stars in globular clusters. I - The period-shift effect, the luminosity of the horizontal branch, and the age-metallicity relation

    NASA Technical Reports Server (NTRS)

    Lee, Young-Wook; Demarque, Pierre; Zinn, Robert

    1990-01-01

    Synthetic models of the horizontal branches in globular clusters are constructed from a grid of the standard horizontal branch evolutionary tracks. The models are used to study the period shifts at constant T(eff) between RR Lyrae variables in globular clusters of different metallicities and the variation in horizontal-branch luminosity with the Fe/H ratio. The results suggest that the observed differences in the mean periods of the ab variables and the fraction of c-type variables between the two Oosterhoff groups are caused by a difference in the mean luminosity of the ab variables of about 0.18 bolometric mass and by the uneven distribution of variables across the instability strip in the group II clusters.

  4. Activation of Methane and Carbon Dioxide Mediated by Transition-Metal Doped Magnesium Oxide Clusters [MMgO](+/0/-) (M=Sc-Zn).

    PubMed

    Li, Jilai; González-Navarrete, Patricio; Schlangen, Maria; Schwarz, Helmut

    2015-05-18

    Mission: impossible? DFT calculations show that the trends in the thermochemistry are very different for the activation of CO2 and CH4 mediated by transition-metal doped magnesium oxide clusters [MMgO](+/0/-) (M=Sc-Zn). Thus, seeking a "simple" reagent to simultaneously mediate activation and coupling of CH4 and CO2 with high efficiency seems extremely daunting, if not impossible. PMID:25867011

  5. Observations of the Hot Horizontal Branch Stars in the Metal-Rich Bulge Globular Cluster NGC 6388

    NASA Technical Reports Server (NTRS)

    Moehler, S.; Sweigart, A. V.

    2006-01-01

    The metal-rich bulge globular cluster NGC 6388 shows a distinct blue horizontal-branch tail in its colour-magnitude diagram (Rich et al. 1997) and is thus a strong case of the well-known 2nd Parameter Problem. In addition, its horizontal branch (HB) shows an upward tilt toward bluer colours, which cannot be explained by canonical evolutionary models. Several non-canonical scenarios have been proposed to explain these puzzling observations. In order to test the predictions of these scenarios, we have obtained medium resolution spectra to determine the atmospheric parameters of a sample of the blue HB stars in NGC 6388.Using the medium resolution spectra, we determine effective temperatures, surface gravities and helium abundances by fitting the observed Balmer and helium lines with appropriate theoretical stellar spectra. As we know the distance to the cluster, we can verify our results by determining masses for the stars. During the data reduction we took special care to correctly subtract the background, which is dominated by the overlapping spectra of cool stars. The cool blue tail stars in our sample with T(sub eff) approximately 10000 K have lower than canonical surface gravities, suggesting that these stars are, on average, approximately equal to 0.4 mag brighter than canonical HB stars in agreement with the observed upward slope of the HB in NGC 6388. Moreover, the mean mass of these stars agrees well with theoretical predictions. In contrast, the hot blue tail stars in our sample with T(sub eff) greater than or equal to 12000 K show significantly lower surface gravities than predicted by any scenario, which can reproduce the photometric observations. Their masses are also too low by about a factor of 2 compared to theoretical predictions. The physical parameters of the blue HB stars at about 10,000 K support the helium pollution scenario. The low gravities and masses of the hot blue tail stars, however, are probably caused by problems with the data reduction

  6. Heavy Metal Content in Airborne Dust of Childhood Leukemia Cluster Areas: Even Small Towns Have Air Pollutants

    NASA Astrophysics Data System (ADS)

    Sheppard, P. R.; Witten, M. L.

    2004-12-01

    Currently in the US, there are at least two ongoing clusters of childhood leukemia, where the incidence rate over the last several years has exceeded the national norm. In Fallon, Nevada, a town of 8,000 people, 16 children have been diagnosed with leukemia since 1995, three of whom have died. In Sierra Vista, Arizona, a town of 38,000 people, 12 children have been diagnosed since 1998, two of whom have died. A possible third cluster of childhood leukemia and other cancers is being monitored in Elk Grove, California, a suburb of Sacramento. For the purpose of characterizing the heavy metal content of airborne dust of these three communities, total suspended particulate samples were collected from each town as well as from nearby towns that could be considered as control comparisons. Sampling was done using portable high-volume blowers and glass- or quartz-fiber filter media. Filters were measured for elemental concentrations using inductively coupled plasma mass spectroscopy. To date, our most notable results are from the Nevada region. Compared to other control towns in the region, Fallon had significantly more tungsten in its airborne dust. Uranium was also higher in dust of Fallon than in other control towns. Uranium is a known health hazard, though it is not necessarily specifically related to childhood leukemia. The role of tungsten in childhood leukemia has not been widely studied. However, other research has identified tungsten exposure as an environmental concern in Fallon. A CDC study of human tissue samples from Fallon has shown high tungsten levels in people of Fallon, and a USGS study of drinking water in Fallon also has shown high tungsten there. Tree-ring research on selected trees has shown high tungsten values in recent rings compared to earlier rings. While these multiple indications of tungsten in the Fallon environment do not directly lead to the conclusion that tungsten causes leukemia, they do combine to suggest that biomedical research on the

  7. Investigation of metal and metal oxide clusters small enough to constitute the critical size for gas phase nucleation in combustion processes. Final report, 1 October 1975-30 June 1979

    SciTech Connect

    Stein, G.D.

    1980-11-01

    Over the course of this contract a variety of techniques have been employed to study the properties of small atomic and molecular clusters formed in the gas phase via homogeneous nucleation. The clustering occurs either in an adiabatic expansion of a condensable species (e.g. argon, krypton, xenon, or sulfur hexafluoride) in an inert carrier gas (e.g. helium), or as a mixing process using a hot condensable (e.g. lead, silver, copper, indium or bismuth) and a cold carrier gas (e.g. argon, helium, carbon dioxide or sulfur hexafluoride). A continuous development several types of cluster sources has been carried out and includes free jets, very small hypersonic laval nozzles, and a series of metal ovens with carrier gas mixing. Any one, of these sources, constitutes the first stage of a differentially pumped, molecular beam system which the produces a continuous beam of clusters. The denisty in the beam is so low that it is collisionless and thus the clusters do not interact with each other or with any other foreign molecule or surface. The study of these isolated clusters is carried out primarily using high energy electron beams (40 to 75 KeV). The resulting diffraction patterns are obtained either on film or through use of a single channel, scintillation, pulse counting system employing synchronous detection.

  8. 21 CFR 201.5 - Drugs; adequate directions for use.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 4 2010-04-01 2010-04-01 false Drugs; adequate directions for use. 201.5 Section...) DRUGS: GENERAL LABELING General Labeling Provisions § 201.5 Drugs; adequate directions for use. Adequate directions for use means directions under which the layman can use a drug safely and for the purposes...

  9. 21 CFR 201.5 - Drugs; adequate directions for use.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 4 2011-04-01 2011-04-01 false Drugs; adequate directions for use. 201.5 Section...) DRUGS: GENERAL LABELING General Labeling Provisions § 201.5 Drugs; adequate directions for use. Adequate directions for use means directions under which the layman can use a drug safely and for the purposes...

  10. 4 CFR 200.14 - Responsibility for maintaining adequate safeguards.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 4 Accounts 1 2010-01-01 2010-01-01 false Responsibility for maintaining adequate safeguards. 200.14 Section 200.14 Accounts RECOVERY ACCOUNTABILITY AND TRANSPARENCY BOARD PRIVACY ACT OF 1974 § 200.14 Responsibility for maintaining adequate safeguards. The Board has the responsibility for maintaining adequate technical, physical, and...

  11. 10 CFR 1304.114 - Responsibility for maintaining adequate safeguards.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 10 Energy 4 2010-01-01 2010-01-01 false Responsibility for maintaining adequate safeguards. 1304.114 Section 1304.114 Energy NUCLEAR WASTE TECHNICAL REVIEW BOARD PRIVACY ACT OF 1974 § 1304.114 Responsibility for maintaining adequate safeguards. The Board has the responsibility for maintaining adequate technical, physical, and security...

  12. 10 CFR 1304.114 - Responsibility for maintaining adequate safeguards.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... 10 Energy 4 2012-01-01 2012-01-01 false Responsibility for maintaining adequate safeguards. 1304.114 Section 1304.114 Energy NUCLEAR WASTE TECHNICAL REVIEW BOARD PRIVACY ACT OF 1974 § 1304.114 Responsibility for maintaining adequate safeguards. The Board has the responsibility for maintaining adequate technical, physical, and security...

  13. 4 CFR 200.14 - Responsibility for maintaining adequate safeguards.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... 4 Accounts 1 2011-01-01 2011-01-01 false Responsibility for maintaining adequate safeguards. 200....14 Responsibility for maintaining adequate safeguards. The Board has the responsibility for maintaining adequate technical, physical, and security safeguards to prevent unauthorized disclosure...

  14. Formation of Metal Clusters or Nitrogen-Bridged Adducts by Reaction of a Bis(amino)stannylene with Halides of Two-Valent Transition Metals.

    PubMed

    Veith, Michael; Müller, Alice; Stahl, Lothar; Nötzel, Martin; Jarczyk, Maria; Huch, Volker

    1996-06-19

    be isostructural. The molecules have an inner Sn(4)M pentametallic core (mean distances: Sn-Ni 2.463 Å, Sn-Pd 2.544 Å) with the transition metal in the center of a slightly distorted square formed by the four tin atoms, the distortion from planarity resulting in a weak paramagnetism of 0.2 &mgr;(B) for the nickel compound. The halogen atoms form bridges between two of the tin atoms and have no bonding interaction with the transition metal. The nickel compound has also been prepared by direct interaction of Br(2) or NR(4)Br(3) with [Me(2)Si(NtBu)(2)Sn](4)Ni as a minor product, the main products being Me(2)Si(NtBu)(2)Sn(NtBu)(2)SiMe(2,) Me(2)Si(NtBu)(2)SnBr(2), NiBr(2) and SnBr(2). Other metal clusters have been obtained by the reaction of Me(2)Si(NtBu)(2)Sn with tetrakis(triphenyphosphine)palladium or by the reaction of Me(2)Si(NtBu)(2)Ge with RhCl(PPh(3))(3). In the first case Ph(3)PPd[Sn(NtBu)(2)SiMe(2)](3)PdPPh(3) (rhombohedral, space group R3c, a = b = 21.397(12) Å, c = 57.01(5) Å, alpha = beta = 90 degrees, gamma = 120 degrees, Z = 12) is formed and is characterized by X-ray techniques to be composed of a central PdSn(3)Pd trigonal bipyramid with the tin atoms occupying the equatorial positions (Pd-Sn = 2.702(5) Å). In the second reaction all the triphenylphosphine ligands are replaced from rhodium and Rh[Ge(NtBu)(2)SiMe(2)](4)Cl is formed (monoclinic, space group P2(1)/n, a = 12.164(2) Å, b = 23.625(5) Å, c = 24.128(5) Å, beta = 102.74(3) degrees, Z = 4). The central core of this molecule is made up of a rhodium atom which is almost square planarly coordinated by the germanium atoms, two of which are bridged by chlorine (mean Ge-Rh = 2.355 Å). PMID:11666574

  15. A quantum Monte Carlo study on electron correlation in all-metal aromatic clusters MAl4(-) (M = Li, Na, K, Rb, Cu, Ag and Au).

    PubMed

    Brito, Bráulio Gabriel A; Hai, G-Q; Teixeira Rabelo, J N; Cândido, Ladir

    2014-05-14

    Using fixed-node diffusion quantum Monte Carlo (FN-DMC) simulation we investigate the electron correlation in all-metal aromatic clusters MAl4(-) (with M = Li, Na, K, Rb, Cu, Ag and Au). The electron detachment energies and electron affinities of the clusters are obtained. The vertical electron detachment energies obtained from the FN-DMC calculations are in very good agreement with the available experimental results. Calculations are also performed within the Hartree-Fock approximation, density-functional theory (DFT), and the couple-cluster (CCSD(T)) method. From the obtained results, we analyse the impact of the electron correlation effects in these bimetallic clusters and find that the correlation of the valence electrons contributes significantly to the detachment energies and electron affinities, varying between 20% and 50% of their total values. Furthermore, we discuss the electron correlation effects on the stability of the clusters as well as the accuracy of the DFT and CCSD(T) calculations in the present systems. PMID:24676470

  16. Barrierless growth of precursor-free, ultrafast laser-fragmented noble metal nanoparticles by colloidal atom clusters - A kinetic in situ study.

