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Sample records for nanoscale metal clusters

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

    NASA Astrophysics Data System (ADS)

    Staikov, Georgi

    2016-07-01

    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.

  2. Nanoscale metal-organic materials.

    PubMed

    Carné, Arnau; Carbonell, Carlos; Imaz, Inhar; Maspoch, Daniel

    2011-01-01

    Metal-organic materials are found to be a fascinating novel class of functional nanomaterials. The limitless combinations between inorganic and organic building blocks enable researchers to synthesize 0- and 1-D metal-organic discrete nanostructures with varied compositions, morphologies and sizes, fabricate 2-D metal-organic thin films and membranes, and even structure them on surfaces at the nanometre length scale. In this tutorial review, the synthetic methodologies for preparing these miniaturized materials as well as their potential properties and future applications are discussed. This review wants to offer a panoramic view of this embryonic class of nanoscale materials that will be of interest to a cross-section of researchers working in chemistry, physics, medicine, nanotechnology, materials chemistry, etc., in the next years.

  3. Nanoscale fullerene compression of an yttrium carbide cluster.

    PubMed

    Zhang, Jianyuan; Fuhrer, Tim; Fu, Wujun; Ge, Jiechao; Bearden, Daniel W; Dallas, Jerry; Duchamp, James; Walker, Kenneth; Champion, Hunter; Azurmendi, Hugo; Harich, Kim; Dorn, Harry C

    2012-05-23

    The nanoscale parameters of metal clusters and lattices have a crucial influence on the macroscopic properties of materials. Herein, we provide a detailed study on the size and shape of isolated yttrium carbide clusters in different fullerene cages. A family of diyttrium endohedral metallofullerenes with the general formula of Y(2)C(2n) (n = 40-59) are reported. The high field (13)C nuclear magnetic resonance (NMR) and density functional theory (DFT) methods are employed to examine this yttrium carbide cluster in certain family members, Y(2)C(2)@D(5)(450)-C(100), Y(2)C(2)@D(3)(85)-C(92), Y(2)C(2)@C(84), Y(2)C(2)@C(3v)(8)-C(82), and Y(2)C(2)@C(s)(6)-C(82). The results of this study suggest that decreasing the size of a fullerene cage with the same (Y(2)C(2))(4+) cluster results in nanoscale fullerene compression (NFC) from a nearly linear stretched geometry to a constrained "butterfly" structure. The (13)C NMR chemical shift and scalar (1)J(YC) coupling parameters provide a very sensitive measure of this NFC effect for the (Y(2)C(2))(4+) cluster. The crystal structural parameters of a previously reported metal carbide, Y(2)C(3) are directly compared to the (Y(2)C(2))(4+) cluster in the current metallofullerene study.

  4. Label-free colorimetric detection of mercury via Hg2+ ions-accelerated structural transformation of nanoscale metal-oxo clusters

    PubMed Central

    Chen, Kun; She, Shan; Zhang, Jiangwei; Bayaguud, Aruuhan; Wei, Yongge

    2015-01-01

    Mercury and its compounds are known to be extremely toxic but widely distributed in environment. Although many works have been reported to efficiently detect mercury, development of simple and convenient sensors is still longed for quick analyzing mercury in water. In this work, a nanoscale metal-oxo cluster, (n-Bu4N)2[Mo5NaO13(OCH3)4(NO)], (MLPOM), organically-derivatized from monolacunary Lindqvist-type polyoxomolybdate, is found to specifically react with Hg2+ in methanol/water via structural transformation. The MLPOM methanol solution displays a color change from purple to brown within seconds after being mixed with an aqueous solution containing Hg2+. By comparing the structure of polyoxomolybdate before and after reaction, the color change is revealed to be the essentially structural transformation of MLPOM accelerated by Hg2+. Based on this discovery, MLPOM could be utilized as a colorimetric sensor to sense the existence of Hg2+, and a simple and label-free method is developed to selectively detect aqueous Hg2+. Furthermore, the colorimetric sensor has been applied to indicating mercury contamination in industrial sewage. PMID:26559602

  5. Electrochemical dynamics of nanoscale metallic inclusions in dielectrics.

    PubMed

    Yang, Yuchao; Gao, Peng; Li, Linze; Pan, Xiaoqing; Tappertzhofen, Stefan; Choi, ShinHyun; Waser, Rainer; Valov, Ilia; Lu, Wei D

    2014-06-23

    Nanoscale metal inclusions in or on solid-state dielectrics are an integral part of modern electrocatalysis, optoelectronics, capacitors, metamaterials and memory devices. The properties of these composite systems strongly depend on the size, dispersion of the inclusions and their chemical stability, and are usually considered constant. Here we demonstrate that nanoscale inclusions (for example, clusters) in dielectrics dynamically change their shape, size and position upon applied electric field. Through systematic in situ transmission electron microscopy studies, we show that fundamental electrochemical processes can lead to universally observed nucleation and growth of metal clusters, even for inert metals like platinum. The clusters exhibit diverse dynamic behaviours governed by kinetic factors including ion mobility and redox rates, leading to different filament growth modes and structures in memristive devices. These findings reveal the microscopic origin behind resistive switching, and also provide general guidance for the design of novel devices involving electronics and ionics.

  6. Properties of nanoscale metal hydrides.

    PubMed

    Fichtner, Maximilian

    2009-05-20

    Nanoscale hydride particles may exhibit chemical stabilities which differ from those of a macroscopic system. The stabilities are mainly influenced by a surface energy term which contains size-dependent values of the surface tension, the molar volume and an additional term which takes into account a potential reduction of the excess surface energy. Thus, the equilibrium of a nanoparticular hydride system may be shifted to the hydrogenated or to the dehydrogenated side, depending on the size and on the prefix of the surface energy term of the hydrogenated and dehydrogenated material. Additional complexity appears when solid-state reactions of complex hydrides are considered and phase segregation has to be taken into account. In such a case the reversibility of complex hydrides may be reduced if the nanoparticles are free standing on a surface. However, it may be enhanced if the system is enclosed by a nanoscale void which prevents the reaction partners on the dehydrogenated side from diffusing away from each other. Moreover, the generally enhanced diffusivity in nanocrystalline systems may lower the kinetic barriers for the material's transformation and, thus, facilitate hydrogen absorption and desorption. PMID:19420657

  7. Solvation at nanoscale: Alkali-halides in water clusters

    SciTech Connect

    Partanen, Leena; Mikkelae, Mikko-Heikki; Huttula, Marko; Tchaplyguine, Maxim; Zhang Chaofan; Andersson, Tomas; Bjoerneholm, Olle

    2013-01-28

    The solvation of alkali-halides in water clusters at nanoscale is studied by photoelectron spectroscopy using synchrotron radiation. The Na 2p, K 3p, Cl 2p, Br 3d, and I 4d core level binding energies have been measured for salt-containing water clusters. The results have been compared to those of alkali halide clusters and the dilute aqueous salt solutions. It is found that the alkali halides dissolve in small water clusters as ions.

  8. Nanoscale growth twins in sputtered metal films

    SciTech Connect

    Misra, Amit; Anderoglu, Osman; Hoagland, Richard G; Zhang, X

    2008-01-01

    We review recent studies on the mechanical properties of sputtered Cu and 330 stainless steel films with {l_brace}1 1 1{r_brace} nanoscale growth twins preferentially oriented perpendicular to growth direction. The mechanisms of formation of growth twins during sputtering and the deformation mechanisms that enable usually high strengths in nanotwinned structures are highlighted. Growth twins in sputtered films possess good thermal stability at elevated temperature, providing an approach to extend the application of high strength nanostructured metals to higher temperatures.

  9. Structure of nanoscale gas bubbles in metals

    SciTech Connect

    Caro, A. Schwen, D.; Martinez, E.

    2013-11-18

    A usual way to estimate the amount of gas in a bubble inside a metal is to assume thermodynamic equilibrium, i.e., the gas pressure P equals the capillarity force 2γ/R, with γ the surface energy of the host material and R the bubble radius; under this condition there is no driving force for vacancies to be emitted or absorbed by the bubble. In contrast to the common assumption that pressure inside a gas or fluid bubble is constant, we show that at the nanoscale this picture is no longer valid. P and density can no longer be defined as global quantities determined by an equation of state (EOS), but they become functions of position because the bubble develops a core-shell structure. We focus on He in Fe and solve the problem using both continuum mechanics and empirical potentials to find a quantitative measure of this effect. We point to the need of redefining an EOS for nanoscale gas bubbles in metals, which can be obtained via an average pressure inside the bubble. The resulting EOS, which is now size dependent, gives pressures that differ by a factor of two or more from the original EOS for bubble diameters of 1 nm and below.

  10. Instabilities of structured metal films on nanoscale

    NASA Astrophysics Data System (ADS)

    Dong, Nanyi; Wu, Yueying; Fowlkes, Jason; Rack, Philip; Kondic, Lou

    2014-11-01

    We consider instabilities of metal films on nanoscale, with particular focus on the interplay between the initial geometry and instability development. In experiments, metal films are deposited lithographically, allowing for precise control of the initial shape, and then exposed to laser pulses that liquefy them. The considered geometries involve various shapes (cylinders or prisms) superimposed on top of a flat film. We consider this problem within the framework of the long wave (lubrication) theory. Our simulations show that the main features of the instability development could be captured, as long as destabilizing liquid-solid interaction is considered in the model. We conclude by discussing the influence of the distance between the imposed perturbations, their shape, as well as experimental noise on the evolution. Supported by NSF Grant No. CBET-1235710.

  11. Nanoscale Structure, Dynamics, and Aging Behavior of Metallic Glass Thin Films.

    PubMed

    Burgess, J A J; Holt, C M B; Luber, E J; Fortin, D C; Popowich, G; Zahiri, B; Concepcion, P; Mitlin, D; Freeman, M R

    2016-01-01

    Scanning tunnelling microscopy observations resolve the structure and dynamics of metallic glass Cu100-xHfx films and demonstrate scanning tunnelling microscopy control of aging at a metallic glass surface. Surface clusters exhibit heterogeneous hopping dynamics. Low Hf concentration films feature an aged surface of larger, slower clusters. Argon ion-sputtering destroys the aged configuration, yielding a surface in constant fluctuation. Scanning tunnelling microscopy can locally restore the relaxed state, allowing for nanoscale lithographic definition of aged sections. PMID:27498698

  12. Nanoscale Structure, Dynamics, and Aging Behavior of Metallic Glass Thin Films

    PubMed Central

    Burgess, J. A. J.; Holt, C. M. B.; Luber, E. J.; Fortin, D. C.; Popowich, G.; Zahiri, B.; Concepcion, P.; Mitlin, D.; Freeman, M. R.

    2016-01-01

    Scanning tunnelling microscopy observations resolve the structure and dynamics of metallic glass Cu100−xHfx films and demonstrate scanning tunnelling microscopy control of aging at a metallic glass surface. Surface clusters exhibit heterogeneous hopping dynamics. Low Hf concentration films feature an aged surface of larger, slower clusters. Argon ion-sputtering destroys the aged configuration, yielding a surface in constant fluctuation. Scanning tunnelling microscopy can locally restore the relaxed state, allowing for nanoscale lithographic definition of aged sections. PMID:27498698

  13. Nanoscale Structure, Dynamics, and Aging Behavior of Metallic Glass Thin Films

    NASA Astrophysics Data System (ADS)

    Burgess, J. A. J.; Holt, C. M. B.; Luber, E. J.; Fortin, D. C.; Popowich, G.; Zahiri, B.; Concepcion, P.; Mitlin, D.; Freeman, M. R.

    2016-08-01

    Scanning tunnelling microscopy observations resolve the structure and dynamics of metallic glass Cu100-xHfx films and demonstrate scanning tunnelling microscopy control of aging at a metallic glass surface. Surface clusters exhibit heterogeneous hopping dynamics. Low Hf concentration films feature an aged surface of larger, slower clusters. Argon ion-sputtering destroys the aged configuration, yielding a surface in constant fluctuation. Scanning tunnelling microscopy can locally restore the relaxed state, allowing for nanoscale lithographic definition of aged sections.

  14. Nanoscale Cluster Detection in Massive Atom Probe Tomography Data

    SciTech Connect

    Seal, Sudip K; Yoginath, Srikanth B; Miller, Michael K

    2014-01-01

    Recent technological advances in atom probe tomography (APT) have led to unprecedented data acquisition capabilities that routinely generate data sets containing hundreds of millions of atoms. Detecting nanoscale clusters of different atom types present in these enormous amounts of data and analyzing their spatial correlations with one another are fundamental to understanding the structural properties of the material from which the data is derived. Extant algorithms for nanoscale cluster detection do not scale to large data sets. Here, a scalable, CUDA-based implementation of an autocorrelation algorithm is presented. It isolates spatial correlations amongst atomic clusters present in massive APT data sets in linear time using a linear amount of storage. Correctness of the algorithm is demonstrated using large synthetically generated data with known spatial distributions. Benefits and limitations of using GPU-acceleration for autocorrelation-based APT data analyses are presented with supporting performance results on data sets with up to billions of atoms. To our knowledge, this is the first nanoscale cluster detection algorithm that scales to massive APT data sets and executes on commodity hardware.

  15. On nanoscale metallic iron for groundwater remediation.

    PubMed

    Noubactep, C; Caré, S

    2010-10-15

    This communication challenges the concept that nanoscale metallic iron (nano-Fe(0)) is a strong reducing agents for contaminant reductive transformation. It is shown that the inherent relationship between contaminant removal and Fe(0) oxidative dissolution which is conventionally attributed to contaminant reduction by nano-Fe(0) (direct reduction) could equally be attributed to contaminant removal by adsorption and co-precipitation. For reducible contaminants, indirect reduction by adsorbed Fe(II) or adsorbed H produced by corroding iron (indirect reduction) is even a more probable reaction path. As a result, the contaminant removal efficiency is strongly dependent on the extent of iron corrosion which is larger for nano-Fe(0) than for micro-Fe(0) in the short term. However, because of the increased reactivity, nano-Fe(0) will deplete in the short term. No more source of reducing agents (Fe(II), H and H(2)) will be available in the system. Therefore, the efficiency of nano-Fe(0) as a reducing agent for environmental remediation is yet to be demonstrated.

  16. Nanoscale Metal Oxide Semiconductors for Gas Sensing

    NASA Technical Reports Server (NTRS)

    Hunter, Gary W.; Evans, Laura; Xu, Jennifer C.; VanderWal, Randy L.; Berger, Gordon M.; Kulis, Michael J.

    2011-01-01

    A report describes the fabrication and testing of nanoscale metal oxide semiconductors (MOSs) for gas and chemical sensing. This document examines the relationship between processing approaches and resulting sensor behavior. This is a core question related to a range of applications of nanotechnology and a number of different synthesis methods are discussed: thermal evaporation- condensation (TEC), controlled oxidation, and electrospinning. Advantages and limitations of each technique are listed, providing a processing overview to developers of nanotechnology- based systems. The results of a significant amount of testing and comparison are also described. A comparison is made between SnO2, ZnO, and TiO2 single-crystal nanowires and SnO2 polycrystalline nanofibers for gas sensing. The TECsynthesized single-crystal nanowires offer uniform crystal surfaces, resistance to sintering, and their synthesis may be done apart from the substrate. The TECproduced nanowire response is very low, even at the operating temperature of 200 C. In contrast, the electrospun polycrystalline nanofiber response is high, suggesting that junction potentials are superior to a continuous surface depletion layer as a transduction mechanism for chemisorption. Using a catalyst deposited upon the surface in the form of nanoparticles yields dramatic gains in sensitivity for both nanostructured, one-dimensional forms. For the nanowire materials, the response magnitude and response rate uniformly increase with increasing operating temperature. Such changes are interpreted in terms of accelerated surface diffusional processes, yielding greater access to chemisorbed oxygen species and faster dissociative chemisorption, respectively. Regardless of operating temperature, sensitivity of the nanofibers is a factor of 10 to 100 greater than that of nanowires with the same catalyst for the same test condition. In summary, nanostructure appears critical to governing the reactivity, as measured by electrical

  17. Nanoscale Imaging of Epidermal Growth Factor Receptor Clustering

    PubMed Central

    Abulrob, Abedelnasser; Lu, Zhengfang; Baumann, Ewa; Vobornik, Dusan; Taylor, Rod; Stanimirovic, Danica; Johnston, Linda J.

    2010-01-01

    The development of some solid tumors is associated with overexpression of the epidermal growth factor receptor (EGFR) and often correlates with poor prognosis. Near field scanning optical microscopy, a technique with subdiffraction-limited optical resolution, was used to examine the influence of two inhibitors (the chimeric 225 antibody and tyrosine phosphorylation inhibitor AG1478) on the nanoscale clustering of EGFR in HeLa cells. The EGFR is organized in small clusters, average diameter of 150 nm, on the plasma membrane for both control and EGF-treated cells. The numbers of receptors in individual clusters vary from as few as one or two proteins to greater than 100. Both inhibitors yield an increased cluster density and an increase in the fraction of clusters with smaller diameters and fewer receptors. Exposure to AG1478 also decreases the fraction of EGFR that colocalizes with both rafts and caveolae. EGF stimulation results in a significant loss of the full-length EGFR from the plasma membrane with the concomitant appearance of low molecular mass proteolytic products. By contrast, AG1478 reduces the level of EGFR degradation. Changes in receptor clustering provide one mechanism for regulating EGFR signaling and are relevant to the design of strategies for therapeutic interventions based on modulating EGFR signaling. PMID:19959837

  18. Cluster-assembled metallic glasses

    NASA Astrophysics Data System (ADS)

    Kartouzian, Aras

    2013-07-01

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

  19. Cluster-assembled metallic glasses.

    PubMed

    Kartouzian, Aras

    2013-07-30

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

  20. Reverse micelle synthesis of nanoscale metal containing catalysts

    SciTech Connect

    Darab, J.G.; Fulton, J.L.; Linehan, J.C.

    1993-03-01

    The need for morphological control during the synthesis of catalyst precursor powders is generally accepted to be important. In the liquefaction of coal, for example, iron-bearing catalyst precursor particles containing individual crystallites with diameters in the 1-100 nanometer range are believed to achieve good dispersion through out the coal-solvent slurry during liquefaction 2 runs and to undergo chemical transformations to catalytically active iron sulfide phases. The production of the nanoscale powders described here employs the confining spherical microdomains comprising the aqueous phase of a modified reverse micelle (MRM) microemulsion system as nanoscale reaction vessels in which polymerization, electrochemical reduction and precipitation of solvated salts can occur. The goal is to take advantage of the confining nature of micelles to kinetically hinder transformation processes which readily occur in bulk aqueous solution in order to control the morphology and phase of the resulting powder. We have prepared a variety of metal, alloy, and metal- and mixed metal-oxide nanoscale powders from appropriate MRM systems. Examples of nanoscale powders produced include Co, Mo-Co, Ni{sub 3}Fe, Ni, and various oxides and oxyhydroxides of iron. Here, we discuss the preparation and characterization of nickel metal (with a nickel oxide surface layer) and iron oxyhydroxide MRM nanoscale powders. We have used extended x-ray absorption fine structure (EXAFS) spectroscopy to study the chemical polymerization process in situ, x-ray diffraction (XRD), scanning and transmission electron microcroscopies (SEM and TEM), elemental analysis and structural modelling to characterize the nanoscale powders produced. The catalytic activity of these powders is currently being studied.

  1. Instability of nanoscale metallic particles under electron irradiation in TEM

    NASA Astrophysics Data System (ADS)

    Chen, X. Y.; Zhang, S. G.; Xia, M. X.; Li, J. G.

    2016-03-01

    The stability of nano metallic glass under electron beam in transmission electron microscope (TEM) was investigated. The most common voltage of TEM used in metallic materials characterization was either 200 kV or 300 kV. Both situations were investigated in this work. An amorphous metallic particle with a dimension of a few hundred nanometers was tested under 300 keV electron irradiation. New phase decomposed from the parent phase was observed. Moreover, a crystal particle with the same composition and dimension was tested under 200 keV irradiation. Decomposition process also occurred in this situation. Besides, crystal orientation modification was observed during irradiation. These results proved that the electron beam in TEM have an effect on the stability of nanoscale samples during long time irradiation. Atomic displacement was induced and diffusion was enhanced by electron irradiation. Thus, artifacts would be induced when a nanoscale metallic sample was characterized in TEM.

  2. Residual stress within nanoscale metallic multilayer systems during thermal cycling

    SciTech Connect

    Economy, David Ross; Cordill, Megan Jo; Payzant, E. Andrew; Kennedy, Marian S.

    2015-09-21

    Projected applications for nanoscale metallic multilayers will include wide temperature ranges. Since film residual stress has been known to alter system reliability, stress development within new film structures with high interfacial densities should be characterized to identify potential long-term performance barriers. To understand factors contributing to thermal stress evolution within nanoscale metallic multilayers, stress in Cu/Nb systems adhered to Si substrates was calculated from curvature measurements collected during cycling between 25 °C and 400 °C. Additionally, stress within each type of component layers was calculated from shifts in the primary peak position from in-situ heated X-ray diffraction. The effects of both film architecture (layer thickness) and layer order in metallic multilayers were tracked and compared with monolithic Cu and Nb films. Analysis indicated that the thermoelastic slope of nanoscale metallic multilayer films depends on thermal expansion mismatch, elastic modulus of the components, and also interfacial density. The layer thickness (i.e. interfacial density) affected thermoelastic slope magnitude while layer order had minimal impact on stress responses after the initial thermal cycle. When comparing stress responses of monolithic Cu and Nb films to those of the Cu/Nb systems, the nanoscale metallic multilayers show a similar increase in stress above 200 °C to the Nb monolithic films, indicating that Nb components play a larger role in stress development than Cu. Local stress calculations from X-ray diffraction peak shifts collected during heating reveal that the component layers within a multilayer film respond similarly to their monolithic counterparts.

  3. Residual stress within nanoscale metallic multilayer systems during thermal cycling

    DOE PAGES

    Economy, David Ross; Cordill, Megan Jo; Payzant, E. Andrew; Kennedy, Marian S.

    2015-09-21

    Projected applications for nanoscale metallic multilayers will include wide temperature ranges. Since film residual stress has been known to alter system reliability, stress development within new film structures with high interfacial densities should be characterized to identify potential long-term performance barriers. To understand factors contributing to thermal stress evolution within nanoscale metallic multilayers, stress in Cu/Nb systems adhered to Si substrates was calculated from curvature measurements collected during cycling between 25 °C and 400 °C. Additionally, stress within each type of component layers was calculated from shifts in the primary peak position from in-situ heated X-ray diffraction. The effects ofmore » both film architecture (layer thickness) and layer order in metallic multilayers were tracked and compared with monolithic Cu and Nb films. Analysis indicated that the thermoelastic slope of nanoscale metallic multilayer films depends on thermal expansion mismatch, elastic modulus of the components, and also interfacial density. The layer thickness (i.e. interfacial density) affected thermoelastic slope magnitude while layer order had minimal impact on stress responses after the initial thermal cycle. When comparing stress responses of monolithic Cu and Nb films to those of the Cu/Nb systems, the nanoscale metallic multilayers show a similar increase in stress above 200 °C to the Nb monolithic films, indicating that Nb components play a larger role in stress development than Cu. Local stress calculations from X-ray diffraction peak shifts collected during heating reveal that the component layers within a multilayer film respond similarly to their monolithic counterparts.« less

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

    PubMed

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

    2015-03-24

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

  5. On Charged Insulated Metallic Clusters

    NASA Astrophysics Data System (ADS)

    Dietrich, K.; Garny, M.; Pomorski, K.

    We determine the wavefunctions and eigen-values of electrons bound to a positively charged mesoscopic metallic cluster covered by an insulating surface layer. The radius of the metal core and the thickness of the insulating surface layer are of the order of a couple of Ångström. We study in particular the electromagnetic decay of externally located electrons into unoccupied internally located states which exhibits a resonance behaviour. This resonance structure has the consequence that the lifetime of the "mesoscopic atoms" may vary by up to 6 orders of magnitude depending on the values of the parameters (from sec to years).

  6. Nanoconstruction by welding individual metallic nanowires together using nanoscale solder

    NASA Astrophysics Data System (ADS)

    Peng, Y.; Cullis, A. G.; Inkson, B. J.

    2010-07-01

    This work presents a new bottom-up nanowelding technique enabling building blocks to be assembled and welded together into complex 3D nanostructures using nanovolumes of metal solder. The building blocks of gold nanowires, (Co72Pt28/Pt)n multilayer nanowires, and nanosolder Sn99Au1 alloy nanowires were successfully fabricated by a template technique. Individual metallic nanowires were picked up and assembled together. Conductive nanocircuits were then welded together using similar or dissimilar nanosolder material. At the weld sites, nanoscale volumes of a chosen metal are deposited using nanosolder of a sacrificial nanowire, which ensures that the nanoobjects to be bonded retain their structural integrity. The whole nanowelding process is clean, controllable and reliable, and ensures both mechanically strong and electrically conductive contacts.

  7. Tunable all-optical plasmonic rectifier in nanoscale metal-insulator-metal waveguides.

    PubMed

    Xu, Yi; Wang, Xiaomeng; Deng, Haidong; Guo, Kangxian

    2014-10-15

    We propose a tunable all-optical plasmonic rectifier based on the nonlinear Fano resonance in a metal-insulator-metal plasmonic waveguide and cavities coupling system. We develop a theoretical model based on the temporal coupled-mode theory to study the device physics of the nanoscale rectifier. We further demonstrate via the finite difference time domain numerical experiment that our idea can be realized in a plasmonic system with an ultracompact size of ~120×800  nm². The tunable plasmonic rectifier could facilitate the all-optical signal processing in nanoscale.

  8. Improving proton therapy by metal-containing nanoparticles: nanoscale insights

    PubMed Central

    Schlathölter, Thomas; Eustache, Pierre; Porcel, Erika; Salado, Daniela; Stefancikova, Lenka; Tillement, Olivier; Lux, Francois; Mowat, Pierre; Biegun, Aleksandra K; van Goethem, Marc-Jan; Remita, Hynd; Lacombe, Sandrine

    2016-01-01

    The use of nanoparticles to enhance the effect of radiation-based cancer treatments is a growing field of study and recently, even nanoparticle-induced improvement of proton therapy performance has been investigated. Aiming at a clinical implementation of this approach, it is essential to characterize the mechanisms underlying the synergistic effects of nanoparticles combined with proton irradiation. In this study, we investigated the effect of platinum- and gadolinium-based nanoparticles on the nanoscale damage induced by a proton beam of therapeutically relevant energy (150 MeV) using plasmid DNA molecular probe. Two conditions of irradiation (0.44 and 3.6 keV/μm) were considered to mimic the beam properties at the entrance and at the end of the proton track. We demonstrate that the two metal-containing nanoparticles amplify, in particular, the induction of nanosize damages (>2 nm) which are most lethal for cells. More importantly, this effect is even more pronounced at the end of the proton track. This work gives a new insight into the underlying mechanisms on the nanoscale and indicates that the addition of metal-based nanoparticles is a promising strategy not only to increase the cell killing action of fast protons, but also to improve tumor targeting. PMID:27143877

  9. Actin Mediates the Nanoscale Membrane Organization of the Clustered Membrane Protein Influenza Hemagglutinin

    PubMed Central

    Gudheti, Manasa V.; Curthoys, Nikki M.; Gould, Travis J.; Kim, Dahan; Gunewardene, Mudalige S.; Gabor, Kristin A.; Gosse, Julie A.; Kim, Carol H.; Zimmerberg, Joshua; Hess, Samuel T.

    2013-01-01

    The influenza viral membrane protein hemagglutinin (HA) is required at high concentrations on virion and host-cell membranes for infectivity. Because the role of actin in membrane organization is not completely understood, we quantified the relationship between HA and host-cell actin at the nanoscale. Results obtained using superresolution fluorescence photoactivation localization microscopy (FPALM) in nonpolarized cells show that HA clusters colocalize with actin-rich membrane regions (ARMRs). Individual molecular trajectories in live cells indicate restricted HA mobility in ARMRs, and actin disruption caused specific changes to HA clustering. Surprisingly, the actin-binding protein cofilin was excluded from some regions within several hundred nanometers of HA clusters, suggesting that HA clusters or adjacent proteins within the same clusters influence local actin structure. Thus, with the use of imaging, we demonstrate a dynamic relationship between glycoprotein membrane organization and the actin cytoskeleton at the nanoscale. PMID:23708358

  10. Cluster-assembled cubic zirconia films with tunable and stable nanoscale morphology against thermal annealing

    NASA Astrophysics Data System (ADS)

    Borghi, F.; Sogne, E.; Lenardi, C.; Podestà, A.; Merlini, M.; Ducati, C.; Milani, P.

    2016-08-01

    Nanostructured zirconium dioxide (zirconia) films are very promising for catalysis and biotechnological applications: a precise control of the interfacial properties of the material at different length scales and, in particular, at the nanoscale, is therefore necessary. Here, we present the characterization of cluster-assembled zirconia films produced by supersonic cluster beam deposition possessing cubic structure at room temperature and controlled nanoscale morphology. We characterized the effect of thermal annealing in reducing and oxidizing conditions on the crystalline structure, grain dimensions, and topography. We highlight the mechanisms of film growth and phase transitions, which determine the observed interfacial morphological properties and their resilience against thermal treatments.

  11. Simple Methods for Production of Nanoscale Metal Oxide Films from Household Sources

    ERIC Educational Resources Information Center

    Campbell, Dean J.; Baliss, Michelle S.; Hinman, Jordan J.; Ziegenhorn, John W.; Andrews, Mark J.; Stevenson, Keith J.

    2013-01-01

    Production of thin metal oxide films was recently explored as part of an outreach program with a goal of producing nanoscale structures with household items. Household items coated with various metals or titanium compounds can be heated to produce colorful films with nanoscale thicknesses. As part of a materials chemistry laboratory experiment…

  12. Enhanced light-matter interaction at nanoscale by utilizing high-aspect-ratio metallic gratings.

    PubMed

    Yang, Shang-Hua; Jarrahi, Mona

    2013-09-15

    We report the design, fabrication, and experimental characterization of high-aspect-ratio metallic gratings integrated with nanoscale semiconductor structures, which enable efficient light-matter interaction at the nanoscale over interaction lengths as long as two times of the effective optical wavelength. The efficient light-matter interaction at the nanoscale is enabled by excitation of the guided modes of subwavelength slab waveguides formed by the high-aspect-ratio metallic gratings. By controlling the height of the high-aspect-ratio gratings, the wavelength of the guided modes through the nanoscale semiconductor structures is determined.

  13. The mechanical behavior of nanoscale metallic multilayers: A survey

    NASA Astrophysics Data System (ADS)

    Zhou, Q.; Xie, J. Y.; Wang, F.; Huang, P.; Xu, K. W.; Lu, T. J.

    2015-06-01

    The mechanical behavior of nanoscale metallic multilayers (NMMs) has attracted much attention from both scientific and practical views. Compared with their monolithic counterparts, the large number of interfaces existing in the NMMs dictates the unique behavior of this special class of structural composite materials. While there have been a number of reviews on the mechanical mechanism of microlaminates, the rapid development of nanotechnology brought a pressing need for an overview focusing exclusively on a property-based definition of the NMMs, especially their size-dependent microstructure and mechanical performance. This article attempts to provide a comprehensive and up-to-date review on the microstructure, mechanical property and plastic deformation physics of NMMs. We hope this review could accomplish two purposes: (1) introducing the basic concepts of scaling and dimensional analysis to scientists and engineers working on NMM systems, and (2) providing a better understanding of interface behavior and the exceptional qualities the interfaces in NMMs display at atomic scale.

  14. 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.

  15. Negative ion photoelectron spectroscopy of metal clusters, metal-organic clusters, metal oxides, and metal-doped silicon clusters

    NASA Astrophysics Data System (ADS)

    Zheng, Weijun

    The techniques of time-of-flight mass spectrometry and negative ion photoelectron spectroscopy were utilized to study metal clusters (Mgn -, Znn-, Can -, Mnn-, CuAln -, LiAln-, and NmSn n-), metal-organic complexes (Tin(benzene) m-, Fn(benzene)m- , Nin(benzene)m-), metal oxides(AuO-, PtO-, TaOn -, HfO2-, and MnnO -), and metal-doped semiconductor clusters (CrSin -, GdmSin- and HoSi n-). The study of magnesium and zinc cluster anions shows that they have magic numbers at size 9, 19 and 34, and the closures and reopenings of the s-p band gap are related to the mass spectra magic numbers. The evolution of electronic structure in Can clusters resembles that of Mgn - and Znn- with band gap closure and reopening. However, the electronic structures Can- clusters are more complicated and the magic numbers are different from those of Mgn- and Znn -. That might due to the involvement of calcium's empty d orbitals. In Mn clusters, a dramatic change of electronic structure was observed at Mn5-. The transition of metallic and magnetic properties is strongly related to the s-d hybridization. The photoelectron study of LiAln- is consistent with theoretical predictions, which described LiAl13 as alkali-halide-like ionic entity, Li+(Al13)-. The results of CuAln- show that copper atom might occupy interior position in these clusters. The results of Nam Snn- implied that Na4Sn 4 and NaSn5- could be described as (Na +)4Sn44- and (Na +)Sn52-, respectively. The formation of these species indicates the existence of Zintl phase structure in the gas phase. Tin(Bz)n+1- clusters have multiple-decker sandwich structures with each titanium atom located between two parallel benzene rings. The structures of Fen(Bz)m - and Nin(Bz)m- are characterized with a metal cluster core caged by benzene molecules. The information for the electronic states of PtO, AuO, and TaOn (n = 1--3) were obtained from the photoelectron spectra of their corresponding negative ions. The coincidence between electron

  16. Adamantyl- and Furanyl-Protected Nanoscale Silver Sulfide Clusters.

    PubMed

    Bestgen, Sebastian; Yang, Xiaoxun; Issac, Ibrahim; Fuhr, Olaf; Roesky, Peter W; Fenske, Dieter

    2016-07-11

    The silver salts of 1-adamantanethiol (AdSH) and furan-2-ylmethanethiol (FurCH2 SH) were successfully applied as building blocks for ligand-protected Ag2 S nanoclusters. The reaction of the silver thiolates [AgSAd]x and [AgSCH2 Fur]x with S(SiMe3 )2 and 1,5-bis(diphenylphosphino)pentane (dpppt) afforded three different clusters with 58, 94 and, 190 silver atoms. The intensely colored compounds [Ag58 S13 (SAd)32 ] (1), [Ag94 S34 (SAd)26 (dpppt)6 ] (2), and [Ag190 S58 (SCH2 Fur)74 (dpppt)8 ] (3) were structurally characterized by single-crystal X-ray diffraction and exhibit different cluster core geometries and ligand shells. The diameters of the well-defined sphere-shaped nanoclusters range from 2.2 nm to 3.5 nm. PMID:27297587

  17. Nanoscale Metallic Iron for Environmental Remediation: Prospects and Limitations.

    PubMed

    Noubactep, Chicgoua; Caré, Sabine; Crane, Richard

    2012-03-01

    The amendment of the subsurface with nanoscale metallic iron particles (nano-Fe(0)) has been discussed in the literature as an efficient in situ technology for groundwater remediation. However, the introduction of this technology was controversial and its efficiency has never been univocally established. This unsatisfying situation has motivated this communication whose objective was a comprehensive discussion of the intrinsic reactivity of nano-Fe(0) based on the contemporary knowledge on the mechanism of contaminant removal by Fe(0) and a mathematical model. It is showed that due to limitations of the mass transfer of nano-Fe(0) to contaminants, available concepts cannot explain the success of nano-Fe(0) injection for in situ groundwater remediation. It is recommended to test the possibility of introducing nano-Fe(0) to initiate the formation of roll-fronts which propagation would induce the reductive transformation of both dissolved and adsorbed contaminants. Within a roll-front, Fe(II) from nano-Fe(0) is the reducing agent for contaminants. Fe(II) is recycled by biotic or abiotic Fe(III) reduction. While the roll-front concept could explain the success of already implemented reaction zones, more research is needed for a science-based recommendation of nano-Fe(0) for subsurface treatment by roll-fronts.

  18. 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)

  19. Nanoscale strengthening mechanisms in metallic thin film systems

    NASA Astrophysics Data System (ADS)

    Schoeppner, Rachel Lynn

    Nano-scale strengthening mechanisms for thin films were investigated for systems governed by two different strengthening techniques: nano-laminate strengthening and oxide dispersion strengthening. Films were tested under elevated temperature conditions to investigate changes in deformation mechanisms at different operating temperatures, and the structural stability. Both systems exhibit remarkable stability after annealing and thus long-term reliability. Nano-scale metallic multilayers with smaller layer thicknesses show a greater relative resistance to decreasing strength at higher temperature testing conditions than those with larger layer thicknesses. This is seen in both Cu/Ni/Nb multilayers as well as a similar tri-component bi-layer system (Cu-Ni/Nb), which removed the coherent interface from the film. Both nanoindentation and micro-pillar compression tests investigated the strain-hardening ability of these two systems to determine what role the coherent interface plays in this mechanism. Tri-layer films showed a higher strain-hardening ability as the layer thickness decreased and a higher strain-hardening exponent than the bi-layer system: verifying the presence of a coherent interface increases the strain-hardening ability of these multilayer systems. Both systems exhibited hardening of the room temperature strength after annealing, suggesting a change in microstructure has occurred, unlike that seen in other multilayer systems. Oxide dispersion strengthened Au films showed a marked increase in hardness and wear resistance with the addition of ZnO particles. The threshold for stress-induced grain-refinement as opposed to grain growth is seen at concentrations of at least 0.5 vol%. These systems exhibited stable microstructures during thermal cycling in films containing at least 1.0%ZnO. Nanoindentation experiments show the drop in hardness following annealing is almost completely attributed to the resulting grain growth. Four-point probe resistivity

  20. Heat diode effect and negative differential thermal conductance across nanoscale metal-dielectric interfaces

    NASA Astrophysics Data System (ADS)

    Ren, Jie; Zhu, Jian-Xin

    2013-06-01

    Controlling heat flow by phononic nanodevices has received significant attention recently because of its fundamental and practical implications. Elementary phononic devices such as thermal rectifiers, transistors, and logic gates are essentially based on two intriguing properties: heat diode effect and negative differential thermal conductance. However, little is known about these heat transfer properties across metal-dielectric interfaces, especially at nanoscale. Here we analytically resolve the microscopic mechanism of the nonequilibrium nanoscale energy transfer across metal-dielectric interfaces, where the inelastic electron-phonon scattering directly assists the energy exchange. We demonstrate the emergence of heat diode effect and negative differential thermal conductance in nanoscale interfaces and explain why these novel thermal properties are usually absent in bulk metal-dielectric interfaces. These results will generate exciting prospects for the nanoscale interfacial energy transfer, which should have important implications in designing hybrid circuits for efficient thermal control and open up potential applications in thermal energy harvesting with low-dimensional nanodevices.