    PubMed

    Jendrzej, Sandra; Gökce, Bilal; Amendola, Vincenzo; Barcikowski, Stephan

    2016-02-01

    Unintended post-synthesis growth of noble metal colloids caused by excess amounts of reactants or highly reactive atom clusters represents a fundamental problem in colloidal chemistry, affecting product stability or purity. Hence, quantified kinetics could allow defining nanoparticle size determination in dependence of the time. Here, we investigate in situ the growth kinetics of ps pulsed laser-fragmented platinum nanoparticles in presence of naked atom clusters in water without any influence of reducing agents or surfactants. The nanoparticle growth is investigated for platinum covering a time scale of minutes to 50days after nanoparticle generation, it is also supplemented by results obtained from gold and palladium. Since a minimum atom cluster concentration is exceeded, a significant growth is determined by time resolved UV/Vis spectroscopy, analytical disc centrifugation, zeta potential measurement and transmission electron microscopy. We suggest a decrease of atom cluster concentration over time, since nanoparticles grow at the expense of atom clusters. The growth mechanism during early phase (<1day) of laser-synthesized colloid is kinetically modeled by rapid barrierless coalescence. The prolonged slow nanoparticle growth is kinetically modeled by a combination of coalescence and Lifshitz-Slyozov-Wagner kinetic for Ostwald ripening, validated experimentally by the temperature dependence of Pt nanoparticle size and growth quenching by Iodide anions. PMID:26555960

  17. Silver-copper nanoalloys-an efficient sensitizer for metal-cluster-sensitized solar cells delivering stable current and high open circuit voltage

    NASA Astrophysics Data System (ADS)

    Shahzad, Naveed; Chen, Fuyi; He, Lirong; Li, Weiyin; Wang, Hongkai

    2015-10-01

    Metal clusters (CLs) are recognized as a new class of sensitizers in a metal-cluster-sensitized solar cell (MCSC) which is an extension to well-recognized dye-sensitized solar cells (DSSCs). The function performed by dyes in DSSCs has predominately been executed by metal CLs in MCSCs. The distinct behavior of CLs at nano-scaled level can enhance their significance in photovoltaic applications. Recently, metal CLs have been explored as sensitizers in a solar cell, and the efficiency of the cell has been reported to be more than 2%. Herein, we present glutathione-protected Ag-Cu bimetallic CLs (alloyed CLs or nanoalloys) as sensitizer in MCSCs. Spray-coating technique has been employed to deposit CLs on photoanodes. The TiO2 modified with Cu rich alloyed CLs exhibit the short circuit photocurrent (Jsc) of 2.87 mAcm-2 with Voc of 691 mV. EIS and Mott-Schottky analysis have been performed to explicate the processes occurring inside MCSCs. Comparative study has been conducted to elucidate the effect of alloying on photo-electrochemical (PEC) response. Our results lay the foundations for exploring other nanoalloys as sensitizers in solar cells because nanoalloys present a greater degree of flexibility in properties, structure, size, and the composition of the constituent elements.

  18. Au25 cluster functionalized metal-organic nanostructures for magnetically targeted photodynamic/photothermal therapy triggered by single wavelength 808 nm near-infrared light

    NASA Astrophysics Data System (ADS)

    Yang, Dan; Yang, Guixin; Gai, Shili; He, Fei; An, Guanghui; Dai, Yunlu; Lv, Ruichan; Yang, Piaoping

    2015-11-01

    Near-infrared (NIR) light-induced cancer therapy has gained considerable interest, but pure inorganic anti-cancer platforms usually suffer from degradation issues. Here, we designed metal-organic frameworks (MOFs) of Fe3O4/ZIF-8-Au25 (IZA) nanospheres through a green and economic procedure. The encapsulated Fe3O4 nanocrystals not only produce hyperthemal effects upon NIR light irradiation to effectively kill tumor cells, but also present targeting and MRI imaging capability. More importantly, the attached ultrasmall Au25(SR)18- clusters (about 2.5 nm) produce highly reactive singlet oxygen (1O2) to cause photodynamic effects through direct sensitization under NIR light irradiation. Furthermore, the Au25(SR)18- clusters also give a hand to the hyperthemal effect as photothermal fortifiers. This nanoplatform exhibits high biocompatibility and an enhanced synergistic therapeutic effect superior to any single therapy, as verified by in vitro and in vivo assay. This image-guided therapy based on a metal-organic framework may stimulate interest in developing other kinds of metal-organic materials with multifunctionality for tumor diagnosis and therapy.Near-infrared (NIR) light-induced cancer therapy has gained considerable interest, but pure inorganic anti-cancer platforms usually suffer from degradation issues. Here, we designed metal-organic frameworks (MOFs) of Fe3O4/ZIF-8-Au25 (IZA) nanospheres through a green and economic procedure. The encapsulated Fe3O4 nanocrystals not only produce hyperthemal effects upon NIR light irradiation to effectively kill tumor cells, but also present targeting and MRI imaging capability. More importantly, the attached ultrasmall Au25(SR)18- clusters (about 2.5 nm) produce highly reactive singlet oxygen (1O2) to cause photodynamic effects through direct sensitization under NIR light irradiation. Furthermore, the Au25(SR)18- clusters also give a hand to the hyperthemal effect as photothermal fortifiers. This nanoplatform exhibits high

  19. Adsorption of propane, isopropyl, and hydrogen on cluster models of the M1 phase of Mo-V-Te-Nb-O mixed metal oxide catalyst

    SciTech Connect

    Govindasamy, Agalya; Muthukumar, Kaliappan; Yu, Junjun; Xu, Ye; Guliants, Vadim V.

    2010-01-01

    The Mo-V-Te-Nb-O mixed metal oxide catalyst possessing the M1 phase structure is uniquely capable of directly converting propane into acrylonitrile. However, the mechanism of this complex eight-electron transformation, which includes a series of oxidative H-abstraction and N-insertion steps, remains poorly understood. We have conducted a density functional theory study of cluster models of the proposed active and selective site for propane ammoxidation, including the adsorption of propane, isopropyl (CH{sub 3}CHCH{sub 3}), and H which are involved in the first step of this transformation, that is, the methylene C-H bond scission in propane, on these active site models. Among the surface oxygen species, the telluryl oxo (Te=O) is found to be the most nucleophilic. Whereas the adsorption of propane is weak regardless of the MO{sub x} species involved, isopropyl and H adsorption exhibits strong preference in the order of Te=O > V=O > bridging oxygens > empty Mo apical site, suggesting the importance of TeO{sub x} species for H abstraction. The adsorption energies of isopropyl and H and consequently the reaction energy of the initial dehydrogenation of propane are strongly dependent on the number of ab planes included in the cluster, which points to the need to employ multilayer cluster models to correctly capture the energetics of surface chemistry on this mixed metal oxide catalyst.

  20. The LLNL Cluster Tool

    SciTech Connect

    Hunter, S L

    2007-03-27

    {lg_bullet} The Cluster Tool -is a set of linked vacuum chambers -can deposit multiple layers of metal and metal oxides {lg_bullet} Each layer can be deposited without breaking vacuum {lg_bullet} Shadow masks can give each layer a different pattern {lg_bullet} The Cluster Tool will be operational in April

  1. Elevated levels of ferrimagnetic metals in foodchains supporting the Guam cluster of neurodegeneration: do metal nucleated crystal contaminants [corrected] evoke magnetic fields that initiate the progressive pathogenesis of neurodegeneration?

    PubMed

    Purdey, Mark

    2004-01-01

    Elevated levels of aluminium (Al), strontium (Sr), barium (Ba), iron (Fe), manganese (Mn) cations - combined with deficiencies of magnesium (Mg)/calcium (Ca) - have been observed in the foodchains that traditionally support the Chamorro populations affected by high incidence clusters of Alzheimer (AD), Parkinson-like (PD), motor neurone diseases and multiple sclerosis on the island of Guam. Soils drawn from the cluster region demonstrated an excessive fivefold increase in 'magnetic susceptibility' readings in relation to soils from disease free adjoining regions. A multifactorial aetiological hypothesis is proposed that pivots upon the combined exposure to high levels of natural/industrial sources of ferrimagnetic/ferroelectric compounds incorporating Al, Fe, Mn, Sr, Ba (e.g., via yam/seafood consumption or exposure to world war 2 (WW2) munitions) and to low levels of Mg/Ca in all S. Pacific locations where these clusters of neurodegenerative disease have simultaneously erupted. Once gut/blood brain barrier permeability is impaired, the increased uptake of Al, Fe, Sr, Ba, or Mn into the Mg/Ca depleted brain leads to rogue metal substitutions at the Mg/Ca vacated binding domains on various enzyme/proteoglycan groups, causing a broad ranging disruption in Mg/Ca dependent systems - such as the glutamine synthetase which prevents the accumulation of neurotoxic glutamate. The rogue metals chelate sulphate, disrupting sulphated-proteoglycan mediated inhibition of crystal proliferation, as well as its regulation of the Fibroblast growth factor receptor complex which disturbs the molecular conformation of those receptors and their regulation of transphosphorylation between intracellular kinase domains; ultimately collapsing proteoglycan mediated cell-cell signalling pathways which maintain the growth and structural integrity of the neuronal networks. The depression of Mg/Ca dependent systems in conjunction with the progressive ferrimagnetisation of the CNS due to an

  2. Structures and Stabilities of the Metal Doped Gold Nano-Clusters: M@Au10 (M = W, Mo, Ru, Co).

    PubMed

    Hossain, Delwar; Pittman, Charles U; Gwaltney, Steven R

    2014-01-01

    The structures and stabilities of a series of endohedral gold clusters containing ten gold atoms M@Au10 (M = W, Mo, Ru, Co) have been determined using density functional theory. The gradient-corrected functional BP86, the Tao-Perdew-Staroverov-Scuseria TPSS meta-GGA functional, and the hybrid density functionals B3LYP and PBE1PBE were employed to calculate the structures, binding energies, adiabatic ionization potentials, and adiabatic electron affinities for these clusters. The LanL2DZ effective core potentials and the corresponding valence basis sets were employed. The M@Au10 (M = W, Mo, Ru, Co) clusters have higher binding energies than an empty Au10 cluster. In addition, the large HOMO-LUMO gaps suggest that the M@Au10 (M = W, Mo, Ru, Co) clusters are all likely to be stable chemically. The ionization potentials and electron affinities for these clusters are very high, and the W@Au10 and Mo@Au10 clusters have electron affinities similar to the super-halogen Al13. PMID:24611036

  3. A2111: A z= 0.23 Butcher-Oemler Cluster with a Non-Isothermal Atmosphere and Normal Metallicity

    NASA Technical Reports Server (NTRS)

    Wang, Q. Daniel; Henriksen, Mark

    1998-01-01

    We report results from an x-ray spectral study of the z=0.23 Abell 2111 galaxy cluster using the Advanced Satellite for Astrophysics and Cosmology and the ROSAT Position Sensitive Proportional Counter. By correcting for the energy-dependent point-spread function of the instruments, we have examined the temperature structure of the cluster. The cluster's core within 3 is found to have a temperature of 5.4 +/- 0.5 keV, significantly higher than 2.8 +/-0.7 keV in the surrounding region of r = 3-6. This radially decreasing temperature structure can be parameterized by a polytropic index of gamma less than 1.4. Furthermore, the intracluster medium appears clumpy on scales less than 1. Early studies have revealed that the x-ray centroid of the cluster shifts with spatial scale and the overall optical and x-ray morphology is strongly elongated. These results together suggest that A2111 in undergoing a merger, which is likely responsible for the high fraction of blue galaxies observed in the cluster. We have further measured the abundance of the medium as 0.25 +/- 0.14 solar. This value is similar to those of nearby clusters which do not show a large blue galaxy function, suggesting that star formation in disk galaxies and subsequent loss to the intracluster medium do not drastically alter the average abundance of a cluster since z=0.23.

  4. Double aromaticity in transition metal centered double-ring boron clusters M@B2n (M = Ti, Cr, Fe, Ni, Zn; n = 6, 7, 8)

    NASA Astrophysics Data System (ADS)

    Xu, Chang; Cheng, Longjiu; Yang, Jinlong

    2014-09-01

    It is well known that double-ring boron clusters have got the special double aromaticity with delocalized π orbitals in two directions (tangential and radial), which are potential ligands centered by a transition metal. In this article, the transition metal centered double-ring boron clusters M@B2n (M = Ti, Cr, Fe, Ni, Zn; n = 6, 7, 8) are theoretically investigated by density functional theory calculations. These endohedral compounds have also got double aromaticity in both tangential and radial directions. Interestingly, the tangential delocalized π orbitals of boron ligands following the Huckle's (4n + 2) rule do not interact with the central metal, while the radial π orbitals of boron ligands are bonded with the central mental to form spd-π endohedral bonding. The spd-π endohedral bonding follows the 18e-principle in Ni@B14 and Fe@B16. However, due to the flat shape of the compounds, 14e (Cr@B14) and 16e (Ni@B12) can also be electronically very stable where the energy levels of the spd-π orbitals delocalized in z-direction rise up. This intriguing bonding model makes sense in further study of the boron chemistry.

  5. Basis set limit electronic excitation energies, ionization potentials, and electron affinities for the 3d transition metal atoms: Coupled cluster and multireference methods

    NASA Astrophysics Data System (ADS)

    Balabanov, Nikolai B.; Peterson, Kirk A.

    2006-08-01

    Recently developed correlation consistent basis sets for the first row transition metal elements Sc-Zn have been utilized to determine complete basis set (CBS) scalar relativistic electron affinities, ionization potentials, and 4s23dn -2-4s1dn -1 electronic excitation energies with single reference coupled cluster methods [CCSD(T), CCSDT, and CCSDTQ] and multireference configuration interaction with three reference spaces: 3d4s, 3d4s4p, and 3d4s4p3d'. The theoretical values calculated with the highest order coupled cluster techniques at the CBS limit, including extrapolations to full configuration interaction, are well within 1kcal/mol of the corresponding experimental data. For the early transition metal elements (Sc-Mn) the internally contracted multireference averaged coupled pair functional method yielded excellent agreement with experiment; however, the atomic properties for the late transition metals (Mn-Zn) proved to be much more difficult to describe with this level of theory, even with the largest reference function of the present work.

  6. Metal-binding properties and structural characterization of a self-assembled coiled coil: formation of a polynuclear Cd-thiolate cluster.

    PubMed

    Zaytsev, Daniil V; Morozov, Vasily A; Fan, Jiufeng; Zhu, Xianchun; Mukherjee, Madhumita; Ni, Shuisong; Kennedy, Michael A; Ogawa, Michael Y

    2013-02-01

    This paper describes the design, characterization, and metal-binding properties of a 32-residue polypeptide called AQ-C16C19. The sequence of this peptide is composed of four repeats of the seven residue sequence Ile-Ala-Ala-Leu-Glu-Gln-Lys but with a Cys-X-X-Cys metal-binding motif substituted at positions 16-19. Size exclusion chromatography with multiangle light scattering detection (SEC-MALS) and circular dichroism (CD) spectroscopy studies showed that the apo peptide exhibits a pH-dependent oligomerization state in which a three-stranded α-helical coiled coil is dominant between pH5.4 and 8.5. The Cd(2+)-binding properties of the AQ-C16C19 peptide were studied by ultraviolet-visible spectroscopy (UV-vis), electrospray ionization mass spectrometry (ESI MS), and (113)Cd NMR techniques. The holoprotein was found to contain a polynuclear cadmium-thiolate center formed within the hydrophobic core of the triple-stranded α-helical coiled-coil structure. The X-ray crystal structure of the Cd-loaded peptide, resolved at 1.85Å resolution, revealed an adamantane-like configuration of the polynuclear metal center consisting of four cadmium ions, six thiolate sulfur ligands from cysteine residues and four oxygen-donor ligands. Three of these are from glutamic acid residues and one is from an exogenous water molecule. Thus, each cadmium ion is coordinated in a distorted tetrahedral S(3)O geometry. The metal cluster was found to form cooperatively at pH5.4 but in a stepwise fashion at pH>7. The results demonstrate that synthetic coiled-coils can be designed to incorporate multinuclear metal clusters, a proof-of-concept for their potential use in developing synthetic metalloenzymes and multi-electron redox agents. PMID:23160144

  7. Implications of the new globular-cluster metal-abundance scale for the helium abundance in the Galactic halo

    NASA Astrophysics Data System (ADS)

    Demarque, P.; McClure, R. D.

    1980-11-01

    In the adoption of the new abundance scale for globular clusters (Cohen, 1980; Pilachowski et al, 1980) a difficulty in fitting main sequences of 47 Tucanae and other well-studied globular clusters, like M 3, M 5, and M 13 is pointed out. In order to circumvent this problem, a substantial difference in helium abundance must be invoked. Such differences can also cause the very faint turnoff magnitudes found recently by Alcaino and Liller (1980) for NGC 6397 and by Cannon (1974) for Omega Centauri, without the need to assign excessive ages to these clusters. Other consequences of this helium-abundance variation are discussed.

  8. THE EFFECT OF SECOND-GENERATION POPULATIONS ON THE INTEGRATED COLORS OF METAL-RICH GLOBULAR CLUSTERS IN EARLY-TYPE GALAXIES

    SciTech Connect

    Chung, Chul; Lee, Sang-Yoon; Yoon, Suk-Jin; Lee, Young-Wook

    2013-05-20

    The mean color of globular clusters (GCs) in early-type galaxies is in general bluer than the integrated color of halo field stars in host galaxies. Metal-rich GCs often appear more associated with field stars than metal-poor GCs, yet show bluer colors than their host galaxy light. Motivated by the discovery of multiple stellar populations in Milky Way GCs, we present a new scenario in which the presence of second-generation (SG) stars in GCs is responsible for the color discrepancy between metal-rich GCs and field stars. The model assumes that the SG populations have an enhanced helium abundance as evidenced by observations, and it gives a good explanation of the bluer optical colors of metal-rich GCs than field stars as well as strong Balmer lines and blue UV colors of metal-rich GCs. Ours may be complementary to the recent scenario suggesting the difference in stellar mass functions (MFs) as an origin for the GC-to-star color offset. A quantitative comparison is given between the SG and MF models.

  9. Tracking Rh Atoms in Zeolite HY: First Steps of Metal Cluster Formation and Influence of Metal Nuclearity on Catalysis of Ethylene Hydrogenation and Ethylene Dimerization.

    PubMed

    Yang, Dong; Xu, Pinghong; Browning, Nigel D; Gates, Bruce C

    2016-07-01

    The initial steps of rhodium cluster formation from zeolite-supported mononuclear Rh(C2H4)2 complexes in H2 at 373 K and 1 bar were investigated by infrared and extended X-ray absorption fine structure spectroscopies and scanning transmission electron microscopy (STEM). The data show that ethylene ligands on the rhodium react with H2 to give supported rhodium hydrides and trigger the formation of rhodium clusters. STEM provided the first images of the smallest rhodium clusters (Rh2) and their further conversion into larger clusters. The samples were investigated in a plug-flow reactor as catalysts for the conversion of ethylene + H2 in a molar ratio of 4:1 at 1 bar and 298 K, with the results showing how the changes in catalyst structure affect the activity and selectivity; the rhodium clusters are more active for hydrogenation of ethylene than the single-site complexes, which are more selective for dimerization of ethylene to give butenes. PMID:27315020

  10. Hydride mobility in trinuclear sulfido clusters with the core [Rh3(μ-H)(μ3-S)2]: molecular models for hydrogen migration on metal sulfide hydrotreating catalysts.

    PubMed

    Jiménez, M Victoria; Lahoz, Fernando J; Lukešová, Lenka; Miranda, José R; Modrego, Francisco J; Nguyen, Duc H; Oro, Luis A; Pérez-Torrente, Jesús J

    2011-07-11

    The treatment of [{Rh(μ-SH){P(OPh)(3)}(2)}(2)] with [{M(μ-Cl)(diolef)}(2)] (diolef=diolefin) in the presence of NEt(3) affords the hydrido-sulfido clusters [Rh(3)(μ-H)(μ(3)-S)(2)(diolef){P(OPh)(3)}(4)] (diolef=1,5-cyclooctadiene (cod) for 1, 2,5-norbornadiene (nbd) for 2, and tetrafluorobenzo[5,6]bicyclo[2.2.2]octa-2,5,7-triene (tfb) for 3) and [Rh(2)Ir(μ-H)(μ(3)-S)(2)(cod){P(OPh)(3)}(4)] (4). Cluster 1 can be also obtained by treating [{Rh(μ-SH){P(OPh)(3)}(2)}(2)] with [{Rh(μ-OMe)(cod)}(2)], although the main product of the reaction with [{Ir(μ-OMe)(cod)}(2)] was [RhIr(2)(μ-H)(μ(3)-S)(2)(cod)(2){P(OPh)(3)}(2)] (5). The molecular structures of clusters 1 and 4 have been determined by X-ray diffraction methods. The deprotonation of a hydrosulfido ligand in [{Rh(μ-SH)(CO)(PPh(3))}(2)] by [M(acac)(diolef)] (acac=acetylacetonate) results in the formation of hydrido-sulfido clusters [Rh(3)(μ-H)(μ(3)-S)(2)(CO)(2) (diolef)(PPh(3))(2)] (diolef=cod for 6, nbd for 7) and [Rh(2)Ir(μ-H)(μ(3)-S)(2)(CO)(2)(cod)(PPh(3))(2)] (8). Clusters 1-3 and 5 exist in solution as two interconverting isomers with the bridging hydride ligand at different edges. Cluster 8 exists as three isomers that arise from the disposition of the PPh(3) ligands in the cluster (cis and trans) and the location of the hydride ligand. The dynamic behaviour of clusters with bulky triphenylphosphite ligands, which involves hydrogen migration from rhodium to sulfur with a switch from hydride to proton character, is significant to understand hydrogen diffusion on the surface of metal sulfide hydrotreating catalysts. PMID:21633978

  11. 7 CFR 4290.200 - Adequate capital for RBICs.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... 7 Agriculture 15 2011-01-01 2011-01-01 false Adequate capital for RBICs. 4290.200 Section 4290.200 Agriculture Regulations of the Department of Agriculture (Continued) RURAL BUSINESS-COOPERATIVE SERVICE AND... Qualifications for the RBIC Program Capitalizing A Rbic § 4290.200 Adequate capital for RBICs. You must meet...

  12. 13 CFR 107.200 - Adequate capital for Licensees.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... 13 Business Credit and Assistance 1 2011-01-01 2011-01-01 false Adequate capital for Licensees... INVESTMENT COMPANIES Qualifying for an SBIC License Capitalizing An Sbic § 107.200 Adequate capital for... Licensee, and to receive Leverage. (a) You must have enough Regulatory Capital to provide...

  13. 13 CFR 107.200 - Adequate capital for Licensees.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 13 Business Credit and Assistance 1 2010-01-01 2010-01-01 false Adequate capital for Licensees... INVESTMENT COMPANIES Qualifying for an SBIC License Capitalizing An Sbic § 107.200 Adequate capital for... Licensee, and to receive Leverage. (a) You must have enough Regulatory Capital to provide...

  14. 7 CFR 4290.200 - Adequate capital for RBICs.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 7 Agriculture 15 2010-01-01 2010-01-01 false Adequate capital for RBICs. 4290.200 Section 4290.200 Agriculture Regulations of the Department of Agriculture (Continued) RURAL BUSINESS-COOPERATIVE SERVICE AND... Qualifications for the RBIC Program Capitalizing A Rbic § 4290.200 Adequate capital for RBICs. You must meet...

  15. 10 CFR 1304.114 - Responsibility for maintaining adequate safeguards.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... 10 Energy 4 2011-01-01 2011-01-01 false Responsibility for maintaining adequate safeguards. 1304.114 Section 1304.114 Energy NUCLEAR WASTE TECHNICAL REVIEW BOARD PRIVACY ACT OF 1974 § 1304.114 Responsibility for maintaining adequate safeguards. The Board has the responsibility for maintaining...