  1. Molecular dynamics simulation of nanoscale surface diffusion of heterogeneous adatoms clusters

    NASA Astrophysics Data System (ADS)

    Muhammad, Imran; Fayyaz, Hussain; Muhammad, Rashid; Muhammad, Ismail; Hafeez, Ullah; Yongqing, Cai; M Arshad, Javid; Ejaz, Ahmad; S, A. Ahmad

    2016-07-01

    Molecular dynamics simulation employing the embedded atom method potential is utilized to investigate nanoscale surface diffusion mechanisms of binary heterogeneous adatoms clusters at 300 K, 500 K, and 700 K. Surface diffusion of heterogeneous adatoms clusters can be vital for the binary island growth on the surface and can be useful for the formation of alloy-based thin film surface through atomic exchange process. The results of the diffusion process show that at 300 K, the diffusion of small adatoms clusters shows hopping, sliding, and shear motion; whereas for large adatoms clusters (hexamer and above), the diffusion is negligible. At 500 K, small adatoms clusters, i.e., dimer, show almost all possible diffusion mechanisms including the atomic exchange process; however no such exchange is observed for adatoms clusters greater than dimer. At 700 K, the exchange mechanism dominates for all types of clusters, where Zr adatoms show maximum tendency and Ag adatoms show minimum or no tendency toward the exchange process. Separation and recombination of one or more adatoms are also observed at 500 K and 700 K. The Ag adatoms also occupy pop-up positions over the adatoms clusters for short intervals. At 700 K, the vacancies are also generated in the vicinity of the adatoms cluster, vacancy formation, filling, and shifting can be observed from the results.

  2. Reverse micelle synthesis of nanoscale metal containing catalysts. [Nickel metal (with a nickel oxide surface layer) and iron oxyhydroxide nanoscale powders

    SciTech Connect

    Darab, J.G.; Fulton, J.L.; Linehan, J.C.

    1993-03-01

    The need for morphological control during the synthesis of catalyst precursor powders is generally accepted to be important. In the liquefaction of coal, for example, iron-bearing catalyst precursor particles containing individual crystallites with diameters in the 1-100 nanometer range are believed to achieve good dispersion through out the coal-solvent slurry during liquefaction 2 runs and to undergo chemical transformations to catalytically active iron sulfide phases. The production of the nanoscale powders described here employs the confining spherical microdomains comprising the aqueous phase of a modified reverse micelle (MRM) microemulsion system as nanoscale reaction vessels in which polymerization, electrochemical reduction and precipitation of solvated salts can occur. The goal is to take advantage of the confining nature of micelles to kinetically hinder transformation processes which readily occur in bulk aqueous solution in order to control the morphology and phase of the resulting powder. We have prepared a variety of metal, alloy, and metal- and mixed metal-oxide nanoscale powders from appropriate MRM systems. Examples of nanoscale powders produced include Co, Mo-Co, Ni[sub 3]Fe, Ni, and various oxides and oxyhydroxides of iron. Here, we discuss the preparation and characterization of nickel metal (with a nickel oxide surface layer) and iron oxyhydroxide MRM nanoscale powders. We have used extended x-ray absorption fine structure (EXAFS) spectroscopy to study the chemical polymerization process in situ, x-ray diffraction (XRD), scanning and transmission electron microcroscopies (SEM and TEM), elemental analysis and structural modelling to characterize the nanoscale powders produced. The catalytic activity of these powders is currently being studied.

  3. Metals Cluster. Secondary Curriculum Guide.

    ERIC Educational Resources Information Center

    Watkins, James F.; And Others

    This curriculum guide was designed for use in secondary metal trades education in Georgia. Its purpose is to provide for development of entry level skills in metal trades in the areas of knowledge, theoretical structure, tool usage, diagnostic ability, related supportive skills, and occupational survival skills. The first section of six explains…

  4. Packing transition in alkali metallic clusters

    NASA Astrophysics Data System (ADS)

    Kawai, R.; Sung, Ming Wen; Weare, John H.

    1996-03-01

    Small metallic clusters form a local geometric configuration quite different from the bulk crystals. As the cluster size increases, several transitions in the local coordination take place before the bulk structure appears. These transitions involve change in the nature of chemical bonds. We have systematically investigated the structural transition of various alkali metal clusters including binary compounds using an ab initio molecular dynamics simulation. Among them, Li clusters exhibit unusual transition in their packing pattern. Small lithium clusters (N <= 21) form open structures based on a ``solvation shell''.(M. Sung, R. Kawai, and J. Weare, Phys. Rev. Lett. 73) (1994) 3552., which is quite different from other alkali metal clusters. The bonding of these small clusters is partially ionic. Above N=25, a close-packed structure is established. However, the local configuration still differ from that of the bulk crystal. As the size further increases, the ionic nature decreases and the system reaches another close-packed structure based on the Mackay icosahedron, which is similar to the bulk crystal structure.

  5. Nanoscale electrical characteristics of metal (Au, Pd)-graphene-metal (Cu) contacts

    NASA Astrophysics Data System (ADS)

    Ruffino, F.; Meli, G.; Grimaldi, M. G.

    2016-01-01

    Free-standing graphene presents exceptional physical properties (as a high carrier mobility) making it the ideal candidate for the next generation nanoelectronics. However, when graphene layers are inserted in real electronics devices, metal contacting is required. The metal-graphene interaction significantly affects the graphene electrical properties, drastically changing its behavior with respect to the free-standing configuration. So, this work presents an experimental study on the nanoscale electric characteristics of metal/graphene/metal contacts. In particular, starting from single-layer graphene grown on Cu foil we deposited on the graphene surface two different metal films (Au or Pd) and the Au/graphene/Cu and Pd/graphene/Cu current-voltage characteristics are acquired, on the nanometric scale, by the conductive atomic force microscopy. Both systems presented a current voltage rectifying behavior. However, the Au/graphene/Cu system conducts significantly at negative applied bias (graphene behaves as a p-type semiconductor in a meta/semiconductor contact), while in the Pd/graphene/Cu at positive applied bias (graphene behaves as a n-type semiconductor in a metal/semiconductor contact). This difference is discussed on the basis of the band energy diagram at the metal/graphene interface and the modification of the graphene Fermi level due to the Au/graphene or Pd/graphene interaction.

  6. 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

  7. Rational control of nano-scale metal-catalysts for biomass conversion.

    PubMed

    Wang, Yunzhu; De, Sudipta; Yan, Ning

    2016-05-01

    Nano-scale metal particles have huge potential due to their wide range of diverse catalytic applications. Recently, they have found numerous applications in the field of biomass conversion. The proposed contribution is aimed at providing a brief account of remarkable recent findings and advances in the design of metal-based nanocatalysts for biomass valorization. We have discussed the rational control of the size, shape, composition and surface properties of nano-scale metal catalysts. Following that, the interplay between various structural parameters and the catalytic properties in the transformation of cellulose, chitin, lignin and lipids has been critically discussed. PMID:27022992

  8. Study of nanoscale photopolymerized fullerene clusters in solution droplets using an ultrasonic nebulizer unit.

    PubMed

    Yeo, Seung Jun; Cha, Jeong Ok; Cho, Dae Hee; Pode, Ramchandra; Ahn, Jeung Sun

    2011-07-01

    In a designed and developed ultrasonic nebulizer system for obtaining macroscopic-quantity photopolymerized fullerene (C60) clusters, a C60 solution was vaporized to several micro-sized droplets in vacuum, resulting in the formation of C60 aggregates by evaporating the solvent (toluene). The system was invented to produce nanoscale photopolymerized carbon clusters through the irradiation of ultraviolet (UV) light on the C60 aggregates in vacuum. The products, photopolymerized C60 clusters obtained from the system using UV-visible (UV-Vis) absorption and high-performance (or high-pressure) liquid chromatography (HPLC) spectra, were characterized. Compared with the non-irradiating C60 solution, the UV-Vis absorption spectrum of the irradiated C60 solution was drastically decreased, especially at lambda = 335 nm and in the visible region from lambda = 450-650 nm. As such, the UV-Vis absorption spectra provide information about the polymerization of C60 molecules. These photopolymerized C60 clusters can be detected as having a heavy molecular mass order through the HPLC system, and the C60 and photopolymerized C60 cluster can be extracted from the trapped solution on the molecular mass. Although there is a possibility that the products include various forms of C60 clusters, the results suggest that the products obtained from the system using a vaporizer establish a new method of obtaining macroscopic-quantity C60 clusters. PMID:22121736

  9. Controlling the plasmon resonance of single metal nanoparticles by near-field anisotropic nanoscale photopolymerization.

    PubMed

    Ibn-El-Ahrach, H; Bachelot, R; Lérondel, G; Vial, A; Grimault, A-S; Plain, J; Royer, P; Soppera, O

    2008-03-01

    We propose a new approach for tuning the Surface Plasmon (SP) resonance wavelength using hybrid nanoparticles. Our approach is based on nanoscale photopolymerization around metal nanoparticles. The enhanced optical near-field of silver nanoparticles triggers local photopolymerization. As a result, atomic force microscopy reveals two nanoscale polymerized lobes around nanoparticles, with a controlled effective index distribution. A spectral breaking degeneracy of surface plasmon resonance of the nanoparticles has been demonstrated by polarized extinction spectroscopy.

  10. 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.}

  11. Using Dynamic Quantum Clustering to Analyze Hierarchically Heterogeneous Samples on the Nanoscale

    SciTech Connect

    Hume, Allison; /Princeton U. /SLAC

    2012-09-07

    Dynamic Quantum Clustering (DQC) is an unsupervised, high visual data mining technique. DQC was tested as an analysis method for X-ray Absorption Near Edge Structure (XANES) data from the Transmission X-ray Microscopy (TXM) group. The TXM group images hierarchically heterogeneous materials with nanoscale resolution and large field of view. XANES data consists of energy spectra for each pixel of an image. It was determined that DQC successfully identifies structure in data of this type without prior knowledge of the components in the sample. Clusters and sub-clusters clearly reflected features of the spectra that identified chemical component, chemical environment, and density in the image. DQC can also be used in conjunction with the established data analysis technique, which does require knowledge of components present.

  12. (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.

  13. 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.

  14. Hybrid nanostructures using pi-conjugated polymers and nanoscale metals: synthesis, characteristics, and optoelectronic applications.

    PubMed

    Park, Dong Hyuk; Kim, Mi Suk; Joo, Jinsoo

    2010-07-01

    Pi-conjugated organic systems have been used as optoelectronic and sensing materials due to their characteristics of efficient light emission or absorption, and p-type charge transport. The hybrid nanostructures of pi-conjugated organic systems with nanoscale metals offer surface plasmon (SP)-enhanced luminescence, which can be applied to organic-based optoelectronics, photonics, and sensing. Various hybrid nanostructures using light-emitting polymers with nanoscale metals have been fabricated and have shown considerable enhancement of photoluminescence efficiency due to energy and charge transfer effects in SP resonance coupling. In this tutorial review, recent conceptual and technological achievements in light-emitting polymers-based hybrid nanostructures are described.

  15. Synthesis, characterization and catalytic application of nanoscale metal and metal oxide heterogeneous catalysts

    NASA Astrophysics Data System (ADS)

    Wang, Xue

    Nanoscale metals or metal oxides with high surface area to volume ratios have been widely used as catalysts for various chemical reactions. A major challenge to utilize metal nanocatalysts commercially is their tendency to sinter under working reaction conditions. To overcome this, much research is being done to anchor metal nanocatalysts on various supports to prevent their agglomeration. Mesoporous silica, SBA-15 is an attractive support material candidate because of its high surface area, stable structure and chemical inertness. Scientists have anchored metal nanocatalysts onto the pore of SBA-15 and observed some improvement in the stability. However, the interactions between the nanocatalysts and SBA-15 are relatively weak and sintering still occurs resulting in a loss of activity. In order to impart enhanced robustness, a new type of stable metal/SBA-15 nanocomposite has been prepared by intercalating metal nanoparticles into the walls of mesoporous silica SBA-15 by a unique synthetic strategy using metal coordinating agents such as bis[3-(triethoxysilyl) propyl]-tetrasulfide (TESPTS). In this dissertation, systemic research on the preparation parameters and extension to other metals will be presented. The structure changes caused by addition of TESPTS to the preparation of mesoporous silica were investigated. The relationship between increasing amounts of TESPTS and the structural change was obtained. Afterwards, a new type of PdMS catalyst with Pd intercalated in the walls of SBA-15 was synthesized for the first time using a modified preparation pathway. These materials were characterized by N2 physisorption, X-ray diffraction, transmission electron microscopy and inductively coupled plasma. The PdMS system was utilized as an active and robust catalyst for Heck reactions. Notably, after the catalytic reaction, the PdMS catalysts maintained its reactivity and size without undergoing any agglomeration due to the stable nanocomposite structure. Carbon

  16. Engineered Bacterial Metal-binding Proteins for Nanoscale Self-assembly and heavy Metal Tolerance

    NASA Astrophysics Data System (ADS)

    Hall Sedlak, Ruth Amanda

    Implementing biological principles in material synthesis and assembly is one way to expand our abilities to efficiently assemble nanoscale materials and devices. Specifically, recent advances in identifying peptides that bind inorganic materials with high affinity and specificity has spurred investigation of protein models for nanoscale inorganic assembly. This dissertation presents the results of my studies of several E. coli proteins engineered to bind inorganic materials through simple peptide motifs. I demonstrate that these proteins modulate the self-assembly of DNA-based nanostructures and can introduce heavy metal tolerance into metal-sensitive bacteria. Chapter 2 explores use of the engineered F plasmid DNA relaxase/helicase TraI for the self-assembly of complex DNA-protein-gold nanostructures. The full-length protein is engineered with a gold binding motif at an internal permissive site (TraI369GBP1-7x), while a truncated version of TraI is engineered with the same gold binding motif at the C-terminus (TraI361GBP1-7x). Both constructs bind gold nanoparticles while maintaining their DNA binding activity, and transmission electron microscopy reveals TraI369GBP1-7x utilizes its non-specific DNA binding activity to decorate single-stranded and double-stranded DNA with gold nanoparticles. The self assembly principles demonstrated in this work will be fundamental to constructing higher ordered hybrid nanostructures through DNA-protein-nanoparticle interactions. Chapter 3 studies the effects of expressing inorganic binding peptides within cells. I identified a silver binding peptide that, when fused to the periplasmic maltose binding protein, protects E. coli from silver toxicity in batch culture and reduces silver ions to silver nanoparticles within the bacterial periplasm. Engineered metal-ion tolerant microorganisms such as this E. coli could potentially be used in applications ranging from remediation to interrogation of biomolecule-metal interactions in vivo

  17. 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.

  18. Laser-induced nanoscale superhydrophobic structures on metal surfaces.

    PubMed

    Jagdheesh, R; Pathiraj, B; Karatay, E; Römer, G R B E; Huis in't Veld, A J

    2011-07-01

    The combination of a dual-scale (nano and micro) roughness with an inherent low-surface energy coating material is an essential factor for the development of superhydrophobic surfaces. Ultrashort pulse laser (USPL) machining/structuring is a promising technique for obtaining the dual-scale roughness. Sheets of stainless steel (AISI 304 L SS) and Ti-6Al-4V alloys were laser-machined with ultraviolet laser pulses of 6.7 ps, with different numbers of pulses per irradiated area. The surface energy of the laser-machined samples was reduced via application of a layer of perfluorinated octyltrichlorosilane (FOTS). The influence of the number of pulses per irradiated area on the geometry of the nanostructure and the wetting properties of the laser-machined structures has been studied. The results show that with an increasing number of pulses per irradiated area, the nanoscale structures tend to become predominantly microscale. The top surface of the microscale structures is seen covered with nanoscale protrusions that are most pronounced in Ti-6Al-4V. The laser-machined Ti-6Al-4V surface attained superhydrophobicity, and the improvement in the contact angle was >27% when compared to that of a nontextured surface.

  19. Empty, filled, and condensed metal clusters

    NASA Astrophysics Data System (ADS)

    Simon, Arndt

    1985-03-01

    Aspects of structure, bonding, physical, and chemical properties are discussed for (a) compounds containing discrete empty clusters and clusters with interstitial H atoms: Nb 6I 11, HNb 6I 11, HCsNb 6I 11, (b) metal-rich lanthanide halides and halide carbides,-nitrides and -hydrides, focusing on the role of interstitial atoms: Gd 2Br 2C 2, Gd 2Br 2C, Gd 3Cl 3C, Gd 10Cl 18C 4, Gd 10Il 17C 4, Gd 10I 16C 4, GD 2Cl 3N, Gd XH n ( X=Cl, Br, I; 0.6< n<0.9), GdBrD 2; (c) metal-rich oxides of the alkali metals rubidium and cesium. Chemical bonding in the suboxide clusters Rb 9O 2 and Cs 11O 3 is discussed along the lines valid for (a) and (b) and covers recently described "hypervalent" species as Li 6C, Li 4O, etc.

  20. Recent applications of liquid metals featuring nanoscale surface oxides

    NASA Astrophysics Data System (ADS)

    Neumann, Taylor V.; Dickey, Michael D.

    2016-05-01

    This proceeding describes recent efforts from our group to control the shape and actuation of liquid metal. The liquid metal is an alloy of gallium and indium which is non-toxic, has negligible vapor pressure, and develops a thin, passivating surface oxide layer. The surface oxide allows the liquid metal to be patterned and shaped into structures that do not minimize interfacial energy. The surface oxide can be selectively removed by changes in pH or by applying a voltage. The surface oxide allows the liquid metal to be 3D printed to form free-standing structures. It also allows for the liquid metal to be injected into microfluidic channels and to maintain its shape within the channels. The selective removal of the oxide results in drastic changes in surface tension that can be used to control the flow behavior of the liquid metal. The metal can also wet thin, solid films of metal that accelerates droplets of the liquid along the metal traces .Here we discuss the properties and applications of liquid metal to make soft, reconfigurable electronics.

  1. Nanoscale size effects in crystallization of metallic glass nanorods

    PubMed Central

    Sohn, Sungwoo; Jung, Yeonwoong; Xie, Yujun; Osuji, Chinedum; Schroers, Jan; Cha, Judy J.

    2015-01-01

    Atomistic understanding of crystallization in solids is incomplete due to the lack of appropriate materials and direct experimental tools. Metallic glasses possess simple metallic bonds and slow crystallization kinetics, making them suitable to study crystallization. Here, we investigate crystallization of metallic glass-forming liquids by in-situ heating metallic glass nanorods inside a transmission electron microscope. We unveil that the crystallization kinetics is affected by the nanorod diameter. With decreasing diameters, crystallization temperature decreases initially, exhibiting a minimum at a certain diameter, and then rapidly increases below that. This unusual crystallization kinetics is a consequence of multiple competing factors: increase in apparent viscosity, reduced nucleation probability and enhanced heterogeneous nucleation. The first two are verified by slowed grain growth and scatter in crystallization temperature with decreasing diameters. Our findings provide insight into relevant length scales in crystallization of supercooled metallic glasses, thus offering accurate processing conditions for predictable metallic glass nanomolding. PMID:26323828

  2. Nanoscale size effects in crystallization of metallic glass nanorods.

    PubMed

    Sohn, Sungwoo; Jung, Yeonwoong; Xie, Yujun; Osuji, Chinedum; Schroers, Jan; Cha, Judy J

    2015-09-01

    Atomistic understanding of crystallization in solids is incomplete due to the lack of appropriate materials and direct experimental tools. Metallic glasses possess simple metallic bonds and slow crystallization kinetics, making them suitable to study crystallization. Here, we investigate crystallization of metallic glass-forming liquids by in-situ heating metallic glass nanorods inside a transmission electron microscope. We unveil that the crystallization kinetics is affected by the nanorod diameter. With decreasing diameters, crystallization temperature decreases initially, exhibiting a minimum at a certain diameter, and then rapidly increases below that. This unusual crystallization kinetics is a consequence of multiple competing factors: increase in apparent viscosity, reduced nucleation probability and enhanced heterogeneous nucleation. The first two are verified by slowed grain growth and scatter in crystallization temperature with decreasing diameters. Our findings provide insight into relevant length scales in crystallization of supercooled metallic glasses, thus offering accurate processing conditions for predictable metallic glass nanomolding.

  3. A transition in mechanisms of size dependent electrical transport at nanoscale metal-oxide interfaces

    SciTech Connect

    Hou, Jiechang; Nonnenmann, Stephen S.; Qin, Wei; Bonnell, Dawn A.

    2013-12-16

    As device miniaturization approaches nanoscale dimensions, interfaces begin to dominate electrical properties. Here the system archetype Au/SrTiO{sub 3} is used to examine the origin of size dependent transport properties along metal-oxide interfaces. We demonstrate that a transition between two classes of size dependent electronic transport mechanisms exists, defined by a critical size ε. At sizes larger than ε an edge-related tunneling effect proportional to 1/D (the height of the supported Au nanoparticle) is observed; interfaces with sizes smaller than ε exhibit random fluctuations in current. The ability to distinguish between these mechanisms is important to future developments in nanoscale device design.

  4. Assembly of Fe-substituted Dawson-type nanoscale selenotungstate clusters with photocatalytic H2 evolution activity.

    PubMed

    Chen, Wei-Chao; Qin, Chao; Wang, Xin-Long; Li, Yang-Guang; Zang, Hong-Ying; Jiao, Yan-Qing; Huang, Peng; Shao, Kui-Zhan; Su, Zhong-Min; Wang, En-Bo

    2014-11-11

    Two Fe-substituted Dawson-type nanoscale selenotungstate clusters, {Fe6Se6W34} and {Fe10Se8W62} involving {α-Se2W14} and {γ-Se2W14} building blocks, have been isolated, which exhibit photocatalytic H2 evolution activity. Their electrochemical behaviours and magnetic properties were also investigated.

  5. A high fat diet containing saturated but not unsaturated fatty acids enhances T cell receptor clustering on the nanoscale

    PubMed Central

    Shaikh, Saame Raza; Boyle, Sarah; Edidin, Michael

    2015-01-01

    Cell culture studies show that the nanoscale lateral organization of surface receptors, their clustering or dispersion, can be altered by changing the lipid composition of the membrane bilayer. However, little is known about similar changes in vivo, which can be effected by changing dietary lipids. We describe the use of a newly developed method, k-space image correlation spectroscopy, kICS, for analysis of quantum dot fluorescence to show that a high fat diet can alter the nanometer-scale cluster of the murine T cell receptor, TCR on the surface of naïve CD4+ T cells. We found that diets enriched primarily in saturated fatty acids increased TCR nanoscale clustering to a level usually seen only on activated cells. Diets enriched in monounsaturated or n-3 polyunsaturated fatty acids had no effect on TCR clustering. Also none of the high fat diets affected TCR clustering on the micrometer scale. Furthermore, the effect of the diets was similar in young and middle aged mice. Our data establish proof-of-principle that TCR nanoscale clustering is sensitive to the composition of dietary fat. PMID:26143085

  6. Metal clusters in catalysis: Hydrocarbon reactions*

    PubMed Central

    Caulton, K. G.; Thomas, M. G.; Sosinsky, B. A.; Muetterties, E. L.

    1976-01-01

    A set of metal carbonyl clusters, Ru3(CO)12, Os3(CO)12, and Ir4(CO)12, has been evaluated as catalysts for a series of hydrocarbon reactions which comprise skeletal rearrangement, metathesis, dehydrogenation, hydrogenation, isomerization, and H-D exchange. None was especially effective as a hydrogenation catalyst even for olefins. Os3(CO)12 was a catalyst for H-D exchange between C6H6 and D2 at 195° but the ruthenium congener was inactive at temperatures below 175°, a temperature where ruthenium metal formed at an appreciable rate. Deuterium incorporation in the benzene was a single-step process. Ir4(CO)12 was an effective catalyst for the conversion of cyclohexadiene to cyclohexene and benzene. A similar reaction occurred with cyclohexene but the rate was extremely low at 160°. The ruthenium and osmium clusters catalyzed the isomerization of linear hexenes, with the former the more active. Relative rates for the hexenes were 1 > 2 > 3. At high temperatures, the osmium and iridium clusters catalyzed skeletal reactions of 2-hexene, as evidenced by the formation of pentenes, heptenes, heptanes, and small amounts of propane. PMID:16592366

  7. Optical Focusing by Planar Lenses Based on Nano-scale Metallic Slits in Visible Regime

    NASA Astrophysics Data System (ADS)

    Feng, Di; Zhang, Chunxi

    A kind of planar metallic lenses is proposed to realize optical focusing in the visible wavelength through a metallic film with nano-scale slit arrays, which have the same depth but tuning widths. Due to the subwavelength and aperiodic nature of planar metallic lenses, we present the rigorous electromagnetic analysis by using two dimensional finite difference time domain method. The electromagnetic wave transports through the tuning slits in the form of surface plasmon polaritons, and gets the required phase retardations to focusing at the focal plane. We analyze the focusing characteristics of planar dielectric lens and metallic lens with tuning widths that are obtained by generalizing the relevant phase delay, for different incidence polarization waves (TM polarized case and TE polarized case). The computational calculation results show that, extraordinary optical transmission of surface plasmon polaritions through non uniform nano-scale metallic slits is observed, and it has contributions to the optical focusing, but cannot increase the focal energy compared with dielectric planar lens with the same profile, and the metallic lenses are more sensitive to the polarization of incidence wave than that of dielectric lenses. The influence of metallic lenses' thickness on the focal characteristics has been analyzed also.

  8. Structural Signature of Plasticity Unveiled by Nano-Scale Viscoelastic Contact in a Metallic Glass

    PubMed Central

    Lu, Y. M.; Zeng, J. F.; Wang, S.; Sun, B. A.; Wang, Q.; Lu, J.; Gravier, S.; Bladin, J. J.; Wang, W. H.; Pan, M. X.; Liu, C. T.; Yang, Y.

    2016-01-01

    Room-temperature plasticity in metallic glasses (MGs) is commonly associated with local structural heterogeneity; however, direct observation of the subtle structural change caused by plasticity is vitally important but the data are extremely scarce. Based on dynamic atomic force microscopy (DAFM), here we show that plasticity-induced structural evolution in a Zr-Ni MG can be revealed via nano-scale viscoelastic contacts between an AFM tip and plastically deformed MG surface layers. Our experimental results clearly show a spatial amplification of the nano-scale structural heterogeneity caused by the distributed plastic flow, which can be linked to the limited growth, reorientation and agglomeration of some nano-scale energy-absorbing regions, which are reminiscent of the behavior of the defect-like regions with non-affine deformation as conceived in many theories and models. Furthermore, we are able to experimentally extract the thermodynamic properties of these nano-scale regions, which possess an energy barrier of 0.3–0.5 eV, about half of that for a typical shear transformation event that usually occurs at the onset of plasticity. The outcome of our current work sheds quantitative insights into the correlation between plasticity and structural heterogeneity in MGs. PMID:27383387

  9. Structural Signature of Plasticity Unveiled by Nano-Scale Viscoelastic Contact in a Metallic Glass

    NASA Astrophysics Data System (ADS)

    Lu, Y. M.; Zeng, J. F.; Wang, S.; Sun, B. A.; Wang, Q.; Lu, J.; Gravier, S.; Bladin, J. J.; Wang, W. H.; Pan, M. X.; Liu, C. T.; Yang, Y.

    2016-07-01

    Room-temperature plasticity in metallic glasses (MGs) is commonly associated with local structural heterogeneity; however, direct observation of the subtle structural change caused by plasticity is vitally important but the data are extremely scarce. Based on dynamic atomic force microscopy (DAFM), here we show that plasticity-induced structural evolution in a Zr-Ni MG can be revealed via nano-scale viscoelastic contacts between an AFM tip and plastically deformed MG surface layers. Our experimental results clearly show a spatial amplification of the nano-scale structural heterogeneity caused by the distributed plastic flow, which can be linked to the limited growth, reorientation and agglomeration of some nano-scale energy-absorbing regions, which are reminiscent of the behavior of the defect-like regions with non-affine deformation as conceived in many theories and models. Furthermore, we are able to experimentally extract the thermodynamic properties of these nano-scale regions, which possess an energy barrier of 0.3-0.5 eV, about half of that for a typical shear transformation event that usually occurs at the onset of plasticity. The outcome of our current work sheds quantitative insights into the correlation between plasticity and structural heterogeneity in MGs.

  10. Structural Signature of Plasticity Unveiled by Nano-Scale Viscoelastic Contact in a Metallic Glass.

    PubMed

    Lu, Y M; Zeng, J F; Wang, S; Sun, B A; Wang, Q; Lu, J; Gravier, S; Bladin, J J; Wang, W H; Pan, M X; Liu, C T; Yang, Y

    2016-01-01

    Room-temperature plasticity in metallic glasses (MGs) is commonly associated with local structural heterogeneity; however, direct observation of the subtle structural change caused by plasticity is vitally important but the data are extremely scarce. Based on dynamic atomic force microscopy (DAFM), here we show that plasticity-induced structural evolution in a Zr-Ni MG can be revealed via nano-scale viscoelastic contacts between an AFM tip and plastically deformed MG surface layers. Our experimental results clearly show a spatial amplification of the nano-scale structural heterogeneity caused by the distributed plastic flow, which can be linked to the limited growth, reorientation and agglomeration of some nano-scale energy-absorbing regions, which are reminiscent of the behavior of the defect-like regions with non-affine deformation as conceived in many theories and models. Furthermore, we are able to experimentally extract the thermodynamic properties of these nano-scale regions, which possess an energy barrier of 0.3-0.5 eV, about half of that for a typical shear transformation event that usually occurs at the onset of plasticity. The outcome of our current work sheds quantitative insights into the correlation between plasticity and structural heterogeneity in MGs. PMID:27383387

  11. Structural Signature of Plasticity Unveiled by Nano-Scale Viscoelastic Contact in a Metallic Glass

    NASA Astrophysics Data System (ADS)

    Lu, Y. M.; Zeng, J. F.; Wang, S.; Sun, B. A.; Wang, Q.; Lu, J.; Gravier, S.; Bladin, J. J.; Wang, W. H.; Pan, M. X.; Liu, C. T.; Yang, Y.

    2016-07-01

    Room-temperature plasticity in metallic glasses (MGs) is commonly associated with local structural heterogeneity; however, direct observation of the subtle structural change caused by plasticity is vitally important but the data are extremely scarce. Based on dynamic atomic force microscopy (DAFM), here we show that plasticity-induced structural evolution in a Zr-Ni MG can be revealed via nano-scale viscoelastic contacts between an AFM tip and plastically deformed MG surface layers. Our experimental results clearly show a spatial amplification of the nano-scale structural heterogeneity caused by the distributed plastic flow, which can be linked to the limited growth, reorientation and agglomeration of some nano-scale energy-absorbing regions, which are reminiscent of the behavior of the defect-like regions with non-affine deformation as conceived in many theories and models. Furthermore, we are able to experimentally extract the thermodynamic properties of these nano-scale regions, which possess an energy barrier of 0.3–0.5 eV, about half of that for a typical shear transformation event that usually occurs at the onset of plasticity. The outcome of our current work sheds quantitative insights into the correlation between plasticity and structural heterogeneity in MGs.

  12. High Temperature In Situ Compression of Thermoplastically Formed Nano-scale Metallic Glass

    NASA Astrophysics Data System (ADS)

    Mridha, Sanghita; Arora, Harpreet Singh; Lefebvre, Joseph; Bhowmick, Sanjit; Mukherjee, Sundeep

    2016-05-01

    The mechanical behavior of nano-scale metallic glasses was investigated by in situ compression tests in a scanning electron microscope. Platinum-based metallic glass nano-pillars were fabricated by thermoplastic forming. The nano-pillars and corresponding bulk substrate were tested in compression over the range of room temperature to glass transition. Stress-strain curves of the nano-pillars were obtained along with in situ observation of their deformation behavior. The bulk substrate as well as nano-pillars showed an increase in elastic modulus with temperature which is explained by diffusive rearrangement of atomic-scale viscoelastic units.

  13. Deviations from mean-field behavior in disordered nanoscale superconductor normal-metal superconductor arrays

    NASA Astrophysics Data System (ADS)

    Kouh, Taejoon; Valles, J. M.

    2003-04-01

    We have fabricated quasi-two-dimensional disordered arrays of nanoscale Pb grains coupled by an overlayer of Ag grains. Their temperature-dependent resistive transitions follow predictions for an array of mesoscopic superconductor normal-metal superconductor junctions. The decrease of their transition temperatures with Ag overlayer thickness systematically deviates from the Cooper limit theory of the proximity effect as the Pb grain size decreases. The deviations occur when the estimated number of Cooper pairs per grain is <1 and suggest the approach to a superconductor-to-metal transition.

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

    DOE PAGES

    Yin, Panchao; Wu, Bin; Li, Tao; Bonnesen, Peter V.; Hong, Kunlun; Seifert, Soenke; Porcar, Lionel; Do, Changwoo; Keum, Jong Kahk

    2016-07-26

    A 2.9 nm molybdenum oxide cluster {Mo132} (Formula: [MoVI72MoV60O372(CH3COO)30(H2O)72]42-) can be obtained by reducing ammonium molybdate with hydrazine sulfate in weakly acidic CH3COOH/CH3COO- buffers. This reaction has been monitored by time-resolved UV-Vis, 1H-NMR, small angle X-ray/neutron scattering, and X-ray absorption near edge structure spectroscopy. The growth of {Mo132} cluster shows a typical sigmoid curve, suggesting a multi-step assembly mechanism for this reaction. The reaction starts with a lag phase period when partial MoVI centers of molybdate precursors are reduced to form {MoV2(acetate)} structures under the coordination effect of the acetate groups. Once the concentration of {MoV2(acetate)} reaches a critical value,more » it triggers the assembly of MoV and MoVI species into {Mo132} clusters. Parameters such as the type and amount of reducing agent, the pH, the type of cation, and the type of organic ligand in the reaction buffer, have been studied for the roles they play in the formation of the target clusters.Understanding the formation mechanism of giant molecular clusters is essential for rational design and synthesis of cluster-based nanomaterials with required morphologies and functionalities. Here, typical synthetic reactions of a 2.9 nm spherical molybdenum oxide cluster, {Mo132} (formula: [MoVI72MoV60O372(CH3COO)30(H2O)72]42), with systematically varied reaction parameters have been fully explored to determine the morphologies and concentration of products, reduction of metal centers, and chemical environments of the organic ligands. The growth of these clusters shows a typical sigmoid curve, suggesting a general multistep self-assembly mechanism for the formation of giant molecular clusters. The reaction starts with a lag phase period when partial MoVI centers of molybdate precursors are reduced to form {MoV2(acetate)} structures under the coordination effect of the acetate groups. Once the concentration of {MoV2(acetate)} reaches a

  15. Investigating Deformation and Failure Mechanisms in Nanoscale Multilayer Metallic Composites

    SciTech Connect

    Zbib, Hussein M; Bahr, David F

    2014-10-22

    Over the history of materials science there are many examples of materials discoveries that have made superlative materials; the strongest, lightest, or toughest material is almost always a goal when we invent new materials. However, often these have been a result of enormous trial and error approaches. A new methodology, one in which researchers design, from the atoms up, new ultra-strong materials for use in energy applications, is taking hold within the science and engineering community. This project focused on one particular new classification of materials; nanolaminate metallic composites. These materials, where two metallic materials are intimately bonded and layered over and over to form sheets or coatings, have been shown over the past decade to reach strengths over 10 times that of their constituents. However, they are not yet widely used in part because while extremely strong (they don’t permanently bend), they are also not particularly tough (they break relatively easily when notched). Our program took a coupled approach to investigating new materials systems within the laminate field. We used computational materials science to explore ways to institute new deformation mechanisms that occurred when a tri-layer, rather than the more common bi-layer system was created. Our predictions suggested that copper-nickel or copper-niobium composites (two very common bi-layer systems) with layer thicknesses on the order of 20 nm and then layered 100’s of times, would be less tough than a copper-nickel-niobium metallic composite of similar thicknesses. In particular, a particular mode of permanent deformation, cross-slip, could be activated only in the tri-layer system; the crystal structure of the other bi-layers would prohibit this particular mode of deformation. We then experimentally validated this predication using a wide range of tools. We utilized a DOE user facility, the Center for Integrated Nanotechnology (CINT), to fabricate, for the first time, these

  16. Local traps as nanoscale reaction-diffusion probes: B clustering in c-Si

    SciTech Connect

    Pawlak, B. J.; Cowern, N. E. B.; Ahn, C.; Vandervorst, W.; Gwilliam, R.; Berkum, J. G. M. van

    2014-12-01

    A series of B implantation experiments into initially amorphized and not fully recrystallized Si, i.e., into an existing a/c-Si bi-layer material, have been conducted. We varied B dose, energy, and temperature during implantation process itself. Significant B migration has been observed within c-Si part near the a/c-interface and near the end-of-range region before any activation annealing. We propose a general concept of local trapping sites as experimental probes of nanoscale reaction-diffusion processes. Here, the a/c-Si interface acts as a trap, and the process itself is explored as the migration and clustering of mobile BI point defects in nearby c-Si during implantation at temperatures from 77 to 573 K. We find that at room temperature—even at B concentrations as high as 1.6 atomic %, the key B-B pairing step requires diffusion lengths of several nm owing to a small, ∼0.1 eV, pairing energy barrier. Thus, in nanostructures doped by ion implantation, the implant distribution can be strongly influenced by thermal migration to nearby impurities, defects, and interfaces.

  17. Nanoscale Imaging Reveals a Tetraspanin-CD9 Coordinated Elevation of Endothelial ICAM-1 Clusters

    PubMed Central

    Franz, Jonas; Brinkmann, Benjamin F.; König, Michael; Hüve, Jana; Stock, Christian; Ebnet, Klaus; Riethmüller, Christoph

    2016-01-01

    Endothelial barriers have a central role in inflammation as they allow or deny the passage of leukocytes from the vasculature into the tissue. To bind leukocytes, endothelial cells form adhesive clusters containing tetraspanins and ICAM-1, so-called endothelial adhesive platforms (EAPs). Upon leukocyte binding, EAPs evolve into docking structures that emanate from the endothelial surface while engulfing the leukocyte. Here, we show that TNF-α is sufficient to induce apical protrusions in the absence of leukocytes. Using advanced quantitation of atomic force microscopy (AFM) recordings, we found these structures to protrude by 160 ± 80 nm above endothelial surface level. Confocal immunofluorescence microscopy proved them positive for ICAM-1, JAM-A, tetraspanin CD9 and f-actin. Microvilli formation was inhibited in the absence of CD9. Our findings indicate that stimulation with TNF-α induces nanoscale changes in endothelial surface architecture and that—via a tetraspanin CD9 depending mechanism—the EAPs rise above the surface to facilitate leukocyte capture. PMID:26731655

  18. Nanoscale metals and semiconductors for the storage of solar energy in chemical bonds

    NASA Astrophysics Data System (ADS)

    Manthiram, Karthish

    The transduction of electrical energy into chemical bonds represents one potential strategy for storing energy derived from intermittent sources such as solar and wind. Driving the electrochemical reduction of carbon dioxide using light requires (1) developing light absorbers which convert photons into electron-hole pairs and (2) catalysts which utilize these electrons and holes to reduce carbon dioxide and oxidize water, respectively. For both the light absorbers and catalysts, the use of nanoscale particles is advantageous, as charge transport length scales are minimized in the case of nanoscale light absorbers and catalytic surface-area-to-volume ratio is maximized for nanoscale catalysts. In many cases, although semiconductors and metals in the form of thin films and foils are increasingly well-characterized as photoabsorbers and electrocatalysts for carbon dioxide reduction, respectively, the properties of their nanoscale counterparts remain poorly understood. This dissertation explores the nature of the light absorption mode of non-stoichiometric semiconductors which are utilized as light absorbers and the development of catalysts with enhanced stability, activity, and selectivity for carbon dioxide reduction. Chapter 1 provides an overview of the state of development of methods of transducing the energy of photons into chemical bonds. Chapters 2 and 3 investigate the development of stable, active, and selective catalysts for the electrochemical reduction of carbon dioxide. Chapter 2 examines how copper nanoparticles have enhanced activities and selectivities for methanation compared to copper foils. Chapter 3 focuses on the development of strategies to stabilize high-surface-area catalysts to prevent surface area loss during electrochemical carbon dioxide reduction. Chapters 4 and 5 entail a fundamental understanding of the light absorption mode of nanoscale photoabsorbers used in both photoelectrochemical cells and in photovoltaics. Chapter 4 focuses on the

  19. 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

  20. Impact of biogenic nanoscale metals Fe, Cu, Zn and Se on reproductive LV chickens

    NASA Astrophysics Data System (ADS)

    Khiem Nguyen, Quy; Dieu Nguyen, Duy; Kien Nguyen, Van; Thinh Nguyen, Khac; Chau Nguyen, Hoai; Tin Tran, Xuan; Nguyen, Huu Cuong; Tien Phung, Duc

    2015-09-01

    Using biogenic nanoscale metals (Fe, Cu, ZnO, Se) to supplement into diet premix of reproductive LV (a Vietnamese Luong Phuong chicken breed) chickens resulted in certain improvement of poultry farming. The experimental data obtained showed that the farming indices depend mainly on the quantity of nanocrystalline metals which replaced the inorganic mineral component in the feed premix. All four experimental groups with different quantities of the replacement nano component grew and developed normally with livability reaching 91 to 94%, hen’s bodyweight at 38 weeks of age and egg weight ranged from 2.53-2.60 kg/hen and 50.86-51.55 g/egg, respectively. All these farming indices together with laying rate, egg productivity and chick hatchability peaked at group 5 with 25% of nanoscale metals compared to the standard inorganic mineral supplement, while feed consumption was lowest. The results also confirmed that nanocrystalline metals Fe, Cu, ZnO and Se supplemented to chicken feed were able to decrease inorganic minerals in the diet premixes at least four times, allowing animals to more effectively absorb feed minerals, consequently decreasing environmental pollution risks.

  1. A Technique to Transfer Metallic Nanoscale Patterns to Small and Non-Planar Surfaces

    PubMed Central

    Smythe, Elizabeth J.; Dickey, Michael D.; Whitesides, George M.; Capasso, Federico

    2009-01-01

    Conventional lithographic methods (e.g. electron-beam writing, photolithography) are capable of producing high-resolution structures over large areas, but are generally limited to large (>1 cm2) planar substrates. Incorporation of these features on unconventional substrates (i.e., small (<1 mm2) and/or non-planar substrates) would open possibilities for many applications, including remote fiber-based sensing, nanoscale optical lithography, three-dimensional fabrication, and integration of compact optical elements on fiber and semiconductor lasers. Here we introduce a simple method in which a thin thiol-ene film strips arbitrary nanoscale metallic features from one substrate and is then transferred, along with the attached features, to a substrate that would be difficult or impossible to pattern with conventional lithographic techniques. An oxygen plasma removes the sacrificial film, leaving behind the metallic features. The transfer of dense and sparse patterns of isolated and connected gold features ranging from 30 nm to 1 μm, to both an optical fiber facet and a silica microsphere, demonstrates the versatility of the method. A distinguishing feature of this technique is the use of a thin, sacrificial film to strip and transfer metallic nanopatterns and its ability to directly transfer metallic structures produced by conventional lithography. PMID:19206249

  2. 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.

  3. Atomistic simulations of electrochemical metallization cells: mechanisms of ultra-fast resistance switching in nanoscale devices

    NASA Astrophysics Data System (ADS)

    Onofrio, Nicolas; Guzman, David; Strachan, Alejandro

    2016-07-01

    We describe a new method that enables reactive molecular dynamics (MD) simulations of electrochemical processes and apply it to study electrochemical metallization cells (ECMs). The model, called EChemDID, extends the charge equilibration method to capture the effect of external electrochemical potential on partial atomic charges and describes its equilibration over connected metallic structures, on-the-fly, during the MD simulation. We use EChemDID to simulate resistance switching in nanoscale ECMs; these devices consist of an electroactive metal separated from an inactive electrode by an insulator and can be reversibly switched to a low-resistance state by the electrochemical formation of a conducting filament between electrodes. Our structures use Cu as the active electrode and SiO2 as the dielectric and have dimensions at the foreseen limit of scalability of the technology, with a dielectric thickness of approximately 1 nm. We explore the effect of device geometry on switching timescales and find that nanowires with an electroactive shell, where ions migrate towards a smaller inactive electrode core, result in faster switching than planar devices. We observe significant device-to-device variability in switching timescales and intermittent switching for these nanoscale devices. To characterize the evolution in the electronic structure of the dielectric as dissolved metallic ions switch the device, we perform density functional theory calculations on structures obtained from an EChemDID MD simulation. These results confirm the appearance of states around the Fermi energy as the metallic filament bridges the electrodes and show that the metallic ions and not defects in the dielectric contribute to the majority of those states.

  4. Nanoscale wavy fracture surface of a Pd-based bulk metallic glass

    SciTech Connect

    Chen, N.; Louzguine-Luzgin, D. V.; Inoue, A.; Xie, G. Q.

    2009-03-30

    The authors report the observations of nanoscale wavy steps on fracture surface of a Pd-based bulk metallic glass. The wavy steps are generated by crack front waves. Besides this kind of steps, it is also found that there is a dispersive microscale wavy trace aligned along a backbone ''branch line,'' which is induced by dynamic instability of a rapidly propagating crack front. Such microbranching events are evidenced as dissipating energy accumulated at the crack front by creating the additional fracture surface area when the crack propagation exceeds a critical velocity.

  5. Influence of reactive gas admixture on transition metal cluster nucleation in a gas aggregation cluster source

    NASA Astrophysics Data System (ADS)

    Peter, Tilo; Polonskyi, Oleksandr; Gojdka, Björn; Mohammad Ahadi, Amir; Strunskus, Thomas; Zaporojtchenko, Vladimir; Biederman, Hynek; Faupel, Franz

    2012-12-01

    We quantitatively assessed the influence of reactive gases on the formation processes of transition metal clusters in a gas aggregation cluster source. A cluster source based on a 2 in. magnetron is used to study the production rate of titanium and cobalt clusters. Argon served as working gas for the DC magnetron discharge, and a small amount of reactive gas (oxygen and nitrogen) is added to promote reactive cluster formation. We found that the cluster production rate depends strongly on the reactive gas concentration for very small amounts of reactive gas (less than 0.1% of total working gas), and no cluster formation takes place in the absence of reactive species. The influence of discharge power, reactive gas concentration, and working gas pressure are investigated using a quartz micro balance in a time resolved manner. The strong influence of reactive gas is explained by a more efficient formation of nucleation seeds for metal-oxide or nitride than for pure metal.

  6. Ruprecht 106 - A young metal-poor Galactic globular cluster

    SciTech Connect

    Buonanno, R.; Buscema, G.; Fusi Pecci, F.; Richer, H.B.; Fahlman, G.G. Bologna Universita British Columbia Univ., Vancouver )

    1990-12-01

    The first CCD photometric survey in the Galactic globular cluster Ruprecht 106 has been performed. The results show that Ruprecht 106 is a metal-poor cluster with (Fe/H) about -2 located at about 25 kpc from the Galactic center. A sizable, high centrally concentrated population of blue stragglers was detected. Significant differences in the positions of the turnoffs in the color-magnitude diagram are found compared to those in metal-poor clusters. The cluster appears younger than other typical metal-poor Galactic globulars by about 4-5 Gyr; if true, this object would represent the first direct proof of the existence of a significant age spread among old, very metal-poor clusters. 51 refs.

  7. 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.

  8. Thermochemistry and Reactivity of Transition Metal Cluster Ions

    NASA Astrophysics Data System (ADS)

    Armentrout, P. B.; Griffin, J. B.; Conceićão, J.

    Reactions of transition metal cluster cations with several small molecules have been examined using guided ion beam mass spectrometry. This technique allows the kinetic energy dependence of the reactions to be measured, thereby allowing thermodynamic information to be extracted. Reactions of iron, chromium, and vanadium clusters with D2, O2, and CO2 are described. Reactions with D2 are endothermic and yield only two types of products. Oxidation of metal clusters by O2 proceeds is very efficient, proceeding at the collision limit, and forms many different products. The CO2 systems exhibit interesting dynamics that appears to be related to interactions of two surfaces of different spin. Bond energies for cluster monodeuterides, monoxides, and dioxides are derived from these studies. The deuteride bond energies appear to be sensitive to the cluster geometry while little variation in oxide bond energies is observed as a function of cluster size. Comparison of these cluster bond energies to bulk phase values finds similar thermochemistry.

  9. Biologically activated noble metal alloys at the nanoscale: for lithium ion battery anodes.

    PubMed

    Lee, Yun Jung; Lee, Youjin; Oh, Dahyun; Chen, Tiffany; Ceder, Gerbrand; Belcher, Angela M

    2010-07-14

    We report the synthesis and electrochemical activity of gold and silver noble metals and their alloy nanowires using multiple virus clones as anode materials for lithium ion batteries. Using two clones, one for specificity (p8#9 virus) and one versatility (E4 virus), noble metal nanowires of high-aspect ratio with diameters below 50 nm were successfully synthesized with control over particle sizes, morphologies, and compositions. The biologically derived noble metal alloy nanowires showed electrochemical activities toward lithium even when the electrodes were prepared from bulk powder forms. The improvement in capacity retention was accomplished by alloy formation and surface stabilization. Although the cost of noble metals renders them a less ideal choice for lithium ion batteries, these noble metal/alloy nanowires serve as great model systems to study electrochemically induced transformation at the nanoscale. Given the demonstration of the electrochemical activity of noble metal alloy nanowires with various compositions, the M13 biological toolkit extended its utility for the study on the basic electrochemical property of materials.

  10. Nanoscale zero-valent metals: a review of synthesis, characterization, and applications to environmental remediation.

    PubMed

    Li, Lingyun; Hu, Jiwei; Shi, Xuedan; Fan, Mingyi; Luo, Jin; Wei, Xionghui

    2016-09-01

    Engineered nanoscale zero-valent metals (NZVMs) representing the forefront of technologies have been considered as promising materials for environmental remediation and antimicrobial effect, due to their high reducibility and strong adsorption capability. This review is focused on the methodology for synthesis of bare NZVMs, supported NZVMs, modified NZVMs, and bimetallic systems with both traditional and green methods. Recent studies have demonstrated that self-assembly methods can play an important role for obtaining ordered, controllable, and tunable NZVMs. In addition to common characterization methods, the state-of-the-art methods have been developed to obtain the properties of NZVMs (e.g., granularity, size distribution, specific surface area, shape, crystal form, and chemical bond) with the resolution down to subnanometer scale. These methods include spherical aberration corrected scanning transmission electron microscopy (Cs-corrected STEM), electron energy-loss spectroscopy (EELS), and near edge X-ray absorption fine structure (NEXAFS). A growing body of experimental data has proven that nanoscale zero-valent iron (NZVI) is highly effective and versatile. This article discusses the applications of NZVMs to treatment of heavy metals, halogenated organic compounds, polycyclic aromatic hydrocarbons, nutrients, radioelements, and microorganisms, using both ex situ and in situ methods. Furthermore, this paper briefly describes the ecotoxicological effects for NZVMs and the research prospects related to their synthesis, modification, characterization, and applications. PMID:27094266

  11. Nanoscale dynamics of the Insulator-to-Metal transition in VO2

    NASA Astrophysics Data System (ADS)

    Sternbach, Aaron

    We have improved upon the technique of time resolved scanning near-field optical microscopy to study the development of inhomogeneous phase transitions in the time domain with 20 nanometer spatial resolution and 100 femtosecond temporal resolution. In our present work, we study Vanadium Dioxide (VO2) , which is a canonical correlated electron system that exhibits an insulator-to-metal transition (IMT) above room temperature. We observe inhomogeneous dynamics that are related to mesoscopic strain variations. Our measurement resolves the dynamical evolution of the IMT on length scales that are short compared with the typical sizes of metallic domains in VO2. By using Near-Infrared radiation, measured on a pulse-to-pulse basis, we are able to achieve an unprecedented Signal-to-Noise ratio. Our advances pave a pathway to study a wide range of systems with inhomogeneities properties on the nanoscale with high sensitivity, nanoscopic spatial, and ultrafast temporal resolution.

  12. A Nanoscale Multiresponsive Luminescent Sensor Based on a Terbium(III) Metal-Organic Framework.

    PubMed

    Dang, Song; Wang, Ting; Yi, Feiyan; Liu, Qinghui; Yang, Weiting; Sun, Zhong-Ming

    2015-08-01

    A nanoscale terbium-containing metal-organic framework (nTbL), with a layer-like structure and [H2 NMe2 ](+) cations located in the framework channels, was synthesized under hydrothermal conditions. The structure of the as-prepared sample was systematically confirmed by powder XRD and elemental analysis; the morphology was characterized by field-emission SEM and TEM. The photoluminescence studies revealed that rod-like nTbL exhibited bright-green emission, corresponding to (5)D4 →(7)FJ (J=6-3) transitions of the Tb(3+) ion under excitation. Further sensing measurements revealed that as-prepared nTbL could be utilized as a multiresponsive luminescent sensor, which showed significant and exclusive detection ability for Fe(3+) ions and phenylmethanol. These results highlight the practical applications of lanthanide-containing metal-organic frameworks as fluorescent probes.

  13. 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.

  14. 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.

  15. Bottom-up synthesis of ordered metal/oxide/metal nanodots on substrates for nanoscale resistive switching memory

    PubMed Central

    Han, Un-Bin; Lee, Jang-Sik

    2016-01-01

    The bottom-up approach using self-assembled materials/processes is thought to be a promising solution for next-generation device fabrication, but it is often found to be not feasible for use in real device fabrication. Here, we report a feasible and versatile way to fabricate high-density, nanoscale memory devices by direct bottom-up filling of memory elements. An ordered array of metal/oxide/metal (copper/copper oxide/copper) nanodots was synthesized with a uniform size and thickness defined by self-organized nanotemplate mask by sequential electrochemical deposition (ECD) of each layer. The fabricated memory devices showed bipolar resistive switching behaviors confirmed by conductive atomic force microscopy. This study demonstrates that ECD with bottom-up growth has great potential to fabricate high-density nanoelectronic devices beyond the scaling limit of top-down device fabrication processes. PMID:27157385

  16. Bottom-up synthesis of ordered metal/oxide/metal nanodots on substrates for nanoscale resistive switching memory

    NASA Astrophysics Data System (ADS)

    Han, Un-Bin; Lee, Jang-Sik

    2016-05-01

    The bottom-up approach using self-assembled materials/processes is thought to be a promising solution for next-generation device fabrication, but it is often found to be not feasible for use in real device fabrication. Here, we report a feasible and versatile way to fabricate high-density, nanoscale memory devices by direct bottom-up filling of memory elements. An ordered array of metal/oxide/metal (copper/copper oxide/copper) nanodots was synthesized with a uniform size and thickness defined by self-organized nanotemplate mask by sequential electrochemical deposition (ECD) of each layer. The fabricated memory devices showed bipolar resistive switching behaviors confirmed by conductive atomic force microscopy. This study demonstrates that ECD with bottom-up growth has great potential to fabricate high-density nanoelectronic devices beyond the scaling limit of top-down device fabrication processes.

  17. 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.

  18. Symmetry analysis in the investigation of clusters in complex metallic alloys

    NASA Astrophysics Data System (ADS)

    Sikora, W.; Malinowski, J.; Kuna, A.; Pytlik, L.

    2008-03-01

    In the complex metallic alloys (CMA) it is often found that some parts of the unit cell form well-defined nanoscale building blocks, called clusters, which are characterized by a specific local symmetry and separated from the 'matrix' crystal lattice by a partially disordered interface zone. The interior of the cluster is usually a close packed structure, the structure of which is not always exactly known, because of the partial disorder in the outer coordination shells. In many CMA's the clusters form a high-symmetry superlattice structure, what usually leads to a giant cubic or pseudo cubic unit cell. The present paper shows a possibility to analyze the changes in local symmetry of the clusters (objects decorating the superlattice nodes) during transformations of the global crystal symmetry. The symmetry analysis method applied to tensor objects, attributed to the clusters, provides information about the symmetry relations between the objects located in different nodes as well as the local symmetry of individual objects (local principal axes, local anisotropy etc.)

  19. Nanoscale surface modifications of medically relevant metals: state-of-the art and perspectives

    NASA Astrophysics Data System (ADS)

    Variola, Fabio; Brunski, John B.; Orsini, Giovanna; Tambasco de Oliveira, Paulo; Wazen, Rima; Nanci, Antonio

    2011-02-01

    Evidence that nanoscale surface properties stimulate and guide various molecular and biological processes at the implant/tissue interface is fostering a new trend in designing implantable metals. Cutting-edge expertise and techniques drawn from widely separated fields, such as nanotechnology, materials engineering and biology, have been advantageously exploited to nanoengineer surfaces in ways that control and direct these processes in predictable manners. In this review, we present and discuss the state-of-the-art of nanotechnology-based approaches currently adopted to modify the surface of metals used for orthopedic and dental applications, and also briefly consider their use in the cardiovascular field. The effects of nanoengineered surfaces on various in vitro molecular and cellular events are firstly discussed. This review also provides an overview of in vivo and clinical studies with nanostructured metallic implants, and addresses the potential influence of nanotopography on biomechanical events at interfaces. Ultimately, the objective of this work is to give the readership a comprehensive picture of the current advances, future developments and challenges in the application of the infinitesimally small to biomedical surface science. We believe that an integrated understanding of the in vitro and particularly of the in vivo behavior is mandatory for the proper exploitation of nanostructured implantable metals and, indeed, of all biomaterials.

  20. Nanoscale surface modifications of medically-relevant metals: state-of-the art and perspectives

    PubMed Central

    Variola, Fabio; Brunski, John; Orsini, Giovanna; de Oliveira, Paulo Tambasco; Wazen, Rima; Nanci, Antonio

    2011-01-01

    Evidence that nanoscale surface properties stimulate and guide various molecular and biological processes at the implant/tissue interface is fostering a new trend in designing implantable metals. Cutting-edge expertise and techniques drawn from widely separated fields, such as nanotechnology, materials engineering and biology, have been advantageously exploited to nanoengineer surfaces in ways that control and direct these processes in predictable manners. In this review, we present and discuss the state-of-the-art of nanotechnology-based approaches currently used to modify the surface of metals used for orthopedic and dental applications, and also briefly consider their use in the cardiovascular field. The effects of nanoengineered surfaces on various in vitro molecular and cellular events are firstly discussed. Importantly, this review also provides an overview of in vivo and clinical studies with nanostructured metallic implants, and addresses the potential influence of nanotopography on biomechanical events at interfaces. Ultimately the objective of this work is to give the readership a comprehensive picture of the current advances, future developments and challenges in the application of the infinitesimally small to biomedical surface science. We believe that an integrated understanding of the in vitro and particularly of the in vivo behavior is mandatory for the proper exploitation of nanostructured implantable metals and, as a matter of fact, all biomaterials. PMID:20976359

  1. Layered reduced graphene oxide with nanoscale interlayer gaps as a stable host for lithium metal anodes

    NASA Astrophysics Data System (ADS)

    Lin, Dingchang; Liu, Yayuan; Liang, Zheng; Lee, Hyun-Wook; Sun, Jie; Wang, Haotian; Yan, Kai; Xie, Jin; Cui, Yi

    2016-07-01

    Metallic lithium is a promising anode candidate for future high-energy-density lithium batteries. It is a light-weight material, and has the highest theoretical capacity (3,860 mAh g–1) and the lowest electrochemical potential of all candidates. There are, however, at least three major hurdles before lithium metal anodes can become a viable technology: uneven and dendritic lithium deposition, unstable solid electrolyte interphase and almost infinite relative dimension change during cycling. Previous research has tackled the first two issues, but the last is still mostly unsolved. Here we report a composite lithium metal anode that exhibits low dimension variation (∼20%) during cycling and good mechanical flexibility. The anode is composed of 7 wt% ‘lithiophilic’ layered reduced graphene oxide with nanoscale gaps that can host metallic lithium. The anode retains up to ∼3,390 mAh g–1 of capacity, exhibits low overpotential (∼80 mV at 3 mA cm–2) and a flat voltage profile in a carbonate electrolyte. A full-cell battery with a LiCoO2 cathode shows good rate capability and flat voltage profiles.

  2. Layered reduced graphene oxide with nanoscale interlayer gaps as a stable host for lithium metal anodes.

    PubMed

    Lin, Dingchang; Liu, Yayuan; Liang, Zheng; Lee, Hyun-Wook; Sun, Jie; Wang, Haotian; Yan, Kai; Xie, Jin; Cui, Yi

    2016-07-01

    Metallic lithium is a promising anode candidate for future high-energy-density lithium batteries. It is a light-weight material, and has the highest theoretical capacity (3,860 mAh g(-1)) and the lowest electrochemical potential of all candidates. There are, however, at least three major hurdles before lithium metal anodes can become a viable technology: uneven and dendritic lithium deposition, unstable solid electrolyte interphase and almost infinite relative dimension change during cycling. Previous research has tackled the first two issues, but the last is still mostly unsolved. Here we report a composite lithium metal anode that exhibits low dimension variation (∼20%) during cycling and good mechanical flexibility. The anode is composed of 7 wt% 'lithiophilic' layered reduced graphene oxide with nanoscale gaps that can host metallic lithium. The anode retains up to ∼3,390 mAh g(-1) of capacity, exhibits low overpotential (∼80 mV at 3 mA cm(-2)) and a flat voltage profile in a carbonate electrolyte. A full-cell battery with a LiCoO2 cathode shows good rate capability and flat voltage profiles.

  3. Layered reduced graphene oxide with nanoscale interlayer gaps as a stable host for lithium metal anodes

    NASA Astrophysics Data System (ADS)

    Lin, Dingchang; Liu, Yayuan; Liang, Zheng; Lee, Hyun-Wook; Sun, Jie; Wang, Haotian; Yan, Kai; Xie, Jin; Cui, Yi

    2016-07-01

    Metallic lithium is a promising anode candidate for future high-energy-density lithium batteries. It is a light-weight material, and has the highest theoretical capacity (3,860 mAh g-1) and the lowest electrochemical potential of all candidates. There are, however, at least three major hurdles before lithium metal anodes can become a viable technology: uneven and dendritic lithium deposition, unstable solid electrolyte interphase and almost infinite relative dimension change during cycling. Previous research has tackled the first two issues, but the last is still mostly unsolved. Here we report a composite lithium metal anode that exhibits low dimension variation (˜20%) during cycling and good mechanical flexibility. The anode is composed of 7 wt% ‘lithiophilic’ layered reduced graphene oxide with nanoscale gaps that can host metallic lithium. The anode retains up to ˜3,390 mAh g-1 of capacity, exhibits low overpotential (˜80 mV at 3 mA cm-2) and a flat voltage profile in a carbonate electrolyte. A full-cell battery with a LiCoO2 cathode shows good rate capability and flat voltage profiles.

  4. The investigation of nanoscale effects on schottky interfaces and the scattering rates of high resistivity metals

    NASA Astrophysics Data System (ADS)

    Durcan, Christopher

    Understanding the transport of electrons through materials and across interfaces is fundamental to modern day electronics. As electrons travel, interactions with defects within the crystal lattice induce scattering which gives rise to resistivity. At the interface between two materials, electrostatic barriers exist which can impede the flow of electrons. The work of this thesis is to further the understanding of electron transport by measuring the transport across metal-semiconductor interfaces at the nanoscale and measure scattering phenomena in metals. The measurement technique ballistic electron emission microscopy (BEEM) was used due to its ability to probe the scattering processes within a metal film and across metal semiconductor interfaces with nanoscale resolution. It was discovered that the hot electron transmission of the W/Si(001) Schottky barrier decreases over a period of 21 days with the initial Schottky barrier height of 0.71eV decreasing to 0.62eV. The spatial map changes dramatically from 98% of the spectra able to be fit to only 27%. This is supported by transmission electron microscopy (TEM) showing the formation of a tungsten silicide which increases in thickness. It was discovered that the deposition of tungsten on silicon using electron beam evaporation and RF magnetron sputtering resulted in dramatic differences in the Schottky barrier height and transport of hot electrons. A difference of ˜70meV was measured in the Schottky barrier height's for both p-type and n-type silicon. Spatial maps show a uniform barrier height for the sputter film and varying barrier height for the e-beam film. Histograms show a symmetric gaussian profile for the sputtered film and an asymmetric profile for the evaporated film, arising from an increase in elastic scattering. The hot electron attenuation length of tungsten and chromium thin films were measured on Si(001) and Si(111) substrates. An attenuation length of 2.26nm was measured at 1.0V bias for tungsten

  5. Quantitative binomial distribution analyses of nanoscale like-solute atom clustering and segregation in atom probe tomography data.

    PubMed

    Moody, Michael P; Stephenson, Leigh T; Ceguerra, Anna V; Ringer, Simon P

    2008-07-01

    The applicability of the binomial frequency distribution is outlined for the analysis of the evolution nanoscale atomic clustering of dilute solute in an alloy subject to thermal ageing in 3D atom probe data. The conventional chi(2) statistics and significance testing are demonstrated to be inappropriate for comparison of quantity of solute segregation present in two or more different sized system. Pearson coefficient, mu, is shown to normalize chi(2) with respect to sample size over an order of magnitude. A simple computer simulation is implemented to investigate the binomial analysis and infer meaning in the measured value of mu over a series of systems at different solute concentrations and degree of clustering. The simulations replicate the form of experimental data and demonstrate the effect of detector efficiency to significantly underestimate the measured segregation. The binomial analysis is applied to experimental atom probe data sets and complementary simulations are used to interpret the results.

  6. Probing Stochastic Nano-Scale Inelastic Events in Stressed Amorphous Metal

    PubMed Central

    Yang, Y.; Fu, X. L.; Wang, S.; Liu, Z. Y.; Ye, Y. F.; Sun, B. A.; Liu, C. T.

    2014-01-01

    One fundamental yet longstanding issue in materials science is how local inelasticity arises within an amorphous structure before yielding occurs. Although many possible scenarios were postulated or predicted by theories and simulations,however, direct experimental evidence has been lacking today due to the lack of a sensitive way to detect nano-scale inelasticity. Through the carefully designed microcompression method as coupled with the state-of-art nano-scale electric resistance measurement, we here unfold a stochastic inelastic deformation process in a Zr-based metallic glass, which takes place via the recurrence of two types of short-lived inelastic events causing structural damage and recovery, respectively, prior to yielding. Our current findings reveal that these stochastic events not only self-organize into sub-critical events due to elastic coupling, but also compete with each other in a way that enables the whole amorphous structure to self-heal as well as to sustain local damage. PMID:25331932

  7. Chemical bonding and dynamic fluxionality of a B15(+) cluster: a nanoscale double-axle tank tread.

    PubMed

    Wang, Ying-Jin; You, Xue-Rui; Chen, Qiang; Feng, Lin-Yan; Wang, Kang; Ou, Ting; Zhao, Xiao-Yun; Zhai, Hua-Jin; Li, Si-Dian

    2016-06-21

    A planar, elongated B15(+) cationic cluster is shown to be structurally fluxional and functions as a nanoscale tank tread on the basis of electronic structure calculations, bonding analyses, and molecular dynamics simulations. The outer B11 peripheral ring behaves like a flexible chain gliding around an inner B4 rhombus core, almost freely at the temperature of 500 K. The rotational energy barrier is only 1.37 kcal mol(-1) (0.06 eV) at the PBE0/6-311+G* level, further refined to 1.66 kcal mol(-1) (0.07 eV) at the single-point CCSD(T)/6-311G*//CCSD/6-311G* level. Two soft vibrational modes of 166.3 and 258.3 cm(-1) are associated with the rotation, serving as double engines for the system. Bonding analysis suggests that the "island" electron clouds, both σ and π, between the peripheral ring and inner core flow and shift continuously during the intramolecular rotation, facilitating the dynamic fluxionality of the system with a small rotational barrier. The B15(+) cluster, roughly 0.6 nm in dimension, is the first double-axle nanoscale tank tread equipped with two engines, which expands the concepts of molecular wheels, Wankel motors, and molecular tanks.

  8. Chemical bonding and dynamic fluxionality of a B15(+) cluster: a nanoscale double-axle tank tread.

    PubMed

    Wang, Ying-Jin; You, Xue-Rui; Chen, Qiang; Feng, Lin-Yan; Wang, Kang; Ou, Ting; Zhao, Xiao-Yun; Zhai, Hua-Jin; Li, Si-Dian

    2016-06-21

    A planar, elongated B15(+) cationic cluster is shown to be structurally fluxional and functions as a nanoscale tank tread on the basis of electronic structure calculations, bonding analyses, and molecular dynamics simulations. The outer B11 peripheral ring behaves like a flexible chain gliding around an inner B4 rhombus core, almost freely at the temperature of 500 K. The rotational energy barrier is only 1.37 kcal mol(-1) (0.06 eV) at the PBE0/6-311+G* level, further refined to 1.66 kcal mol(-1) (0.07 eV) at the single-point CCSD(T)/6-311G*//CCSD/6-311G* level. Two soft vibrational modes of 166.3 and 258.3 cm(-1) are associated with the rotation, serving as double engines for the system. Bonding analysis suggests that the "island" electron clouds, both σ and π, between the peripheral ring and inner core flow and shift continuously during the intramolecular rotation, facilitating the dynamic fluxionality of the system with a small rotational barrier. The B15(+) cluster, roughly 0.6 nm in dimension, is the first double-axle nanoscale tank tread equipped with two engines, which expands the concepts of molecular wheels, Wankel motors, and molecular tanks. PMID:27229290

  9. 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.

  10. Second harmonic generation in nanoscale films of transition metal chalcogenides: Taking into account multibeam interference

    NASA Astrophysics Data System (ADS)

    Lavrov, S. D.; Kudryavtsev, A. V.; Shestakova, A. P.; Kulyuk, L.; Mishina, E. D.

    2016-05-01

    Second harmonic generation is studied in structures containing nanoscale layers of transition metal chalcogenides that are two-dimensional semiconductors and deposited on a SiO2/Si substrate. The second harmonic generation intensity is calculated with allowance for multibeam interference in layers of dichalcogenide and silicon oxide. The coefficient of reflection from the SiO2-layer-based Fabry-Perot cavity is subsequently calculated for pump wave fields initiating nonlinear polarization at every point of dichalcogenide, which is followed by integration of all second harmonic waves generated by this polarization. Calculated second harmonic intensities are presented as functions of dichalcogenide and silicon oxide layer thicknesses. The dependence of the second harmonic intensity on the MoS2 layer thickness is studied experimentally in the layer of 2-140 nm. A good coincidence of the experimental data and numerical simulation results has been obtained.

  11. Controlling terahertz radiation with nanoscale metal barriers embedded in nano slot antennas.

    PubMed

    Park, Hyeong-Ryeol; Bahk, Young-Mi; Ahn, Kwang Jun; Park, Q-Han; Kim, Dai-Sik; Martín-Moreno, Luis; García-Vidal, Francisco J; Bravo-Abad, Jorge

    2011-10-25

    Nanoscale metallic barriers embedded in terahertz (THz) slot antennas are shown to provide unprecedented control of the transition state arising at the crossover between the full- and half-wavelength resonant modes of such antennas. We demonstrate strong near-field coupling between two paired THz slot antennas separated by a 5 nm wide nanobarrier, almost fully inducing the shift to the resonance of the double-length slot antenna. This increases by a factor of 50 the length-scale needed to observe similar coupling strengths in conventional air-gap antennas (around 0.1 nm), making the transition state readily accessible to experiment. Our measurements are in good agreement with a quantitative theoretical modeling, which also provides a simple physical picture of our observations.

  12. Controlling terahertz radiation with nanoscale metal barriers embedded in nano slot antennas.

    PubMed

    Park, Hyeong-Ryeol; Bahk, Young-Mi; Ahn, Kwang Jun; Park, Q-Han; Kim, Dai-Sik; Martín-Moreno, Luis; García-Vidal, Francisco J; Bravo-Abad, Jorge

    2011-10-25

    Nanoscale metallic barriers embedded in terahertz (THz) slot antennas are shown to provide unprecedented control of the transition state arising at the crossover between the full- and half-wavelength resonant modes of such antennas. We demonstrate strong near-field coupling between two paired THz slot antennas separated by a 5 nm wide nanobarrier, almost fully inducing the shift to the resonance of the double-length slot antenna. This increases by a factor of 50 the length-scale needed to observe similar coupling strengths in conventional air-gap antennas (around 0.1 nm), making the transition state readily accessible to experiment. Our measurements are in good agreement with a quantitative theoretical modeling, which also provides a simple physical picture of our observations. PMID:21961910

  13. Direct in situ observation of metallic glass deformation by real-time nano-scale indentation

    PubMed Central

    Gu, Lin; Xu, Limei; Zhang, Qingsheng; Pan, Deng; Chen, Na; Louzguine-Luzgin, Dmitri V.; Yao, Ke-Fu; Wang, Weihua; Ikuhara, Yuichi

    2015-01-01

    A common understanding of plastic deformation of metallic glasses (MGs) at room temperature is that such deformation occurs via the formation of runaway shear bands that usually lead to catastrophic failure of MGs. Here we demonstrate that inhomogeneous plastic flow at nanoscale can evolve in a well-controlled manner without further developing of shear bands. It is suggested that the sample undergoes an elasto-plastic transition in terms of quasi steady-state localized shearing. During this transition, embryonic shear localization (ESL) propagates with a very slow velocity of order of ~1 nm/s without the formation of a hot matured shear band. This finding further advances our understanding of the microscopic deformation process associated with the elasto-plastic transition and may shed light on the theoretical development of shear deformation in MGs. PMID:25773051

  14. Direct in situ observation of metallic glass deformation by real-time nano-scale indentation.

    PubMed

    Gu, Lin; Xu, Limei; Zhang, Qingsheng; Pan, Deng; Chen, Na; Louzguine-Luzgin, Dmitri V; Yao, Ke-Fu; Wang, Weihua; Ikuhara, Yuichi

    2015-03-16

    A common understanding of plastic deformation of metallic glasses (MGs) at room temperature is that such deformation occurs via the formation of runaway shear bands that usually lead to catastrophic failure of MGs. Here we demonstrate that inhomogeneous plastic flow at nanoscale can evolve in a well-controlled manner without further developing of shear bands. It is suggested that the sample undergoes an elasto-plastic transition in terms of quasi steady-state localized shearing. During this transition, embryonic shear localization (ESL) propagates with a very slow velocity of order of ~1 nm/s without the formation of a hot matured shear band. This finding further advances our understanding of the microscopic deformation process associated with the elasto-plastic transition and may shed light on the theoretical development of shear deformation in MGs.

  15. Probing elasticity at the nanoscale: Terahertz acoustic vibration of small metal nanoparticles.

    PubMed

    Juvé, Vincent; Crut, Aurélien; Maioli, Paolo; Pellarin, Michel; Broyer, Michel; Del Fatti, Natalia; Vallée, Fabrice

    2010-05-12

    The acoustic response of surface-controlled metal (Pt) nanoparticles is investigated in the small size range, between 1.3 and 3 nm (i.e., 75-950 atoms), using time-resolved spectroscopy. Acoustic vibration of the nanoparticles is demonstrated, with frequencies ranging from 1.1 to 2.6 THz, opening the way to the development of THz acoustic resonators. The frequencies, measured with a noncontact optical method, are in excellent agreement with the prediction of a macroscopic approach based on the continuous elastic model, together with the bulk material elastic constants. This demonstrates the validity of this model at the nanoscale and the weak impact of size reduction on the elastic properties of a material, even for nanoparticles formed by less than 100 atoms.

  16. 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

  17. Controlled reactivity tuning of metal-functionalized vanadium oxide clusters.

    PubMed

    Kastner, Katharina; Forster, Johannes; Ida, Hiromichi; Newton, Graham N; Oshio, Hiroki; Streb, Carsten

    2015-05-18

    Controlling the assembly and functionalization of molecular metal oxides [Mx Oy ](n-) (M=Mo, W, V) allows the targeted design of functional molecular materials. While general methods exist that enable the predetermined functionalization of tungstates and molybdates, no such routes are available for molecular vanadium oxides. Controlled design of polyoxovanadates, however, would provide highly active materials for energy conversion, (photo-) catalysis, molecular magnetism, and materials science. To this end, a new approach has been developed that allows the reactivity tuning of vanadium oxide clusters by selective metal functionalization. Organic, hydrogen-bonding cations, for example, dimethylammonium are used as molecular placeholders to block metal binding sites within vanadate cluster shells. Stepwise replacement of the placeholder cations with reactive metal cations gives mono- and difunctionalized clusters. Initial reactivity studies illustrate the tunability of the magnetic, redox, and catalytic activity.

  18. Trinuclear Metal Clusters in Catalysis by Terpenoid Synthases.

    PubMed

    Aaron, Julie A; Christianson, David W

    2010-01-01

    Terpenoid synthases are ubiquitous enzymes that catalyze the formation of structurally and stereochemically diverse isoprenoid natural products. Many isoprenoid coupling enzymes and terpenoid cyclases from bacteria, fungi, protists, plants, and animals share the class I terpenoid synthase fold. Despite generally low amino acid sequence identity among these examples, class I terpenoid synthases contain conserved metal binding motifs that coordinate to a trinuclear metal cluster. This cluster not only serves to bind and orient the flexible isoprenoid substrate in the precatalytic Michaelis complex, but it also triggers the departure of the diphosphate leaving group to generate a carbocation that initiates catalysis. Additional conserved hydrogen bond donors assist the metal cluster in this function. Crystal structure analysis reveals that the constellation of three metal ions required for terpenoid synthase catalysis is generally identical among all class I terpenoid synthases of known structure.

  19. Nanoscale Assessment of Water Incursion to the Metal/Coating Interface

    NASA Astrophysics Data System (ADS)

    Lee, Hyungjin; Browning, Jim; Foster, Mark

    2012-04-01

    While a great deal of research on macroscopic corrosion phenomena has been done and an empirical knowledge of effective corrosion mitigation strategies is available, a fundamental understanding of many nanoscale aspects of corrosion or precorrosion processes at metal interface is lacking. Neutron reflectometry (NR) can be used to nondestructively determine depth profile of a substance near an interface with a resolution of 1-2 nm. Key precorrosion phenomena that we have focused on are ingress of small molecules such as water and salt into coating or coating/metal interface. To simulate a practical precorrosion process, an in situ experiment in which the sample is in the presence of water vapor can be performed. Samples of a thin epoxy coating containing siloxane on an aluminum substrate having a native oxide have been studied by NR. Composition depth profile of water at coating/oxide interface can be inferred using a comparison of the data from samples under dry and humid conditions. We have shown that water incursion along coating/metal interface is fast compared to incursion through face of coating. Also, our work has provided evidence that, with a more highly crosslinked coating, after a small amount of water has entered along the interface water incursion slows dramatically.