  16. 40 CFR 716.25 - Adequate file search.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Adequate file search. 716.25 Section 716.25 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT HEALTH AND SAFETY DATA REPORTING General Provisions § 716.25 Adequate file search. The scope of...

  17. 40 CFR 51.354 - Adequate tools and resources.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 2 2011-07-01 2011-07-01 false Adequate tools and resources. 51.354... Requirements § 51.354 Adequate tools and resources. (a) Administrative resources. The program shall maintain the administrative resources necessary to perform all of the program functions including...

  18. 40 CFR 51.354 - Adequate tools and resources.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 2 2012-07-01 2012-07-01 false Adequate tools and resources. 51.354... Requirements § 51.354 Adequate tools and resources. (a) Administrative resources. The program shall maintain the administrative resources necessary to perform all of the program functions including...

  19. 40 CFR 51.354 - Adequate tools and resources.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 2 2014-07-01 2014-07-01 false Adequate tools and resources. 51.354... Requirements § 51.354 Adequate tools and resources. (a) Administrative resources. The program shall maintain the administrative resources necessary to perform all of the program functions including...

  20. 40 CFR 51.354 - Adequate tools and resources.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 2 2013-07-01 2013-07-01 false Adequate tools and resources. 51.354... Requirements § 51.354 Adequate tools and resources. (a) Administrative resources. The program shall maintain the administrative resources necessary to perform all of the program functions including...

  1. 40 CFR 716.25 - Adequate file search.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Adequate file search. 716.25 Section... ACT HEALTH AND SAFETY DATA REPORTING General Provisions § 716.25 Adequate file search. The scope of a person's responsibility to search records is limited to records in the location(s) where the...

  2. 40 CFR 716.25 - Adequate file search.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Adequate file search. 716.25 Section... ACT HEALTH AND SAFETY DATA REPORTING General Provisions § 716.25 Adequate file search. The scope of a person's responsibility to search records is limited to records in the location(s) where the...

  3. 40 CFR 716.25 - Adequate file search.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Adequate file search. 716.25 Section... ACT HEALTH AND SAFETY DATA REPORTING General Provisions § 716.25 Adequate file search. The scope of a person's responsibility to search records is limited to records in the location(s) where the...

  4. 40 CFR 716.25 - Adequate file search.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Adequate file search. 716.25 Section... ACT HEALTH AND SAFETY DATA REPORTING General Provisions § 716.25 Adequate file search. The scope of a person's responsibility to search records is limited to records in the location(s) where the...

  5. 10 CFR 1304.114 - Responsibility for maintaining adequate safeguards.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... 10 Energy 4 2014-01-01 2014-01-01 false Responsibility for maintaining adequate safeguards. 1304.114 Section 1304.114 Energy NUCLEAR WASTE TECHNICAL REVIEW BOARD PRIVACY ACT OF 1974 § 1304.114 Responsibility for maintaining adequate safeguards. The Board has the responsibility for maintaining...

  6. 10 CFR 1304.114 - Responsibility for maintaining adequate safeguards.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... 10 Energy 4 2013-01-01 2013-01-01 false Responsibility for maintaining adequate safeguards. 1304.114 Section 1304.114 Energy NUCLEAR WASTE TECHNICAL REVIEW BOARD PRIVACY ACT OF 1974 § 1304.114 Responsibility for maintaining adequate safeguards. The Board has the responsibility for maintaining...

  7. 10 CFR 503.35 - Inability to obtain adequate capital.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 10 Energy 4 2010-01-01 2010-01-01 false Inability to obtain adequate capital. 503.35 Section 503.35 Energy DEPARTMENT OF ENERGY (CONTINUED) ALTERNATE FUELS NEW FACILITIES Permanent Exemptions for New Facilities § 503.35 Inability to obtain adequate capital. (a) Eligibility. Section 212(a)(1)(D)...

  8. 10 CFR 503.35 - Inability to obtain adequate capital.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... 10 Energy 4 2011-01-01 2011-01-01 false Inability to obtain adequate capital. 503.35 Section 503.35 Energy DEPARTMENT OF ENERGY (CONTINUED) ALTERNATE FUELS NEW FACILITIES Permanent Exemptions for New Facilities § 503.35 Inability to obtain adequate capital. (a) Eligibility. Section 212(a)(1)(D)...

  9. 15 CFR 970.404 - Adequate exploration plan.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... ENVIRONMENTAL DATA SERVICE DEEP SEABED MINING REGULATIONS FOR EXPLORATION LICENSES Certification of Applications § 970.404 Adequate exploration plan. Before he may certify an application, the Administrator must find... 15 Commerce and Foreign Trade 3 2011-01-01 2011-01-01 false Adequate exploration plan....

  10. 15 CFR 970.404 - Adequate exploration plan.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... ENVIRONMENTAL DATA SERVICE DEEP SEABED MINING REGULATIONS FOR EXPLORATION LICENSES Certification of Applications § 970.404 Adequate exploration plan. Before he may certify an application, the Administrator must find... 15 Commerce and Foreign Trade 3 2010-01-01 2010-01-01 false Adequate exploration plan....

  11. "Something Adequate"? In Memoriam Seamus Heaney, Sister Quinlan, Nirbhaya

    ERIC Educational Resources Information Center

    Parker, Jan

    2014-01-01

    Seamus Heaney talked of poetry's responsibility to represent the "bloody miracle", the "terrible beauty" of atrocity; to create "something adequate". This article asks, what is adequate to the burning and eating of a nun and the murderous gang rape and evisceration of a medical student? It considers Njabulo…

  12. The Ages, Metallicities, and Alpha Element Enhancements of Globular Clusters in the Elliptical NGC 5128: A Homogeneous Spectroscopic Study with Gemini/Gemini Multi-Object Spectrograph

    NASA Astrophysics Data System (ADS)

    Woodley, Kristin A.; Harris, William E.; Puzia, Thomas H.; Gómez, Matías; Harris, Gretchen L. H.; Geisler, Doug

    2010-01-01

    We present new integrated light spectroscopy of globular clusters (GCs) in NGC 5128, a nearby giant elliptical galaxy less than 4 Mpc away, in order to measure radial velocities and derive ages, metallicities, and alpha-element abundance ratios. Using the Gemini South 8 meter telescope with the instrument Gemini Multi-Object Spectrograph, we obtained spectroscopy in the range of ~3400-5700 Å for 72 GCs with a signal-to-noise ratio greater than 30 Å-1 and we have also discovered 35 new GCs within NGC 5128 from our radial velocity measurements. We measured and compared the Lick indices from Hδ A through Fe5406 with the single stellar population models of Thomas et al. in order to derive age, metallicity, and [α/Fe] values. We also measure Lick indices for 41 Milky Way GCs from Puzia et al. and Schiavon et al. with the same methodology for direct comparison. Our results show that 68% of the NGC 5128 GCs have old ages (>8 Gyr), 14% have intermediate ages (5-8 Gyr), and 18% have young ages (<5 Gyr). However, when we look at the metallicity of the GCs as a function of age, we find 92% of metal-poor GCs and 56% of metal-rich GCs in NGC 5128 have ages >8 Gyr, indicating that the majority of both metallicity subpopulations of GCs formed earlier, with a significant population of young and metal-rich GCs forming later. Our metallicity distribution function generated directly from spectroscopic Lick indices is clearly bimodal, as is the color distribution of the same set of GCs. Thus, the metallicity bimodality is real and not an artifact of the color to metallicity conversion. However, the metallicity distribution function obtained from comparison with the single stellar population models is consistent with a unimodal, bimodal, or multimodal shape. The [α/Fe] values are supersolar with a mean value of 0.14 ± 0.04, indicating a fast formation timescale. However, the GCs in NGC 5128 are not as [α/Fe] enhanced as the Milky Way GCs also examined in this study. Our measured

  13. Opening of Carborane Cages by Metal Cluster Complexes: The Reaction of a Thiolate-Substituted Carborane with Triosmium Carbonyl Cluster Complexes.

    PubMed

    Adams, Richard D; Kiprotich, Joseph; Peryshkov, Dmitry V; Wong, Yuen Onn

    2016-08-15

    The reaction of Os3(CO)10(NCMe)2 with closo-o-(1-SCH3)C2B10H11 has yielded the complex Os3(CO)9[μ3-η(3)-C2B10H9(SCH3)](μ-H)2, 1, by the loss of the two NCMe ligands and one CO ligand from the Os3 cluster and the coordination of the sulfur atom and the activation of two B-H bonds with transfer of the hydrogen atoms to the cluster. Reaction of 1 with a second equivalent of Os3(CO)10(NCMe)2 yielded the complex Os3(CO)9(μ-H)[(μ3-η(3)-1,4,5-μ3-η(3)-6,10,11-C2B10H8S(CH3)]Os3(CO)9(μ-H)2, 2, that contains two triosmium triangles attached to the same carborane cage. The carborane cage was opened by cleavage of two B-C bonds and one B-B bond. The B-H group that was pulled out of the cage became a triply bridging group on one of the Os3 triangles but remains bonded to the cage by two B-B bonds. When heated to 150 °C, 2 was transformed into the complex Os3(CO)9(μ-H)[(μ3-η(3)-μ3-η(3)-C2B10H7S(CH3)]Os3(CO)9(μ-H), 3, by the loss of two hydrogen atoms and a rearrangement that led to further opening of the carborane cage. Reaction of 1 with a second equivalent of closo-o-(1-SCH3)C2B10H11 has yielded the complex Os3(CO)6)(μ3-η(3)-C2B10H9-R-SCH3) (μ3-η(3)-C2B10H10-S-SCH3)(μ-H)3, 4a, containing two carborane cages coordinated to one Os3 cluster. Compound 4a was isomerized to the compound Os3(CO)6(μ3-η(3)-C2B10H9-R-SCH3)(μ3-η(3)-C2B10H10-R-SCH3)(μ-H)3, 4b, by an inversion of stereochemistry at one of the sulfur atoms by heating to 174 °C. PMID:27487332

  14. Metallicities and Alpha-to-Iron Ratios in Globular Cluster Stars on a Homogeneous Scale: Search for Multiple Populations

    NASA Astrophysics Data System (ADS)

    Dias, B.; Saviane, I.; Barbuy, B.; Held, E.; Da Costa, G.; Ortolani, S.; Vasquez, S.

    2015-05-01

    We are carrying out a survey of 51 poorly studied Milky Way globular clusters by means of spectroscopy of ˜20 red giant stars per cluster. Optical spectra (4600-5800 Å) were obtained with FORS2@VLT/ESO, at a resolution Δλ ˜ 2.5 Å. We used the ETOILE code to derive radial velocities, Teff, log g, [Fe/H], and [Mg/Fe] for each star by identifying the best fitted spectrum among a grid of stellar spectra. The stellar library can be a collection of observed or synthetic spectra. The main contributions of this work are to provide a homogeneous scale of [Fe/H], [Mg/Fe], and radial velocities for 51 clusters (in particular for the 29 distant and/or highly reddened ones), to provide a catalogue of confirmed member stars for each cluster, and to identify interesting clusters for follow-up with high resolution data (e.g., the massive clusters M 22 and NGC 5824, for which a spread in [Fe/H] was found).

  15. Fermi-level depinning and contact resistance reduction in metal/n-Ge junctions by insertion of W-encapsulating Si cluster films

    SciTech Connect

    Okada, Naoya; Uchida, Noriyuki; Kanayama, Toshihiko

    2014-02-10

    We demonstrate Fermi-level depinning in metal/Ge junctions and a significant reduction of specific contact resistivity of n-Ge by inserting an ultra-thin semiconducting Si-rich W silicide film (WSi{sub n}, n = 12–14) composed of W-encapsulating Si clusters. Dependence of the specific contact resistivity on the electron Schottky barrier height followed the ideal exponential relation for various contact metal species. This result indicates that the insertion of the WSi{sub n} film provides a negligible contribution to contact resistivity because its tunneling resistance is very low owing to the low offset of the conduction band edge of Ge.