  20. Magnetic sulfide-modified nanoscale zerovalent iron (S-nZVI) for dissolved metal ion removal.

    PubMed

    Su, Yiming; Adeleye, Adeyemi S; Keller, Arturo A; Huang, Yuxiong; Dai, Chaomeng; Zhou, Xuefei; Zhang, Yalei

    2015-05-01

    Sulfide-modified nanoscale zerovalent iron (S-nZVI) is attracting a lot of attention due to its ease of production and high reactivity with organic pollutants. However, its structure is still poorly understood and its potential application in heavy metal remediation has not been explored. Herein, the structure of S-nZVI and its cadmium (Cd) removal performance under different aqueous conditions were carefully investigated. Transmission electron microscopy (TEM) with an energy-dispersive X-ray spectroscopy (EDS) analysis suggested that sulfur was incorporated into the zerovalent iron core. Scanning electron microscopy (SEM) with EDS analysis demonstrated that sulfur was also homogeneously distributed within the nanoparticles. When the concentration of Na2S2O4 was increased during synthesis, a flake-like structure (FeSx) increased significantly. S-nZVI had an optimal Cd removal capacity of 85 mg/g, which was >100% higher than for pristine nZVI. Even at pH 5, over 95% removal efficiency was observed, indicating sulfide compounds played a crucial role in metal ion removal and particle chemical stability. Oxygen impaired the structure of S-nZVI but enhanced Cd removal capacity to about 120 mg/g. Particle aging had no negative effect on removal capacity of S-nZVI, and Cd-containing mixtures remained stable in a two months experiment. S-nZVI can efficiently sequester dissolved metal ions from different contaminated water matrices. PMID:25706223

  1. Carbonized nanoscale metal-organic frameworks as high performance electrocatalyst for oxygen reduction reaction.

    PubMed

    Zhao, Shenlong; Yin, Huajie; Du, Lei; He, Liangcan; Zhao, Kun; Chang, Lin; Yin, Geping; Zhao, Huijun; Liu, Shaoqin; Tang, Zhiyong

    2014-12-23

    The oxygen reduction reaction (ORR) is one of the key steps in clean and efficient energy conversion techniques such as in fuel cells and metal-air batteries; however, several disadvantages of current ORRs including the kinetically sluggish process and expensive catalysts hinder mass production of these devices. Herein, we develop carbonized nanoparticles, which are derived from monodisperse nanoscale metal organic frameworks (MIL-88B-NH3), as the high performance ORR catalysts. The onset potential and the half-wave potential for the ORR at these carbonized nanoparticles is up to 1.03 and 0.92 V (vs RHE) in 0.1 M KOH solution, respectively, which represents the best ORR activity of all the non-noble metal catalysts reported so far. Furthermore, when used as the cathode of the alkaline direct fuel cell, the power density obtained with the carbonized nanoparticles reaches 22.7 mW/cm2, 1.7 times higher than the commercial Pt/C catalysts. PMID:25426850

  2. 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.

  3. 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

  4. Chemiluminescence in the Agglomeration of Metal Clusters

    PubMed

    König; Rabin; Schulze; Ertl

    1996-11-22

    The agglomeration of copper or silver atoms in a matrix of noble gas atoms to form small clusters may be accompanied by the emission of visible light. Spectral analysis reveals the intermediate formation of electronically excited atoms and dimers as the source of the chemiluminescence. A mechanism is proposed, according to which the gain in binding energy upon cluster formation may even lead to the ejection of excited fragments as a result of unstable intermediate configurations. A similar concept was introduced in the field of nuclear reactions by Niels Bohr 60 years ago.

  5. 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.

  6. 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.

  7. Nanoscale mechano-electronic behavior of a metalloprotein as a variable of metal content.

    PubMed

    Rakshit, Tatini; Banerjee, Siddhartha; Mishra, Sourav; Mukhopadhyay, Rupa

    2013-10-01

    In this work, we have explored an approach to finding a correlation between the mechanical response of a metalloprotein against a range of applied force (by force curve analysis) and its electrical response under pressure stimulation (by current sensing atomic force spectroscopy) at the nanoscale. Iron-storage protein ferritin has been chosen as an experimental model system because it naturally contains a semiconducting iron core. This core consists of a large number of iron atoms and is therefore expected to exert a clear influence on the overall mechanical response of the protein structure. Four different ferritins (apoferritin, Fe(III)-ferritins containing ~750 and ~1400 iron atoms, and holoferritin containing ~2600 iron atoms) were chosen in order to identify any relation between the mechano-electronic behavior of the ferritins and their metal content. We report the measurement of Young's modulus values of the ferritin proteins as applicable in a nanoscale environment, for the first time, and show that these values are directly linked to the iron content of the individual ferritin type. The greater the iron content, the greater the Young's modulus and in general the slower the rate of deformation against the application of force. When compressed, all the four ferritins exhibited increased electronic conductivity. A correlation between the iron content of the ferritins and the current values observed at certain bias voltages could be made at higher bias values (beyond 0.7 V), but no such discrimination among the four compressed ferritins could be made at the lower voltages. We propose that only at higher voltages can the iron atoms that reside deeper inside the core of the ferritins be accessed. The iron atoms that could be situated at the inner wall of the protein shell appear to make a general contribution to the electronic conductivity of the four ferritin systems.

  8. Nanoscale Twinning and Martensitic Transformation in Shock-Deformed BCC Metals

    SciTech Connect

    Hsiung, L L

    2005-03-22

    Shock-induced twinning and martensitic transformation in BCC-based polycrystalline metals (Ta and U-6wt%Nb) have been observed and studied using transmission electron microscopy (TEM). The length-scale of domain thickness for both twin lamella and martensite phase is found to be smaller than 100 nm. While deformation twinning of {l_brace}112{r_brace}<111>-type is found in Ta when shock-deformed at 15 GPa, both twinning and martensitic transformation are found in Ta when shock-deformed at 45 GPa. Similar phenomena of nanoscale twinning and martensitic transformation are also found in U6Nb shock-deformed at 30 GPa. Since both deformation twinning and martensitic transformation occurred along the {l_brace}211{r_brace}{sub b} planes associated with high resolved shear stresses, it is suggested that both can be regarded as alternative paths for shear transformations to occur in shock-deformed BCC metals. Heterogeneous nucleation mechanisms for shock-induced twinning and martensitic transformation are proposed and discussed.

  9. 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.

  10. 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.

  11. 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.

  12. Metal-Insulator Transition of Dirac Fermions: Variational Cluster Study

    NASA Astrophysics Data System (ADS)

    Ebato, Masaki; Kaneko, Tatsuya; Ohta, Yukinori

    2015-04-01

    A comparative study is made on the metal-insulator transition of Dirac fermions in the honeycomb and π-flux Hubbard models at half filling by means of the variational cluster approximation and cluster dynamical impurity approximation. Paying particular attention to the choice of the geometry of solver clusters and the inclusion of particle-bath sites, we show that the direct transition from the Dirac semimetallic state to the antiferromagnetic Mott insulator state occurs in these models, and therefore, the spin liquid phase is absent in the intermediate region, in agreement with recent quantum-Monte-Carlo-based calculations.

  13. Formation and photodetachment of cold metal cluster negative ions

    NASA Astrophysics Data System (ADS)

    Zheng, L.-S.; Brucat, P. J.; Pettiette, C. L.; Yang, S.; Smalley, R. E.

    1985-10-01

    A general method is described for the formation of cold metal cluser negative ion beams which serve as excellent sources for photodetachment experiments. The method involves the pulsed laser vaporization of a metal target at the throat of a pulsed supersonic helium expansion. By the optimization of source conditions, intense beams (greater than 105 ions/pulse) of both positive and negative ions are produced routinely. Ionization of the metal cluster molecules, either during vaporization or by irradiation with 193 nm light, occurs prior to supersonic expansion and produces a cold plasma entrained in the neural flow that is renitent to stray electric and magnetic fields, unlike photoions produced in the collisionless downstream molecular beam. The enhancement of the negative ion flux by 193 nm irradiation is believed to be evidence for efficient electron attachment of low energy photoelectrons generated in the nozzle region. This attachment process, however, is apparently not effective for molecules containing less than ˜4 metal atoms. Laser irradition of mass-selected cluster anions extracted from these cold ion beams reveal that photodetachment of the metal cluster negative ion is always the preferred pathway, even when fragmentation of the ion is possible. This new negative ion production technique should therefore permit measurement of both electron affinities and photoelectron spectra as a function of cluster size and composition.

  14. Nucleation and growth of nanoscale metal silicides in nanowires of silicon

    NASA Astrophysics Data System (ADS)

    Chou, Yi-Chia

    Transition metal silicides have been used in the SALICIDE process to form gate and source/drain contacts in MOSFET devices. How to control silicide formation in shallow junction devices and the kinetics of single silicide phase formation between the Si and metal thin films have received extensive attention and study. As the trend of miniaturization of Si devices moves from 45 rim to smaller sizes, the formation of nanoscale metal silicides has attracted renewed interest. Nanostructures in Si nanowires have been studied for basic components in electronic and optoelectronics devices, especially for biosensors. Well-defined nanoscale building blocks such as ohmic contacts and gates on Si nanowires must be developed in order to be assembled into functional circuit components in future nanotechnology. It requires a systematic study of solid state chemical reactions in the nanoscale to form these circuit components. In the dissertation, the nucleation and growth of epitaxial silicides in Si nanowires has been discussed and the comparison of silicide formation in thin films and in nanowires has been made. The difference of silicide formation between the thin film case and the nanowire case, especially the kinetics of nucleation and growth, will be emphasized. In this dissertation, I focused on the nucleation and growth of Ni and Co silicides formation in Si nanowires and used in situ high resolution transmission electron microscopy (TEM) to investigate kinetics of the silicides formation. Heterostructures of silicide/Si/silicide, such as NiSi/Si/NiSi, NiSi2/Si/NiSi2, and CoSi2/Si/CoSi 2, have been produced with sharp interfaces. Periodic multi-heterostructures of NiSi/Si and NiSi2/Si have been synthesized by in-situ TEM. The NiSi, NiSi2, and CoSi2 were found to have epitaxial growth with Si and the growth can be decomposed into nucleation periods and growth periods instead of continues growth as thin film silicides formation on Si wafers. The silicides grow atomic layer

  15. Nanoscale semiconductor-insulator-metal core/shell heterostructures: facile synthesis and light emission

    NASA Astrophysics Data System (ADS)

    Li, Gong Ping; Chen, Rui; Guo, Dong Lai; Wong, Lai Mun; Wang, Shi Jie; Sun, Han Dong; Wu, Tom

    2011-08-01

    Controllably constructing hierarchical nanostructures with distinct components and designed architectures is an important theme of research in nanoscience, entailing novel but reliable approaches of bottom-up synthesis. Here, we report a facile method to reproducibly create semiconductor-insulator-metal core/shell nanostructures, which involves first coating uniform MgO shells onto metal oxide nanostructures in solution and then decorating them with Au nanoparticles. The semiconductor nanowire core can be almost any material and, herein, ZnO, SnO2 and In2O3 are used as examples. We also show that linear chains of short ZnO nanorods embedded in MgO nanotubes and porous MgO nanotubes can be obtained by taking advantage of the reduced thermal stability of the ZnO core. Furthermore, after MgO shell-coating and the appropriate annealing treatment, the intensity of the ZnO near-band-edge UV emission becomes much stronger, showing a 25-fold enhancement. The intensity ratio of the UV/visible emission can be increased further by decorating the surface of the ZnO/MgO nanowires with high-density plasmonic Au nanoparticles. These heterostructured semiconductor-insulator-metal nanowires with tailored morphologies and enhanced functionalities have great potential for use as nanoscale building blocks in photonic and electronic applications.Controllably constructing hierarchical nanostructures with distinct components and designed architectures is an important theme of research in nanoscience, entailing novel but reliable approaches of bottom-up synthesis. Here, we report a facile method to reproducibly create semiconductor-insulator-metal core/shell nanostructures, which involves first coating uniform MgO shells onto metal oxide nanostructures in solution and then decorating them with Au nanoparticles. The semiconductor nanowire core can be almost any material and, herein, ZnO, SnO2 and In2O3 are used as examples. We also show that linear chains of short ZnO nanorods embedded in

  16. 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.

  17. Supersonic metal cluster beams. Technical progress report, March 16, 1984-April 1, 1985

    SciTech Connect

    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.

  18. 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.

  19. 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.

  20. 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.

  1. Photodissociation Studies of Metal-Containing Clusters and Complexes

    NASA Astrophysics Data System (ADS)

    Pilgrim, Jeffrey Scott

    1995-01-01

    There have been two major areas of investigation for researchers working with laser ablation in molecular beams. The first area is the study of weakly-bound complexes. These complexes are bound by electrostatic interactions. In the present study the weakly bound interactions of the rare gases with the magnesium ion are investigated with electronic spectroscopy. The second major area is the study of metal and metal-containing clusters. Examples of previous investigations are the alkali metal clusters and the fullerenes. The present investigation is on metal -carbon clusters. The so-called metallo-carbohedrenes and metal-carbon nanocrystals are studied. Resonance enhanced photodissociation spectroscopy is used to obtain electronic excitation spectra of the Mg^+-rare gas species in the ultraviolet region. This investigation is facilitated by a reflectron time-of-flight mass spectrometer. The interaction of the rare gas with the metal ion is attributed to a "solvation" of the atomic ion transition. Simple bonding arguments predict that the excited state is more bound than the ground state for these complexes. This will result in a shift of the complex vibronic origin to lower energy from the atomic ion transition. This is exactly what is observed in the experiment with progressively larger shifts for the heavier rare gases. The electronic excitation spectra allow the vibrational frequencies and anharmonicities for these complexes to be obtained for the excited state. In turn, the excited state bond dissociation energies can be determined. Finally, conservation of energy allows calculation of the ground state bond dissociation energies. In the metal-carbon systems the stability of the metallo-carbohedrene, met-car, stoichiometry is shown to extend into the transition period at least to the iron group. Photodissociation with a 532 nm laser causes a loss of metal atoms for met-cars formed with first row transition metals and a loss of metal-carbon units for met

  2. Nanoscale spatial organization of the HoxD gene cluster in distinct transcriptional states.

    PubMed

    Fabre, Pierre J; Benke, Alexander; Joye, Elisabeth; Nguyen Huynh, Thi Hanh; Manley, Suliana; Duboule, Denis

    2015-11-10

    Chromatin condensation plays an important role in the regulation of gene expression. Recently, it was shown that the transcriptional activation of Hoxd genes during vertebrate digit development involves modifications in 3D interactions within and around the HoxD gene cluster. This reorganization follows a global transition from one set of regulatory contacts to another, between two topologically associating domains (TADs) located on either side of the HoxD locus. Here, we use 3D DNA FISH to assess the spatial organization of chromatin at and around the HoxD gene cluster and report that although the two TADs are tightly associated, they appear as spatially distinct units. We measured the relative position of genes within the cluster and found that they segregate over long distances, suggesting that a physical elongation of the HoxD cluster can occur. We analyzed this possibility by super-resolution imaging (STORM) and found that tissues with distinct transcriptional activity exhibit differing degrees of elongation. We also observed that the morphological change of the HoxD cluster in developing digits is associated with its position at the boundary between the two TADs. Such variations in the fine-scale architecture of the gene cluster suggest causal links among its spatial configuration, transcriptional activation, and the flanking chromatin context. PMID:26504220

  3. Tetrathiomolybdate Inhibits Copper Trafficking Proteins Through Metal Cluster Formation

    SciTech Connect

    Alvarez, Hamsell M.; Xue, Yi; Robinson, Chandler D.; Canalizo-Hernández, Mónica A.; Marvin, Rebecca G.; Kelly, Rebekah A.; Mondragón, Alfonso; Penner-Hahn, James E.; O’Halloran, Thomas V.

    2010-05-06

    Tetrathiomolybdate (TM) is an orally active agent for treatment of disorders of copper metabolism. Here we describe how TM inhibits proteins that regulate copper physiology. Crystallographic results reveal that the surprising stability of the drug complex with the metallochaperone Atx1 arises from formation of a sulfur-bridged copper-molybdenum cluster reminiscent of those found in molybdenum and iron sulfur proteins. Spectroscopic studies indicate that this cluster is stable in solution and corresponds to physiological clusters isolated from TM-treated Wilson's disease animal models. Finally, mechanistic studies show that the drug-metallochaperone inhibits metal transfer functions between copper-trafficking proteins. The results are consistent with a model wherein TM can directly and reversibly down-regulate copper delivery to secreted metalloenzymes and suggest that proteins involved in metal regulation might be fruitful drug targets.

  4. Structure of fluorescent metal clusters on a DNA template.

    NASA Astrophysics Data System (ADS)

    Vdovichev, A. A.; Sych, T. S.; Reveguk, Z. V.; Smirnova, A. A.; Maksimov, D. A.; Ramazanov, R. R.; Kononov, A. I.

    2016-08-01

    Luminescent metal clusters are a subject of growing interest in recent years due to their bright emission from visible to near infrared range. Detailed structure of the fluorescent complexes of Ag and other metal clusters with ligands still remains a challenging task. In this joint experimental and theoretical study we synthesized Ag-DNA complexes on a DNA oligonucleotide emitting in violet- green spectral range. The structure of DNA template was determined by means of various spectral measurements (CD, MS, XPS). Comparison of the experimental fluorescent excitation spectra and calculated absorption spectra for different QM/MM optimized structures allowed us to determine the detailed structure of the green cluster containing three silver atoms in the stem of the DNA hairpin structure stabilized by cytosine-Ag+-cytosine bonds.

  5. Metal Structural Environment in ZnxNi1-xO Macroscale and Nanoscale Solid Solutions

    SciTech Connect

    Peck, Matthea A.; Langell, Marjorie A.

    2014-08-21

    The metal structural environments in macroscale and nanoscale ZnxNi1–xO solid solutions were examined using X-ray diffraction (XRD), X-ray absorption spectroscopy (XAS), and X-ray photoelectron spectroscopy (XPS). XRD demonstrates that solid solutions form for both macroscale (bulk) and nanoscale crystallites, and that the lattice parameter increases linearly as the amount of zinc increases, an indication of a homogeneous solid solution. XAS for both the bulk material and the nanoparticles reveals that the zinc atoms are incorporated into the rocksalt lattice and do not form zinc oxide clusters. The X-ray absorption near edge spectroscopy (XANES) of the Zn k-edge region in the solid solution is similar to the Ni k-edge region of NiO, and not the Zn k-edge region of ZnO. XPS confirms that solid solutions are formed; Auger parameters for zinc are consistent with a different geometry than the tetrahedral coordination of wurtzite ZnO. Nanoscaled solid solutions show evidence of a lattice contraction relative to macroscale solutions of the same concentration. While the contraction persists across the entire concentration range, the nanoparticle lattice parameter approaches the bulk ZnxNi1–xO value as the concentration of zinc increases to predict ZnO rocksalt lattice parameters that are in agreement with observed ZnO data.

  6. 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.

  7. Identifying Deformation and Strain Hardening Behaviors of Nanoscale Metallic Multilayers Through Nano-wear Testing

    DOE PAGES

    Economy, David Ross; Mara, Nathan A.; Schoeppner, R.; Schultz, Bradley M.; Unocic, Raymond R.; Kennedy, Marian S.

    2016-01-13

    In complex loading conditions (e.g. sliding contact), mechanical properties, such as strain hardening and initial hardness, will dictate the long-term performance of materials systems. With this in mind, the strain hardening behaviors of Cu/Nb nanoscale metallic multilayer systems were examined by performing nanoindentation tests within nanoscratch wear boxes and undeformed, as-deposited regions. Both the architecture and substrate influence were examined by utilizing three different individual layer thicknesses (2, 20, and 100 nm) and two total film thicknesses (1 and 10 μm). After nano-wear deformation, multilayer systems with thinner layers showed less volume loss as measured by laser scanning microscopy. Additionally,more » the hardness of the deformed regions significantly rose with respect to the as-deposited measurements, which further increased with greater wear loads. Strain hardening exponents for multilayers with thinner layers (2 and 20 nm, n ≈ 0.018 and n ≈ 0.022 respectively) were less than was determined for 100 nm systems (n ≈ 0.041). These results suggest that singledislocation based deformation mechanisms observed for the thinner systems limit the extent of achievable strain hardening. This conclusion indicates that impacts of both architecture strengthening and strain hardening must be considered to accurately predict multilayer performance during sliding contact across varying length scales.« less

  8. Nanoscale size dependence on pulsed laser sintering of hydroxyapatite/titanium particles on metal implants

    NASA Astrophysics Data System (ADS)

    Zhang, Martin Yi; Cheng, Gary J.

    2010-12-01

    Nanoscale size effects on pulsed laser coating of hydroxyapatite/titanium nanoparticles (nanoTi) on metal substrate is discussed in this article. Laser coating method has recently been developed to coat bioceramics material on Ti-6Al-4V substrate. Laser-coated bioceramics implants have several advantages due to the use of nanosized materials: strong interfacial bonding strength, good biocompatibility and potentially longer lifetime cycle. These advantages benefit from intrinsic properties of nanoparticles. Size effects on melting point, heat capacity, thermal, and electrical conductivities have been discussed. Multiphysics model is built to reveal the mechanism of laser coating process. Two submodules are included in the model: electromagnetic module to represent the laser-nanoparticle interactions and heat transfer module to simulate the heat conduction. Both simulation and experimental results showed that nanoTi, functioning as nanoheaters, effectively enhances the laser coating sinterability. For large nanoTi (>100 nm), sinterability enhancement mainly attributes to the stronger laser-particle interactions due to higher plasmon resonance; for small nanoparticles (<100 nm), not only stronger laser-nanoparticle interactions, reduction on melting point also contributes to sinterability enhancement.

  9. Identifying Deformation and Strain Hardening Behaviors of Nanoscale Metallic Multilayers Through Nano-wear Testing

    NASA Astrophysics Data System (ADS)

    Economy, D. Ross; Mara, N. A.; Schoeppner, R. L.; Schultz, B. M.; Unocic, R. R.; Kennedy, M. S.

    2016-03-01

    In complex loading conditions ( e.g., sliding contact), mechanical properties, such as strain hardening and initial hardness, will dictate the long-term performance of materials systems. With this in mind, the strain hardening behaviors of Cu/Nb nanoscale metallic multilayer systems were examined by performing nanoindentation tests within nanoscratch wear boxes and undeformed regions (as-deposited). Both the architecture and substrate influence were examined by utilizing three different individual layer thicknesses (2, 20, and 100 nm) and two total film thicknesses (1 and 10 µm). After nano-wear deformation, multilayer systems with thinner layers showed less volume loss as measured by laser scanning microscopy. Additionally, the hardness of the deformed regions significantly rose with respect to the as-deposited measurements, which further increased with greater wear loads. Strain hardening exponents for multilayers with thinner layers (2 and 20 nm, n ≈ 0.018 and n ≈ 0.022, respectively) were less than that determined for 100 nm systems ( n ≈ 0.041). These results suggest that single-dislocation-based deformation mechanisms observed for the thinner systems limit the extent of achievable strain hardening. This conclusion indicates that impacts of both architecture strengthening and strain hardening must be considered to accurately predict multilayer performance during sliding contact across varying length scales.

  10. Manganese-based nanoscale metal-organic frameworks for magnetic resonance imaging.

    PubMed

    Taylor, Kathryn M L; Rieter, William J; Lin, Wenbin

    2008-11-01

    Manganese-containing nanoscale metal-organic frameworks (NMOFs) with controllable morphologies were synthesized using reverse-phase microemulsion techniques at room temperature and a surfactant-assisted procedure at 120 degrees C with microwave heating. The nanoparticles were characterized using a variety of methods including SEM, TEM, TGA, PXRD, and ICP-MS. Although the nanoparticles gave a modest longitudinal relaxivity (r1) on a per Mn basis, they provided an efficient vehicle for the delivery of large doses of Mn2+ ions which exhibited very high in vitro and in vivo r1 values and afforded excellent MR contrast enhancement. The particle surface was also modified with a silica shell to allow covalent attachment of a cyclic RGD peptide and an organic fluorophore. The cell-targeting molecules on the Mn NMOFs enhanced their delivery to cancer cells to allow for target-specific MR imaging in vitro. The MR contrast enhancement was also demonstrated in vivo using a mouse model. Such core-shell hybrid nanostructures provide an ideal platform for targeted delivery of other imaging and therapeutic agents to diseased tissues. PMID:18844356

  11. Complex nanoscale cage clusters built from uranyl polyhedra and phosphate tetrahedra

    SciTech Connect

    Unruh, Daniel K.; Ling, Jie; Qiu, Jie; Pressprich, Laura; Baranay, Melissa; Ward, Matthew; Burns, Peter C.

    2011-06-20

    Five cage clusters that self-assemble in alkaline aqueous solution have been isolated and characterized. Each is built from uranyl hexagonal bipyramids with two or three equatorial edges occupied by peroxide, and three also contain phosphate tetrahedra. These clusters contain 30 uranyl polyhedra; 30 uranyl polyhedra and six pyrophosphate groups; 30 uranyl polyhedra, 12 pyrophosphate groups, and one phosphate tetrahedron; 42 uranyl polyhedra; and 40 uranyl polyhedra and three pyrophosphate groups. These clusters present complex topologies as well as a range of compositions, sizes, and charges. Two adopt fullerene topologies, and the others contain combinations of topological squares, pentagons, and hexagons. An analysis of possible topologies further indicates that higher-symmetry topologies are favored.

  12. Evolution of nanoscale clusters in γ' precipitates of a Ni-Al-Ti model alloy.

    PubMed

    Vogel, F; Wanderka, N; Balogh, Z; Ibrahim, M; Stender, P; Schmitz, G; Fedorova, T; Banhart, J

    2015-12-01

    The evolution of phase separation and ordering processes determines the structure and properties of Ni-based superalloys. Here we use atom probe tomography to clarify the origin of γ particles occurring in ordered (L12) γ' precipitates in a Ni86.1Al8.5Ti5.4 alloy. Particularly, we elucidate the evolution from nanoscaled Ni-rich heterogeneities (Ni-rich clusters) to γ spheres and then γ plates inside γ' precipitates from the compositional and the thermodynamic point of view. We find that Ni supersaturation of γ' precipitates is relieved by formation of Ni-rich clusters, which results in an energetically more favorable state. Subsequently, coalescence introduces necking between the Ni-rich clusters and leads to the formation of γ particles. Our results demonstrate that phase separation of γ' precipitates is characterized by different stages with various governing driving forces. PMID:26141253

  13. Clusters for biology: immobilization of proteins by size-selected metal clusters

    NASA Astrophysics Data System (ADS)

    Collins, J. A.; Xirouchaki, C.; Palmer, R. E.; Heath, J. K.; Jones, C. H.

    2004-03-01

    Lateral features of size 1-10 nm are created on graphite, using an RF magnetron gas-condensation cluster beam deposition source. Specifically, size-selected gold clusters, Au55+ and Au70+, are pinned to the graphite surface, in order to explore the immobilization of protein molecules. Refined sample preparation protocols enable the utilization of the atomic force microscope (AFM) to visualize two proteins, histidine affinity tagged green fluorescent protein (pHAT-GFP) and Human Oncostatin M, both in air, and in physiological buffer solution, which mimics their natural environment. Both protein islands (complexes) and individual (or a few) protein molecules are identified. The impetus for single molecule science studies lies in the possible observation of the structural conformation changes of proteins as they perform their individual functions in their native environments. The manner in which specific proteins organize themselves spatially is a key consideration in understanding how they function, e.g., in disease control. The cluster approach creates sufficiently dilute arrays of truly nanoscale features that single molecule optical experiments may also be feasible in the future. Experiments on the re-usability of the nanocluster films provide further proof of the resilience and versatility of this type of nanostructured surface for protein immobilization work.

  14. Visualizing the HoxD Gene Cluster at the Nanoscale Level.

    PubMed

    Fabre, Pierre J; Benke, Alexander; Manley, Suliana; Duboule, Denis

    2015-01-01

    Transcription of HoxD cluster genes in limbs is coordinated by two topologically associating domains (TADs), neighboring the cluster and containing various enhancers. Here, we use a combination of microscopy approaches and chromosome conformation capture to assess the structural changes occurring in this global architecture in various functional states. We observed that despite their spatial juxtaposition, the TADs are consistently kept as distinct three-dimensional units. Hox genes located at their boundary can show significant spatial segregation over long distances, suggesting that physical elongation of the HoxD cluster occurs. The use of superresolution imaging (STORM [stochastic optical reconstruction microscopy]) revealed that the gene cluster can be in an either compact or elongated shape. The latter configuration is observed in transcriptionally active tissue and in embryonic stem cells, consistent with chromosome conformation capture results. Such morphological changes at HoxD in developing digits seem to be associated with its position at the boundary between two TADs and support the idea that chromatin dynamics is important in the establishment of transcriptional activity. PMID:26767994

  15. Valence bond cluster studies of alkali metal/semiconductor bonding

    NASA Astrophysics Data System (ADS)

    Tatar, Robert C.; Messmer, Richard P.

    1986-12-01

    We present results of cluster studies of alkali metal/semiconductor bonding. Using the Generalized Valence Bond (GVB) method, we find a remarkable consistency in the behavoir of bonding orbitals for a variety of systems, including: LiH, CLi4, LiH4 and several hypervalent systems, such as SiH3Li2, SiH4Li2. Our results show that the metal-semiconductor bonding in these systems can be understood in terms of a pairing between McAdon-Goddard type metallic bonding orbitals and a set of equivalent orbitals of the non-metallic species. We propose that the results are relevant to the initial stages of alkali overlayer growth on semiconductor surfaces and lead to a simple picture of the bonding including the transition from a non-conducting to a conducting layer. We have considered numerous proposed hypervalent structures in light of the above results and find that they can be understood.

  16. 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.

  17. Spectral degeneracy breaking of the plasmon resonance of single metal nanoparticles by nanoscale near-field photopolymerization.

    PubMed

    El Ahrach, H Ibn; Bachelot, R; Vial, A; Lérondel, G; Plain, J; Royer, P; Soppera, O

    2007-03-01

    We report on controlled nanoscale photopolymerization triggered by enhanced near fields of silver nanoparticles excited close to their dipolar plasmon resonance. By anisotropic polymerization, symmetry of the refractive index of the surrounding medium was broken: C infinity v symmetry turned to C2v symmetry. This allowed for spectral degeneracy breaking in particles plasmon resonance whose apparent peak became continuously tunable with the incident polarization. From the spectral peak, we deduced the refractive-index ellipsoid fabricated around the particles. In addition to this control of optical properties of metal nanoparticles, this method opens new routes for nanoscale photochemistry and provides a new way of quantification of the magnitude of near fields of localized surface plasmons.

  18. 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.

  19. Atomic and electronic properties of neutral and cationic metallic clusters

    NASA Astrophysics Data System (ADS)

    Kolchin, Andrew Marc

    2000-10-01

    We find optimal atomic and electronic structures for neutral and singly, positively charged clusters of beryllium and beryllium-lithium (of the form BeLik) using density functional theory in the local spin density approximation. Ions are moved with a steepest descent method, and the electronic wave functions optimized using a fictitious dynamics with simulated annealing, as conceived by Car and Parrinello. Shell-like orbitals, filling angular momentum states in the order: 1s 2p 2s 1d, are obtained for the beryllium clusters. The same ordering is found for the BeLik clusters which indicates a departure from the ordering found in pure alkali clusters by the lowering of the 2s level to below the 1d level due to the larger electron affinity of the Be impurity. We similarly calculate an atomic basis to which we relate these shell-like orbitals, and employ a Mulliken population analysis to visualize how the atomic orbitals might hybridize to create them. This analysis also allows us to observe an increasingly metallic behavior with cluster size, by associating the electron density distribution, and in the case of a charged cluster, the distribution of the hole, with atomic sites, and with regions of overlap between atom pairs. We quantitatively show the increase in density associated with bonding as cluster size increases, and the tendency of the hole to distribute itself near the most exterior atomic sites in clusters of high symmetry. Our results are compared with the predictions of the shell/jellium model in the context of our calculated binding energies and ionization potentials.

  20. Aggregation of nanoscale iron oxyhydroxides and corresponding effects on metal uptake, retention, and speciation: II. Temperature and time

    NASA Astrophysics Data System (ADS)

    Stegemeier, J. P.; Reinsch, B. C.; Lentini, C. J.; Dale, J. G.; Kim, C. S.

    2015-01-01

    The aggregation and growth of nanosized particles can greatly impact their capacity to sorb and retain dissolved metals, thus affecting metal fate and transport in contaminated systems. Aqueous suspensions of synthesized nanoscale iron oxyhydroxides were exposed to dissolved Zn(II) or Cu(II) and aged at room temperature (∼20 °C), 50 °C, and 75 °C for timeframes ranging from 0 to 96 h before sorbed metal ions were desorbed by lowering the suspension pH. Atomic absorption spectroscopic analysis of supernatants both before and after the desorption step determined how temperature and time affect macroscopic metal uptake and retention capacities. Extended X-ray absorption fine structure (EXAFS) spectroscopy analysis described the local binding environment of the sorbed/retained metals on the solid phase. With increasing aging temperature and time, the initial ∼5-nm oblong nanoparticles formed dense aggregates, lost reactive surface area, and retained progressively larger fractions of the initially-introduced Zn(II) and Cu(II) following the desorption step, with the copper species inhibiting the oriented aggregation of the nanoparticles into nanorods. Based on EXAFS analysis, the speciation of the sorbed metal species evolves with increasing time and temperature from surface-sorbed metal ions, which readily desorb and return to solution, to more strongly-bound, structurally-incorporated metal ions. These retained metals appear to associate intimately with the nanoparticle aggregates by substituting for iron in the nanoparticle lattice or by binding within nanoparticle aggregate pore spaces.

  1. Unusual Electro-Optic Kerr Response in a Self-Stabilized Amorphous Blue Phase with Nanoscale Smectic Clusters.

    PubMed

    Le, Khoa V; Hafuri, Miho; Ocak, Hale; Bilgin-Eran, Belkız; Tschierske, Carsten; Sasaki, Takeo; Araoka, Fumito

    2016-05-18

    We investigated the electro-optic response in the "foggy" amorphous blue phase (BPIII) as well as in the isotropic phase. To the best of our knowledge, such a study has not yet been performed due to the very limited thermal range of BPIII. In this study, we used a single-component chiral bent-core liquid crystal with a self-stabilized BPIII, which is stable over a wide temperature range. The results show that the response time is on the order of hundreds of microseconds in the isotropic phase and increases to 1-2 ms in the BPIII (at TI-BP -T <1), then drastically increases up to a few tens of milliseconds upon further cooling in BPIII. Such an unusual behavior was explained on the basis of the high rotational viscosity and/or the existence of nanoscale smectic (Sm) clusters. The Kerr constant was also measured and found to be ∼500 pm V(-2) , which is the largest among bent-core BP systems reported so far and comparable with that of polymer-stabilized BPs.

  2. Negative differential conductance in nano-scale normal metal/superconductor/normal metal junctions featuring Fe1 + y Te1 - x Se x

    NASA Astrophysics Data System (ADS)

    De, Debtanu; Diaz-Pinto, Carlos; Wu, Zheng; Peng, Haibing

    2012-11-01

    Iron-based superconductors have been the subject of intensive study due to their high transition temperature and intriguing physical mechanisms. We describe a unique experimental approach to fabricate nano-scale normal metal/superconductor/normal metal junctions involving microcrystals of Fe1 + y Te1 - x Se x , for which we have observed a distinct phenomenon of negative differential conductance (NDC) dips along with multiple plateau features in differential conductance spectra. The evolution of the NDC dips and the plateau features is further explored as a function of both temperature and magnetic field, and their physical origin is discussed.

  3. 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

  4. 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

  5. Harnessing microbial subsurface metal reduction activities to synthesise nanoscale cobalt ferrite with enhanced magnetic properties

    SciTech Connect

    Coker, Victoria S.; Telling, Neil D.; van der Laan, Gerrit; Pattrick, Richard A.D.; Pearce, Carolyn I.; Arenholz, Elke; Tuna, Floriana; Winpenny, Richard E.P.; Lloyd, Jonathan R.

    2009-03-24

    Nanoscale ferrimagnetic particles have a diverse range of uses from directed cancer therapy and drug delivery systems to magnetic recording media and transducers. Such applications require the production of monodisperse nanoparticles with well-controlled size, composition, and magnetic properties. To fabricate these materials purely using synthetic methods is costly in both environmental and economical terms. However, metal-reducing microorganisms offer an untapped resource to produce these materials. Here, the Fe(III)-reducing bacterium Geobacter sulfurreducens is used to synthesize magnetic iron oxide nanoparticles. A combination of electron microscopy, soft X-ray spectroscopy, and magnetometry techniques was employed to show that this method of biosynthesis results in high yields of crystalline nanoparticles with a narrow size distribution and magnetic properties equal to the best chemically synthesized materials. In particular, it is demonstrated here that cobalt ferrite (CoFe{sub 2}O{sub 4}) nanoparticles with low temperature coercivity approaching 8 kOe and an effective anisotropy constant of {approx} 10{sup 6} erg cm{sup -3} can be manufactured through this biotechnological route. The dramatic enhancement in the magnetic properties of the nanoparticles by the introduction of high quantities of Co into the spinel structure represents a significant advance over previous biomineralization studies in this area using magnetotactic bacteria. The successful production of nanoparticulate ferrites achieved in this study at high yields could open up the way for the scaled-up industrial manufacture of nanoparticles using environmentally benign methodologies. Production of ferromagnetic nanoparticles for pioneering cancer therapy, drug delivery, chemical sensors, catalytic activity, photoconductive materials, as well as more traditional uses in data storage embodies a large area of inorganic synthesis research. In particular, the addition of transition metals other than

  6. Protein-protected luminescent noble metal quantum clusters: an emerging trend in atomic cluster nanoscience

    PubMed Central

    Xavier, Paulrajpillai Lourdu; Chaudhari, Kamalesh; Baksi, Ananya; Pradeep, Thalappil

    2012-01-01

    Noble metal quantum clusters (NMQCs) are the missing link between isolated noble metal atoms and nanoparticles. NMQCs are sub-nanometer core sized clusters composed of a group of atoms, most often luminescent in the visible region, and possess intriguing photo-physical and chemical properties. A trend is observed in the use of ligands, ranging from phosphines to functional proteins, for the synthesis of NMQCs in the liquid phase. In this review, we briefly overview recent advancements in the synthesis of protein protected NMQCs with special emphasis on their structural and photo-physical properties. In view of the protein protection, coupled with direct synthesis and easy functionalization, this hybrid QC-protein system is expected to have numerous optical and bioimaging applications in the future, pointers in this direction are visible in the literature. PMID:22312454

  7. 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.

  8. 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

  9. 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.

  10. 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

  11. The Sound Parameter Effect in Metal-Rich Globular Clusters

    NASA Technical Reports Server (NTRS)

    Hall, D. K

    1998-01-01

    Recent Hubble Space Telescope observations have found that the horizontal branches (HBs) in the metal-rich globular clusters NGC 6388 and NGC 6441 slope upward with decreasing B - V. Such a slope is not predicted by canonical HB models and cannot be produced by either a greater cluster age or enhanced mass loss along the red giant branch (RGB). The peculiar HB morphology in these clusters may provide an important clue for understanding the second-parameter effect. We have carried out extensive evolutionary calculations and numerical simulations in order to explore three noncanonical scenarios for explaining the sloped HBs in NGC 6388 and NGC 6441: (1) a high cluster helium abundance scenario, in which the HB evolution is characterized by long blue loops; (2) a rotation scenario, in which internal rotation during the RGB phase increases the HB core mass; and (3) a helium-mixing scenario, in which deep mixing on the RGB enhances the envelope helium abundance. All of these scenarios predict sloped HBs with anomalously bright RR Lyrae variables. We compare this prediction with the properties of the two known RR Lyrae variables in NGC 6388. Additional observational tests of these scenarios are suggested.

  12. 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.

  13. 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

  14. 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.

  15. The electronic structure of free aluminum clusters: metallicity and plasmons.

    PubMed

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

    2012-05-28

    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.

  16. 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.

  17. 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.

  18. 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

  19. 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.

  20. 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

  1. Implementation of nanoscale circuits using dual metal gate engineered nanowire MOSFET with high-k dielectrics for low power applications

    NASA Astrophysics Data System (ADS)

    Charles Pravin, J.; Nirmal, D.; Prajoon, P.; Ajayan, J.