  16. Mixed-metal chloro sulfido cluster complex of molybdenum and platinum, (Mo sub 3 Pt sub 2 S sub 4 Cl sub 4 (PEt sub 3 ) sub 6 )

    SciTech Connect

    Saito, Taro; Tsuboi, Toshio; Kajitani, Yoshimichi; Yamagata, Tsuneaki; Imoto, Hideo )

    1991-09-04

    In the authors recent publication, syntheses of mixed-metal chloro sulfido and chloro selenido complexes of molybdenum and nickel were reported. They were prepared by the reaction of (Mo{sub 3}X{sub 4}Cl{sub 4}(PEt{sub 3}){sub 3}(MeOH){sub 2}) (X = S, Se){sup 2} with Ni(cod){sub 2} (cod = 1,5-cyclooctadiene). In the present study, another excellent building block compound, Pt(cot){sub 2}, was reacted with the same trinuclear molybdenum complex, and the mixed-metal cluster complex (Mo{sub 3}Pt{sub 2}S{sub 4}Cl{sub 4}(PEt{sub 3}){sub 6}) (1) with an unexpected structure was obtained.

  17. Analysis of heterogeneous water vapor uptake by metal iodide cluster ions via differential mobility analysis-mass spectrometry

    SciTech Connect

    Oberreit, Derek; Rawat, Vivek K.; Larriba-Andaluz, Carlos; Ouyang, Hui; McMurry, Peter H.; Hogan, Christopher J.

    2015-09-14

    The sorption of vapor molecules onto pre-existing nanometer sized clusters is of importance in understanding particle formation and growth in gas phase environments and devising gas phase separation schemes. Here, we apply a differential mobility analyzer-mass spectrometer based approach to observe directly the sorption of vapor molecules onto iodide cluster ions of the form (MI){sub x}M{sup +} (x = 1-13, M = Na, K, Rb, or Cs) in air at 300 K and with water saturation ratios in the 0.01-0.64 range. The extent of vapor sorption is quantified in measurements by the shift in collision cross section (CCS) for each ion. We find that CCS measurements are sensitive enough to detect the transient binding of several vapor molecules to clusters, which shift CCSs by only several percent. At the same time, for the highest saturation ratios examined, we observed CCS shifts of up to 45%. For x < 4, cesium, rubidium, and potassium iodide cluster ions are found to uptake water to a similar extent, while sodium iodide clusters uptake less water. For x ≥ 4, sodium iodide cluster ions uptake proportionally more water vapor than rubidium and potassium iodide cluster ions, while cesium iodide ions exhibit less uptake. Measured CCS shifts are compared to predictions based upon a Kelvin-Thomson-Raoult (KTR) model as well as a Langmuir adsorption model. We find that the Langmuir adsorption model can be fit well to measurements. Meanwhile, KTR predictions deviate from measurements, which suggests that the earliest stages of vapor uptake by nanometer scale species are not well described by the KTR model.

  18. Analysis of heterogeneous water vapor uptake by metal iodide cluster ions via differential mobility analysis-mass spectrometry

    NASA Astrophysics Data System (ADS)

    Oberreit, Derek; Rawat, Vivek K.; Larriba-Andaluz, Carlos; Ouyang, Hui; McMurry, Peter H.; Hogan, Christopher J.

    2015-09-01

    The sorption of vapor molecules onto pre-existing nanometer sized clusters is of importance in understanding particle formation and growth in gas phase environments and devising gas phase separation schemes. Here, we apply a differential mobility analyzer-mass spectrometer based approach to observe directly the sorption of vapor molecules onto iodide cluster ions of the form (MI)xM+ (x = 1-13, M = Na, K, Rb, or Cs) in air at 300 K and with water saturation ratios in the 0.01-0.64 range. The extent of vapor sorption is quantified in measurements by the shift in collision cross section (CCS) for each ion. We find that CCS measurements are sensitive enough to detect the transient binding of several vapor molecules to clusters, which shift CCSs by only several percent. At the same time, for the highest saturation ratios examined, we observed CCS shifts of up to 45%. For x < 4, cesium, rubidium, and potassium iodide cluster ions are found to uptake water to a similar extent, while sodium iodide clusters uptake less water. For x ≥ 4, sodium iodide cluster ions uptake proportionally more water vapor than rubidium and potassium iodide cluster ions, while cesium iodide ions exhibit less uptake. Measured CCS shifts are compared to predictions based upon a Kelvin-Thomson-Raoult (KTR) model as well as a Langmuir adsorption model. We find that the Langmuir adsorption model can be fit well to measurements. Meanwhile, KTR predictions deviate from measurements, which suggests that the earliest stages of vapor uptake by nanometer scale species are not well described by the KTR model.

  19. Analysis of heterogeneous water vapor uptake by metal iodide cluster ions via differential mobility analysis-mass spectrometry.

    PubMed

    Oberreit, Derek; Rawat, Vivek K; Larriba-Andaluz, Carlos; Ouyang, Hui; McMurry, Peter H; Hogan, Christopher J

    2015-09-14

    The sorption of vapor molecules onto pre-existing nanometer sized clusters is of importance in understanding particle formation and growth in gas phase environments and devising gas phase separation schemes. Here, we apply a differential mobility analyzer-mass spectrometer based approach to observe directly the sorption of vapor molecules onto iodide cluster ions of the form (MI)xM(+) (x = 1-13, M = Na, K, Rb, or Cs) in air at 300 K and with water saturation ratios in the 0.01-0.64 range. The extent of vapor sorption is quantified in measurements by the shift in collision cross section (CCS) for each ion. We find that CCS measurements are sensitive enough to detect the transient binding of several vapor molecules to clusters, which shift CCSs by only several percent. At the same time, for the highest saturation ratios examined, we observed CCS shifts of up to 45%. For x < 4, cesium, rubidium, and potassium iodide cluster ions are found to uptake water to a similar extent, while sodium iodide clusters uptake less water. For x ≥ 4, sodium iodide cluster ions uptake proportionally more water vapor than rubidium and potassium iodide cluster ions, while cesium iodide ions exhibit less uptake. Measured CCS shifts are compared to predictions based upon a Kelvin-Thomson-Raoult (KTR) model as well as a Langmuir adsorption model. We find that the Langmuir adsorption model can be fit well to measurements. Meanwhile, KTR predictions deviate from measurements, which suggests that the earliest stages of vapor uptake by nanometer scale species are not well described by the KTR model. PMID:26374028

  20. The Color-Magnitude Relation for Metal-Poor Globular Clusters in M87: Confirmation from Deep HST/ACS Imaging

    NASA Astrophysics Data System (ADS)

    Peng, Eric W.; Jordán, Andrés; Blakeslee, John P.; Mieske, Steffen; Côté, Patrick; Ferrarese, Laura; Harris, William E.; Madrid, Juan P.; Meurer, Gerhardt R.

    2009-09-01

    Metal-poor globular clusters (GCs) are our local link to the earliest epochs of star formation and galaxy building. Studies of extragalactic GC systems using deep, high-quality imaging have revealed a small but significant slope to the color-magnitude relation for metal-poor GCs in a number of galaxies. We present a study of the M87 GC system using deep, archival HST/ACS imaging with the F606W and F814W filters, in which we find a significant color-magnitude relation for the metal-poor GCs. The slope of this relation in the I versus V-I color-magnitude diagram (γ I = -0.024 ± 0.006) is perfectly consistent with expectations based on previously published results using data from the ACS Virgo Cluster Survey. The relation is driven by the most luminous GCs, those with MI lsim -10, and its significance is largest when fitting metal-poor GCs brighter than MI = -7.8, a luminosity which is ~1 mag fainter than our fitted Gaussian mean for the luminosity function (LF) of blue, metal-poor GCs (~0.8 mag fainter than the mean for all GCs). These results indicate that there is a mass scale at which the correlation begins, and is consistent with a scenario where self-enrichment drives a mass-metallicity relationship. We show that previously measured half-light radii of M87 GCs from best-fit PSF-convolved King models are consistent with the more accurate measurements in this study, and we also explain how the color-magnitude relation for metal-poor GCs is real and cannot be an artifact of the photometry. We fit Gaussian and evolved Schechter functions to the luminosity distribution of GCs across all colors, as well as divided into blue and red subpopulations, finding that the blue GCs have a brighter mean luminosity and a narrower distribution than the red GCs. Finally, we present a catalog of astrometry and photometry for 2250 M87 GCs. Based on observations with the NASA/ESA Hubble Space Telescope obtained at the Space Telescope Science Institute, which is operated by the

  1. The Old, Super-metal-rich Open Cluster, NGC 6791—Elemental Abundances in Turn-off Stars from Keck/HIRES Spectra

    NASA Astrophysics Data System (ADS)

    Boesgaard, Ann Merchant; Lum, Michael G.; Deliyannis, Constantine P.

    2015-02-01

    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 are corrected for small nLTE effects. We find consistent ratios of [O/Fe]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.

  2. THE OLD, SUPER-METAL-RICH OPEN CLUSTER, NGC 6791—ELEMENTAL ABUNDANCES IN TURN-OFF STARS FROM KECK/HIRES SPECTRA

    SciTech Connect

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

    2015-02-01

    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 are 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.

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

    SciTech Connect

    Goudfrooij, Paul; Diederik Kruijssen, J. M. 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 parent 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.

  4. All-metal aromatic clusters M4(2-) (M = B, Al, and Ga). Are π-electrons distortive or not?

    PubMed

    Poater, Jordi; Feixas, Ferran; Bickelhaupt, F Matthias; Solà, Miquel

    2011-12-14

    The π-electrons in benzene, the quintessential aromatic molecule, were previously shown to be distortive, i.e., they prefer localized double bonds alternating with single bonds. It is the σ-electrons that force the double bonds to delocalize, leading to a regular, D(6h) geometry. Herein, we computationally investigate the double-bond localizing or delocalizing propensities of σ- and π-electrons in the archetypal all-metal aromatic cluster Al(4)(2-) and its second- and fourth-period analogs B(4)(2-) and Ga(4)(2-), using Kohn-Sham molecular orbital (MO) theory at BP86/TZ2P in combination with quantitative bond energy decomposition analyses (EDA). We compare the three all-metal aromatic clusters with the structurally related organic species C(4)H(4)(2+), C(4)H(4), and C(4)H(4)(2-). Our analyses reveal that the π-electrons in the group-13 M(4)(2-) molecules have a weak preference for localizing the double bonds. Instead, the σ-electrons enforce the regular D(4h) equilibrium geometry with delocalized double bonds. PMID:22011729

  5. Modeling the Break-up of Nano-particle Clusters in Aluminum- and Magnesium-Based Metal Matrix Nano-composites

    NASA Astrophysics Data System (ADS)

    Manoylov, Anton; Bojarevics, Valdis; Pericleous, Koulis

    2015-07-01

    Aluminum- and magnesium-based metal matrix nano-composites with ceramic nano-reinforcements promise low weight with high durability and superior strength, desirable properties in aerospace, automobile, and other applications. However, nano-particle agglomerations lead to adverse effects on final properties: large-size clusters no longer act as dislocation anchors, but instead become defects; the resulting particle distribution will be uneven, leading to inconsistent properties. To prevent agglomeration and to break-up clusters, ultrasonic processing is used via an immersed sonotrode, or alternatively via electromagnetic vibration. A study of the interaction forces holding the nano-particles together shows that the choice of adhesion model significantly affects estimates of break-up force and that simple Stokes drag due to stirring is insufficient to break-up the clusters. The complex interaction of flow and co-joint particles under a high frequency external field (ultrasonic, electromagnetic) is addressed in detail using a discrete-element method code to demonstrate the effect of these fields on de-agglomeration.

  6. Oligomeric rare-earth-metal halide clusters. Three structures built of (Y{sub 16}Z{sub 4})Br{sub 36} units (Z = Ru, Ir)

    SciTech Connect

    Steinward, S.J.; Corbett, J.D.

    1996-11-20

    Suitable reactions in sealed Nb tubing at 850-950 {degrees}C gave good yields of a family of oligomeric cluster phases that were characterized by single-crystal X-ray diffraction means. The basic Y{sub 16}Z{sub 4} units ({approximately}{bar 4} symmetry) can be derived from 2+2 condensation of centered Y{sub 6}Br{sub 12}Z-type clusters or as tetracapped truncated tetrahedra Y{sub 16} that are centered by a large tetrahedral Z{sub 4}. These are surrounded by 36 bromine atoms which bridge edges or cap faces of the Y{sub 16}Z{sub 4} nuclei and, in part, bridge to metal atoms in other clusters. The principal bonding appears to be Y-Z and Y-Br, with weaker Y-Y ({bar d} {approximately} 3.70 {angstrom}) and negligible Z-Z interactions. The phase Y{sub 16}Br{sub 20}Ru{sub 4} (P4{sub 2}/nnm, Z = 2; a = 11.662(1) {angstrom}, c = 16.992 (2) {angstrom}) is isostructural with Y{sub 16}I{sub 20}Ru{sub 4} and with the new Sc{sub 16-} Br{sub 20}Z{sub 4} (Z = Fe, Os). Syntheses only in the presence of Ir and ABr-YBr{sub 3} fluxes (A = K-Cs) produce Y{sub 16-} Br{sub 24}Ir{sub 4} (Fddd, Z = 8; a = 11.718(3) {angstrom}, b = 22.361(7) {angstrom}, c = 44.702(2) {angstrom}), in which the electron-richer Ir interstitials are compensated by four additional bromine atoms and altered bridging between macroclusters. Larger amounts of YBr{sub 3} yield a third example, Y{sub 20}Br{sub 36}Ir{sub 4} (Y{sub 16}Br{sub 24}Ir{sub 4}{center_dot}4YBr{sub 3}, I4{sub 1}a, Z = 4; a = 12.699(1) {angstrom}, c = 45.11- (1){angstrom}). Here infinite zigzag chains of YBr{sub 6/2} octahedra that share cis edges lie between and bridge to the Y{sub 16}Ir{sub 4} clusters. All of these phases contain 60-electron, closed-shell macroclusters. Y{sub 16}Br{sub 20}Ru{sub 4} and Y{sub 20}Br{sub 36}ir{sub 4} were found to exhibit temperature-independent (Van Vleck) paramagnetism with values typical of those found for other rare-earth-metal, zirconium, niobium, and tantalum cluster halides.

  7. Strömgren and near-infrared photometry of metal-rich bulge globular clusters. I. NGC 6528 and its surrounding field

    NASA Astrophysics Data System (ADS)

    Calamida, A.; Bono, G.; Lagioia, E. P.; Milone, A. P.; Fabrizio, M.; Saviane, I.; Moni Bidin, C.; Mauro, F.; Buonanno, R.; Ferraro, I.; Iannicola, G.; Zoccali, M.

    2014-05-01

    We present Strömgren and near-infrared (NIR) photometry of the bulge cluster NGC 6528 and its surrounding field in Baade's Window. uvby images were collected with EFOSC2 on the New Technology Telescope (NTT, La Silla, ESO). The NIR catalogs are based on J,K-band VIRCAM at VISTA (Paranal, ESO) and SOFI at NTT photometry. We matched the aforementioned data sets with Hubble Space Telescope photometry to obtain proper-motion-cleaned samples of NGC 6528 and bulge stars. Furthermore, we were able to correct the Strömgren-NIR photometry for differential reddening. The huge color sensitivity of the Strömgren-NIR color-magnitude-diagrams (CMDs) helped us in separating age and metallicity effects. The red giant branch (RGB) of NGC 6528 is well reproduced in all the CMDs by adopting scaled solar isochrones with solar abundance, that is Z = 0.0198, or α-enhanced isochrones with the same iron content, that is Z = 0.04, and an age range of t = 10-12 Gyr. The same isochrones well reproduce most of the color spread of Baade's Window RGB. These findings support the literature age estimates for NGC 6528. We also performed a new theoretical visual-NIR metallicity calibration based on the Strömgren index m1 and on visual-NIR colors for red giant (RG) stars. Scaled solar and α-enhanced models were adopted and we validated the new metallicity-index-color (MIC) relations by applying them to estimate the photometric metal abundance of a sample of field RGs and of a metal-poor (M 92, [Fe/H] ~-2.3) and a metal-rich (NGC 6624, [Fe/H] ~ -0.7) globular cluster. We applied the calibration to estimate the mean metal abundance of NGC 6528, finding [Fe/H] = [M/H] = -0.04 ± 0.02, with a mean intrinsic dispersion of σ = 0.27 dex, by averaging the metallicities obtained with the scaled solar [m], y - J and [m], y - K MIC relations, and of -0.11 ± 0.01, with σ = 0.27 dex, by using the m1, y - J and m1, y - K relations. These findings support results based on high-resolution spectroscopy

  8. Atomic collisions in suprafluid helium-nanodroplets: timescales for metal-cluster formation derived from He-density functional theory

    PubMed Central

    Volk, Alexander; Thaler, Philipp

    2015-01-01

    Collision times for the coinage metal atoms Cu, Ag and Au in He-droplets are derived from helium density functional theory and molecular dynamics simulations. The strength of the attractive interaction between the metal atoms turns out to be less important than the mass of the propagating metal atoms. Even for small droplets consisting of a few thousand helium atoms, the collision times are shortest for Cu, followed by Ag and Au, despite the higher binding energy of Au2 compared to Cu2. PMID:25812719

  9. 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

  10. Metallicities and alpha-to-iron ratios in globular clusters stars in a homogeneous scale - Search for multiple populations

    NASA Astrophysics Data System (ADS)

    Dias, B.; Saviane, I.; Barbuy, B.; Held, E.; Da Costa, G.; Ortolani, S.

    We are carrying out a survey of 51 poorly studied globular clusters, by means of spectroscopy of ˜20 red giants per cluster. Optical spectra (4600-5800 Å) were obtained with the FORS2@VLT/ESO, at a resolution Delta lambda ˜ 2.5 Å. We are using ETOILE code to derive [Fe/H], T_eff, log g for each star, by finding the best fitting spectrum among a grid of ˜ 2000 stars of the ELODIE library. These parameters represent the initial guess for HALO, which finds [Mg/Fe] values by comparing the observed spectrum to a grid of 4000 synthetic spectra. The main contributions of this work are: to provide a homogeneous scale of [Fe/H], [Mg/Fe], and radial velocities for the 51 clusters -- in particular for the 29 distant and/or highly reddened ones -- to provide a catalogue of confirmed member stars for each cluster, as well as to find interesting cases for follow-up with high resolution (like M 22, and NGC 5824, for which we found a spread in [Fe/H]).

  11. CuCl2 for the isolation of a broad array of endohedral fullerenes containing metallic, metallic carbide, metallic nitride, and metallic oxide clusters, and separation of their structural isomers.

    PubMed

    Stevenson, Steven; Rottinger, Khristina A

    2013-08-19

    A typical arc-synthesis generates many types of fullerenes and endohedrals. Resulting soot extracts contain a complex mixture of >50 types of fullerenes, metallofullerenes, and their structural isomers. Prior to application development, novel separation methods are required to fractionate this rich array of metallic, metallic carbide, metallic nitride, and metallic oxide endohedrals, all of which can be present in a single, soot extract. Herein, we report the discovery of CuCl2 as a Lewis acid that will selectively precipitate only the more reactive members of each of these endohedral families. The more reactive Sc4O2@Ih-C80, Sc3C2@Ih-C80, and Sc3N@D3h-C78 endohedrals are quickly removed from extracts to greatly decrease the number of endohedrals present in a sample. Experiments indicate that enrichment factors of several orders of magnitude can be achieved within minutes of reaction time. CuCl2 also has sufficient selectivity to resolve and separate structural isomers, as demonstrated with Er2@C82 (isomer I, Cs(6)-C82 versus isomer III). The selective complexation of CuCl2 with fullerenes can be correlated to their first oxidation potential. We estimate a significantly lower threshold of precipitation for CuCl2 (<0.19 V) compared to stronger Lewis acids. Fullerenes and metallofullerenes having first oxidation potentials above 0.19 V tend to remain unreacted in solution. In contrast, species with first oxidation potentials below 0.19 V (vs Fc/Fc(+)) precipitate via complexation, and are easily decomplexed. CuCl2 is compared to Lewis acids having higher precipitation thresholds (e.g., FeCl3) in our goal to predict a priori which endohedrals would remain in solution versus which endohedral species would complex and precipitate. The ability to predict endohedral precipitation a priori is beneficial to the design of purification strategies for metallofullerenes. PMID:23952569

  12. Copper Sensing Function of Drosophila Metal-Responsive Transcription Factor-1 Is Mediated By a Tetranuclear Cu(I) Cluster

    SciTech Connect

    Chen, X.; Hua, H.; Balamurugan, K.; Kong, X.; Zhang, L.; George, G.N.; Georgiev, O.; Schaffner, W.; Giedroc, D.P.

    2009-05-12

    Drosophila melanogaster MTF-1 (dMTF-1) is a copper-responsive transcriptional activator that mediates resistance to Cu, as well as Zn and Cd. Here, we characterize a novel cysteine-rich domain which is crucial for sensing excess intracellular copper by dMTF-1. Transgenic flies expressing mutant dMTF-1 containing alanine substitutions of two, four or six cysteine residues within the sequence {sup 547}CNCTNCKCDQTKSCHGGDC{sup 565} are significantly or completely impaired in their ability to protect flies from copper toxicity and fail to up-regulate MtnA (metallothionein) expression in response to excess Cu. In contrast, these flies exhibit wild-type survival in response to copper deprivation thus revealing that the cysteine cluster domain is required only for sensing Cu load by dMTF-1. Parallel studies show that the isolated cysteine cluster domain is required to protect a copper-sensitive S. cerevisiae ace1 strain from copper toxicity. Cu(I) ligation by a Cys-rich domain peptide fragment drives the cooperative assembly of a polydentate [Cu{sub 4}-S{sub 6}] cage structure, characterized by a core of trigonally S{sub 3} coordinated Cu(I) ions bound by bridging thiolate ligands. While reminiscent of Cu{sub 4}-L{sub 6} (L = ligand) tetranuclear clusters in copper regulatory transcription factors of yeast, the absence of significant sequence homology is consistent with convergent evolution of a sensing strategy particularly well suited for Cu(I).

  13. Metallic behavior and negative differential resistance properties of (InAs){sub n} (n = 2 − 4) molecule cluster junctions via a combined non–equilibrium Green's function and density functional theory study

    SciTech Connect

    Wang, Qi; Li, Rong; Xu, Yuanlan; Zhang, Jianbing; Miao, Xiangshui; Zhang, Daoli

    2014-06-21

    In this present work, the geometric structures and electronic transport properties of (InAs){sub n} (n = 2, 3, 4) molecule cluster junctions are comparatively investigated using NEGF combined with DFT. Results indicate that all (InAs){sub n} molecule cluster junctions present metallic behavior at the low applied biases ([−2V, 2V]), while NDR appears at a certain high bias range. Our calculation shows that the current of (InAs){sub 4} molecule cluster–based junction is almost the largest at any bias. The mechanisms of the current–voltage characteristics of all the three molecule cluster junctions are proposed.

  14. The X-Ray Luminosity Function of Low-mass X-Ray Binaries in Early-type Galaxies, Their Metal-rich, and Metal-poor Globular Clusters

    NASA Astrophysics Data System (ADS)

    Peacock, Mark B.; Zepf, Stephen E.

    2016-02-01

    We present the X-ray luminosity function (XLF) of low-mass X-ray binaries (LMXBs) in the globular clusters (GCs) and fields of seven early-type galaxies. These galaxies are selected to have both deep Chandra observations, which allow their LMXB populations to be observed to X-ray luminosities of 1037-1038 erg s-1, and Hubble Space Telescope optical mosaics that enable the X-ray sources to be separated into field LMXBs, GC LMXBs, and contaminating background and foreground sources. We find that at all luminosities the number of field LMXBs per stellar mass is similar in these galaxies. This suggests that the field LMXB populations in these galaxies are not effected by the GC specific frequency, and that properties such as binary fraction and the stellar initial mass function are either similar across the sample or change in a way that does not affect the number of LMXBs. We compare the XLF of the field LMXBs to that of the GC LMXBs and find that they are significantly different with a p-value of 3 × 10-6 (equivalent to 4.7σ for a normal distribution). The difference is such that the XLF of the GC LMXBs is flatter than that of the field LMXBs, with the GCs hosting relatively more bright sources and fewer faint sources. A comparison of the XLF of the metal-rich and metal-poor GCs hints that the metal-poor clusters may have more bright LMXBs, but the difference is not statistically significant.