    2016-09-01

    This work covers the impact of dual metal gate engineered Junctionless MOSFET with various high-k dielectric in Nanoscale circuits for low power applications. Due to gate engineering in junctionless MOSFET, graded potential is obtained and results in higher electron velocity of about 31% for HfO2 than SiO2 in the channel region, which in turn improves the carrier transport efficiency. The simulation is done using sentaurus TCAD, ON current, OFF current, ION/IOFF ratio, DIBL, gain, transconductance and transconductance generation factor parameters are analysed. When using HfO2, DIBL shows a reduction of 61.5% over SiO2. The transconductance and transconductance generation factor shows an improvement of 44% and 35% respectively. The gain and output resistance also shows considerable improvement with high-k dielectrics. Using this device, inverter circuit is implemented with different high-k dielectric material and delay have been decreased by 4% with HfO2 when compared to SiO2. In addition, a significant reduction in power dissipation of the inverter circuit is obtained with high-k dielectric Dual Metal Surround Gate Junctionless Transistor than SiO2 based device. From the analysis, it is found that HfO2 will be a better alternative for the future nanoscale device.

  2. 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.

  3. Metallic-nanowire-loaded silicon-on-insulator structures: a route to low-loss plasmon waveguiding on the nanoscale

    NASA Astrophysics Data System (ADS)

    Bian, Yusheng; Gong, Qihuang

    2015-02-01

    The simultaneous realization of nanoscale field localization and low transmission loss remains one of the major challenges in nanophotonics. Metal nanowire waveguides can fulfill this goal to a certain extent by confining light within subwavelength space, yet their optical performances are still restricted by the tradeoff between confinement and loss, which results in quite limited propagation distances when their mode sizes are reduced down to the nanometer scale. Here we introduce a class of low-loss guiding schemes by integrating silicon-on-insulator (SOI) waveguides with plasmon nanowire structures. The closely spaced silicon and metal configurations allow efficient light squeezing within the nanometer, low-index silica gaps between them, enabling deep-subwavelength light transmission with low modal attenuation. Optimizations of key structural parameters unravel the wide-range existence of the high-performance hybrid nanowire plasmon mode, which demonstrates improved guiding properties compared to the conventional hybrid and nanowire plasmon polaritons. The excitation strategy of the guided mode and the feasibility of the waveguide for compact photonic integration as well as active components are also discussed to lay the foundation for its practical implementation. The remarkable properties of these metallic-nanowire-loaded SOI waveguides potentially lend themselves to the implementation of high performance nanophotonic components, and open up promising opportunities for a variety of intriguing applications on the nanoscale.The simultaneous realization of nanoscale field localization and low transmission loss remains one of the major challenges in nanophotonics. Metal nanowire waveguides can fulfill this goal to a certain extent by confining light within subwavelength space, yet their optical performances are still restricted by the tradeoff between confinement and loss, which results in quite limited propagation distances when their mode sizes are reduced

  4. 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

  5. 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.

  6. Synthesis and reactivities of cubane-type sulfido clusters containing noble metals.

    PubMed

    Hidai, M; Kuwata, S; Mizobe, Y

    2000-01-01

    Cubane-type sulfido clusters containing noble metals are newcomers compared with the corresponding clusters of the first transition series metals and molybdenum, which have been extensively studied in relation to metalloenzymes and industrial hydrodesulfurization catalysts. This Account reviews the recent progress in studies on the synthesis and reactivities of these noble metal cubane-type clusters. One of the goals in this new area lies in development of the unique catalysis of the noble metals embedded in the robust and redox-active cubane-type cores. Rational synthetic approaches indispensable to the preparation of such effective cluster catalysts are discussed to a significant extent.

  7. A new nanomaterial synthesized from size-selected, ligand-free metal clusters

    NASA Astrophysics Data System (ADS)

    Li, X.; Wepasnick, K.; Tang, X.; Fairbrother, D. H.; Bowen, K. H.; Dollinger, A.; Strobel, C. H.; Huber, J.; Mangler, T.; Luo, Y.; Proch, S.; Gantefoer, G.

    2014-03-01

    Thins films are synthesized by deposition of size-selected Mon- cluster anions on an inert substrate. Scanning tunneling microscopy pictures indicate that the deposited material consists of individual particles with diameters corresponding to the size of the preformed clusters from the gas phase. Previous attempts to manufacture cluster materials from metals failed since these clusters coalesced at room temperature. Our data suggest the possibility to synthesize new nanomaterials from clusters of high fusing metals. This may prove to be the key to harness size-dependent and tuneable properties of clusters for creating novel classes of functional tailor-made materials.

  8. 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)

  9. All-metal clusters that mimic the chemistry of halogens.

    PubMed

    Zhao, Tianshan; Li, Yawei; Wang, Qian; Jena, Puru

    2013-10-01

    Owing to their s(2)p(5) electronic configuration, halogen atoms are highly electronegative and constitute the anionic components of salts. Whereas clusters that contain no halogen atoms, such as AlH(4), mimic the chemistry of halogens and readily form salts (e.g., Na(+)(AlH(4))(-)), clusters that are solely composed of metal atoms and yet behave in the same manner as a halogen are rare. Because coinage-metal atoms (Cu, Ag, and Au) only have one valence electron in their outermost electronic shell, as in H, we examined the possibility that, on interacting with Al, in particular as AlX(4) (X=Cu, Ag, Au), these metal atoms may exhibit halogen-like properties. By using density functional theory, we show that AlAu(4) not only mimics the chemistry of halogens, but also, with a vertical detachment energy (VDE) of 3.98 eV in its anionic form, is a superhalogen. Similarly, analogous to XHX superhalogens (X=F, Cl, Br), XAuX species with VDEs of 4.65, 4.50, and 4.34 eV in their anionic form, respectively, also form superhalogens. In addition, Au can also form hyperhalogens, a recently discovered species that show electron affinities (EAs) that are even higher than those of their corresponding superhalogen building blocks. For example, the VDEs of M(AlAu(4))(2)(-) (M=Na and K) and anionic (FAuF)Au(FAuF) range from 4.06 to 5.70 eV. Au-based superhalogen anions, such as AlAu(4)(-) and AuF(2)(-), have the additional advantage that they exhibit wider optical absorption ranges than their H-based analogues, AlH(4)(-) and HF(2)(-). Because of the catalytic properties and the biocompatibility of Au, Au-based superhalogens may be multifunctional. However, similar studies that were carried out for Cu and Ag atoms have shown that, unlike AlAu(4), AlX(4) (X=Cu, Ag) clusters are not superhalogens, a property that can be attributed to the large EA of the Au atom.

  10. 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.

  11. 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.

  12. A complementary metal-oxide-semiconductor compatible monocantilever 12-point probe for conductivity measurements on the nanoscale

    NASA Astrophysics Data System (ADS)

    Gammelgaard, L.; Bøggild, P.; Wells, J. W.; Handrup, K.; Hofmann, Ph.; Balslev, M. B.; Hansen, J. E.; Petersen, P. R. E.

    2008-09-01

    We present a complementary metal-oxide-semiconductor compatible, nanoscale 12-point-probe based on TiW electrodes placed on a SiO2 monocantilever. Probes are mass fabricated on Si wafers by a combination of electron beam and UV lithography, realizing TiW electrode tips with a width down to 250nm and a probe pitch of 500nm. In-air four-point measurements have been performed on indium tin oxide, ruthenium, and titanium-tungsten, showing good agreement with values obtained by other four-point probes. In-vacuum four-point resistance measurements have been performed on clean Bi(111) using different probe spacings. The results show the expected behavior for bulk Bi, indicating that the contribution of electronic surface states to the transport properties is very small.

  13. Effect of geometrical constraint condition on the formation of nanoscale twins in the Ni-based metallic glass composite

    SciTech Connect

    Lee, M H; Kim, B S; Kim, D H; Ott, R T; Sansoz, F; Eckert, J

    2014-04-25

    We investigated the effect of geometrically constrained stress-strain conditions on the formation of nanotwins in alpha-brass phase reinforced Ni59Zr20Ti16Si2Sn3 metallic glass (MG) matrix deformed under macroscopic uniaxial compression. The specific geometrically constrained conditions in the samples lead to a deviation from a simple uniaxial state to a multi-axial stress state, for which nanocrystallization in the MG matrix together with nanoscale twinning of the brass reinforcement is observed in localized regions during plastic flow. The nanocrystals in the MG matrix and the appearance of the twinned structure in the reinforcements indicate that the strain energy is highly confined and the local stress reaches a very high level upon yielding. Both the effective distribution of reinforcements on the strain enhancement of composite and the effects of the complicated stress states on the development of nanotwins in the second-phase brass particles are discussed.

  14. Effect of geometrical constraint condition on the formation of nanoscale twins in the Ni-based metallic glass composite

    NASA Astrophysics Data System (ADS)

    Lee, M. H.; Kim, B. S.; Kim, D. H.; Ott, R. T.; Sansoz, F.; Eckert, J.

    2014-06-01

    We investigated the effect of geometrically constrained stress-strain conditions on the formation of nanotwins in α-brass phase reinforced Ni59Zr20Ti16Si2Sn3 metallic glass (MG) matrix deformed under macroscopic uniaxial compression. The specific geometrically constrained conditions in the samples lead to a deviation from a simple uniaxial state to a multi-axial stress state, for which nanocrystallization in the MG matrix together with nanoscale twinning of the brass reinforcement is observed in localized regions during plastic flow. The nanocrystals in the MG matrix and the appearance of the twinned structure in the reinforcements indicate that the strain energy is highly confined and the local stress reaches a very high level upon yielding. Both the effective distribution of reinforcements on the strain enhancement of composite and the effects of the complicated stress states on the development of nanotwins in the second-phase brass particles are discussed.

  15. Performance of nanoscale metallic multilayer systems under mechanical and thermal loading

    NASA Astrophysics Data System (ADS)

    Economy, David Ross

    Reports of nanoscale metallic multilayers (NMM) performance show a relatively high strength and radiation damage resistance when compared their monolithic components. Hardness of NMMs has been shown to increase with increasing interfacial density (i.e. decreasing layer thickness). This interface density-dependent behavior within NMMs has been shown to deviate from Hall-Petch strengthening, leading to higher measured strengths during normal loading than those predicted by a rule of mixtures. To fully understand why this occurs, other researchers have looked at the influence of the crystal structures of the component layers, orientations, and compositions on deformation processes. Additionally, a limited number of studies have focused on the structural stability and possible performance variation between as-deposited systems and those exposed to mechanical and thermal loading. This dissertation identified how NMM as-deposited structures and performance are altered by mechanical loading (sliding/wear contact) and/or thermal (such as diffusion, relaxation) loading. These objectives were pursued by tracking hardness evolution during sliding wear and after thermal loading to as-deposited stress and mechanical properties. Residual stress progression was also examined during thermal loading and supporting data was collected to detail structural and chemical changes. All of these experimental observations were conducted using Cu/Nb NMMs with 2 nm, 20 nm, or 100 nm thick individual layers deposited with either 1 microm or 10 microm total thicknesses with two geometries (Cu/Nb and Nb/Cu) on (100) Si. Wear boxes were performed on Cu/Nb NMM using a nanoindentation system with a 1 microm conical diamond counterface. After nano-wear deformation, the hardness of the deformed regions significantly rose with respect to as-deposited measurements, which further increased with greater wear loads. Additionally, NMMs with thinner layers showed less volume loss as measured by laser

  16. Nanocrystalline metal/carbon composites produced by supersonic cluster beam deposition.

    PubMed

    Bongiorno, G; Lenardi, C; Ducati, C; Agostino, R G; Caruso, T; Amati, M; Blomqvist, M; Barborini, E; Piseri, P; La Rosa, S; Colavita, E; Milani, P

    2005-07-01

    In this work we show that supersonic cluster beam deposition is a viable method for the synthesis of nanocrystalline metal/carbon composites. By assembling carbon and metallic clusters seeded in a supersonic beam, we have grown films consisting of metal nanoparticles embedded in a nano-structured carbon matrix. Samples containing 3d transition metals (Ti, Ni) and noble metals (Au, Pd, Pt) with different metal abundances, particle size and dilution have been characterized by transmission electron microscopy. The influence of different metals on the structure of the carbon matrix has been investigated. Spatially resolved ultraviolet photoemission electron spectroscopy showed substantial surface oxidation of 3d transition metal clusters. On a micrometric scale, the spatial distribution of the metallic nanoparticles appeared to be homogeneous.

  17. 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.

  18. Electron-electron scattering-induced channel hot electron injection in nanoscale n-channel metal-oxide-semiconductor field-effect-transistors with high-k/metal gate stacks

    SciTech Connect

    Tsai, Jyun-Yu; Liu, Kuan-Ju; Lu, Ying-Hsin; Liu, Xi-Wen; Chang, Ting-Chang; Chen, Ching-En; Ho, Szu-Han; Tseng, Tseung-Yuen; Cheng, Osbert; Huang, Cheng-Tung; Lu, Ching-Sen

    2014-10-06

    This work investigates electron-electron scattering (EES)-induced channel hot electron (CHE) injection in nanoscale n-channel metal-oxide-semiconductor field-effect-transistors (n-MOSFETs) with high-k/metal gate stacks. Many groups have proposed new models (i.e., single-particle and multiple-particle process) to well explain the hot carrier degradation in nanoscale devices and all mechanisms focused on Si-H bond dissociation at the Si/SiO{sub 2} interface. However, for high-k dielectric devices, experiment results show that the channel hot carrier trapping in the pre-existing high-k bulk defects is the main degradation mechanism. Therefore, we propose a model of EES-induced CHE injection to illustrate the trapping-dominant mechanism in nanoscale n-MOSFETs with high-k/metal gate stacks.

  19. 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

  20. 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.

  1. 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

  2. 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.

  3. In situ electron microscopy studies of electromechanical behavior in metals at the nanoscale using a novel microdevice-based system

    NASA Astrophysics Data System (ADS)

    Kang, Wonmo; Beniam, Iyoel; Qidwai, Siddiq M.

    2016-09-01

    Electrically assisted deformation (EAD) is an emerging technique to enhance formability of metals by applying an electric current through them. Despite its increasing importance in manufacturing applications, there is still an unresolved debate on the nature of the fundamental deformation mechanisms underlying EAD, mainly between electroplasticity (non-thermal effects) and resistive heating (thermal effects). This status is due to two critical challenges: (1) a lack of experimental techniques to directly observe fundamental mechanisms of material deformation during EAD, and (2) intrinsic coupling between electric current and Joule heating giving rise to unwanted thermally activated mechanisms. To overcome these challenges, we have developed a microdevice-based electromechanical testing system (MEMTS) to characterize nanoscale metal specimens in transmission electron microscopy (TEM). Our studies reveal that MEMTS eliminates the effect of Joule heating on material deformation, a critical advantage over macroscopic experiments, owing to its unique scale. For example, a negligible change in temperature (<0.02 °C) is predicted at ˜3500 A/mm2. Utilizing the attractive features of MEMTS, we have directly investigated potential electron-dislocation interactions in single crystal copper (SCC) specimens that are simultaneously subjected to uniaxial loading and electric current density up to 5000 A/mm2. Our in situ TEM studies indicate that for SCC, electroplasticity does not play a key role as no differences in dislocation activities, such as depinning and movement, are observed.

  4. Association of the sites of heavy metals with nanoscale carbon in a Kentucky electrostatic precipitator fly ash

    SciTech Connect

    James C. Hower; Uschi M. Graham; Alan Dozier; Michael T. Tseng; Rajesh A. Khatri

    2008-11-15

    A combination of high-resolution transmission electron microscopy, scanning transmission electron microscopy, and electron energy-loss spectroscopy (HRTEM-STEM-EELS) was used to study fly ashes produced from the combustion of an eastern Kentucky coal at a southeastern-Kentucky wall-fired pulverized coal utility boiler retrofitted for low-NOx combustion. Fly ash was collected from individual hoppers in each row of the electrostatic precipitators (ESP) pollution-control system, with multiple hoppers sampled within each of the three rows. Temperatures within the ESP array range from about 200 {degree}C at the entry to the first row to <150{degree}C at the exit of the third row. HRTEM-STEM-EELS study demonstrated the presence of nanoscale (10 s nm) C agglomerates with typical soot-like appearance and others with graphitic fullerene-like nanocarbon structures. The minute carbon agglomerates are typically juxtaposed and intergrown with slightly larger aluminosilicate spheres and often form an ultrathin halo or deposit on the fly ash particles. The STEM-EELS analyses revealed that the nanocarbon agglomerates host even finer (<3 nm) metal and metal oxide particles. Elemental analysis indicated an association of Hg with the nanocarbon. Arsenic, Se, Pb, Co, and traces of Ti and Ba are often associated with Fe-rich particles within the nanocarbon deposits. 57 refs., 5 figs.

  5. Association of the sites of heavy metals with nanoscale carbon in a Kentucky electrostatic precipitator fly ash.

    PubMed

    Hower, James C; Graham, Uschi M; Dozier, Alan; Tseng, Michael T; Khatri, Rajesh A

    2008-11-15

    A combination of high-resolution transmission electron microscopy, scanning transmission electron microscopy, and electron energy-loss spectroscopy (HRTEM-STEM-EELS) was used to study fly ashes produced from the combustion of an eastern Kentucky coal at a southeastern-Kentucky wall-fired pulverized coal utility boiler. Fly ash was collected from individual hoppers in each row of the electrostatic precipitators (ESP) pollution-control system, with multiple hoppers sampled within each of the three rows. Temperatures within the ESP array range from about 200 degrees C at the entry to the first row to < 150 degrees C at the exit of the third row. HRTEM-STEM-EELS study demonstrated the presence of nanoscale (10 s nm) C agglomerates with typical soot-like appearance and others with graphitic fullerene-like nanocarbon structures. The minute carbon agglomerates are typically juxtaposed and intergrown with slightly larger aluminosilicate spheres and often form an ultrathin halo or deposit on the fly ash particles. The STEM-EELS analyses revealed that the nanocarbon agglomerates host even finer (< 3 nm) metal and metal oxide particles. Elemental analysis indicated an association of Hg with the nanocarbon. Arsenic, Se, Pb, Co, and traces of Ti and Ba are often associated with Fe-rich particles within the nanocarbon deposits.

  6. Near-Infrared Imaging of the Central Regions of Metal-Poor Inner Spheroid Globular Clusters

    NASA Astrophysics Data System (ADS)

    Davidge, T. J.

    2001-06-01

    JHK images obtained with the Canada-France-Hawaii Telescope adaptive optics bonnette are used to investigate the near-infrared photometric properties of red giant branch (RGB) and horizontal-branch (HB) stars in eight metal-poor globular clusters with RGC<=2 kpc. The slope of the RGB on the (K, J-K) CMDs confirms the metal-poor nature of these clusters, four of which (NGC 6287, 6293, 6333, and 6355) are found to have metallicities that are comparable to M92. The luminosity functions of RGB stars in inner spheroid and outer halo clusters have similar slopes, although there is a tendency for core-collapsed clusters to have slightly flatter luminosity functions than noncollapsed clusters. The distribution of red HB stars on the (K, J-K) CMDs of inner spheroid clusters with [Fe/H]~-1.5 is very different from that of clusters with [Fe/H]~-2.2, suggesting that metallicity is the main parameter defining HB content among these objects. The RGB bump is detected in four of the inner spheroid clusters, and this feature is used to compute distances to these objects. Finally, the specific frequency of globular clusters in the inner Galaxy is discussed in the context of the early evolution of the bulge. Based on the ratio of metal-poor to metal-rich clusters in the inner Galaxy it is suggested that the metal-poor clusters formed during an early intense burst of star formation. It is also demonstrated that if the globular cluster formation efficiency for the inner Galaxy is similar to that measured in other spheroidal systems, then the main body of the bulge could have formed from gas that was chemically enriched in situ; hence, material from a separate pre-enriched reservoir, such as the disk or outer halo, may not be required to form the bulge.

  7. 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.

  8. Determination of the Structures of Silicon and Metal Doped Silicon Clusters

    NASA Astrophysics Data System (ADS)

    Lyon, Jonathan T.; Fielicke, Andre; Janssens, Ewald; Lievens, Peter

    2014-06-01

    Strongly bound clusters are often used as convenient models for bulk material. Silicon clusters are particularly interesting due to their importance in the electronics industry. We perform experimental IR multiple photon dissociation spectroscopy in the gas-phase, which makes use of a free electron laser, and compare the results with that predicted by density functional and MP2 theory calculations. Comparison of the vibrational spectra with that predicted by theoretical calculations for several structural isomers for each cluster size leads to accurate structural assignments. Here, we present our results for silicon clusters, and compare the structures with those of select transition metal doped SinM clusters. Of particular interest is the transition from exohedral to endoheral metal doped silicon clusters and how the transition size changes for different metal dopant atoms. Journal of Chemical Physics 2012, 136, 064301 e.g., ChemPhysChem 2014, 15, 328.

  9. 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.

  10. Performance enhancement of metal nanowire-based transparent electrodes by electrically driven nanoscale nucleation of metal oxides

    NASA Astrophysics Data System (ADS)

    Shiau, Yu-Jeng; Chiang, Kai-Ming; Lin, Hao-Wu

    2015-07-01

    Solution-processed silver nanowire (AgNW) electrodes have been considered to be promising materials for next-generation flexible transparent conductive electrodes. Despite the fact that a single AgNW has extremely high conductivities, the high junction resistance between nanowires limits the performance of the AgNW matrix. Therefore, post-treatments are usually required to approach better NW-NW contact. Herein, we report a novel linking method that uses joule heating to accumulate sol-gel ZnO near nanowire junctions. The nanoscale ZnO nucleation successfully restrained the thermal instability of the AgNW under current injection and acted as an efficient tightening medium to realize good NW-NW contacts. A low process temperature (<50 °C), and thus low energy consumption, are required for ZnO nucleation. This made the use of substrates with very low operating temperatures, such as PET and PEN, feasible. The optimized AgNW transparent conductive electrodes (TCE) fabricated using this promising linking method exhibited a low sheet resistance (13 Ω sq-1), a high transmission (92% at 550 nm), a high figure of merit (FOM; up to σDC/σOp = 340) and can be applied to wide range of next-generation flexible optoelectronic devices.Solution-processed silver nanowire (AgNW) electrodes have been considered to be promising materials for next-generation flexible transparent conductive electrodes. Despite the fact that a single AgNW has extremely high conductivities, the high junction resistance between nanowires limits the performance of the AgNW matrix. Therefore, post-treatments are usually required to approach better NW-NW contact. Herein, we report a novel linking method that uses joule heating to accumulate sol-gel ZnO near nanowire junctions. The nanoscale ZnO nucleation successfully restrained the thermal instability of the AgNW under current injection and acted as an efficient tightening medium to realize good NW-NW contacts. A low process temperature (<50 °C), and thus

  11. Noble metals on the nanoscale: optical and photothermal properties and some applications in imaging, sensing, biology, and medicine.

    PubMed

    Jain, Prashant K; Huang, Xiaohua; El-Sayed, Ivan H; El-Sayed, Mostafa A

    2008-12-01

    result of field coupling. A universal scaling model, relating the plasmon resonance frequency to the interparticle distance in terms of the particle size, becomes potentially useful for measuring nanoscale distances (and their changes) in biological systems. The strong plasmon absorption and photothermal conversion of gold nanoparticles has been exploited in cancer therapy through the selective localized photothermal heating of cancer cells. For nanorods or nanoshells, the LSPR can be tuned to the near-infrared region, making it possible to perform in vivo imaging and therapy. The examples of the applications of noble metal nanostructures provided herein can be readily generalized to other areas of biology and medicine because plasmonic nanomaterials exhibit great range, versatility, and systematic tunability of their optical attributes. PMID:18447366

  12. Noble metals on the nanoscale: optical and photothermal properties and some applications in imaging, sensing, biology, and medicine.

    PubMed

    Jain, Prashant K; Huang, Xiaohua; El-Sayed, Ivan H; El-Sayed, Mostafa A

    2008-12-01

    result of field coupling. A universal scaling model, relating the plasmon resonance frequency to the interparticle distance in terms of the particle size, becomes potentially useful for measuring nanoscale distances (and their changes) in biological systems. The strong plasmon absorption and photothermal conversion of gold nanoparticles has been exploited in cancer therapy through the selective localized photothermal heating of cancer cells. For nanorods or nanoshells, the LSPR can be tuned to the near-infrared region, making it possible to perform in vivo imaging and therapy. The examples of the applications of noble metal nanostructures provided herein can be readily generalized to other areas of biology and medicine because plasmonic nanomaterials exhibit great range, versatility, and systematic tunability of their optical attributes.

  13. First examples of hybrids based on polyoxometalates, metal halide clusters and organic ligands

    SciTech Connect

    Wang Lamei; Fan Yong; Wang Yan; Xiao Lina; Hu Yangyang; Peng Yu; Wang Tiegang; Gao Zhongmin; Zheng Dafang; Cui Xiaobing; Xu Jiqing

    2012-07-15

    Two new organic-inorganic compounds based on polyoxometalates, metal halide clusters and organic ligands: [BW{sub 12}O{sub 40}]{sub 2}[Cu{sub 2}(Phen){sub 4}Cl](H{sub 2}4, 4 Prime -bpy){sub 4}{center_dot}H{sub 3}O{center_dot}5H{sub 2}O (1) and [HPW{sub 12}O{sub 40}][Cd{sub 2}(Phen){sub 4}Cl{sub 2}](4, 4 Prime -bpy) (2) (Phen=1, 10-phenanthroline, bpy=bipyridine), have been prepared and characterized by IR, UV-vis, XPS, XRD and single crystal X-ray diffraction analyses. Crystal structure analyses reveal that compound 1 is constructed from [BW{sub 12}O{sub 40}]{sup 5-}, metal halide clusters [Cu{sub 2}(Phen){sub 4}Cl]{sup +}and 4, 4 Prime -bpy ligands, while compound 2 is constructed from [PW{sub 12}O{sub 40}]{sup 3-}, metal halide cluster [Cd{sub 2}(Phen){sub 4}Cl{sub 2}]{sup 2+} and 4, 4 Prime -bpy ligands. Compound 1 and compound 2 are not common hybrids based on polyoxometalates and metal halide clusters, they also contain dissociated organic ligands, therefore, compound 1 and 2 are the first examples of hybrids based on polyoxometalates, metal halide clusters and organic ligands. - Graphical Abstract: Two new compounds have been synthesized and characterized. Structure analyses revealed that the two compounds are the first examples of hybrids based on polyoxometalates, metal halide clusters and organic ligands. Highlights: Black-Right-Pointing-Pointer First examples of hybrids based on polyoxometalates, metal halide clusters and organic ligands. Black-Right-Pointing-Pointer Two different kinds of metal halide clusters. Black-Right-Pointing-Pointer Supramolecular structures based on polyoxometalates, metal halide clusters and organic ligands. Black-Right-Pointing-Pointer Hybridization of three different of building blocks.

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

    NASA Astrophysics Data System (ADS)

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

    1995-03-01

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

  15. All-in-One Beaker Method for Large-Scale Production of Metal Oxide Hollow Nanospheres Using Nanoscale Kirkendall Diffusion.

    PubMed

    Cho, Jung Sang; Kang, Yun Chan

    2016-02-17

    A simple and easily scalable process for the formation of metal oxide hollow nanospheres using nanoscale Kirkendall diffusion called the "all-in-one beaker method" is introduced. The Fe2O3, SnO2, NiO, and Co3O4 hollow nanospheres are successfully prepared by the all-in-one beaker method. The detailed formation mechanism of aggregate-free hematite hollow nanospheres is studied. Dimethylformamide solution containing Fe acetate, polyacrylonitrile (PAN), and polystyrene (PS) transforms into aggregate-free Fe2O3 hollow nanospheres. The porous structure formed by the combustion of PS provides a good pathway for the reducing gas. The carbon matrix formed from PAN acts as a barrier, which can prevent the aggregation of metallic Fe nanopowders by surrounding each particle. The Fe-C bulk material formed as an intermediate product transforms into aggregate-free Fe2O3 hollow nanospheres by the nanoscale Kirkendall diffusion process. The mean size and shell thickness of the hollow Fe2O3 nanospheres measured from the TEM images are 52 and 9 nm, respectively. The discharge capacities of the Fe2O3 nanopowders with hollow and dense structures and the bulk material for the 200th cycle at a current density of 0.5 A g(-1) are 1012, 498, and 637 mA h g(-1), respectively, and their capacity retentions calculated compared to those in the second cycles are 92, 45, and 59%, respectively. Additionally, Fe2O3 hollow nanospheres cycled at 1 A g(-1) after 1000 cycles showed a high discharge capacity of 871 mA h g(-1) (capacity retention was 80% from the second cycle). The Fe2O3, SnO2, NiO, and Co3O4 hollow nanospheres show excellent cycling performances for lithium-ion storage because they have a high contact area with the liquid electrolyte and space for accommodating a huge volume change during cycling.

  16. The Gaia-ESO Survey: Detailed abundances in the metal-poor globular cluster NGC 4372

    NASA Astrophysics Data System (ADS)

    San Roman, I.; Muñoz, C.; Geisler, D.; Villanova, S.; Kacharov, N.; Koch, A.; Carraro, G.; Tautvaišiene, G.; Vallenari, A.; Alfaro, E. J.; Bensby, T.; Flaccomio, E.; Francois, P.; Korn, A. J.; Pancino, E.; Recio-Blanco, A.; Smiljanic, R.; Bergemann, M.; Costado, M. T.; Damiani, F.; Heiter, U.; Hourihane, A.; Jofré, P.; Lardo, C.; de Laverny, P.; Masseron, T.; Morbidelli, L.; Sbordone, L.; Sousa, S. G.; Worley, C. C.; Zaggia, S.

    2015-07-01

    We present the abundance analysis for a sample of 7 red giant branch stars in the metal-poor globular cluster NGC 4372 based on UVES spectra acquired as part of the Gaia-ESO Survey. This is the first extensive study of this cluster from high-resolution spectroscopy. We derive abundances of O, Na, Mg, Al, Si, Ca, Sc, Ti, Fe, Cr, Ni, Y, Ba, and La. We find a metallicity of [Fe/H] = -2.19 ± 0.03 and find no evidence of any metallicity spread. This metallicity makes NGC 4372 one of the most metal-poor Galactic globular clusters. We also find an α-enhancement typical of halo globular clusters at this metallicity. Significant spreads are observed in the abundances of light elements. In particular, we find a Na-O anticorrelation. Abundances of O are relatively high compared with other globular clusters. This could indicate that NGC 4372 was formed in an environment with high O for its metallicity. A Mg-Al spread is also present that spans a range of more than 0.5 dex in Al abundances. Na is correlated with Al and Mgabundances at a lower significance level. This pattern suggests that the Mg-Al burning cycle is active. This behavior can also be seen in giant stars of other massive, metal-poor clusters. A relation between light and heavy s-process elements has been identified.

  17. Formation of Cu-Zr-M ternary bulk metallic glasses based on atomic clusters

    NASA Astrophysics Data System (ADS)

    Li, Y. H.; Wang, Q.; Wu, J.; Dong, C.

    2008-02-01

    Ternary Cu-Zr-M (M= Al, Ti and Ag) bulk metallic glasses are investigated using a cluster line approach. New bulk metallic glass rods with compositions lying along the cluster line Cu5Zr6-M were fabricated by copper mould suction, where binary cluster Cu5Zr6 is an Archimedean octahedral antiprism, M being about 4~13.2 at.% for Al, 8.3 at.% for Ti and 9 at.% for Ag. The relevant mechanism was discussed in the light of the cluster-plus-glue-atom model.

  18. Ab initio calculations of optical properties of silver clusters: cross-over from molecular to nanoscale behavior

    NASA Astrophysics Data System (ADS)

    Titantah, John T.; Karttunen, Mikko

    2016-05-01

    Electronic and optical properties of silver clusters were calculated using two different ab initio approaches: (1) based on all-electron full-potential linearized-augmented plane-wave method and (2) local basis function pseudopotential approach. Agreement is found between the two methods for small and intermediate sized clusters for which the former method is limited due to its all-electron formulation. The latter, due to non-periodic boundary conditions, is the more natural approach to simulate small clusters. The effect of cluster size is then explored using the local basis function approach. We find that as the cluster size increases, the electronic structure undergoes a transition from molecular behavior to nanoparticle behavior at a cluster size of 140 atoms (diameter ~1.7 nm). Above this cluster size the step-like electronic structure, evident as several features in the imaginary part of the polarizability of all clusters smaller than Ag147, gives way to a dominant plasmon peak localized at wavelengths 350 nm ≤ λ ≤ 600 nm. It is, thus, at this length-scale that the conduction electrons' collective oscillations that are responsible for plasmonic resonances begin to dominate the opto-electronic properties of silver nanoclusters.

  19. Probing the nanoscale Schottky barrier of metal/semiconductor interfaces of Pt/CdSe/Pt nanodumbbells by conductive-probe atomic force microscopy.

    PubMed

    Kwon, Sangku; Lee, Seon Joo; Kim, Sun Mi; Lee, Youngkeun; Song, Hyunjoon; Park, Jeong Young

    2015-08-01

    The electrical nature of the nanoscale contact between metal nanodots and semiconductor rods has drawn significant interest because of potential applications for metal-semiconductor hybrid nanostructures in energy conversion or heterogeneous catalysis. Here, we studied the nanoscale electrical character of the Pt/CdSe junction in Pt/CdSe/Pt nanodumbbells on connected Au islands by conductive-probe atomic force microscopy under ultra-high vacuum. Current-voltage plots measured in contact mode revealed Schottky barrier heights of individual nanojunctions of 0.41 ± 0.02 eV. The measured value of the Schottky barrier is significantly lower than that of planar thin-film diodes because of a reduction in the barrier width and enhanced tunneling probability at the interface.

  20. Probing the nanoscale Schottky barrier of metal/semiconductor interfaces of Pt/CdSe/Pt nanodumbbells by conductive-probe atomic force microscopy

    NASA Astrophysics Data System (ADS)

    Kwon, Sangku; Lee, Seon Joo; Kim, Sun Mi; Lee, Youngkeun; Song, Hyunjoon; Park, Jeong Young

    2015-07-01

    The electrical nature of the nanoscale contact between metal nanodots and semiconductor rods has drawn significant interest because of potential applications for metal-semiconductor hybrid nanostructures in energy conversion or heterogeneous catalysis. Here, we studied the nanoscale electrical character of the Pt/CdSe junction in Pt/CdSe/Pt nanodumbbells on connected Au islands by conductive-probe atomic force microscopy under ultra-high vacuum. Current-voltage plots measured in contact mode revealed Schottky barrier heights of individual nanojunctions of 0.41 +/- 0.02 eV. The measured value of the Schottky barrier is significantly lower than that of planar thin-film diodes because of a reduction in the barrier width and enhanced tunneling probability at the interface.The electrical nature of the nanoscale contact between metal nanodots and semiconductor rods has drawn significant interest because of potential applications for metal-semiconductor hybrid nanostructures in energy conversion or heterogeneous catalysis. Here, we studied the nanoscale electrical character of the Pt/CdSe junction in Pt/CdSe/Pt nanodumbbells on connected Au islands by conductive-probe atomic force microscopy under ultra-high vacuum. Current-voltage plots measured in contact mode revealed Schottky barrier heights of individual nanojunctions of 0.41 +/- 0.02 eV. The measured value of the Schottky barrier is significantly lower than that of planar thin-film diodes because of a reduction in the barrier width and enhanced tunneling probability at the interface. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr02285a

  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. Communication: New insight into electronic shells of metal clusters: Analogues of simple molecules

    NASA Astrophysics Data System (ADS)

    Cheng, Longjiu; Yang, Jinlong

    2013-04-01

    A new concept of super valence bond is proposed, of which superatoms can share both valence pairs and nuclei for shell closure thus forming delocalized super bonding. Using Li clusters as a test case, we theoretically find that metal clusters can mimic the behavior of simple molecules in electronic shells. It is found that Li14, Li10, and Li8 clusters are analogues of F2, N2, and CH4 molecules, respectively, in molecular orbital diagrams and bonding patterns. This new concept shows new insights in understanding the stability of clusters and designing the cluster-assembling materials.

  3. Non-planar grain boundary structures in fcc metals and their role in nano-scale deformation mechanisms

    NASA Astrophysics Data System (ADS)

    Smith, Laura; Farkas, Diana

    2014-01-01

    This work presents the results of a comparative molecular dynamics study showing that relaxed random grain boundary structures can be significantly non-planar at the nano-scale in fcc metals characterized by low stacking fault values. We studied the relaxed structures of random [1 1 0] tilt boundaries in a polycrystal using interatomic potentials describing Cu and Pd. Grain boundaries presenting non-planar features were observed predominantly for the Cu potential but not for the Pd potential, and we relate these differences to the stacking fault values. We also show that these non-planar structures can have a strong influence on dislocation emission from the grain boundaries as well as on grain boundary strain accommodation processes, such as grain boundary sliding. We studied the loading response in polycrystals of 40 nm grain size to a level of 9% strain and found that the non-planar grain boundaries favour dislocation emission as a deformation mechanism and hinder grain boundary sliding. This has strong implications for the mechanical behaviour of nano-crystalline materials, which is determined by the competition between dislocation activity and grain boundary accommodation of the strain. Thus, the two interatomic potentials for Cu and Pd considered in this work resulted in the same overall stress-strain curve, but significantly different fractions of the strain accommodated by the intergranular versus intragranular deformation mechanisms. Strain localization patterns are also influenced by the non-planarity of the grain boundary structures.

  4. Capturing heterogeneous nucleation of nanoscale pits and subsequent crystal shrinkage during Ostwald ripening of a metal phosphate.

    PubMed

    Chung, Sung-Yoon; Kim, Young-Min; Choi, Si-Young; Kim, Jin-Gyu

    2015-01-27

    It has been generally accepted that crystal shrinkage during Ostwald ripening can be understood simply as a reverse process of crystal growth, and as a result, little attention has been paid to shrinkage behavior. The entire microstructure of polycrystalline materials, however, forms as a consequence of both growing and shrinking crystals. Thus, scrutiny of shrinking characteristics in addition to growth aspects is essential for a complete understanding of the evolution of microstructure during Ostwald ripening. By capturing real-time in situ high-resolution electron micrographs at high temperature, we herein demonstrate the shrinkage behavior of nanocrystals embedded in a solid crystalline matrix during the ripening process of a metal phosphate. Unlike typical crystal growth behavior based on two-dimensional homogeneous nucleation, heterogeneous types of nucleation with nanoscale pits at solid-solid interfaces (or crystal edges) are observed to dominantly occur during shrinkage of the crystals. The findings of this study suggest that crystal shrinkage proceeds with a lower activation energy barrier than that of crystal growth, although both crystal growth and shrinkage take place at the same time during Ostwald ripening.

  5. A spray-drying strategy for synthesis of nanoscale metal-organic frameworks and their assembly into hollow superstructures.

    PubMed

    Carné-Sánchez, Arnau; Imaz, Inhar; Cano-Sarabia, Mary; Maspoch, Daniel

    2013-03-01

    Metal-organic frameworks (MOFs) are among the most attractive porous materials known today. Their miniaturization to the nanoscale--into nanoMOFs--is expected to serve myriad applications from drug delivery to membranes, to open up novel avenues to more traditional storage and catalysis applications, and to enable the creation of sophisticated superstructures. Here, we report the use of spray-drying as a versatile methodology to assemble nanoMOFs, yielding spherical hollow superstructures with diameters smaller than 5 µm. This strategy conceptually mimics the emulsions used by chemists to confine the synthesis of materials, but does not require secondary immiscible solvents or surfactants. We demonstrate that the resulting spherical, hollow superstructures can be processed into stable colloids, whose disassembly by sonication affords discrete, homogeneous nanoMOFs. This spray-drying strategy enables the construction of multicomponent MOF superstructures, and the encapsulation of guest species within these superstructures. We anticipate that this will provide new routes to capsules, reactors and composite materials.