  15. Clustering of metal atoms in organic media. 9. High-activity Ni/MgO catalysts prepared by metal vapor methods. Surface area and particle size effects

    SciTech Connect

    Matsuo, K.; Klabunde, K.J.

    1982-02-01

    A metal vapor method was employed to prepare highly dispersed Ni metal catalysts (solvated metal atom dispersed = SMAD catalyst) supported on MgO. Compared with conventional Ni/MgO compositions, the SMAD catalysts showed much greater activities for all reactions studied (hydrogenolysis of methylcyclopentane, MCP; hydrogenation/hydrogenolysis of toluene, TOL; methanation of carbon monoxide, CO; dehydration of isopropyl alcohol, IPA). These high activities for the SMAD catalysts are attributed to the high surface area of Ni on MgO and the high percentage of this Ni in a zero-valent state (reduction degree). Conventional methods for preparing Ni/MgO catalysts did not yield nearly such favorable surface areas or reduction degrees. Nickel particle size effects were observed during hydrogenolysis studies of MCP and hydrogenation studies of TOL. These phenomena are explained by assuming the size of an active Ni particle to be largest for hydrogenolysis of MCP > hydrogenation of TOL > methanation of CO approx. = dehydrogenation of IPA. 8 figures, 2 tables.

  16. Arabidopsis: An Adequate Model for Dicot Root Systems?

    PubMed

    Zobel, Richard W

    2016-01-01

    The Arabidopsis root system is frequently considered to have only three classes of root: primary, lateral, and adventitious. Research with other plant species has suggested up to eight different developmental/functional classes of root for a given plant root system. If Arabidopsis has only three classes of root, it may not be an adequate model for eudicot plant root systems. Recent research, however, can be interpreted to suggest that pre-flowering Arabidopsis does have at least five (5) of these classes of root. This then suggests that Arabidopsis root research can be considered an adequate model for dicot plant root systems. PMID:26904040

  17. Mechanisms of formation of nonlinear optical light guide structures in metal cluster composites produced by ion beam implantation

    SciTech Connect

    Sarkisov, S.S.; Williams, E.K.; Curley, M.; Smith, C.C.; Ila, D.; Venkateswarlu, P.; Poker, D.B.; Hensley, D.K.

    1997-11-01

    Ion implantation has been shown to produce a high density of metal colloids in glasses and crystalline materials. The high-precipitate volume fraction and small size of metal nanoclusters formed leads to values for the third-order susceptibility much greater than those for metal doped solids. This has stimulated interest in use of ion implantation to make nonlinear optical materials. On the other side, LiNbO{sub 3} has proved to be a good material for optical waveguides produced by MeV ion implantation. Light confinement in these waveguides is produced by refractive index step difference between the implanted region and the bulk material. Implantation of LiNbO{sub 3} with MeV metal ions can therefore result into nonlinear optical waveguide structures with great potential in a variety of device applications. The authors describe linear and nonlinear optical properties of a waveguide structure in LiNbO{sub 3}-based composite material produced by silver ion implantation in connection with mechanisms of its formation.

  18. An Abundance Analysis of Red Giant Stars in the Retrograde Galactic Globular Cluster NGC 3201: Implications for Cluster Formation Scenarios

    NASA Astrophysics Data System (ADS)

    Simmerer, Jennifer A.; Ivans, I. I.

    2011-01-01

    Globular clusters have long been central to the study of Galactic Chemical Evolution. They serve as laboratories for stellar physics, evolution, and nucleosynthesis as well as representing fossil remnants of Galactic assembly processes. Our work addresses two recent areas of interest: globular clusters as accreted objects and globular clusters as hosts for multiple stellar populations. The globular cluster NGC 3201 is a curious object on a retrograde orbit. Some studies suggest that it contains stars of more than one metallicity, a property seen only in the peculiar globular cluster Omega Centauri. Both properties hint at an extra-Galactic origin. We present an elemental abundance pattern for NGC 3201 based on high resolution, high signal-to-noise spectra of red giant stars. We present abundance patterns of similar stars from the globular cluster M5 for comparison. Interpretation of our results is complicated by the discovery that at least two of our giants are variable stars. Though we can derive adequate stellar parameter solutions for both stars in every stage of variability and heavy element abundances do not change with the stellar phase, the abundances of the light elements O, Na, Mg, and Al are extremely unstable and vary greatly. Our inability to correctly model light element line formation in the atmosphere of variable red giant stars has significant implications for studies of star to star abundance variations in exactly these elements in globular clusters, which rely on stars at the same evolutionary stage as the variables in NGC 3201.

  19. A description of how metal pollution occurs in the Tinto-Odiel rias (Huelva-Spain) through the application of cluster analysis.

    PubMed

    Grande, J A; Borrego, J; Morales, J A; de la Torre, M L

    2003-04-01

    In the last few decades, the study of space-time distribution and variations of heavy metals in estuaries has been extensively studied as an environmental indicator. In the case described here, the combination of acid water from mines, industrial effluents and sea water plays a determining role in the evolutionary process of the chemical makeup of the water in the estuary of the Tinto and Odiel Rivers, located in the southwest of the Iberian Peninsula. Based on the statistical treatment of the data from the analysis of the water samples from this system, which has been affected by processes of industrial and mining pollution, the 16 variables analyzed can be grouped into two large families. Each family presents high, positive Pearson r values that suggest common origins (fluvial or sea) for the pollutants present in the water analyzed and allow their subsequent contrast through cluster analysis. PMID:12705921

  20. Synergistic Assembly of Heavy Metal Clusters and Luminescent Organic Bridging Ligands in Metal–Organic Frameworks for Highly Efficient X-ray Scintillation

    PubMed Central

    2015-01-01

    We have designed two metal–organic frameworks (MOFs) to efficiently convert X-ray to visible-light luminescence. The MOFs are constructed from M6(μ3-O)4(μ3-OH)4(carboxylate)12 (M = Hf or Zr) secondary building units (SBUs) and anthracene-based dicarboxylate bridging ligands. The high atomic number of Zr and Hf in the SBUs serves as effective X-ray antenna by absorbing X-ray photons and converting them to fast electrons through the photoelectric effect. The generated electrons then excite multiple anthracene-based emitters in the MOF through inelastic scattering, leading to efficient generation of detectable photons in the visible spectrum. The MOF materials thus serve as efficient X-ray scintillators via synergistic X-ray absorption by the metal-cluster SBUs and optical emission by the bridging ligands. PMID:24730683

  1. Precipitation, pH and metal load in AMD river basins: an application of fuzzy clustering algorithms to the process characterization.

    PubMed

    Grande, J A; Andújar, J M; Aroba, J; de la Torre, M L; Beltrán, R

    2005-04-01

    In the present work, Acid Mine Drainage (AMD) processes in the Chorrito Stream, which flows into the Cobica River (Iberian Pyrite Belt, Southwest Spain) are characterized by means of clustering techniques based on fuzzy logic. Also, pH behavior in contrast to precipitation is clearly explained, proving that the influence of rainfall inputs on the acidity and, as a result, on the metal load of a riverbed undergoing AMD processes highly depends on the moment when it occurs. In general, the riverbed dynamic behavior is the response to the sum of instant stimuli produced by isolated rainfall, the seasonal memory depending on the moment of the target hydrological year and, finally, the own inertia of the river basin, as a result of an accumulation process caused by age-long mining activity. PMID:15798799

  2. Structural variability in transition metal oxide clusters: gas phase vibrational spectroscopy of V3O(6-8)+.

    PubMed

    Asmis, Knut R; Wende, Torsten; Brümmer, Mathias; Gause, Oliver; Santambrogio, Gabriele; Stanca-Kaposta, E Cristina; Döbler, Jens; Niedziela, Andrzej; Sauer, Joachim

    2012-07-14

    We present gas phase vibrational spectra of the trinuclear vanadium oxide cations V(3)O(6)(+)·He(1-4), V(3)O(7)(+)·Ar(0,1), and V(3)O(8)(+)·Ar(0,2) between 350 and 1200 cm(-1). Cluster structures are assigned based on a comparison of the experimental and simulated IR spectra. The latter are derived from B3LYP/TZVP calculations on energetically low-lying isomers identified in a rigorous search of the respective configurational space, using higher level calculations when necessary. V(3)O(7)(+) has a cage-like structure of C(3v) symmetry. Removal or addition of an O-atom results in a substantial increase in the number of energetically low-lying structural isomers. V(3)O(8)(+) also exhibits the cage motif, but with an O(2) unit replacing one of the vanadyl oxygen atoms. A chain isomer is found to be most stable for V(3)O(6)(+). The binding of the rare gas atoms to V(3)O(6-8)(+) clusters is found to be strong, up to 55 kJ/mol for Ar, and markedly isomer-dependent, resulting in two interesting effects. First, for V(3)O(7)(+)·Ar and V(3)O(8)(+)·Ar an energetic reordering of the isomers compared to the bare ion is observed, making the ring motif the most stable one. Second, different isomers bind different number of rare gas atoms. We demonstrate how both effects can be exploited to isolate and assign the contributions from multiple isomers to the vibrational spectrum. The present results exemplify the structural variability of vanadium oxide clusters, in particular, the sensitivity of their structure on small perturbations in their environment. PMID:22499393

  3. Do Globular Clusters Care about AGB Stars? Metallicity Distribution of AGB and RGB Stars in NGC 2808

    NASA Astrophysics Data System (ADS)

    Wang, Y.; Primas, F.; Charbonnel, C.

    2015-08-01

    Galactic globular clusters are known to have multiple stellar populations with different scenarios being debated for their origin. In this context, the core of our project is to disentangle the first and second generation stars based on their chemical properties, in order to test different model predictions. Here we present a preliminary chemical analysis of a new sample of AGB stars in NGC 2808 observed at the VLT with FLAMES, in order to further investigate the recent finding that no Na-rich stars are found on the AGB.

  4. Is the Marketing Concept Adequate for Continuing Education?

    ERIC Educational Resources Information Center

    Rittenburg, Terri L.

    1984-01-01

    Because educators have a social responsibility to those they teach, the marketing concept may not be adequate as a philosophy for continuing education. In attempting to broaden the audience for continuing education, educators should consider a societal marketing concept to meet the needs of the educationally disadvantaged. (SK)

  5. Comparability and Reliability Considerations of Adequate Yearly Progress

    ERIC Educational Resources Information Center

    Maier, Kimberly S.; Maiti, Tapabrata; Dass, Sarat C.; Lim, Chae Young

    2012-01-01

    The purpose of this study is to develop an estimate of Adequate Yearly Progress (AYP) that will allow for reliable and valid comparisons among student subgroups, schools, and districts. A shrinkage-type estimator of AYP using the Bayesian framework is described. Using simulated data, the performance of the Bayes estimator will be compared to…

  6. 9 CFR 305.3 - Sanitation and adequate facilities.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 9 Animals and Animal Products 2 2010-01-01 2010-01-01 false Sanitation and adequate facilities. 305.3 Section 305.3 Animals and Animal Products FOOD SAFETY AND INSPECTION SERVICE, DEPARTMENT OF AGRICULTURE AGENCY ORGANIZATION AND TERMINOLOGY; MANDATORY MEAT AND POULTRY PRODUCTS INSPECTION AND VOLUNTARY INSPECTION AND CERTIFICATION...

  7. Understanding Your Adequate Yearly Progress (AYP), 2011-2012

    ERIC Educational Resources Information Center

    Missouri Department of Elementary and Secondary Education, 2011

    2011-01-01

    The "No Child Left Behind Act (NCLB) of 2001" requires all schools, districts/local education agencies (LEAs) and states to show that students are making Adequate Yearly Progress (AYP). NCLB requires states to establish targets in the following ways: (1) Annual Proficiency Target; (2) Attendance/Graduation Rates; and (3) Participation Rates.…

  8. Assessing Juvenile Sex Offenders to Determine Adequate Levels of Supervision.

    ERIC Educational Resources Information Center

    Gerdes, Karen E.; And Others

    1995-01-01

    This study analyzed the internal consistency of four inventories used by Utah probation officers to determine adequate and efficacious supervision levels and placement for juvenile sex offenders. Three factors accounted for 41.2 percent of variance (custodian's and juvenile's attitude toward intervention, offense characteristics, and historical…

  9. 34 CFR 200.13 - Adequate yearly progress in general.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 34 Education 1 2011-07-01 2011-07-01 false Adequate yearly progress in general. 200.13 Section 200.13 Education Regulations of the Offices of the Department of Education OFFICE OF ELEMENTARY AND SECONDARY EDUCATION, DEPARTMENT OF EDUCATION TITLE I-IMPROVING THE ACADEMIC ACHIEVEMENT OF THE...