  6. Oxidation does not (always) kill reactivity of transition metals: solution-phase conversion of nanoscale transition metal oxides to phosphides and sulfides.

    PubMed

    Muthuswamy, Elayaraja; Brock, Stephanie L

    2010-11-17

    Unexpected reactivity on the part of oxide nanoparticles that enables their transformation into phosphides or sulfides by solution-phase reaction with trioctylphosphine (TOP) or sulfur, respectively, at temperatures of ≤370 °C is reported. Impressively, single-phase phosphide products are produced, in some cases with controlled anisotropy and narrow polydispersity. The generality of the approach is demonstrated for Ni, Fe, and Co, and while manganese oxides are not sufficiently reactive toward TOP to form phosphides, they do yield MnS upon reaction with sulfur. The reactivity can be attributed to the small size of the precursor particles, since attempts to convert bulk oxides or even particles with sizes approaching 50 nm were unsuccessful. Overall, the use of oxide nanoparticles, which are easily accessed via reaction of inexpensive salts with air, in lieu of organometallic reagents (e.g., metal carbonyls), which may or may not be transformed into metal nanoparticles, greatly simplifies the production of nanoscale phosphides and sulfides. The precursor nanoparticles can easily be produced in large quantities and stored in the solid state without concern that "oxidation" will limit their reactivity.

  7. 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.

  8. Nanoscale optical properties of metal nanoparticles probed by Second Harmonic Generation microscopy.

    PubMed

    Shen, Hong; Nguyen, Ngoc; Gachet, David; Maillard, Vincent; Toury, Timothée; Brasselet, Sophie

    2013-05-20

    We report spatial and vectorial imaging of local fields' confinement properties in metal nanoparticles with branched shapes, using Second Harmonic Generation (SHG) microscopy. Taking advantage of the coherent nature of this nonlinear process, the technique provides a direct evidence of the coupling between the excitation polarization and both localization and polarization specificities of local fields at the sub-diffraction scale. These combined features, which are governed by the nanoparticles' symmetry, are not accessible using other contrasts such as linear optical techniques or two-photon luminescence.

  9. 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.

  10. Nanoscale magnetic skyrmions in metallic films and multilayers: a new twist for spintronics

    NASA Astrophysics Data System (ADS)

    Wiesendanger, Roland

    2016-07-01

    Magnetic skyrmions are chiral quasiparticles that show promise for the transportation and storage of information. On a fundamental level, skyrmions are model systems for topologically protected spin textures and can be considered as the counterpart of topologically protected electronic states, emphasizing the role of topology in the classification of complex states of condensed matter. Recent impressive demonstrations of the control of individual nanometre-scale skyrmions — including their creation, detection, manipulation and deletion — have raised expectations for their use in future spintronic devices, including magnetic memories and logic gates. From a materials perspective, it is remarkable that skyrmions can be stabilized in ultrathin transition metal films, such as iron — one of the most abundant elements on earth — if in contact with materials that exhibit high spin–orbit coupling. At present, research in this field is focused on the development of transition-metal-based magnetic multilayer structures that support skyrmionic states at room temperature and allow for the precise control of skyrmions by spin-polarized currents and external fields.

  11. Electrical properties of nanoscale metallic thin films on dielectric elastomer at various strain rates

    NASA Astrophysics Data System (ADS)

    Faisal, Md. Shahnewaz Sabit; Ye, Zhihang; Chen, Zheng; Asmatulu, Ramazan

    2015-04-01

    Dielectric elastomers (DEs) have significant applications in artificial muscle and other biomedical equipment and device fabrications. Metallic thin films by thin film transfer and sputter coating techniques can provide conductive surfaces on the DE samples, and can be used as electrodes for the actuators and other biomedical sensing devices. In the present study, 3M VHB 4910 tape was used as a DE for the coating and electrical characterization tests. A 150 nm thickness of gold was coated on the DE surfaces by sputter coating under vacuum with different pre-strains, ranging from 0 to 100%. Some of the thin films were transferred to the surface of the DEs. Sputter coating, and direct transferring gold leaf coating methods were studied and the results were analyzed in detail in terms of the strain rates and electrical resistivity changes. Initial studies indicated that the metallic surfaces remain conductive even though the DE films were considerably elongated. The coated DEs can be used as artificial muscle by applying electrical stimulation through the conductive surfaces. This study may provide great benefits to the readers, researchers, as well as companies involved in manufacturing of artificial muscles and actuators using smart materials.

  12. Nanoscale magnetic skyrmions in metallic films and multilayers: a new twist for spintronics

    NASA Astrophysics Data System (ADS)

    Wiesendanger, Roland

    2016-07-01

    Magnetic skyrmions are chiral quasiparticles that show promise for the transportation and storage of information. On a fundamental level, skyrmions are model systems for topologically protected spin textures and can be considered as the counterpart of topologically protected electronic states, emphasizing the role of topology in the classification of complex states of condensed matter. Recent impressive demonstrations of the control of individual nanometre-scale skyrmions — including their creation, detection, manipulation and deletion — have raised expectations for their use in future spintronic devices, including magnetic memories and logic gates. From a materials perspective, it is remarkable that skyrmions can be stabilized in ultrathin transition metal films, such as iron — one of the most abundant elements on earth — if in contact with materials that exhibit high spin-orbit coupling. At present, research in this field is focused on the development of transition-metal-based magnetic multilayer structures that support skyrmionic states at room temperature and allow for the precise control of skyrmions by spin-polarized currents and external fields.

  13. 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

  14. A molecular placeholder strategy to access a family of transition-metal-functionalized vanadium oxide clusters.

    PubMed

    Kastner, Katharina; Margraf, Johannes T; Clark, Timothy; Streb, Carsten

    2014-09-15

    Systematic access to metal-functionalized polyoxometalates has thus far been limited to lacunary tungsten oxide and molybdenum oxide clusters. The first controlled, stepwise bottom-up assembly route to metal-functionalized molecular vanadium oxides is now presented. A di-vacant vanadate cluster with two metal binding sites, (DMA)2[V12O32Cl](3-) (DMA = dimethylammonium) is formed spontaneously in solution and characterized by single-crystal X-ray diffraction, ESI mass spectrometry, (51)V NMR spectroscopy, and elemental analyses. In the cluster, the metal binding sites are selectively blocked by hydrogen-bonded DMA placeholder cations. Reaction of the cluster with transition metals TM (Fe(3+), Co(2+), Cu(2+), Zn(2+)) gives access to mono-functionalized vanadate clusters (DMA)[{TM(L)}V12O32Cl](n-) (L = ligand). Metal binding is accomplished by significant distortions of the vanadium oxide framework reminiscent of a pincer movement. Cluster stability under technologically relevant conditions in the solid-state and solution is demonstrated.

  15. Physics of small metal clusters: Topology, magnetism, and electronic structure

    NASA Astrophysics Data System (ADS)

    Rao, B. K.; Jena, P.

    1985-08-01

    The electronic structure of small clusters of lithium atoms has been calculated using the self-consistent-field, molecular-orbital method. The exchange interaction is treated at the unrestricted Hartree-Fock level whereas the correlation is treated perturbatively up to second order by including pair excitations. This is done in two steps, one involving only the valence electrons and the other including all the electrons. A configuration-interaction calculation has also been done with all possible pair excitations. The equilibrium geometries of both the neutral and ionized clusters have been obtained by starting from random configurations and using the Hellmann-Feynman forces to follow the path of steepest descent to a minimum of the energy surface. The clusters of Li atoms each containing one to five atoms are found to be planar. The equilibrium geometry of a cluster is found to be intimately related to its electronic structure. The preferred spin configuration of a cluster has been found by minimizing the total energy of the cluster with respect to various spin assignments. The planar clusters are found to be less magnetic than expected by Hund's-rule coupling. For three-dimensional clusters, however, the magnetism is governed by Hund's rule. The effect of correlation has been found to have decisive influence on the equilibrium topology and magnetism of the clusters. The binding energy per atom, the energy of dissociation, and the ionization potential of the clusters are compared with experiment and with previous calculations. The physical origin of the magic numbers and the effect of the basis functions on the calculated properties have also been investigated.

  16. Synthesis Methods, Microscopy Characterization and Device Integration of Nanoscale Metal Oxide Semiconductors for Gas Sensing

    PubMed Central

    Vander Wal, Randy L.; Berger, Gordon M.; Kulis, Michael J.; Hunter, Gary W.; Xu, Jennifer C.; Evans, Laura

    2009-01-01

    A comparison is made between SnO2, ZnO, and TiO2 single-crystal nanowires and SnO2 polycrystalline nanofibers for gas sensing. Both nanostructures possess a one-dimensional morphology. Different synthesis methods are used to produce these materials: thermal evaporation-condensation (TEC), controlled oxidation, and electrospinning. Advantages and limitations of each technique are listed. Practical issues associated with harvesting, purification, and integration of these materials into sensing devices are detailed. For comparison to the nascent form, these sensing materials are surface coated with Pd and Pt nanoparticles. Gas sensing tests, with respect to H2, are conducted at ambient and elevated temperatures. Comparative normalized responses and time constants for the catalyst and noncatalyst systems provide a basis for identification of the superior metal-oxide nanostructure and catalyst combination. With temperature-dependent data, Arrhenius analyses are made to determine activation energies for the catalyst-assisted systems. PMID:22408484

  17. Possibility of Exciton Mediated Superconductivity in Nano-Sized Sn/Si Core-Shell Clusters: A Process Technology towards Heterogeneous Material in Nano-Scale

    NASA Astrophysics Data System (ADS)

    Kurokawa, Yuichiro; Hihara, Takehiko; Ichinose, Ikuo; Sumiyama, Kenji

    2012-07-01

    We have produced Sn/Si core-shell cluster assemblies by a plasma-gas-condensation cluster beam deposition apparatus. For the sample with Si content = 12 at. %, the temperature dependence of electrical resistivity exhibits a metallic behavior above 10 K and the onset of superconducting transition below 6.1 K. With decreasing temperature, the thermomagnetic curve for the sample with Si content = 8 at. % begins to decrease steadily toward negative value below 7.7 K, indicating the Meissner effect. An increase in the transition temperature, TC is attributable to exciton-type superconductivity.

  18. 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.

  19. 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.

  20. 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.

  1. Nature of excitations in small metal clusters and connection with their geometries

    SciTech Connect

    Bonacic-Koutecky, V.

    1993-12-31

    The contribution of quantum chemical ab-initio studies of optical response properties towards understanding of specific electronic and structural properties of small metal clusters will be presented. The role of cluster size, geometry, number of valence electrons and chemical composition will be pointed out. It will be shown that an appropriate many electron description of excited states for stable cluster structures allows for the quantum molecular interpretation of the absorption spectra and other optical probes. The nature of excitation responsible for characteristic spectroscopic patterns will be discussed. From comparison of predicted and measured spectroscopic observables the structural assignments will be made. Metallization phenomena in finite systems will be addressed.

  2. 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.

  3. 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.

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

    NASA Astrophysics Data System (ADS)

    Toyoda, Noriaki; Yamada, Isao

    2012-11-01

    Mixed gas cluster ion beams were formed using pickup cell for metal etching. O2 neutral clusters pick up acetic acid and formed mixed cluster beam. By using O2-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.

  5. 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

  6. Decoration of Micro-/Nanoscale Noble Metal Particles on 3D Porous Nickel Using Electrodeposition Technique as Electrocatalyst for Hydrogen Evolution Reaction in Alkaline Electrolyte.

    PubMed

    Qian, Xin; Hang, Tao; Shanmugam, Sangaraju; Li, Ming

    2015-07-29

    Micro-/nanoscale noble metal (Ag, Au, and Pt) particle-decorated 3D porous nickel electrodes for hydrogen evolution reaction (HER) in alkaline electrolyte are fabricated via galvanostatic electrodeposition technique. The developed electrodes are characterized by field emission scanning electron microscopy and electrochemical measurements including Tafel polarization curves, cyclic voltammetry, and electrochemical impedance spectroscopy. It is clearly shown that the enlarged real surface area caused by 3D highly porous dendritic structure has greatly reinforced the electrocatalytic activity toward HER. Comparative analysis of electrodeposited Ag, Au, and Pt particle-decorated porous nickel electrodes for HER indicates that both intrinsic property and size of the noble metal particles can lead to distinct catalytic activities. Both nanoscale Au and Pt particles have further reinforcement effect toward HER, whereas microscale Ag particles exhibit the reverse effect. As an effective 3D hydrogen evolution cathode, the nanoscale Pt-particle-decorated 3D porous nickel electrode demonstrates the highest catalytic activity with an extremely low overpotential of -0.045 V for hydrogen production, a considerable exchange current density of 9.47 mA cm(-2) at 25 °C, and high durability in long-term electrolysis, all of which are attributed to the intrinsic catalytic property and the extremely small size of Pt particles.

  7. Local microstructure evolution at shear bands in metallic glasses with nanoscale phase separation.

    PubMed

    He, Jie; Kaban, Ivan; Mattern, Norbert; Song, Kaikai; Sun, Baoan; Zhao, Jiuzhou; Kim, Do Hyang; Eckert, Jürgen; Greer, A Lindsay

    2016-01-01

    At room temperature, plastic flow of metallic glasses (MGs) is sharply localized in shear bands, which are a key feature of the plastic deformation in MGs. Despite their clear importance and decades of study, the conditions for formation of shear bands, their structural evolution and multiplication mechanism are still under debate. In this work, we investigate the local conditions at shear bands in new phase-separated bulk MGs containing glassy nanospheres and exhibiting exceptional plasticity under compression. It is found that the glassy nanospheres within the shear band dissolve through mechanical mixing driven by the sharp strain localization there, while those nearby in the matrix coarsen by Ostwald ripening due to the increased atomic mobility. The experimental evidence demonstrates that there exists an affected zone around the shear band. This zone may arise from low-strain plastic deformation in the matrix between the bands. These results suggest that measured property changes originate not only from the shear bands themselves, but also from the affected zones in the adjacent matrix. This work sheds light on direct visualization of deformation-related effects, in particular increased atomic mobility, in the region around shear bands. PMID:27181922

  8. Second harmonic generation in nanoscale films of transition metal dichalcogenide: Accounting for multipath interference

    NASA Astrophysics Data System (ADS)

    Kudryavtsev, A. V.; Lavrov, S. D.; Shestakova, A. P.; Kulyuk, L. L.; Mishina, E. D.

    2016-09-01

    The transfer matrix method has been widely used to calculate wave propagation through the layered structures consisting entirely of either linear or nonlinear optical materials. In the present work, we develop the transfer matrix method for structures consisting of alternating layers of linear and nonlinear optical materials. The result is presented in a form that allows one to directly substitute the values of material constants, refractive index and absorption coefficient, into the expressions describing the second harmonic generation (SHG) field. The model is applied to the calculation of second harmonic (SH) field generated in nano-thin layers of transition metal dichalcogenides exfoliated on top of silicon oxide/silicon Fabry-Perot cavity. These structures are intensively studied both in view of their unique properties and perspective applications. A good agreement between experimental and numerical results can be achieved by small modification of optical constants, which may arise in an experiment due to a strong electric field of an incident focused pump laser beam. By considering the SHG effect, this paper completes the series of works describing the role of Fabry-Perot cavity in different optical effects (optical reflection, photoluminescence and Raman scattering) in 2D semiconductors that is extremely important for characterization of these unique materials.

  9. Porous metal-organic-framework nanoscale carriers as a potential platform for drug delivery and imaging

    NASA Astrophysics Data System (ADS)

    Horcajada, Patricia; Chalati, Tamim; Serre, Christian; Gillet, Brigitte; Sebrie, Catherine; Baati, Tarek; Eubank, Jarrod F.; Heurtaux, Daniela; Clayette, Pascal; Kreuz, Christine; Chang, Jong-San; Hwang, Young Kyu; Marsaud, Veronique; Bories, Phuong-Nhi; Cynober, Luc; Gil, Sophie; Férey, Gérard; Couvreur, Patrick; Gref, Ruxandra

    2010-02-01

    In the domain of health, one important challenge is the efficient delivery of drugs in the body using non-toxic nanocarriers. Most of the existing carrier materials show poor drug loading (usually less than 5wt% of the transported drug versus the carrier material) and/or rapid release of the proportion of the drug that is simply adsorbed (or anchored) at the external surface of the nanocarrier. In this context, porous hybrid solids, with the ability to tune their structures and porosities for better drug interactions and high loadings, are well suited to serve as nanocarriers for delivery and imaging applications. Here we show that specific non-toxic porous iron(III)-based metal-organic frameworks with engineered cores and surfaces, as well as imaging properties, function as superior nanocarriers for efficient controlled delivery of challenging antitumoural and retroviral drugs (that is, busulfan, azidothymidine triphosphate, doxorubicin or cidofovir) against cancer and AIDS. In addition to their high loadings, they also potentially associate therapeutics and diagnostics, thus opening the way for theranostics, or personalized patient treatments.

  10. Notch sensitivity in nanoscale metallic glass specimens: Insights from continuum simulations

    NASA Astrophysics Data System (ADS)

    Singh, I.; Narasimhan, R.

    2016-01-01

    Recent experiments have shown that nano-sized metallic glass (MG) specimens subjected to tensile loading exhibit increased ductility and work hardening. Failure occurs by necking as opposed to shear banding which is seen in bulk samples. Also, the necking is generally observed at shallow notches present on the specimen surface. In this work, continuum finite element analysis of tensile loading of nano-sized notched MG specimens is conducted using a thermodynamically consistent non-local plasticity model to clearly understand the deformation behavior from a mechanics perspective. It is found that plastic zone size in front of the notch attains a saturation level at the stage when a dominant shear band forms extending across the specimen. This size scales with an intrinsic material length associated with the interaction stress between flow defects. A transition in deformation behavior from quasi-brittle to ductile becomes possible when this critical plastic zone size is larger than the uncracked ligament length. These observations corroborate with atomistic simulations and experimental results.

  11. Local microstructure evolution at shear bands in metallic glasses with nanoscale phase separation

    PubMed Central

    He, Jie; Kaban, Ivan; Mattern, Norbert; Song, Kaikai; Sun, Baoan; Zhao, Jiuzhou; Kim, Do Hyang; Eckert, Jürgen; Greer, A. Lindsay

    2016-01-01

    At room temperature, plastic flow of metallic glasses (MGs) is sharply localized in shear bands, which are a key feature of the plastic deformation in MGs. Despite their clear importance and decades of study, the conditions for formation of shear bands, their structural evolution and multiplication mechanism are still under debate. In this work, we investigate the local conditions at shear bands in new phase-separated bulk MGs containing glassy nanospheres and exhibiting exceptional plasticity under compression. It is found that the glassy nanospheres within the shear band dissolve through mechanical mixing driven by the sharp strain localization there, while those nearby in the matrix coarsen by Ostwald ripening due to the increased atomic mobility. The experimental evidence demonstrates that there exists an affected zone around the shear band. This zone may arise from low-strain plastic deformation in the matrix between the bands. These results suggest that measured property changes originate not only from the shear bands themselves, but also from the affected zones in the adjacent matrix. This work sheds light on direct visualization of deformation-related effects, in particular increased atomic mobility, in the region around shear bands. PMID:27181922

  12. The Globular Cluster System of NGC 5128: Ages, Metallicities, Kinematics and Structural Parameters

    NASA Astrophysics Data System (ADS)

    Woodley, K. A.; Gómez, M.

    2010-10-01

    We review our recent studies of the globular cluster system of NGC 5128. First, we have obtained low-resolution, high signal-to-noise spectroscopy of 72 globular clusters using Gemini-S/GMOS to obtain the ages, metallicities, and the level of alpha enrichment of the metal-poor and metal-rich globular cluster subpopulations. Second, we have explored the rotational signature and velocity dispersion of the galaxy's halo using over 560 globular clusters with radial velocity measurements. We have also compared the dependence of these properties on galactocentric distance and globular cluster age and metallicity. Using globular clusters as tracer objects, we have analyzed the mass, and mass-to-light ratio of NGC 5128. Last, we have measured the structural parameters, such as half-light radii, of over 570 globular clusters from a superb 1.2-square-degree Magellan/IMACS image. We will present the findings of these studies and discuss the connection to the formation and evolution of NGC 5128.

  13. Nanoscale-phase-separated Pd-Rh boxes synthesized via metal migration: an archetype for studying lattice strain and composition effects in electrocatalysis.

    PubMed

    Sneed, Brian T; Brodsky, Casey N; Kuo, Chun-Hong; Lamontagne, Leo K; Jiang, Ying; Wang, Yong; Tao, Franklin Feng; Huang, Weixin; Tsung, Chia-Kuang

    2013-10-01

    Developing syntheses of more sophisticated nanostructures comprising late transition metals broadens the tools to rationally design suitable heterogeneous catalysts for chemical transformations. Herein, we report a synthesis of Pd-Rh nanoboxes by controlling the migration of metals in a core-shell nanoparticle. The Pd-Rh nanobox structure is a grid-like arrangement of two distinct metal phases, and the surfaces of these boxes are {100} dominant Pd and Rh. The catalytic behaviors of the particles were examined in electrochemistry to investigate strain effects arising from this structure. It was found that the trends in activity of model fuel cell reactions cannot be explained solely by the surface composition. The lattice strain emerging from the nanoscale separation of metal phases at the surface also plays an important role.

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

    DOE PAGES

    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

  15. Mo-Cu metal cluster formation and binding in an orange protein isolated from Desulfovibrio gigas.

    PubMed

    Carepo, Marta S P; Pauleta, Sofia R; Wedd, Anthony G; Moura, José J G; Moura, Isabel

    2014-06-01

    The orange protein (ORP) isolated from the sulfate-reducing bacterium Desulfovibrio gigas (11.8 kDa) contains a mixed-metal sulfide cluster of the type [S2MoS2CuS2MoS2](3-) noncovalently bound to the polypeptide chain. The D. gigas ORP was heterologously produced in Escherichia coli in the apo form. Different strategies were used to reconstitute the metal cluster into apo-ORP and obtain insights into the metal cluster synthesis: (1) incorporation of a synthesized inorganic analogue of the native metal cluster and (2) the in situ synthesis of the metal cluster on the addition to apo-ORP of copper chloride and tetrathiomolybdate or tetrathiotungstate. This latter procedure was successful, and the visible spectrum of the Mo-Cu reconstituted ORP is identical to the one reported for the native protein with absorption maxima at 340 and 480 nm. The (1)H-(15)N heteronuclear single quantum coherence spectra of the reconstituted ORP obtained by strategy 2, in contrast to strategy 1, exhibited large changes, which required sequential assignment in order to identify, by chemical shift differences, the residues affected by the incorporation of the cluster, which is stabilized inside the protein by both electrostatic and hydrophobic interactions.

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

    NASA Astrophysics Data System (ADS)

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

    2015-06-01

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

  17. 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.

  18. Formation of nanoscale clusters during the initial stages of CaF{sub 2} growth on miscut Si(111)

    SciTech Connect

    Kidd, T. E.; Davis, S.; Klein, D.; Matveeva, V.; Sifeeva, V.; Becker, N. G.

    2010-09-15

    The initial stages of high temperature CaF{sub 2} growth by molecular beam epitaxy on Si(111) substrates with a 3 deg. miscut were characterized using atomic force microscopy and low energy electron diffraction. At a growth temperature of 750 deg. C, electron diffraction measurements showed that the surface retained the (3x1) surface reconstruction up to a deposition thickness of at least 1.2 nm. The overall topography of the surface was defined by atomically flat terraces decorated with a large number of clusters. These clusters were confined to step edges and were typically 10-20 nm tall. The clusters appear to nucleate at the top of step edges and then grow in size until they extend across the step onto the neighboring terrace below. These results indicate that in this growth regime, the CaF{sub 2} molecules diffuse across terraces to aggregate into relatively large nanostructures after the formation of a thin wetting layer. The unusually rounded features and large heights seen in these clusters appear to arise from the topography of substrate terraces.

  19. 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)

  20. Elucidation of Proton-Assisted Fluxionality in Transition-Metal Oxide Clusters

    NASA Astrophysics Data System (ADS)

    Ramabhadran, Raghunath O.; Mayhall, Nicholas J.; Becher, Edwin L. Becher, Iii; Chowdhury, Arefin; Raghavachari(s), Krishnan

    2012-06-01

    The phenomenon of fluxionality in the reactions of transition-metal oxide clusters provides many opportunities in various industrial and catalytic processes. We present an electronic structure investigation of the fluxionality pathways when anionic W3O6- and Mo3O6- clusters react with three small molecules - water, ammonia and hydrogen sulfide. The presentation features a detailed understanding of (a) how the fluxionality pathway occurs and (b) the various factors that affect the fluxionality pathway - such as the metal, different spin-states and the nature of the non-metal in the reacting small molecule.

  1. 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

  2. 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

  3. Holding onto electrons in alkali metal halide clusters: decreasing polarizability with increasing coordination.

    PubMed

    Zhang, Chaofan; Andersson, Tomas; Svensson, Svante; Björneholm, Olle; Huttula, Marko; Mikkelä, Mikko-Heikki; Anin, Dmitri; Tchaplyguine, Maxim; Öhrwall, Gunnar

    2012-12-13

    The connection between the electronic polarizability and the decrease of the system size from macroscopic solid to nanoscale clusters has been addressed in a combined experimental and model-calculation study. A beam of free neutral potassium chloride clusters has been probed using synchrotron-radiation-based photoelectron spectroscopy. The introduction of "effective" polarizability for chlorine, lower than that in molecules and dimers and decreasing with increasing coordination, has allowed us to significantly improve the agreement between the experimental electron binding energies and the electrostatic model predictions. Using the calculated site-specific binding energies, we have been able to assign the spectral details of the cluster response to the ionizing X-ray radiation, and to explain its change with cluster size. From our assignments we find that the higher-coordination face-atom responses in the K 3p spectra increase significantly with increasing cluster size relative to that of the edge atoms. The reasons behind the decrease of polarizability predicted earlier by ab initio calculations are discussed in terms of the limited mobility of the electron clouds caused by the interaction with the neighboring ions.

  4. 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.

  5. Chemical bonding topology of ternary transition metal-centered bismuth cluster halides: from molecules to metals.

    PubMed

    King, R Bruce

    2003-12-29

    The bismuth polyhedra in ternary transition metal-centered bismuth cluster halides may form discrete molecules or ions, infinite chains, and/or infinite layers. The chemical bonding in many of these diverse structures is related to that in deltahedral boranes exhibiting three-dimensional aromaticity by replacing the multicenter core bond in the boranes with two-center two-electron (2c-2e) bonds from the central transition metal to the nearest neighbor bismuth vertices. Examples of discrete molecules or ions include octahedral MBi(6)(micro-X)(12)(z)()(-) (X = Br, I; M = Rh, Ir, z = 3; M = Ru, z = 4) with exclusively 2c-2e bonds and pentagonal bipyramidal RhBi(7)Br(8) with a 5c-4e bond in the equatorial pentagonal plane indicative of Möbius aromaticity. The compound Ru(3)Bi(24)Br(20) contains a more complicated discrete bismuth cluster ion Ru(2)Bi(17)(micro-Br)(4)(5+), which can be dissected into a RuBi(5) closo octahedron and a RuBi(8) nido capped square antiprism bridged by a Ru(2)Bi(4)(micro-Br)(4) structural unit. In RuBi(4)X(2) (X = Br, I), the same Ru(2)Bi(4)(micro-Br)(4) structural unit bridges Bi(4) squares similar to those found in the known Zintl ion Bi(4)(2)(-) to give infinite chains of Ru(2)Bi(4) octahedra. The electron counts of the RuBi(5), RuBi(8), and Ru(2)Bi(4) polyhedra in these structures follow the Wade-Mingos rules. A different infinite chain structure is constructed from fused RhBi(7/2)Bi bicapped trigonal prisms in Rh(2)Bi(9)Br(3). This Rh(2)Bi(9)Br(3) structure can alternatively be derived from alternating Rh(2/2)Bi(4) octahedra and Rh(2/)(2)Bi(5) pentagonal bipyramids with electron counts obeying the Wade-Mingos rules. Related chemical bonding principles appear to apply to more complicated layer structures such as Pt(3)Bi(13)I(7) containing Kagomé nets of PtBi(8/2) cubes and Ni(4)Bi(12)X(3) containing linked chains of NiBi(6/3)Bi capped trigonal prisms.

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

    PubMed

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

    2014-08-21

    Theoretical studies on the structure, stability, and magnetic properties of icosahedral TM13 (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 TM13 clusters, Co13 is absorbed relatively more strongly on pristine and defective graphene as compared to Fe13 and Ni13 clusters. The adsorbed clusters show reduced magnetic moment compared to the free clusters.

  7. 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.

  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. Atomic Scale Proximity Effects of a Nanoscale Superconductor

    NASA Astrophysics Data System (ADS)

    Latt, Kyaw Zin; Clark, Kendal; Rankin, Rees; Khan, Sajida; Tanaka, H.; Greeley, Jeffery; Hassanien, Abdou; Hla, Saw-Wai

    2014-03-01

    How a superconductor interacts with two dimensional-electron gas is investigated at metal-superconductor interface and boundary using nanoscale superconducting clusters formed by (BETS)2-GaCl4 clusters on a Ag(111) surface at an atomic limit. The superconducting state here is originated from the donor-acceptor charge transfer process of molecular clusters on Ag(111) as confirmed by tunneling spectroscopy and density functional theory investigations. Interestingly, atomic scale tunneling spectroscopy measured across the molecule-metal boundary reveal quenching of the surface state electrons. Moreover, a gap-like state on the Ag(111) surface is observed starting at a far distance from the clusters, which then evolves into a superconducting gap revealing how the superconducting state is formed. This work is supported by DOE BES grant: DE-FG02-02ER46012.

  10. Melting of bcc Transition Metals and Icosahedral Clustering

    SciTech Connect

    Ross, M; Boehler, R; Japel, S

    2006-05-26

    In contrast to polyvalent metals, transition metals have low melting slopes(dT/dP) that are due to partially filled d-bands that allow for a lowering of liquid phase energy through s-d electron transfer and the formation of local structures. In the case of bcc transition metals we show the apparent discrepancy of DAC melting measurements with shock melting of Mo can be understood by reexamining the shock data for V and Ta and introducing the presence of an icosahedral short range order (ISRO) melt phase.

  11. The Catalytic Manganese Cluster: Organization of the Metal Ions

    SciTech Connect

    Yachandra, V.K.

    2007-02-09

    The light-induced oxidation of water to O{sub 2} is catalyzed by a four-manganese atom cluster associated with Photosystem II (PS II). This chapter summarizes ongoing investigations of the oxidation state, the structure and the associated cofactors calcium and chloride of the catalytic Mn cluster using X-ray and electron paramagnetic resonance (EPR) spectroscopy. Manganese K-edge X-ray spectroscopy, K{beta} X-ray emission spectroscopy (XES), and extended X-ray absorption fine structure (EXAFS) studies have not only determined the oxidation states and structural features, but also changes that occur in oxidation state of the Mn cluster and in its structural organization during the accumulation of oxidizing equivalents leading to O{sub 2} formation. Combining X-ray spectroscopy information with X-ray diffraction studies, and consistent with the available EPR data, we have succeeded in limiting the range of likely structures of the Mn cluster. EXAFS studies at the strontium and calcium K-edges have provided evidence that the catalytic center is a Mn/Ca heteronuclear complex. Based on the X-ray spectroscopy data, models for the structure and a mechanism for O{sub 2} evolution are presented.

  12. Nanoscale decomposition of Nb-Ru-O

    NASA Astrophysics Data System (ADS)

    Music, Denis; Geyer, Richard W.; Chen, Yen-Ting

    2016-11-01

    A correlative theoretical and experimental methodology has been employed to explore the decomposition of amorphous Nb-Ru-O at elevated temperatures. Density functional theory based molecular dynamics simulations reveal that amorphous Nb-Ru-O is structurally modified within 10 ps at 800 K giving rise to an increase in the planar metal - oxygen and metal - metal population and hence formation of large clusters, which signifies atomic segregation. The driving force for this atomic segregation process is 0.5 eV/atom. This is validated by diffraction experiments and transmission electron microscopy of sputter-synthesized Nb-Ru-O thin films. Room temperature samples are amorphous, while at 800 K nanoscale rutile RuO2 grains, self-organized in an amorphous Nb-O matrix, are observed, which is consistent with our theoretical predictions. This amorphous/crystalline interplay may be of importance for next generation of thermoelectric devices.

  13. The role of guest molecules in the self-assembly of metal-ligand clusters

    NASA Astrophysics Data System (ADS)

    Johnson, Darren William

    The role guest molecules play in the self-assembly of supramolecular metal-ligand clusters is examined in the context of several predictive design strategies for forming these types of assemblies. Chapter One serves as an introduction and literature survey of this topic. These large assemblies often house guest molecules which play a previously uncharacterized role in the self-assembly processes. Chapter One seeks to categorize this role: Do the guest molecules act as templates in the synthesis? Are the guest molecules necessary for cluster formation? Does the guest drive cluster assembly by forming a stable host-guest complex with the cluster? In Chapter Two a series of heterometallic-hybrid ligand clusters of stoichiometry M2M'3L6 are presented. These result from a predictive design strategy in which two different metals, one hard and one soft, supply all the symmetry elements in these C3h "mesocates." The early examples of these clusters were synthesized in a stepwise manner; however, complete self-assembly of all eleven components can be achieved using appropriate guest molecules. The self-assembly of a novel geometry for metal-ligand clusters, D3 symmetry M6L6 "cylinders," is presented in Chapter Three. This chapter presents the fortuitous synthesis of these cylinders and demonstrates the tendency for discrete clusters to form over oligomers when rigid ligands and labile metals are combined. The ligand presented was designed to assemble M4L4 tetrahedra with trivalent metal ions, however cylinders were formed in all cases examined. Guest molecules were not found to play a role in this self-assembly, but solvent molecules were found disordered within the solid state structures of these clusters. Chapter Four describes a bis-bidentate catecholamide ligand with a structure between the design for M2L3 helicate formation and M 4L6 tetrahedron formation. The two design strategies are briefly discussed, and molecular modeling studies are presented which suggested that

  14. Schrödinger equation Monte Carlo in three dimensions for simulation of carrier transport in three-dimensional nanoscale metal oxide semiconductor field-effect transistors

    NASA Astrophysics Data System (ADS)

    Liu, Keng-Ming; Chen, Wanqiang; Register, Leonard F.; Banerjee, Sanjay K.

    2008-12-01

    A quantum transport simulator, Schrödinger equation Monte Carlo (SEMC) in three dimensions, is presented that provides a rigorous yet reasonably computationally efficient quantum mechanical treatment of real scattering processes within quantum transport simulations of nanoscale three-dimensional (3D) metal oxide semiconductor field-effect transistor (MOSFET) geometries such as quantum wire and multigate field-effect transistors. This work represents an extension of earlier versions of SEMC for simulating quantum transport and scattering in systems with relatively simpler quasi-one-dimensional and quasi-two-dimensional geometries such as quantum-cascade lasers (via SEMC in one dimension) and silicon-on-insulator or dual-gate MOSFETs (via SEMC in two dimensions), respectively. However, the limiting computational considerations can be significantly different. The SEMC approach represents a variation in nonequilibrium Green's function techniques with scattering as well as carrier injection into the simulation region treated via Monte Carlo techniques. Scattering mechanisms include intravalley and intervalley scatterings, intrasubband and intersubband scatterings via acoustic and optical phonons, and, in the former case, surface roughness scattering. SEMC-3D simulations of a silicon omega-gate nanoscale n-channel MOSFET are provided to illustrate the modeling technique as well as the complexity of scattering effects in such nanoscale devices.

  15. An aligned stream of low-metallicity clusters in the halo of the Milky Way.

    PubMed

    Yoon, Suk-Jin; Lee, Young-Wook

    2002-07-26

    One of the long-standing problems in modern astronomy is the curious division of Galactic globular clusters, the "Oosterhoff dichotomy," according to the properties of their RR Lyrae stars. Here, we find that most of the lowest metallicity ([Fe/H] < -2.0) clusters, which are essential to an understanding of this phenomenon, display a planar alignment in the outer halo. This alignment, combined with evidence from kinematics and stellar population, indicates a captured origin from a satellite galaxy. We show that, together with the horizontal-branch evolutionary effect, the factor producing the dichotomy could be a small time gap between the cluster-formation epochs in the Milky Way and the satellite. The results oppose the traditional view that the metal-poorest clusters represent the indigenous and oldest population of the Galaxy.

  16. Metal Transport and Heating in the Core of the Antlia Cluster

    NASA Astrophysics Data System (ADS)

    Machacek, Marie

    2008-10-01

    Understanding the transport of energy and metals from central dominant galaxies in clusters into the intracluster medium (ICM) is vital to any model for the evolution of structure in the Universe. We propose to use a 50ks EPIC MOS+pn observation of the core (inner 12') of the Antlia Cluster to study the role of gas motions and turbulent diffusion in the chemical enrichment and heating of the ICM in a cluster with a sharply rising abundance profile, but without a cool core. We will map temperature, density and abundances throughout the Antlia cluster core, construct pressure and entropy maps to track gas motions and heat flows, and test models of metal enrichment due to turbulent motions powered by episodic outbursts from the central galaxy's AGN.

  17. 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.

  18. 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.

  19. 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

  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.

  1. 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.

  2. Low-metallicity Young Clusters in the Outer Galaxy. I. Sh 2-207

    NASA Astrophysics Data System (ADS)

    Yasui, Chikako; Kobayashi, Naoto; Tokunaga, Alan T.; Saito, Masao; Izumi, Natsuko

    2016-03-01

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

  3. 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

  4. Optical spectra of hot alkali-metal clusters from the random-matrix model

    SciTech Connect

    Akulin, V.M.; Brechignac, C.; Sarfati, A.

    1997-01-01

    We show that the experimentally observed spectra of optical absorption of sodium cluster ions can be explained in the framework of the same random-matrix model, that has been employed earlier [Phys. Rev. Lett. {bold 75}, 220 (1995)] for the ground-state properties of alkali-metal clusters. This approach reveals the effect of cluster symmetry {open_quotes}on average{close_quotes} on the optical-absorption profiles, describes their temperature dependence, and predicts the line shapes of two-photon absorption. {copyright} {ital 1996} {ital The American Physical Society}

  5. DFT study of adsorption of CO2 on palladium cluster doped by transition metal

    NASA Astrophysics Data System (ADS)

    Saputro, A. G.; Agusta, M. K.; Wungu, T. D. K.; Suprijadi; Rusydi, F.; Dipojono, H. K.

    2016-08-01

    We report on a theoretical study of CO2 adsorption on Pd6-M (M: Ni, Cu, Pt, Rh) cluster using first-principles density functional theory (DFT) calculations. We find that CO2 molecule is adsorbed with a bidendate configuration on Pd7 and on most of Pd6M clusters. The bidendate adsorption configuration is formed due to the filling of the unoccupied n* orbital of CO2 molecule upon its interaction with d-orbitals of the cluster. We find that transition metal doping could modify the adsorption energy, adsorption site and adsorption configuration of CO2 molecule on Pd7 cluster. We also predict that the usage of Pd6M clusters as CO2 hydrogenation catalysts might facilitate the formations of HCOO/COOH.

  6. Insulating or metallic: coexistence of different electronic phases in zinc clusters.

    PubMed

    Aguado, Andrés; Vega, Andrés; Lebon, Alexandre; von Issendorff, Bernd

    2015-02-01

    How many of the several attributes of the bulk metallic state persist in a nanoparticle containing a finite number of atoms of a metallic element? Do all those attributes emerge suddenly at a well-defined cluster size or do they rather evolve at different rates and in a broad size range? These fundamental questions have been addressed through a conjoint experimental/theoretical investigation of zinc clusters. We report the observation of novel coexistence phenomena involving different electronic phases: for some sizes, metallic and insulating electronic states coexist within a single, Janus-like, nanoparticle; for the rest of sizes, we report the coexistence of two weakly interacting metallic phases with different dimensionalities, localized at the shell and the core of the nanoparticle. These fascinating features are due to an anomalously long core-shell separation that equips the shell and core regions with largely independent structural, vibrational, and thermal properties.

  7. Advanced use of high-performance liquid chromatography for synthesis of controlled metal clusters

    NASA Astrophysics Data System (ADS)

    Niihori, Yoshiki; Matsuzaki, Miku; Uchida, Chihiro; Negishi, Yuichi

    2014-06-01

    Because the synthesis of metal clusters with multiple ligand types results in a distribution of ligands, high-resolution separation of each unique cluster from the mixture is required for precise control of the ligand composition. Reverse-phase high-performance liquid chromatography combined with appropriate transitioning of the mobile phase composition is an extremely effective means of separating ligand combinations when working with metal clusters protected by two different types of thiolates. We report herein advanced use of this method. The studies involving Au24Pd(SR1)18-x(SR2)x and Au24Pd(SR1)18-x(SeR2)x (SR1, SR2 = thiolate, SeR2 = selenolate) revealed the following. (1) In general, an increase in the difference between the polarities of the functional groups incorporated in the two types of ligands improves the separation resolution. A suitable ligand combination for separation can be predicted from the retention times of Au24Pd(SR1)18 and Au24Pd(SR2)18, which cause the terminal peaks in a series of peaks. (2) The use of a step-gradient program during the mobile phase substitution results in improved resolution compared to that achievable with the linear gradients applied in prior work. (3) This technique is also useful for the evaluation of the chemical compositions of metal clusters protected by two different types of ligands with similar molecular weights. These findings will provide clear design guidelines for the functionalization of metal clusters via control of the ligand composition, and will also improve our understanding of the high-resolution isolation of metal clusters.Because the synthesis of metal clusters with multiple ligand types results in a distribution of ligands, high-resolution separation of each unique cluster from the mixture is required for precise control of the ligand composition. Reverse-phase high-performance liquid chromatography combined with appropriate transitioning of the mobile phase composition is an extremely effective

  8. Environmental Remediation and Application of Nanoscale Zero-Valent Iron and Its Composites for the Removal of Heavy Metal Ions: A Review.

    PubMed

    Zou, Yidong; Wang, Xiangxue; Khan, Ayub; Wang, Pengyi; Liu, Yunhai; Alsaedi, Ahmed; Hayat, Tasawar; Wang, Xiangke

    2016-07-19

    The presence of heavy metals in the industrial effluents has recently been a challenging issue for human health. Efficient removal of heavy metal ions from environment is one of the most important issues from biological and environmental point of view, and many studies have been devoted to investigate the environmental behavior of nanoscale zerovalent iron (NZVI) for the removal of toxic heavy metal ions, present both in the surface and underground wastewater. The aim of this review is to show the excellent removal capacity and environmental remediation of NZVI-based materials for various heavy metal ions. A new look on NZVI-based materials (e.g., modified or matrix-supported NZVI materials) and possible interaction mechanism (e.g., adsorption, reduction and oxidation) and the latest environmental application. The effects of various environmental conditions (e.g., pH, temperature, coexisting oxy-anions and cations) and potential problems for the removal of heavy metal ions on NZVI-based materials with the DFT theoretical calculations and EXAFS technology are discussed. Research shows that NZVI-based materials have satisfactory removal capacities for heavy metal ions and play an important role in the environmental pollution cleanup. Possible improvement of NZVI-based materials and potential areas for future applications in environment remediation are also proposed. PMID:27331413

  9. Environmental Remediation and Application of Nanoscale Zero-Valent Iron and Its Composites for the Removal of Heavy Metal Ions: A Review.

    PubMed

    Zou, Yidong; Wang, Xiangxue; Khan, Ayub; Wang, Pengyi; Liu, Yunhai; Alsaedi, Ahmed; Hayat, Tasawar; Wang, Xiangke

    2016-07-19

    The presence of heavy metals in the industrial effluents has recently been a challenging issue for human health. Efficient removal of heavy metal ions from environment is one of the most important issues from biological and environmental point of view, and many studies have been devoted to investigate the environmental behavior of nanoscale zerovalent iron (NZVI) for the removal of toxic heavy metal ions, present both in the surface and underground wastewater. The aim of this review is to show the excellent removal capacity and environmental remediation of NZVI-based materials for various heavy metal ions. A new look on NZVI-based materials (e.g., modified or matrix-supported NZVI materials) and possible interaction mechanism (e.g., adsorption, reduction and oxidation) and the latest environmental application. The effects of various environmental conditions (e.g., pH, temperature, coexisting oxy-anions and cations) and potential problems for the removal of heavy metal ions on NZVI-based materials with the DFT theoretical calculations and EXAFS technology are discussed. Research shows that NZVI-based materials have satisfactory removal capacities for heavy metal ions and play an important role in the environmental pollution cleanup. Possible improvement of NZVI-based materials and potential areas for future applications in environment remediation are also proposed.

  10. 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.

  11. 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.

  12. Metal-containing carbon clusters. Structures, isomerization, and formation of NbC{sub n}{sup +} clusters

    SciTech Connect

    Clemmer, D.E.; Jarrold, M.E.

    1995-08-30

    Injected ion drift tube techniques, including ion mobility measurements and annealing and fragmentation studies, have been used to examine the isomers present for NbC{sub n}{sup +} (n = 15-50) clusters. Isomers attributed to niobium-containing monocyclic and bicyclic rings, graphitic sheets, and metallofullerenes have been identified. Monocyclic rings, where the niobium atom appears to be either inserted into or bound to the outside of the ring, dominate for NbC{sub n}{sup +} with n < 22. Isomers assigned to bicyclic rings are first observed and become dominant around NbC{sub 22}{sup +}. They probably consist of two rings joined together by a niobium atom. An isomer attributed to NbC{sub n}{sup +} graphitic sheets is present for n > 22 and becomes important for clusters with around 30 carbon atoms. Metallofullerenes are first observed for NbC{sub 28}{sup +} and become a major isomer for clusters with n > 31. Both endohedral metallofullerenes and networked metallofullerenes (where the metal atom is part of the cage) have been identified. For clusters with more than around 30 carbon atoms the NbC{sub n}{sup +} bicyclic rings can be annealed into metallofullerenes and, for the smaller ones, metal-containing graphitic sheets. The isomers observed for NbC{sub n}{sup +} are similar to those found for pure C{sub n}{sup +} and LaC{sub n}{sup +}, but the niobium atom has a substantial effect on the properties and the abundances of the different isomers. 47 refs., 11 figs., 1 tab.

  13. The IMF in galaxy clusters: What is needed to account for high metal production?

    NASA Astrophysics Data System (ADS)

    Morsony, Brian; Heath, Caitlin; Workman, Jared

    2015-08-01

    The gas in galaxy clusters is enriched in metal, typically to about 30% of solar metallicity. However, stars a relatively rare in clusters, meaning that the amount of metal produced per star is about 3 times as much as in the Milky Way. We set out to determine what changes to standard star formation are needed to reproduce the observed metal enhancement. Modifications include expanding the IMF to high mass (>130 M_sun) stars and including metal production from pair-instability supernovae, using an enhanced type-Ia SN rate, and using various modifications of the IMF to make it more top-heavy. For each set of assumptions, we use theoretical nucleosynthesis models to calculate the expected total metal yield per mass of star formation, and to predict the relative abundances of different elements. Including pair-instability supernovae will dramatically increase the amount of metal produced, and, combined with a slightly flatter IMF, can lead to 3 times the metal production per solar mass of star formation, along with an increase abundance of intermediate-mass elements.

  14. 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.

  15. Molecular-dynamics simulations of collisions between energetic clusters of atoms and metal substrates

    NASA Astrophysics Data System (ADS)

    Hsieh, Horngming; Averback, R. S.; Sellers, Harrell; Flynn, C. P.

    1992-02-01

    The collisional dynamics between clusters of Cu, Ni, or Al atoms, with energies of 92 eV to 1.0 keV and sizes of 4 to 92 atoms, and substrates of these same metals were studied using molecular-dynamics computer simulations. A diverse behavior was observed, depending sensitively on the size and energy of the cluster, the elastic and chemical properties of the cluster-substrate combination, and the relative mass of the cluster and substrate atoms. For the 92-atom Cu clusters impacting a Cu substrate, the cluster can form a ``glob'' on the surface at low energy, while penetrating the substrate and heavily deforming it at high energies. When the cluster energy exceeds ~=25 eV/atom, the substrate suffers radiation damage. The 92-atom Al clusters do not much deform Ni substrates, but rather tend to spread epitaxially over the surface, despite the 15% lattice mismatch. For 1-keV collisions, several Al atoms dissociate from the cluster, either reflecting into the vacuum or scattering over the surface. 326-eV Ni clusters embed themselves almost completely within Al substrates and form localized amorphous zones. The potentials for these simulations were derived from the embedded-atom method, although modified to treat the higher-energy events. IAb initioP linear-combination-of-atomic-orbitals-molecular-orbitals calculations were employed to test these potentials over a wide range of energies. A simple model for the expected macroscopic behavior of cluster-solid interactions is included as an appendix for a comparison with the atomistic description offered by the simulations.

  16. 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.

  17. Light-Induced In Situ Transformation of Metal Clusters to Metal Nanocrystals for Photocatalysis.

    PubMed

    Xiao, Fang-Xing; Zeng, Zhiping; Hsu, Shao-Hui; Hung, Sung-Fu; Chen, Hao Ming; Liu, Bin

    2015-12-30

    In situ transformation of glutathione-capped gold (Aux) clusters to gold (Au) nanocrystals under simulated solar light irradiation was achieved and utilized as a facile synthetic approach to rationally fabricate Aux/Au/TiO2 ternary and Au/TiO2 binary heterostructures. Synergistic interaction of Aux clusters and Au nanocrystals contributes to enhanced visible-light-driven photocatalysis.

  18. 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.

  19. Transition-state searches in metal clusters by first-principle methods.

    PubMed

    Cruz-Olvera, Domingo; Vasquez, Alejandra de la Trinidad; Geudtner, Gerald; Vásquez-Pérez, José Manuel; Calaminici, Patrizia; Köster, Andreas M

    2015-03-01

    Elucidation of the chemical reactivity of metal clusters is often cumbersome due to the nonintuitive structures of the corresponding transition states. In this work, a hierarchical transition-state algorithm as implemented in the deMon2k code has been applied to locate transition states of small sodium clusters with 6-10 atoms. This algorithm combines the so-called double-ended interpolation method with the uphill trust region method. The minimum structures needed as input were obtained from Born-Oppenheimer molecular dynamics simulations. To connect the found transition states with the corresponding minimum structures, the intrinsic reaction coordinates were calculated. This work demonstrates how nonintuitive rearrangement mechanisms can be studied in metal clusters. PMID:25072358

  20. 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.

  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. 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.

  3. 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.

  4. 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

  5. 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

  6. 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.

  7. 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.

  8. 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).

  9. The Second-Parameter Effect in Metal-Rich Globular Clusters

    NASA Technical Reports Server (NTRS)

    Sweigart, Allen V.

    1999-01-01

    Recent Hubble Space Telescope (HST) observations have shown that the metal-rich globular clusters (GCs) NGC 6388 and NGC 6441 exhibit a pronounced 2nd parameter effect. Ordinarily metal-rich GCs have only a red horizontal-branch (HB) clump. However, NGC 6388 and NGC 6441 also possess an unexpected population of blue HB stars, indicating that some 2nd parameter is operating in these clusters. Quite remarkably, the HBs in both clusters slope upward with decreasing B -V from the red clump to the top of the blue tail. We review the results of ongoing stellar evolution calculations which indicate (1) that NGC 6388 and NGC 6441 might provide a crucial diagnostic for understanding the origin of the 2nd parameter effect, (2) that differences in age or mass loss along the red-giant branch (RGB) - the two most prominent 2nd parameter candidates - cannot explain the HB morphology of these GCs, and (3) that noncanonical effects involving an enhanced helium abundance or rotation can produce upward sloping HBs. Finally we suggest a new metal-depletion scenario which might help to resolve a baffling conundrum concerning the surface gravities of the blue HB stars in these clusters.

  10. Catalytic Conversion of Short-Chain Alcohols on Atomically Dispersed Au and Pd Supported on Nanoscale Metal Oxides

    NASA Astrophysics Data System (ADS)

    Wang, Chongyang

    With the development of technologies for cellulosic biomass conversion to fuels and chemicals, bio-alcohols are among the main alternative feedstocks to fossil fuels. The research pursued in my thesis was the investigation of gold and palladium as catalysts for the application of short aliphatic alcohols to hydrogen generation and value-added chemicals production. Specifically, selective methanol steam reforming and non-oxidative ethanol dehydrogenation to hydrogen and acetaldehyde were investigated in this thesis work. A major aim of the thesis was to develop atomically efficient catalysts with tuned surface chemistry for the desired reactions, using suitable synthesis methods. Methanol steam reforming (SRM) for hydrogen production has recently been investigated on gold catalysts to overcome the drawbacks of copper catalysts (deactivation, pyrophoricity). Previous work at Tufts University has shown that both CeO2 and ZnO are suitable supports for gold. In this thesis, nanoscale composite oxides ZnZrOx were prepared by a carbon hard-template method, which resulted in homogeneous distribution of Zn species in the matrix of ZrO2. Tunable surface chemistry of ZnZrO x was demonstrated by varying the Zn/Zr ratio to suppress the strong Lewis acidity of ZrO2, which leads to undesired production of CO through methanol decomposition. With atomic dispersion of gold, Au/ZnZrO x catalyzes the SRM reaction exclusively via the methanol self-coupling pathway up to 375°C. The activity of Au/ZnZrOx catalysts was compared to Au/TiO2, which is another catalyst system demonstrating atomic dispersion of gold. Similarity in the apparent activation energy of SRM on all the supported gold catalysts studied in this thesis and in the literature further confirms the same single-site Au-Ox-MO centers as active sites for SRM with indirect effects of the supports exploited. With this fundamental understanding of gold-catalyzed C1 alcohol reforming, the Au/ZnZrOx catalyst was evaluated for the

  11. Metal-Organic Frameworks (MOFs) of a Cubic Metal Cluster with Multicentered Mn(I)-Mn(I) Bonds.

    PubMed

    Hu, Huan-Cheng; Hu, Han-Shi; Zhao, Bin; Cui, Ping; Cheng, Peng; Li, Jun

    2015-09-28

    MOFs with both multicentered metal-metal bonds and low-oxidation-state (LOS) metal ions have been underexplored hitherto. Here we report the first cubic [Mn(I) 8 ] cluster-based MOF (1) with multicentered Mn(I)-Mn(I) bonds and +1 oxidation state of manganese (Mn(I) or Mn(I)), as is supported by single-crystal structure determination, XPS analyses, and quantum chemical studies. Compound 1 possesses the shortest Mn(I)-Mn(I) bond of 2.372 Å. Theoretical studies with density functional theory (DFT) reveal extensive electron delocalization over the [Mn(I) 8 ] cube. The 48 electrons in the [Mn(I) 8 ] cube fully occupy half of the 3d-based and the lowest 4s-based bonding orbitals, with six electrons lying at the nonbonding 3d-orbitals. This bonding feature renders so-called cubic aromaticity. Magnetic properties measurements show that 1 is an antiferromagnet. This work is expected to inspire further investigation of cubic metal-metal bonding, MOF materials with LOS metals, and metalloaromatic theory.

  12. Kinetic description of metal nanocrystal oxidation: a combined theoretical and experimental approach for determining morphology and diffusion parameters in hollow nanoparticles by the nanoscale Kirkendall effect

    NASA Astrophysics Data System (ADS)

    Watanabe, Yoshiki; Mowbray, Ryan W.; Rice, Katherine P.; Stoykovich, Mark P.

    2014-10-01

    The oxidation of colloidal metal nanocrystals to form hollow shells via the nanoscale Kirkendall effect has been investigated using a combined theoretical and experimental approach. A generalized kinetic model for the formation of hollow nanoparticles describes the phenomenon and, unlike prior models, is applicable to any material system and accounts for the effect of surface energies. Phase diagrams of the ultimate oxidized nanoparticle morphology and the time to achieve complete oxidation are calculated, and are found to depend significantly upon consideration of surface energy effects that destabilize the initial formation of small voids. For the oxidation of Cu nanocrystals to Cu2O nanoparticles, we find that the diffusion coefficients dictate the morphological outcomes: the ratio of ? to ? controls the void size, ? determines the time of oxidation and ? is largely irrelevant in the kinetics of oxidation. The kinetic model was used to fit experimental measurements of 11 nm diameter Cu nanocrystals oxidized in air from which temperature-dependent diffusivities of ? and ? for 100 ≤ T ≤ 200 °C were determined. In contrast to previous interpretations of the nanoscale Kirkendall effect in the Cu/Cu2O system, these results are obtained without any a priori assumptions about the relative magnitudes of ? and ?. The theoretical and experimental approaches presented here are broadly applicable to any nanoparticle system undergoing oxidation, and can be used to precisely control the final nanoparticle morphology for applications in catalysis or optical materials.

  13. Trap state passivation improved hot-carrier instability by zirconium-doping in hafnium oxide in a nanoscale n-metal-oxide semiconductor-field effect transistors with high-k/metal gate

    NASA Astrophysics Data System (ADS)

    Liu, Hsi-Wen; Chang, Ting-Chang; Tsai, Jyun-Yu; Chen, Ching-En; Liu, Kuan-Ju; Lu, Ying-Hsin; Lin, Chien-Yu; Tseng, Tseung-Yuen; Cheng, Osbert; Huang, Cheng-Tung; Ye, Yi-Han

    2016-04-01

    This work investigates the effect on hot carrier degradation (HCD) of doping zirconium into the hafnium oxide high-k layer in the nanoscale high-k/metal gate n-channel metal-oxide-semiconductor field-effect-transistors. Previous n-metal-oxide semiconductor-field effect transistor studies demonstrated that zirconium-doped hafnium oxide reduces charge trapping and improves positive bias temperature instability. In this work, a clear reduction in HCD is observed with zirconium-doped hafnium oxide because channel hot electron (CHE) trapping in pre-existing high-k bulk defects is the main degradation mechanism. However, this reduced HCD became ineffective at ultra-low temperature, since CHE traps in the deeper bulk defects at ultra-low temperature, while zirconium-doping only passivates shallow bulk defects.

  14. 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.

  15. Fast Electronic Relaxation in Metal Clusters via Excitation of Coherent Shape Deformations: Slipping Through a Bottleneck

    NASA Astrophysics Data System (ADS)

    Kresin, Vitaly; Ovchinnikov, Yuri; Kresin, Vladimir

    2005-03-01

    We introduce and describe a fast electronic relaxation channel which is particular to free metallic nanoclusters. This channel overcomes the possibility of a phonon bottleneck by invoking the essential role of cluster shape deformations. Such a deformation entails the appearance of coherent surface phonon excitations and enables internal conversion at the level crossing point, thus allowing large energy transfer from an excited electron to the ionic subsystem. As a result, one can show that (unlike usual multiphonon processes) the shape deformation channel is capable of producing short electronic relaxation times, much less than a picosecond. The calculations are in agreement with recent pump-probe photoelectron measurements of relaxation in Aln^- clusters.

  16. Nanoscale imaging of fundamental Li battery chemistry: solid-electrolyte interphase formation and preferential growth of lithium metal nanoclusters

    SciTech Connect

    Sacci, Robert L; Black, Jennifer M.; Wisinger, Nina; Dudney, Nancy J.; More, Karren Leslie; Unocic, Raymond R.

    2015-02-23

    The performance characteristics of Li-ion batteries are intrinsically linked to evolving nanoscale interfacial electrochemical reactions. To probe the mechanisms of solid electrolyte interphase formation and Li electrodeposition from a standard battery electrolyte, we use in situ electrochemical scanning transmission electron microscopy for controlled potential sweep-hold electrochemical measurements with simultaneous BF and ADF STEM image acquisition. Through a combined quantitative electrochemical measurement and quantitative STEM imaging approach, based upon electron scattering theory, we show that chemically sensitive ADF STEM imaging can be used to estimate the density of evolving SEI constituents and distinguish contrast mechanisms of Li-bearing components in the liquid cell.

  17. Filling the gap between the quantum and classical worlds of nanoscale magnetism: giant molecular aggregates based on paramagnetic 3d metal ions.

    PubMed

    Papatriantafyllopoulou, Constantina; Moushi, Eleni E; Christou, George; Tasiopoulos, Anastasios J

    2016-03-21

    In this review, aspects of the syntheses, structures and magnetic properties of giant 3d and 3d/4f paramagnetic metal clusters in moderate oxidation states are discussed. The term "giant clusters" is used herein to denote metal clusters with nuclearity of 30 or greater. Many synthetic strategies towards such species have been developed and are discussed in this paper. Attempts are made to categorize some of the most successful methods to giant clusters, but it will be pointed out that the characteristics of the crystal structures of such compounds including nuclearity, shape, architecture, etc. are unpredictable depending on the specific structural features of the included organic ligands, reaction conditions and other factors. The majority of the described compounds in this review are of special interest not only for their fascinating nanosized structures but also because they sometimes display interesting magnetic phenomena, such as ferromagnetic exchange interactions, large ground state spin values, single-molecule magnetism behaviour or impressively large magnetocaloric effects. In addition, they often possess the properties of both the quantum and the classical world, and thus their systematic study offers the potential for the discovery of new physical phenomena, as well as a better understanding of the existing ones. The research field of giant clusters is under continuous evolution and their intriguing structural characteristics and magnetism properties that attract the interest of synthetic Inorganic Chemists promise a brilliant future for this class of compounds.

  18. Effect of nanoscale zero-valent iron and magnetite (Fe3O4) on the fate of metals during anaerobic digestion of sludge.

    PubMed

    Suanon, Fidèle; Sun, Qian; Mama, Daouda; Li, Jiangwei; Dimon, Biaou; Yu, Chang-Ping

    2016-01-01

    Anaerobic digestion (AD) is one of the most widely used processes to stabilize waste sewage sludge and produce biogas renewable energy. In this study, two different iron nanoparticles [nanoscale zero-valent iron (nZVI) and magnetite (Fe3O4)] were used in the mesophilic AD processes (37 ± 1 °C) to improve biogas production. In addition, changes of heavy metal (Cd, Co, Cu, Zn, Ni and Cr) speciation during AD of sludge with and without iron nanoparticles have been investigated. Concentrations of metals in the initial sludge were as follows: 63.1, 73.4, 1102.2, 2060.3, 483.9 and 604.1 mg kg(-1) (dry sludge basis) for Cd, Co, Cu, Zn, Ni and Cr, respectively. Sequential fractionation showed that metals were predominantly bonded to organic matter and carbonates in the initial sludge. Compared with AD without iron nanoparticles, the application of iron nanoparticles (at dose of 0.5% in this study) showed positive impact not only on biogas production, but also on improvement of metals stabilization in the digestate. Metals were found concentrated in Fe-Mn bound and residual fractions and little was accumulated in the liquid digestate and most mobile fractions of solid digestate (water soluble, exchangeable and carbonates bound). Therefore, iron nanoparticles when properly used, could improve not only biogas yield, but also regulate and control the mobilization of metals during AD process. However, our study also observed that iron nanoparticles could promote the immobilization of phosphorus within the sludge during AD, and more research is needed to fully address the mechanism behind this phenomenon and the impact on future phosphorus reuse.

  19. Deep BV CCD Photometry of the Metal-Rich Globular Cluster M71

    NASA Astrophysics Data System (ADS)

    Yim, H.-S.; Chun, M.-S.; Byun, Y.-I.

    Deep BV photometry for about 15,000 stars in the globular cluster M71 has been obtained from the 2.2 m University Hawaii Telescope using 2k CCD. The frames cover a 7.5' times 7.5' region of the cluster center through 220'' (about 7 core radii). A complete color-magnitude diagram(CMD) from the upper red-giant branch to the lower main sequence(Vlimit ~22 approximately 5 mag below the main-sequence turnoff) has been constructed. From the fitting of the CMD fiducial sequence to the New Yale Isochrone and the similar metallicity globular cluster 47 Tuc, we estimated the absolute and relative ages of this ``disk population'' globluar cluster. A luminosity function to Mv ~8.3 for the cluster main-sequence has been derived. Applying several theoretical mass-luminosity relations, we derived mass function of M71. We discuss the implications of this on recent HST results about low mass main-sequence stars' lumisoty function and on dynamical evolution of the globular cluster.

  20. 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.

  1. Age and metallicity effects in single stellar populations: application to M 31 clusters.

    NASA Astrophysics Data System (ADS)

    de Freitas Pacheco, J. A.

    1997-03-01

    We have recently calculated (Borges et al. 1995AJ....110.2408B) integrated metallicity indices for single stellar populations (SSP). Effects of age, metallicity and abundances were taken into account. In particular, the explicit dependence of the indices Mg_2_ and NaD respectively on the ratios [Mg/Fe] and [Na/Fe] was included in the calibration. We report in this work an application of those models to a sample of 12 globular clusters in M 31. A fitting procedure was used to obtain age, metallicity and the [Mg/Fe] ratio for each object, which best reproduce the data. The mean age of the sample is 15+/-2.8Gyr and the mean [Mg/Fe] ratio is 0.35+/-0.10. These values and the derived metallicity spread are comparable to those found in galactic counterparts.

  2. 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.

  3. Cu(Ir1 − xCrx)2S4: a model system for studying nanoscale phase coexistence at the metal-insulator transition

    PubMed Central

    Božin, E. S.; Knox, K. R.; Juhás, P.; Hor, Y. S.; Mitchell, J. F.; Billinge, S. J. L.

    2014-01-01

    Increasingly, nanoscale phase coexistence and hidden broken symmetry states are being found in the vicinity of metal-insulator transitions (MIT), for example, in high temperature superconductors, heavy fermion and colossal magnetoresistive materials, but their importance and possible role in the MIT and related emergent behaviors is not understood. Despite their ubiquity, they are hard to study because they produce weak diffuse signals in most measurements. Here we propose Cu(Ir1 − xCrx)2S4 as a model system, where robust local structural signals lead to key new insights. We demonstrate a hitherto unobserved coexistence of an Ir4+ charge-localized dimer phase and Cr-ferromagnetism. The resulting phase diagram that takes into account the short range dimer order is highly reminiscent of a generic MIT phase diagram similar to the cuprates. We suggest that the presence of quenched strain from dopant ions acts as an arbiter deciding between the competing ground states. PMID:24518384

  4. Cu(Ir1 - xCrx)2S4: a model system for studying nanoscale phase coexistence at the metal-insulator transition

    NASA Astrophysics Data System (ADS)

    Božin, E. S.; Knox, K. R.; Juhás, P.; Hor, Y. S.; Mitchell, J. F.; Billinge, S. J. L.

    2014-02-01

    Increasingly, nanoscale phase coexistence and hidden broken symmetry states are being found in the vicinity of metal-insulator transitions (MIT), for example, in high temperature superconductors, heavy fermion and colossal magnetoresistive materials, but their importance and possible role in the MIT and related emergent behaviors is not understood. Despite their ubiquity, they are hard to study because they produce weak diffuse signals in most measurements. Here we propose Cu(Ir1 - xCrx)2S4 as a model system, where robust local structural signals lead to key new insights. We demonstrate a hitherto unobserved coexistence of an Ir4+ charge-localized dimer phase and Cr-ferromagnetism. The resulting phase diagram that takes into account the short range dimer order is highly reminiscent of a generic MIT phase diagram similar to the cuprates. We suggest that the presence of quenched strain from dopant ions acts as an arbiter deciding between the competing ground states.

  5. 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.

  6. 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.

  7. Nanoscale imaging of fundamental li battery chemistry: solid-electrolyte interphase formation and preferential growth of lithium metal nanoclusters.

    PubMed

    Sacci, Robert L; Black, Jennifer M; Balke, Nina; Dudney, Nancy J; More, Karren L; Unocic, Raymond R

    2015-03-11

    The performance characteristics of Li-ion batteries are intrinsically linked to evolving nanoscale interfacial electrochemical reactions. To probe the mechanisms of solid electrolyte interphase (SEI) formation and to track Li nucleation and growth mechanisms from a standard organic battery electrolyte (LiPF6 in EC:DMC), we used in situ electrochemical scanning transmission electron microscopy (ec-S/TEM) to perform controlled electrochemical potential sweep measurements while simultaneously imaging site-specific structures resulting from electrochemical reactions. A combined quantitative electrochemical measurement and STEM imaging approach is used to demonstrate that chemically sensitive annular dark field STEM imaging can be used to estimate the density of the evolving SEI and to identify Li-containing phases formed in the liquid cell. We report that the SEI is approximately twice as dense as the electrolyte as determined from imaging and electron scattering theory. We also observe site-specific locations where Li nucleates and grows on the surface and edge of the glassy carbon electrode. Lastly, this report demonstrates the investigative power of quantitative nanoscale imaging combined with electrochemical measurements for studying fluid-solid interfaces and their evolving chemistries.

  8. VizieR Online Data Catalog: On the metallicity of open clusters. II. (Heiter+, 2014)

    NASA Astrophysics Data System (ADS)

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

    2013-11-01

    In Table 1 we list the basic information for each star and each metallicity determination in the starting sample, which should be sufficient to extract the corresponding atmospheric parameters from the PASTEL catalogue. Table 4 lists the weighted mean metallicities for each OC and each paper, which were computed using the metallicities from the references in Table 1. For the weights we used the inverse square of the individual errors quoted by the authors. Table 4 also gives the ranges of effective temperature (Teff) and surface gravity (logg) of the stars corresponding to each paper. After removing all determinations with Teff outside the range 4400 to 6500K and with logg<2.0, we constructed a list of recommended cluster metallicities, which we call the final high-resolution sample. The weighted mean metallicities for each cluster in the final sample are given in Table 11, and the individual determinations included in the final sample are identified in Table 1 (first column). (3 data files).

  9. The puzzle of metallicity and multiple stellar populations in the globular clusters in Fornax

    NASA Astrophysics Data System (ADS)

    D'Antona, F.; Caloi, V.; D'Ercole, A.; Tailo, M.; Vesperini, E.; Ventura, P.; Di Criscienzo, M.

    2013-09-01

    All models for the formation of multiple populations in globular clusters (GCs) imply an initial mass of the systems several times greater than the present mass. A recent study of the dwarf spheroidal galaxy Fornax, where the low-metallicity ([Fe/H] ≲ -2) stars contained in GCs appear to account for ˜20 per cent of the total number, seems to constrain the initial mass of the four low-metallicity GCs in Fornax to be at most a factor of 5-6 greater than their present mass. We examine the photometric data for Fornax clusters, focusing our attention on their horizontal branch (HB) colour distribution and, when available, on the fraction and period distribution of RR Lyrae variables. Based on our understanding of the HB morphology in terms of varying helium content (and red giant mass-loss rate) in the context of multiple stellar generations, we show that the clusters F2, F3 and F5 must contain substantial fractions of second-generation stars (˜54-65 per cent). On the basis of a simple chemical evolution model we show that the helium distribution in these clusters can be reproduced by models with cluster initial masses ranging from values equal to ˜4 to ˜10 times greater than the current masses. Models with a very short second-generation star formation episode can also reproduce the observed helium distribution but require greater initial masses up to about 20 times the current mass. While the lower limit of this range of possible initial GC masses is consistent with those suggested by observations of the low-metallicity field stars, we also discuss the possibility that the metallicity scale of field stars (based on Ca II triplet spectroscopy) and the metallicities derived for the clusters in Fornax may not be consistent with each other. In this case, observational constraints would allow greater initial cluster masses. Two interesting hypotheses are needed in order to reproduce the HB morphology of the clusters F2, F3 and F5. (i) The first-generation HB stars all

  10. 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.

  11. 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

  12. Electron affinities of d1 transition metal chloride clusters and onset of super halogen behavior

    NASA Astrophysics Data System (ADS)

    Behera, Swayamprabha; Joseph, Jorly; Jena, Purusottam

    2011-03-01

    Geometry, electronic structure, and electron affinity of d1 transition metal chloride clusters (MCl n , M = Sc,Y, La; n = 1--5) have been calculated using density functional theory. Chlorine atoms are chemically bound in all cases except for MCl 5 . The electron affinities of MCl n (n = 1--3) are small and increase only marginally as a function of n until the valence of the metal atom is consumed. Beyond this, they rise sharply and reach a value of 5.96, 6.03 and 5.90 eV for ScCl 4 , YCl 4 and LaCl 4 , respectively and remain high for n = 5. MCl n , (n = 4,5) clusters, therefore, behave as superhalogens. Results are compared with available experimental data

  13. Electron affinities of d1 transition metal chloride clusters and onset of super halogen behavior

    NASA Astrophysics Data System (ADS)

    Joseph, Jorly; Behera, Swayamprabha; Jena, Purusottam

    2010-09-01

    Geometry, electronic structure, and electron affinity of d1 transition metal chloride clusters (MCl n, M = Sc, Y, La; n = 1-5) have been calculated using density functional theory. Chlorine atoms are chemically bound in all cases except for MCl 5. The electron affinities of MCl n ( n = 1-3) are small and increase only marginally as a function of n until the valence of the metal atom is consumed. Beyond this, they rise sharply and reach a value of 5.96, 6.03 and 5.90 eV for ScCl 4, YCl 4 and LaCl 4, respectively and remain high for n = 5. MCl n, ( n = 4,5) clusters, therefore, behave as superhalogens. Results are compared with available experimental data.

  14. 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).

  15. On the Metallicity Distribution of the Peculiar Globular Cluster M22

    NASA Astrophysics Data System (ADS)

    Lee, Jae-Woo

    2016-10-01

    In our previous study, we showed that the peculiar globular cluster (GC) M22 contains two distinct stellar populations, namely the Ca-w and Ca-s groups, which have different physical properties, chemical compositions, spatial distributions, and kinematics. We proposed that M22 was most likely formed via a merger of two GCs with heterogeneous metallicities in a dwarf galaxy environment and then later accreted to our Galaxy. In their recent study, Mucciarelli et al. claimed that M22 is a normal monometallic globular cluster without any perceptible metallicity spread among the two groups of stars, which challenges our results and those of others. We devise new strategies for the local thermodynamic equilibrium abundance analysis of red giant branch stars in GCs and show that there exists a spread in the iron abundance distribution in M22.

  16. 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

  17. 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.

  18. Tetrahedral clusters of GaMo{sub 4}S{sub 8-} type compounds: A metal bonding analysis

    SciTech Connect

    Le Beuze, A..; Loirat, H.; Zerrouki, M.C.; Lissillour, R.

    1995-11-15

    Extended Hueckel tight binding calculations have been performed on ligated as well as on ligand-free Mo{sub 4} and Mo{sub 6} extended frames, in order to analyze the metal-metal bonding within the clusters and particularly the appreciable changes of the metal-metal bond lengths through the M{sub 4} tetrahedral units contained in GaM{sub 4}X{sub 8} (M = Mo, Nb, V, Ta; X = S, Se, Te), units of the MMo{sub 6}S{sub 4}Y{sub 4} (Y = Cl, Br, I). A comparison with the M{sub 6} octahedral units of the MMo{sub 6}X{sub 8} (M = Pb, Ag, La; X = S, Se) series is made. By means of DOS, COOP curves, and overlap populations, results clearly display the strong reorganization of the electronic structure of the bare metal clusters network while the ligand interactions occur, inducing a strong reduction of the strength of the metal-metal bonds. We outline the relationship between the metal-metal bond lengths and various parameters such as the valence electron count (VEC) per cluster and the nature of the ligands. Our results indicate that the two series M{sub 4} and M{sub 6} differ: M-M bond lengths are unaffected by the VEC in the regular M{sub 4} cluster; whereas some M-M bond lengths undergo a significant change when the VEC increases in the distorded M{sub 6} clusters. Likewise, it is worthy to note that metal d orbitals have a more significant effect in M{sub 4} cluster series. In contrast, the metal-ligand covalency induces similar enlongations of metal-metal bonds in the two series.

  19. Lithium abundance in the metal-poor open cluster NGC 2243

    NASA Astrophysics Data System (ADS)

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

    2013-04-01

    Context. Lithium is a fundamental element for studying the mixing mechanisms acting in the stellar interiors, for understanding the chemical evolution of the Galaxy and the Big Bang nucleosynthesis. The study of Li in stars of open clusters (OC) allows a detailed comparison with stellar evolutionary models and permits us to trace its galactic evolution. The OC NGC 2243 is particularly interesting because of its low metallicity ([Fe/H] = -0.54 ± 0.10 dex). Aims: We measure the iron and lithium abundance in stars of the metal-poor OC NGC 2243. The first aim is to determine whether the Li dip extends to such low metallicities, the second is to compare the results of our Li analysis in this OC with those present in 47 Tuc, a globular cluster of similar metallicity. Methods: We performed a detailed analysis of high-resolution spectra obtained with the multi-object facility FLAMES at the ESO VLT 8.2 m telescope. Lithium abundance was derived through line equivalent widths and the OSMARCS atmosphere models. Iron abundances from Fe i and Fe ii lines have also been measured and used to check the atmospheric model parameters. Results: The Li line is detected in 27 stars confirmed as likely cluster members by repeated radial velocity measurements. We determine a Li dip center of 1.06 M⊙, which is much 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 Tuc. We estimated an iron abundance of [Fe/H] = -0.54 ± 0.10 dex for NGC 2243, which is similar (within the errors) to previous findings. The [α/Fe] content ranges from 0.00 ± 0.14 for Ca to 0.20 ± 0.22 for Ti, which is low when compared to thick disk stars and to Pop II stars, but compatible with thin disk objects. We found a mean radial velocity of 61

  20. Carbon clusters containing two metals atoms: Structures, growth mechanism, and fullerene formation

    SciTech Connect

    Shelimov, K.B.; Jarrold, M.F.

    1996-02-07

    Gas phase ion mobility measurments have been used to probe the structures and interconversion of La{sub 2}C{sub n}{sup +} (n = 1-100) isomers. The smallest La{sub 2}C{sub n}{sup +} clusters (n = 10) appear to be planar rings. However, planar mono and bicylic rings (the dominant isomers for C{sub n}{sup +} and LaC{sub n}{sup +}, n = 30, clusters) are not observed for the larger La{sub 2}C{sub n}{sup +} species. Instead, isomers which appear to be three-dimensional ring complexes dominate for unannealed La{sub 2}C{sub n}{sup +} (n + 17) clusters. The formation of these complexes is probably driven by electrostatic forces. For n = 30 the three-dimensional ring complexes isomerize into metallofullerenes (and metal-containing graphite sheets for n = 30-37). The estimated activation energies for these isomerization processes are about 1eV lower than those estimated for similar processes for planar C{sub n}{sup +} and LaC{sub n}{sup +} rings. Metallofullerenes with two non-endohedral metal atoms (for n = 28-29), one endohedral metal atom (for n = 31-100), and two endohedral metal atoms (for n > 64, only even n), are identified. Fullerene derivatives (presumably fullerene + ring complexes) are abundant in the unannealed isomer distributions for La{sub 2}C{sub n}{sup +} (n > 50) clusters, but readily isomerize into regular fullerenes upon collisional heating. 47 refs., 9 figs., 2 tabs.