  10. 34 CFR 200.20 - Making adequate yearly progress.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 34 Education 1 2011-07-01 2011-07-01 false Making adequate yearly progress. 200.20 Section 200.20 Education Regulations of the Offices of the Department of Education OFFICE OF ELEMENTARY AND SECONDARY EDUCATION, DEPARTMENT OF EDUCATION TITLE I-IMPROVING THE ACADEMIC ACHIEVEMENT OF THE DISADVANTAGED...

  11. Do Beginning Teachers Receive Adequate Support from Their Headteachers?

    ERIC Educational Resources Information Center

    Menon, Maria Eliophotou

    2012-01-01

    The article examines the problems faced by beginning teachers in Cyprus and the extent to which headteachers are considered to provide adequate guidance and support to them. Data were collected through interviews with 25 school teachers in Cyprus, who had recently entered teaching (within 1-5 years) in public primary schools. According to the…

  12. Anderson-like alkoxo-polyoxovanadate clusters serving as unprecedented second building units to construct metal-organic polyhedra.

    PubMed

    Zhang, Yu-Teng; Wang, Xin-Long; Li, Shuang-Bao; Gong, Ya-Ru; Song, Bai-Qiao; Shao, Kui-Zhan; Su, Zhong-Min

    2016-08-11

    Unprecedented Anderson-like alkoxo-polyoxovanadate [V6O6(OCH3)9(μ6-SO4)(COO)3](2-) polyanions can serve as 3-connected second building units (SBUs) that assemble with dicarboxylate or tricarboxylate ligands to form a new family of metal organic tetrahedrons of V4E6 and V4F4 type (V = vertex, E = edge, and F = face). To our knowledge, this alkoxo-polyoxovanadate-based SBU is the first ever reported. PMID:27363544

  13. Stratification of Metal and Sulphate Loads in Acid Mine Drainage Receiving Water Dams - Variables Regionalization by Cluster Analysis.

    PubMed

    Grande, J A; de la Torre, M L; Valente, T; Fernández, J P; Borrego, J; Santisteban, M; Cerón, J C; Sánchez-Rodas, D

    2015-07-01

    The Sancho Reservoir (Iberian Pyrite Belt, SW Spain) is nourished by the waters of the river Meca, which is affected by acid mine drainage (AMD) processes from the abandoned Tharsis mine. The aim of the present work is to study the hydrochemical variations in this reservoir, in order to define potential stratification processes in metal load and sulphates. A stratified sampling from the surface, with one meter deep intervals to the bottom of the dam, was performed. The results show a clear stratification of temperature, pH, electric conductivity, dissolved oxygen, metal and sulphate loads associated with depth. There is an increase of metal loads at the bottom of the reservoir, though previous studies only detect iron. The proximity between pH and aluminium suggests that water chemistry is strongly influenced by aluminium precipitation processes. This indicates the buffer effect that aluminium exercises, which precipitates as amorphous or low crystalline phases, introducing hydrogen ions to the system, while alkalinity input tends to raise pH. PMID:26163498

  14. A possible formation channel for blue hook stars in globular cluster II - Effects of metallicity, mass ratio, tidal enhancement efficiency and helium abundance

    NASA Astrophysics Data System (ADS)

    Lei, Zhenxin; Zhao, Gang; Zeng, Aihua; Shen, Lihua; Lan, Zhongjian; Jiang, Dengkai; Han, Zhanwen

    2016-09-01

    Employing tidally enhanced stellar wind, we studied in binaries the effects of metallicity, mass ratio of primary to secondary, tidal enhancement efficiency and helium abundance on the formation of blue hook (BHk) stars in globular clusters (GCs). Totally, 28 sets of binary models combined with different input parameters are studied. For each set of binary model, we presented the range of initial orbital periods which is needed to produce BHk stars in binaries. All the binary models could produce BHk stars within different range of initial orbital periods. We also compared our results with the observation in the Teff-logg diagram of GC NGC 2808 and ω Cen. Most of the BHk stars in these two GCs locate well in the region predicted by our theoretical models, especially when C/N enhanced model atmospheres is considered. We found that mass ratio of primary to secondary and tidal enhancement efficiency have little effects on the formation of BHk stars in binaries, while metallicity and helium abundance would play important roles, especially for helium abundance. Specifically, with helium abundance increasing in binary models, the space range of initial orbital periods needed to produce BHk stars becomes obviously wider, regardless of other input parameters adopted. Our results were discussed with recent observations and other theoretical models.

  15. Uncovering multiple Wolf-Rayet star clusters and the ionized ISM in Mrk 178: the closest metal-poor Wolf-Rayet H II galaxy

    NASA Astrophysics Data System (ADS)

    Kehrig, C.; Pérez-Montero, E.; Vílchez, J. M.; Brinchmann, J.; Kunth, D.; García-Benito, R.; Crowther, P. A.; Hernández-Fernández, J.; Durret, F.; Contini, T.; Fernández-Martín, A.; James, B. L.

    2013-07-01

    New integral field spectroscopy (IFS) has been obtained for the nearby metal-poor Wolf-Rayet (WR) galaxy Mrk 178 to examine the spatial correlation between its WR stars and the neighbouring ionized interstellar medium (ISM). The strength of the broad WR features and its low metallicity make Mrk 178 an intriguing object. We have detected the blue and red WR bumps in different locations across the field of view (˜300 pc × 230 pc) in Mrk 178. The study of the WR content has been extended, for the first time, beyond its brightest star-forming knot uncovering new WR star clusters. Using Large/Small Magellanic Cloud-template WR stars, we empirically estimate a minimum of ˜20 WR stars within the region sampled. Maps of the spatial distribution of the emission lines and of the physical-chemical properties of the ionized ISM have been created and analysed. Here, we refine the statistical methodology by Pérez-Montero et al. (2011) to probe the presence of variations in the ISM properties. An error-weighted mean of 12+log(O/H) = 7.72 ± 0.01 is taken as the representative oxygen abundance for Mrk 178. A localized N and He enrichment, spatially correlated with WR stars, is suggested by this analysis. Nebular He II λ4686 emission is shown to be spatially extended reaching well beyond the location of the WR stars. This spatial offset between WRs and He II emission can be explained based on the mechanical energy input into the ISM by the WR star winds, and does not rule out WR stars as the He II ionization source. We study systematic aperture effects on the detection and measurement of the WR features, using Sloan Digital Sky Survey spectra combined with the power of IFS. In this regard, the importance of targeting low metallicity nearby systems is discussed.

  16. Assessment of heavy metal contamination in water and sediments of Trepça and Sitnica rivers, Kosovo, using pollution indicators and multivariate cluster analysis.

    PubMed

    Ferati, Flora; Kerolli-Mustafa, Mihone; Kraja-Ylli, Arjana

    2015-06-01

    The concentrations of As, Cd, Cr, Co, Cu, Ni, Pb, and Zn in water and sediment samples from Trepça and Sitnica rivers were determined to assess the level of contamination. Six water and sediment samples were collected during the period from April to July 2014. Most of the water samples was found within the European and Kosovo permissible limits. The highest concentration of As, Cd, Pb, and Zn originates primarily from anthropogenic sources such discharge of industrial water from mining flotation and from the mine waste eroded from the river banks. Sediment contamination assessment was carried out using the pollution indicators such as contamination factor (CF), degree of contamination (Cd), modified degree of contamination (mCd), pollution load index (PLI), and geo-accumulation index (Igeo). The CF values for the investigated metals indicated a high contaminated nature of sediments, while the Cd values indicated a very high contamination degree of sediments. The mCd values indicate a high degree of contamination of Sitnica river sediment to ultrahigh degree of contamination of Trepça river sediment. The PLI values ranged from 1.89 to 14.1 which indicate that the heavy metal concentration levels in all investigated sites exceeded the background values and sediment quality guidelines. The average values of Igeo revealed the following ranking of intensity of heavy metal contamination of the Trepça and Sitnica river sediments: Cd > As > Pb > Zn > Cu > Co > Cr > Ni. Cluster analysis suggests that As, Cd, Cr, Co, Cu, Ni, Pb, and Zn are derived from anthropogenic sources, particularly discharges from mining flotation and erosion form waste from a zinc mine plant. In order to protect the sediments from further contamination, the designing of a monitoring network and reducing the anthropogenic discharges are suggested. PMID:25958086

  17. Maintaining adequate hydration and nutrition in adult enteral tube feeding.

    PubMed

    Dunn, Sasha

    2015-01-01

    Predicting the nutritional and fluid requirements of enterally-fed patients can be challenging and the practicalities of ensuring adequate delivery must be taken into consideration. Patients who are enterally fed can be more reliant on clinicians, family members and carers to meet their nutrition and hydration needs and identify any deficiencies, excesses or problems with delivery. Estimating a patient's requirements can be challenging due to the limitations of using predictive equations in the clinical setting. Close monitoring by all those involved in the patient's care, as well as regular review by a dietitian, is therefore required to balance the delivery of adequate feed and fluids to meet each patient's individual needs and prevent the complications of malnutrition and dehydration. Increasing the awareness of the signs of malnutrition and dehydration in patients receiving enteral tube feeding among those involved in a patient's care will help any deficiencies to be detected early on and rectified before complications occur. PMID:26087203

  18. Assessing juvenile sex offenders to determine adequate levels of supervision.

    PubMed

    Gerdes, K E; Gourley, M M; Cash, M C

    1995-08-01

    The present study analyzed the internal consistency of four inventories currently being used by probation officers in the state of Utah to determine adequate and efficacious supervision levels and placement for juvenile sex offenders. The internal consistency or reliability of the inventories ranged from moderate to good. Factor analysis was utilized to significantly increase the reliability of the four inventories by collapsing them into the following three factors: (a) Custodian's and Juvenile's Attitude Toward Intervention; (b) Offense Characteristics; and (c) Historical Risk Factors. These three inventories/factors explained 41.2% of the variance in the combined inventories' scores. Suggestions are made regarding the creation of an additional inventory. "Characteristics of the Victim" to account for more of the variance. In addition, suggestions as to how these inventories can be used by probation officers to make objective and consistent decisions about adequate supervision levels and placement for juvenile sex offenders are discussed. PMID:7583754

  19. Electrochemical properties of small clusters of metal atoms and their role in the surface-enhanced Raman scattering

    SciTech Connect

    Plieth, W.J.

    1981-06-01

    Starting with equations for the shift of the reversible redox potential of small metal particles with size, the electrochemical properties of these particles are discussed. Approximate equations are given for the relationship between the particle size and the surface charge, the potential of zero charge, the surface potential, work function and quantities related to this function. The influence of these properties on redox reactions, electrosorption and chemi-sorption are discussed. The results are used to explain experimental observation in connection with the surface enhanced Raman effect.

  20. Simulation and modeling of the electronic structure of GaAs damage clusters

    NASA Astrophysics Data System (ADS)

    Moussa, Jonathan E.; Foiles, Stephen M.; Schultz, Peter A.

    2013-03-01

    In an effort to build a stronger microscopic foundation for radiation damage models in gallium arsenide (GaAs), the electronic properties of radiation-induced damage clusters are studied with atomistic simulations. Molecular dynamics simulations are used to access the time and length scales required for direct simulation of a collision cascade, and density functional theory simulations are used to calculate the electronic properties of isolated damaged clusters that are extracted from these cascades. To study the physical properties of clusters, we analyze the statistics of a randomly generated ensemble of damage clusters because no single cluster adequately represents this class of defects. The electronic properties of damage clusters are accurately described by a classical model of the electrical charging of a semiconducting sphere embedded in a uniform dielectric. The effective band gap of the cluster depends on the degree of internal structural damage, and the gap closes to form a metal in the high-damage limit. We estimate the Fermi level of this metallic state, which corresponds to high-energy amorphous GaAs, to be 0.46±0.07 eV above the valence band edge of crystalline GaAs.