  1. Mie Resonant Absorption and Infrared Emission in InN Related to Metallic Indium Clusters

    NASA Astrophysics Data System (ADS)

    Shubina, T. V.; Ivanov, S. V.; Jmerik, V. N.; Solnyshkov, D. D.; Kop'ev, P. S.; Vasson, A.; Leymarie, J.; Kavokin, A.; Amano, H.; Kamiyama, S.; Iwaya, M.; Akasaki, I.; Lu, H.; Schaff, W. J.; Kasic, A.; Monemar, B.

    2005-06-01

    We demonstrate that resonant optical losses related to metallic In clusters can significantly modify absorption spectra of InN with any optical gap. Thermally detected absorption spectra with a pronounced Mie resonance are successfully simulated using a dielectric function of InN corresponding to the 1.2-1.4 eV optical gap. The resonance is observed in spectra of conventional absorption at low temperatures being smoothed out at room temperature.

  2. 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

  3. Globular cluster system of the galaxy. II. The spatial and metallicity distributions, the second parameter phenomenon, and the formation of the cluster system

    SciTech Connect

    Zinn, R.

    1980-10-15

    The metal abundance measurements that were collected for 84 globular clusters in the first paper of this series are used here to describe the cluster system. The ranking of the clusters by metallicity has been calibrated by a new (Fe/H) scale, which is based in part on the measurement of (Fe/H)=-1.2 for M71. According to this scale, the metal abundance gradient between the inner and outer halo clusters (i.e., R<9 kpc and 9< or =R< 40 kpc) is only a small fraction of that found with previous (Fe/H) scales. It is not clear, however, that the new scale is to be preferred over the old ones; consequently the size of this gradient remains in doubt. The most significant properties of the cluster system that do not depend on the validity of the (Fe/H) scale are the following; (i) there is a wide range in metal abundance among the cluster in the zone 9< or =R<40 kpc, but no evidence of a gradient with R or with distance from the galactic plane, Vertical BarZVertical Bar; (ii) among the clusters with R<9 kpc, there is a metal abundance gradient with Vertical BarZVertical Bar; and (iii) the magnitude of the second parameter effect increases with R, and if age is the second parameter, then over the range 0cluster age declines by approx.3 Gyr and the scatter in age increases from less than 1 Gyr to approx.2 Gyr.

  4. 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

  5. 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

  6. 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.

  7. 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}.

  8. Molecular heterometallic hydride clusters composed of rare-earth and d-transition metals.

    PubMed

    Shima, Takanori; Luo, Yi; Stewart, Timothy; Bau, Robert; McIntyre, Garry J; Mason, Sax A; Hou, Zhaomin

    2011-09-18

    Heteromultimetallic hydride clusters containing both rare-earth and d-transition metals are of interest in terms of both their structure and reactivity. However, such heterometallic complexes have not yet been investigated to a great extent because of difficulties in their synthesis and structural characterization. Here, we report the synthesis, X-ray and neutron diffraction studies, and hydrogen addition and release properties of a family of rare-earth/d-transition-metal heteromultimetallic polyhydride complexes of the core structure type 'Ln(4)MH(n)' (Ln = Y, Dy, Ho; M = Mo, W; n = 9, 11, 13). Monitoring of hydrogen addition to a hydride cluster such as [{(C(5)Me(4)SiMe(3))Y}(4)(μ-H)(9)Mo(C(5)Me(5))] in a single-crystal to single-crystal process by X-ray diffraction has been achieved for the first time. Density functional theory studies reveal that the hydrogen addition process is cooperatively assisted by the Y/Mo heteromultimetallic sites, thus offering unprecedented insight into the hydrogen addition and release process of a metal hydride cluster.

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. 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

  14. 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.

  15. 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.

  16. 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.

  17. Nanoscale imaging of fundamental Li battery chemistry: solid-electrolyte interphase formation and preferential growth of lithium metal nanoclusters

    DOE PAGES

    Sacci, Robert L; Black, Jennifer M.; Wisinger, Nina; Dudney, Nancy J.; More, Karren Leslie; Unocic, Raymond R.

    2015-02-23

    The performance characteristics of Li-ion batteries are intrinsically linked to evolving nanoscale interfacial electrochemical reactions. To probe the mechanisms of solid electrolyte interphase formation and Li electrodeposition from a standard battery electrolyte, we use in situ electrochemical scanning transmission electron microscopy for controlled potential sweep-hold electrochemical measurements with simultaneous BF and ADF STEM image acquisition. Through a combined quantitative electrochemical measurement and quantitative STEM imaging approach, based upon electron scattering theory, we show that chemically sensitive ADF STEM imaging can be used to estimate the density of evolving SEI constituents and distinguish contrast mechanisms of Li-bearing components in the liquidmore » cell.« less

  18. Selective detection of 2,4,6-trinitrophenol based on a fluorescent nanoscale bis(8-hydroxyquinoline) metal complex.

    PubMed

    Lv, Xiao-Jun; Qi, Liang; Gao, Xiang-Yu; Wang, Huan; Huo, Yuan; Zhang, Zhi-Qi

    2016-04-01

    The reliable and accurate detection of explosives such as 2,4,6-trinitrophenol (TNP) and 2,4,6-trinitrotoluene (TNT) is in high demand for homeland security and public safety. Although extremely high sensitivity towards TNT has been demonstrated, detection of TNP remains a challenge. In this work, a fluorescent nanoscale complex composed of bis(8-hydroxyquinoline) and Al(3+) ions has been prepared, characterized and applied in detection of TNP. This complex exhibits the ability to sense the nitro explosive TNP via a fluorescence quenching mechanism with high selectivity. A simple paper test system for the rapid monitoring of TNP was also investigated. The results show that Bhq-Al is a quite ideal sensing material for trace-level detection of TNP. PMID:26838414

  19. A simple method to make an electrical connection between ZnO microwire and substrate through nanoscale metal evaporation

    NASA Astrophysics Data System (ADS)

    Kim, Hakseong; Lee, Jinkyung; Yun, Hoyeol; Lee, Sang; Nano Electonics and Nano Mechanics Team

    2013-03-01

    We developed a simple method to make an electrical connection with nanoscale electrodes on microscale wire using suspended Poly(methyl methacrylate) (PMMA) strings. Less than 90 nm height of Ti/Au made a complete electrical connection on the ZnO microwires of which diameter is around 2 μm. A cross linked PMMA string was bridged between ZnO microwire and substrate for making good electrical connection. The contact resistance of ZnO microwire fabricated by this method was much lower than that of device fabricated by standard E-beam lithography and evaporation. This fabrication method is readily extendible to prepare nano scale electrodes on various micro sized materials and serves as a pathway for studying their mesoscopic transport phenomena. This work is supported by WCU, BK21 and NRF.

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

    NASA Astrophysics Data System (ADS)

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

    2016-06-01

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

  1. Effect of Temperature on Morphology of Metallic Iron and Formation of Clusters of Iron Ore Pellets

    NASA Astrophysics Data System (ADS)

    de Alencar, Jean Philippe Santos Gherardi; de Resende, Valdirene Gonzaga; de Castro, Luiz Fernando Andrade

    2016-02-01

    The increase of the reduction temperature in direct reduction furnaces has been a recurring tool due to the benefits that it provides to the process. However, its increase cannot be performed without taking into account some considerations, since the sticking phenomenon is directly correlated with it and could lead to permeability problems and reactor performance. An analysis of the formation of pellets clusters at different temperatures was carried out with focus on morphological characterization of reduced materials to better understand the causes and effects of these actions. The results showed a correlation between the morphology of the metallic iron present in the samples and the clustering index. At low reduction temperatures, 1123 K (850 °C), the iron formed is eroded and deformed and the cluster hardly remains after tumbling. When forming iron with fibrous structure, 1223 K (950 °C), the clustering index increases because of anchor points which make the material to stick together. Finally, under the effect of high temperature and long time, it generates fresh precipitated iron, enhancing the resistance of the clusters so that they cannot be separated.

  2. Ir Spectroscopy of First-Row Transition Metal Clusters and Their Complexes with Simple Molecules

    NASA Astrophysics Data System (ADS)

    Kiawi, D. M.; Bakker, J.; Oomens, J.; Buma, W. J.; Waters, L. B. F. M.

    2014-06-01

    Iron is an important element in the formation of solids in space. Spectroscopic observations of interstellar iron shows that its atomic gas-phase abundance is strongly depleted with respect to that of hydrogen. In contrast, sulfur is mostly found in the gas phase in low-density regions of interstellar space, but is highly depleted in regions of star- and planet formation. Furthermore, the dominant source of sulfur in our solar system is solid FeS, as found in primitive meteorites, implying an efficient chemical pathway to convert sulphur or sulphur containing compounds into solid FeS during the (early phases of) the star formation process. We address the evolution of iron and sulfur in space on a molecular level by studying metal nanoclusters and their interaction with ligands using IR action spectroscopy. Clusters are formed through laser ablation of solid precursor materials and brought into a molecular beam environment. Complexes with ligands are obtained by directing the beam through a reaction channel containing low-pressure reactant gas. Mass-selected IR action spectra are recorded by irradiating the clusters using the Free Electron Laser for Infrared eXperiments (FELIX). Experimental spectra are then compared with DFT predictions which enables us to determine the structure of the selected cluster and its binding interactions with ligands. As part of this project, we here present IR action spectra of size-selected Fe clusters and the chemically closely related Co clusters, and their complexes with relevant ligands.

  3. 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

  4. 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.

  5. Protected Noble-Metal Clusters at the Transition from Molecules to Materials

    NASA Astrophysics Data System (ADS)

    Whetten, Robert L.

    2015-03-01

    Protected noble-metal clusters are found at a molecular level of definite composition and structure up to a size of 145-165 metal atoms. Curiously, this size-range is also where several key signatures of metallic character begin to converge. These substances have been of great interest for many application-areas in the past couple decades, but the understanding of their structure and bonding, remarkable self-selection, electronic structure and optical properties has only recently started to reach a fundamental or molecular level of definition. This presentation emphasizes this recent progress and also outlines the prospects for extending the molecular domain of metallurgy well beyond the 200- atom range, thanks to advances in experimental & theoretical methods.

  6. 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.

  7. 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.

  8. 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

  9. Conversion of mill-scale waste to nanoscale zero valent iron (nZVI) for 'green' hydrogen generation via metal-steam reforming

    NASA Astrophysics Data System (ADS)

    Kesavan, Sathees Kumar

    The Proton Exchange Membrane Fuel Cells (PEMFCs) are the most preferred and efficient energy conversion devices for automotive applications but demand high purity hydrogen which comes at a premium price. The currently pursued hydrogen generation methods suffer from issues such as, low efficiency, high cost, environmental non-benignity, and, in some cases, commercial non-viability. Many of these drawbacks including the CO contamination and, storage and delivery can be overcome by resorting to metal-steam reforming (MSR) using iron from steel industry's mill-scale waste. A novel solution-based room temperature technique using sodium borohydride (NaBH4) as the reducing agent has been developed that produces highly active nanoscale (30-40 nm) iron particles. A slightly modified version of this technique using a surfactant and water oil microemulsion resulted in the formation of 5 nm Fe particles. By using hydrazine (N2H4) as an inexpensive and more stable (compared to NaBH4) reductant, body centered cubic iron particles with edge dimensions ˜5 nm were obtained under mild solvothermal conditions in ethanol. The nanoscale zero valent iron (nZVI) powder showed improved kinetics and greater propensity for hydrogen generation than the coarser microscale iron obtained through traditional reduction techniques. To initiate and sustain the somewhat endothermic MSR process, a solar concentrator consisting of a convex polyacrylic sheet with aluminum reflective coating was fabricated. This unique combination of mill-scale waste as iron source, hydrazine as the reductant, mild process conditions for nZVI generation and solar energy as the impetus for actuating MSR, obviates several drawbacks plaguing the grand scheme of producing, storing and delivering pure and humidified H2 to a PEMFC stack.

  10. 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

  11. Encapsulation of metal clusters within MFI via interzeolite transformations and direct hydrothermal syntheses and catalytic consequences of their confinement.

    PubMed

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

    2014-10-29

    The encapsulation of metal clusters (Pt, Ru, Rh) within MFI was achieved by exchanging cationic metal precursors into a parent zeolite (BEA, FAU), reducing them with H2 to form metal clusters, and transforming these zeolites into daughter structures of higher framework density (MFI) under hydrothermal conditions. These transformations required MFI seeds or organic templates for FAU parent zeolites, but not for BEA, and occurred with the retention of encapsulated clusters. Clusters uniform in size (1.3-1.7 nm) and exposing clean and accessible surfaces formed in BEA and FAU zeolites; their size remained essentially unchanged upon transformation into MFI. Encapsulation selectivities, determined from the relative hydrogenation rates of small (toluene) and large (alkyl arenes) molecules and defined as the ratio of the surface areas of all the clusters in the sample to that of external clusters, were very high (8.1-40.9) for both parent and daughter zeolites. Encapsulation into MFI via direct hydrothermal syntheses was unsuccessful because metal precursors precipitated prematurely at the pH and temperatures required for MFI synthesis. Delayed introduction of metal precursors and F(-) (instead of OH(-)) as the mineralizing agent in hydrothermal syntheses increased encapsulation selectivities, but they remained lower than those achieved via interzeolite transformations. These interconversions provide a general and robust strategy for encapsulation of metals when precursors can be introduced via exchange into a zeolite that can be transformed into target daughter zeolites with higher framework densities, whether spontaneously or by using seeds or structure-directing agents (SDA).

  12. Scanning tunneling microscopy studies of metal clusters supported on TiO 2 (110): Morphology and electronic structure

    NASA Astrophysics Data System (ADS)

    Lai, X.; Clair, T. P. St.; Valden, M.; Goodman, D. W.

    1998-12-01

    A brief review of our laboratory's recent scanning tunneling microscopy (STM) studies on nanoclusters supported on TiO 2(110) is presented. Particular emphasis is placed on the system {Au}/{TiO2(110) }. The nucleation and growth of the clusters, which were vapor-deposited on TiO 2(110) under ultra high vacuum (UHV) conditions, were investigated using STM. It was found that Au, Pd, and Ag clusters all grow in a three-dimensional (3D) (Volmer-Weber) fashion on TiO 2(110), but that at low coverages, quasi-two dimensional (quasi-2D) Au and Pd clusters were observed. These quasi-2D clusters are characterized by heights of 1-2 atomic layers. Annealing studies show that Au and Pd clusters form large microcrystals with well-defined hexagonal shapes. Al clusters, which have a strong interaction with the substrate, are oxidized upon deposition, “wetting” the surface and forming small clusters. In addition to the topographic studies, the local electronic properties of these clusters have been studied using scanning tunneling spectroscopy (STS) to measure the cluster band gaps. The electronic structure was found to be cluster size-dependent, as seen by the appearance of a band gap as the cluster size decreased. More specifically, the onset of cluster metallic properties correlates with the transition from quasi-2D to 3D cluster growth.

  13. 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)- .

  14. Synthesis of alumina powder by the urea-glycine-nitrate combustion process: a mixed fuel approach to nanoscale metal oxides

    NASA Astrophysics Data System (ADS)

    Sharma, Amit; Rani, Amita; Singh, Ajay; Modi, O. P.; Gupta, Gaurav K.

    2014-03-01

    Main objective of present work is to study the efficiency of mixed fuel towards solution combustion synthesis of alumina powder, which otherwise prepared by single fuel and study of properties of final product with mixed fuel approach. Two different fuels, glycine and urea, along with aluminium nitrates have been used to prepare nanophase alumina powder. Different fuel to oxidizer ratios and different percentage combination of two fuels were used to prepare six samples. In all samples, nanoscale particle size obtained. Parameter which continuously changes the results of various characterisations is percentage combination of two fuels. In case where percentage of urea is higher than glycine reaction takes place with high exothermicity and hence crystallinity in product phase, whereas glycine promotes amorphous character. With mixed fuel approach, crystallinity can be enhanced easily, by calcinations of powder product at low temperature, because due to mixed urea and glycine, there is already some fraction of crystallinity observed. Overall mixed fuel approach has ability to produce nanophase alumina powder with wide range of particles size.

  15. Transition-Metal Planar Boron Clusters: a New Class of Aromatic Compounds with High Coordination

    NASA Astrophysics Data System (ADS)

    Wang, Lai-Sheng

    2012-06-01

    Photoelectron spectroscopy in combination with computational studies over the past decade has shown that boron clusters possess planar or quasi-planar structures, in contrast to that of bulk boron, which is dominated by three-dimensional cage-like building blocks. All planar or quasi-planar boron clusters are observed to consist of a monocyclic circumference with one or more interior atoms. The propensity for planarity has been found to be due to both σ and π electron delocalization throughout the molecular plane, giving rise to concepts of σ and π double aromaticity. We have found further that the central boron atoms can be substituted by transition metal atoms to form a new class of aromatic compounds, which consist of a central metal atom and a monocyclic boron ring (M B_n). Eight-, nine-, and ten-membered rings of boron have been observed, giving rise to octa-, ennea-, and deca-coordinated aromatic transition metal compounds [1-3]. References: [1] ``Aromatic Metal-Centered Monocyclic Boron Rings: Co B_9^- and Ru B_9^-" (Constantin Romanescu, Timur R. Galeev, Wei-Li Li, A. I. Boldyrev, and L. S. Wang), Angew. Chem. Int. Ed. {50}, 9334-9337 (2011). [2] ``Transition-Metal-Centered Nine-Membered Boron Rings: M B_9 and M B_9^- (M = Rh, Ir)" (Wei-Li Li, Constantin Romanescu, Timur R. Galeev, Zachary Piazza, A. I. Boldyrev, and L. S. Wang), J. Am. Chem. Soc. {134}, 165-168 (2012). [3] ``Observation of the Highest Coordination Number in Planar Species: Decacoordinated Ta B10^- and Nb B_9^- Anions" (Timur R. Galeev, Constantin Romanescu, Wei-Li Li, L. S. Wang, and A. I. Boldyrev), Angew. Chem. Int. Ed. {51}, 2101-2105 (2012).

  16. 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.

  17. Radial Velocity and Metallicity Determinations for Remote Globular Clusters in M31 and M33

    NASA Astrophysics Data System (ADS)

    Ferguson, Annette; Barmby, Pauline; Cote, Pat; Harris, Bill; Huxor, Avon; Mackey, Dougal; Puzia, Thomas

    2009-08-01

    We propose to determine radial velocities and metallicities for a sample of ~ 20 remote globular clusters (GCs) which we have discovered in the outer halos of the Local Group galaxies M31 and M33. Most of these objects have been uncovered in the course of the PAndAs survey, an international collaboration which is using CFHT/MegaPrime to map more than 300 square degrees in the g and i bands around M31 and M33. The target clusters, all of which have been identified from high- quality imaging (typically ≲ 0.8'' seeing), lie at projected radii of up to 130 kpc from M31 and 30 kpc from M33 and thus lie significantly beyond all previously-known GCs in these systems. Rather intriguingly, many of the new discoveries exhibit either possible associations with halo tidal streams, or show unusual spatial anisotropies with respect to their host galaxy. Velocity and metallicity data for these objects will provide a detailed characterization of the ensemble properties of the outer halo GC populations, and, through the search for kinematic and metallicity correlations within groups of GCs, help determine what fraction of these objects can be attributed to either late or ongoing accretion events. Ultimately, these data will also provide a basis for improved dynamical mass estimates of both galaxies.

  18. 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.

  19. 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.

  20. 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

  1. Water as an agent for the morphology modification of metal oxalate materials on the nanoscale: from sheets to rods

    PubMed Central

    Kim, Minog; Kim, YooJin; Kwon, WonJong; Yoon, Sungho

    2016-01-01

    A number of approaches have been used to control the shape of metal oxalates, which often used as precursors for metal oxide nanomaterials. However, attempts to use water as a regulator have not been reported. Here in we report systematic studies on related topics: nanosheets, composed of 1-dimensional [M(C2O4)(EG)] (M = Zn or Co) polymeric structure, could be transformed into nanorods by using water as a shape-shifting agent because water can readily substitute EG ligand, leading alternation of inter-chain hydrogen bonding interactions. In addition, heat-treatment of these nanomaterials with diverse morphologies resulted in porous metal oxides with high degrees of shape retention. PMID:26763973

  2. Water as an agent for the morphology modification of metal oxalate materials on the nanoscale: from sheets to rods

    NASA Astrophysics Data System (ADS)

    Kim, Minog; Kim, Yoojin; Kwon, Wonjong; Yoon, Sungho

    2016-01-01

    A number of approaches have been used to control the shape of metal oxalates, which often used as precursors for metal oxide nanomaterials. However, attempts to use water as a regulator have not been reported. Here in we report systematic studies on related topics: nanosheets, composed of 1-dimensional [M(C2O4)(EG)] (M = Zn or Co) polymeric structure, could be transformed into nanorods by using water as a shape-shifting agent because water can readily substitute EG ligand, leading alternation of inter-chain hydrogen bonding interactions. In addition, heat-treatment of these nanomaterials with diverse morphologies resulted in porous metal oxides with high degrees of shape retention.

  3. 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.

  4. 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.

  5. 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.

  6. Chemical Abundances in NGC 5053: A Very Metal-poor and Dynamically Complex Globular Cluster

    NASA Astrophysics Data System (ADS)

    Boberg, Owen M.; Friel, Eileen D.; Vesperini, Enrico

    2015-05-01

    NGC 5053 provides a rich environment to test our understanding of the complex evolution of globular clusters (GCs). Recent studies have found that this cluster has interesting morphological features beyond the typical spherical distribution of GCs, suggesting that external tidal effects have played an important role in its evolution and current properties. Additionally, simulations have shown that NGC 5053 could be a likely candidate to belong to the Sagittarius dwarf galaxy (Sgr dSph) stream. Using the Wisconsin-Indiana-Yale-NOAO-Hydra multi-object spectrograph, we have collected high quality (signal-to-noise ratio ˜ 75-90), medium-resolution spectra for red giant branch stars in NGC 5053. Using these spectra we have measured the Fe, Ca, Ti, Ni, Ba, Na, and O abundances in the cluster. We measure an average cluster [Fe/H] abundance of -2.45 with a standard deviation of 0.04 dex, making NGC 5053 one of the most metal-poor GCs in the Milky Way (MW). The [Ca/Fe], [Ti/Fe], and [Ba/Fe] we measure are consistent with the abundances of MW halo stars at a similar metallicity, with alpha-enhanced ratios and slightly depleted [Ba/Fe]. The Na and O abundances show the Na-O anti-correlation found in most GCs. From our abundance analysis it appears that NGC 5053 is at least chemically similar to other GCs found in the MW. This does not, however, rule out NGC 5053 being associated with the Sgr dSph stream.

  7. 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

  8. Bonding and coordination in Si clusters

    NASA Astrophysics Data System (ADS)

    Fornari, Marco; Jackson, Koblar A.

    2003-03-01

    The features of bonding and coordination in Sin clusters (n=4-28) are analyzed by means of Wannier function characterization. Starting with recently determined equilibrium structures,[1,2] we monitor the metal-semiconductor transition and the shape dependence by first principles pseudopotential calculations. The results illuminate the interplay between structure and electronic properties in nanoscale systems. [1] I. Rata et al., Phys. Rev. Lett. 85, 546 (2000). [2] K. A. Jackson and M. Horoi, unpublished

  9. 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…

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

    DOE PAGES

    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.

  11. 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

  12. 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.

  13. 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.

  14. 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.

  15. 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.

  16. Aggregation of nanoscale iron oxyhydroxides and corresponding effects on metal uptake, retention, and speciation: I. Ionic-strength and pH

    NASA Astrophysics Data System (ADS)

    Dale, J. G.; Stegemeier, J. P.; Kim, C. S.

    2015-01-01

    The capacity of nanosized particles to adsorb and sequester dissolved metals can be significantly impacted by the mechanism and extent of aggregation the particles have undergone, which in turn can affect the long-term fate and transport of potentially toxic metals in natural aqueous systems. Suspensions of monodisperse nanoscale iron oxyhydroxides were synthesized and subjected to increased pH (pH 8.0, 10.0) or ionic strength (0.1, 1.0 M NaNO3) conditions to induce various states of aggregation prior to conducting macroscopic adsorption/desorption experiments with dissolved Cu(II) or Zn(II). The metal adsorption and retention capacities of the nanoparticle aggregates were compared to one another and to non-aggregated control nanoparticles, while the mode(s) of metal sorption to the nanoparticle surfaces were characterized by extended X-ray absorption fine structure (EXAFS) spectroscopy analysis. With increasing aggregation by both pH and ionic strength, the proportion of introduced zinc adsorbed to the iron oxyhydroxide nanoparticles progressively decreased from 45% on the monodispersed control particles to as low as 16% on the aggregates, while the proportion of introduced zinc retained upon desorption (obtained by lowering the suspension pH) increased from 7% on the control particles to as much as 17% on the aggregated particles. Copper exhibited a subtler trend of only slightly declining uptake (from 43% to 36%) and retention (from 35% to 30%) with increasing aggregation state. EXAFS analysis was consistent with the macroscopic results, showing relatively little change in Cu speciation between samples analyzed before and after the desorption step but significant increases in Zn-Fe interatomic distances and coordination numbers after desorption. This suggests the presence of both strongly- and weakly-bound zinc ions; the latter are likely affiliated with less stable, more distorted surface sorption sites and are thus more readily desorbed, resulting in the

  17. Retention of the Cluster Core Structure during Ligand Exchange Reactions of Carboxylato-Substituted Metal Oxo Clusters

    PubMed Central

    Kreutzer, Johannes; Puchberger, Michael; Artner, Christine; Schubert, Ulrich

    2015-01-01

    The exchange of the carboxylato ligands of Zr4O2(methacrylato)12 in reactions with carboxylic acids proceeds with retention of the composition and structure of the cluster core. This was concluded from exchange/re-exchange experiments and from comparison of the IR bands of the cluster core of the original and ligand-exchanged clusters. The IR bands were assigned on the basis of DFT calculations. Scrambling reactions between two Zr4O2(OOCR)12 clusters with different carboxylato ligands are a new way to prepare mixed-ligand oxo clusters. PMID:26113799

  18. Nanoscale Proteomics

    SciTech Connect

    Shen, Yufeng; Tolic, Nikola; Masselon, Christophe D.; Pasa-Tolic, Liljiana; Camp, David G.; Anderson, Gordon A.; Smith, Richard D.; Lipton, Mary S.

    2004-02-01

    This paper describes efforts to develop a liquid chromatography (LC)/mass spectrometry (MS) technology for ultra-sensitive proteomics studies, i.e. nanoscale proteomics. The approach combines high-efficiency nano-scale LC with advanced MS, including high sensitivity and high resolution Fourier transform ion cyclotron resonance (FTICR) MS, to perform both single-stage MS and tandem MS (MS/MS) proteomic analyses. The technology developed enables large-scale protein identification from nanogram size proteomic samples and characterization of more abundant proteins from sub-picogram size complex samples. Protein identification in such studies using MS is feasible from <75 zeptomole of a protein, and the average proteome measurement throughput is >200 proteins/h and ~3 h/sample. Higher throughput (>1000 proteins/h) and more sensitive detection limits can be obtained using a “accurate mass and time” tag approach developed at our laboratory. These capabilities lay the foundation for studies from single or limited numbers of cells.

  19. 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 −})

  20. 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.

  1. 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.

  2. Atomistic Design and Simulations of Nanoscale Machines and Assembly

    NASA Technical Reports Server (NTRS)

    Goddard, William A., III; Cagin, Tahir; Walch, Stephen P.

    2000-01-01

    Over the three years of this project, we made significant progress on critical theoretical and computational issues in nanoscale science and technology, particularly in:(1) Fullerenes and nanotubes, (2) Characterization of surfaces of diamond and silicon for NEMS applications, (3) Nanoscale machine and assemblies, (4) Organic nanostructures and dendrimers, (5) Nanoscale confinement and nanotribology, (6) Dynamic response of nanoscale structures nanowires (metals, tubes, fullerenes), (7) Thermal transport in nanostructures.

  3. Using NV centers to probe magnetization dynamics in normal metal/magnetic insulator hybrid system at the nanoscale

    NASA Astrophysics Data System (ADS)

    Zhang, Huiliang; Ku, Mark J. H.; Han, Minyong; Casola, Francesco; van der Sar, Toeno; Yacoby, Amir; Walsworth, Ronald L.

    2016-05-01

    Understanding magnetization dynamics induced by electric current is of great interest for both fundamental and practical reasons. Great endeavor has been dedicated to spin-orbit torques (SOT) in metallic structures, while quantitative study of analogous phenomena in magnetic insulators remains challenging where transport measurements are not feasible. Recently we have developed techniques using nitrogen vacancy (NV) centers in diamond to probe few-nanometre-scale correlated-electron magnetic excitations (i.e., spin waves). Here we demonstrate how this powerful tool can be implemented to study magnetization dynamics inside ferromagnetic insulator, Yttrium iron garnet (YIG) with spin injection from electrical current through normal metal (Platinum in our case). Particularly our work will focus on NV magnetic detection, imaging, and spectroscopy of coherent auto-oscillations in Pt/YIG microdisc. Magnetic fluctuations and local temperature measurements, both with nearby NV centers, will also be interesting topics relevant to SOT physics in Pt/YIG hybrid system.

  4. Dark Matter Halos in Galaxies and Globular Cluster Populations. II. Metallicity and Morphology

    NASA Astrophysics Data System (ADS)

    Harris, William E.; Harris, Gretchen L.; Hudson, Michael J.

    2015-06-01

    An increasing body of data reveals a one-to-one linear correlation between galaxy halo mass and the total mass in its globular cluster (GC) population, {{M}GCS}∼ Mh1.03+/- 0.03, valid over five orders of magnitude. In this paper we explore the nature of this correlation for galaxies of different morphological types and for the subpopulations of metal-poor (blue) and metal-rich (red) GCs. For the subpopulations of different metallicity, we find {{M}GCS}(blue)∼ Mh0.96+/- 0.03 and {{M}GCS}(red)∼ Mh1.21+/- 0.03 with similar scatter. The numerical values of these exponents can be derived from the detailed behavior of the red and blue GC fractions with galaxy mass and provide a self-consistent set of relations. In addition, all morphological types (E, S0, S/Irr) follow the same relation, but with a second-order trend for spiral galaxies to have a slightly higher fraction of metal-rich GCs for a given mass. These results suggest that the amount of gas available for GC formation at high redshift was in nearly direct proportion to the dark matter halo potential, in strong contrast to the markedly nonlinear behavior of total stellar mass versus halo mass. Of the few available theoretical treatments that directly discuss the formation of GCs in a hierarchical-merging framework, we find that the model of Kravtsov & Gnedin best matches these observations. They find that the blue, metal-poor GCs formed in small halos at z\\gt 3 and did so in nearly direct proportion to halo mass. Similar models addressing the formation rate of the red, more metal-rich GCs in the same detail and continuing to lower redshift are still needed for a comprehensive picture.

  5. Anion-directed assembly of a non-interpenetrated square-grid metal-organic framework with nanoscale porosity.

    PubMed

    Mitra, Atanu; Hubley, Christian T; Panda, Dillip K; Clark, Ronald J; Saha, Sourav

    2013-07-28

    A non-interpenetrated square grid metal-organic framework (MOF) comprised of octahedral Zn(II) ions and linear N,N'-di(4-pyridyl)-1,4,5,8-naphthalenediimide (DPNDI) ligands was formed in the presence of noncoordinating perchlorate counterions that occupied the cavities of the porous network by forming CH···anion hydrogen bonds with DPNDI ligands, whereas a linear coordination polymer was obtained when Zn(II)-coordinated nitrate ions were present as counterions. PMID:23775140

  6. Direct observation of nanoscale Peltier and Joule effects at metal-insulator domain walls in vanadium dioxide nanobeams.

    PubMed

    Favaloro, Tela; Suh, Joonki; Vermeersch, Bjorn; Liu, Kai; Gu, Yijia; Chen, Long-Qing; Wang, Kevin X; Wu, Junqiao; Shakouri, Ali

    2014-05-14

    The metal to insulator transition (MIT) of strongly correlated materials is subject to strong lattice coupling, which brings about the unique one-dimensional alignment of metal-insulator (M-I) domains along nanowires or nanobeams. Many studies have investigated the effects of stress on the MIT and hence the phase boundary, but few have directly examined the temperature profile across the metal-insulating interface. Here, we use thermoreflectance microscopy to create two-dimensional temperature maps of single-crystalline VO2 nanobeams under external bias in the phase coexisting regime. We directly observe highly localized alternating Peltier heating and cooling as well as Joule heating concentrated at the M-I domain boundaries, indicating the significance of the domain walls and band offsets. Utilizing the thermoreflectance technique, we are able to elucidate strain accumulation along the nanobeam and distinguish between two insulating phases of VO2 through detection of the opposite polarity of their respective thermoreflectance coefficients. Microelasticity theory was employed to predict favorable domain wall configurations, confirming the monoclinic phase identification.

  7. Nanoscale zero-valent iron particles supported on reduced graphene oxides by using a plasma technique and their application for removal of heavy-metal ions.

    PubMed

    Li, Jie; Chen, Changlun; Zhang, Rui; Wang, Xiangke

    2015-06-01

    Nanoscale zero-valent iron particles supported on reduced graphene oxides (NZVI/rGOs) from spent graphene oxide (GO)-bound iron ions were developed by using a hydrogen/argon plasma reduction method to improve the reactivity and stability of NZVI. The NZVI/rGOs exhibited excellent water treatment performance with excellent removal capacities of 187.16 and 396.37 mg g(-1) for chromium and lead, respectively. Moreover, the NZVI/rGOs could be regenerated by plasma treatment and maintained high removal ability after four cycles. X-ray photoelectron spectroscopy analysis results implied that the removal mechanisms could be attributed to adsorption/precipitation, reduction, or both. Such multiple removal mechanisms by the NZVI/rGOs were attributed to the reduction ability of the NZVI particles and the role of dispersing and stabilizing abilities of the rGOs. The results indicated that the NZVI/rGOs prepared by a hydrogen/argon plasma reduction method might be an effective composite for heavy-metal-ion removal.

  8. 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.

  9. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2015-01-01

    The existence and characterization of a bond between the Zn atoms in the recently synthesized complex [Zn2(η5- C5Me5)2] (I), as well as between two of the three Ru atoms in [Ru3(μ- H )2(μ3- MeImCH )( CO9] (Me2Im = 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.

  12. 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.

  13. 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.

  14. Membership, binarity and metallicity of red giants in the southern open cluster NGC 2354

    NASA Astrophysics Data System (ADS)

    Clariá, J. J.; Mermilliod, J.-C.; Piatti, A. E.

    1999-01-01

    We present new Coravel radial-velocity observations and photoelectric photometry in the UBV, DDO and Washington systems for a sample of red giant candidates in the field of the intermediate-age open cluster NGC 2354. Photometric membership probabilities show very good agreement with those obtained from Coravel radial velocities. The analysis of the photometric and kinematical data allow us to confirm cluster membership for 9 red giants, one of them being a spectroscopic binary, while 4 confirmed spectroscopic binaries appear to be probable members. We have also discovered 4 spectroscopic binaries not belonging to the cluster. A mean radial velocity of (33.40 +/- 0.27) km s(-1) and a mean reddening E(B-V) = 0.13 +/- 0.03 were derived for the cluster giants. NGC 2354 has a mean ultraviolet excess = -0.03 +/- 0.01, relative to the field K giants, and a mean new cyanogen anomaly Delta CN = -0.035 +/- 0.007, both implying [Fe/H] ~ -0.3. The moderately metal-poor character of NGC 2354 is confirmed using five different metal abundance indicators of the Washington system. The cluster giant branch is formed by a well defined clump of 7 stars and 4 stars with high membership probabilities seem to define an ascending giant branch. The whole red giant locus cannot be reproduced by any theoretical track. Based on observations collected with the Danish\\protect\\linebreak 1.54-m telescope at the European Southern Observatory, La Silla (Chile); at Complejo Astronómico El Leoncito, which is operated under agreement between the Consejo Nacional de Investigaciones Científicas y Técnicas de la República Argentina and the National Universities of La Plata, Córdoba, and San Juan, Argentina, and at Cerro Tololo Inter-American Observatory, National Optical Astronomy Observatories, operated by the Association of Universities for Research in Astronomy, Inc., under contract with the National Science Foundation.

  15. The Role of Thermohaline Mixing in Intermediate- and Low-metallicity Globular Clusters

    NASA Astrophysics Data System (ADS)

    Angelou, George C.; Stancliffe, Richard J.; Church, Ross P.; Lattanzio, John C.; Smith, Graeme H.

    2012-04-01

    It is now widely accepted that globular cluster red giant branch (RGB) stars owe their strange abundance patterns to a combination of pollution from progenitor stars and in situ extra mixing. In this hybrid theory a first generation of stars imprints abundance patterns into the gas from which a second generation forms. The hybrid theory suggests that extra mixing is operating in both populations and we use the variation of [C/Fe] with luminosity to examine how efficient this mixing is. We investigate the observed RGBs of M3, M13, M92, M15, and NGC 5466 as a means to test a theory of thermohaline mixing. The second parameter pair M3 and M13 are of intermediate metallicity and our models are able to account for the evolution of carbon along the RGB in both clusters, although in order to fit the most carbon-depleted main-sequence stars in M13 we require a model whose initial [C/Fe] abundance leads to a carbon abundance lower than is observed. Furthermore, our results suggest that stars in M13 formed with some primary nitrogen (higher C+N+O than stars in M3). In the metal-poor regime only NGC 5466 can be tentatively explained by thermohaline mixing operating in multiple populations. We find thermohaline mixing unable to model the depletion of [C/Fe] with magnitude in M92 and M15. It appears as if extra mixing is occurring before the luminosity function bump in these clusters. To reconcile the data with the models would require first dredge-up to be deeper than found in extant models.

  16. THE ROLE OF THERMOHALINE MIXING IN INTERMEDIATE- AND LOW-METALLICITY GLOBULAR CLUSTERS

    SciTech Connect

    Angelou, George C.; Stancliffe, Richard J.; Church, Ross P.; Lattanzio, John C.; Smith, Graeme H.

    2012-04-20

    It is now widely accepted that globular cluster red giant branch (RGB) stars owe their strange abundance patterns to a combination of pollution from progenitor stars and in situ extra mixing. In this hybrid theory a first generation of stars imprints abundance patterns into the gas from which a second generation forms. The hybrid theory suggests that extra mixing is operating in both populations and we use the variation of [C/Fe] with luminosity to examine how efficient this mixing is. We investigate the observed RGBs of M3, M13, M92, M15, and NGC 5466 as a means to test a theory of thermohaline mixing. The second parameter pair M3 and M13 are of intermediate metallicity and our models are able to account for the evolution of carbon along the RGB in both clusters, although in order to fit the most carbon-depleted main-sequence stars in M13 we require a model whose initial [C/Fe] abundance leads to a carbon abundance lower than is observed. Furthermore, our results suggest that stars in M13 formed with some primary nitrogen (higher C+N+O than stars in M3). In the metal-poor regime only NGC 5466 can be tentatively explained by thermohaline mixing operating in multiple populations. We find thermohaline mixing unable to model the depletion of [C/Fe] with magnitude in M92 and M15. It appears as if extra mixing is occurring before the luminosity function bump in these clusters. To reconcile the data with the models would require first dredge-up to be deeper than found in extant models.

  17. Impact of metal ion's charge on the interatomic Coulombic decay widths in microsolvated clusters

    NASA Astrophysics Data System (ADS)

    Stumpf, V.; Brunken, C.; Gokhberg, K.

    2016-09-01

    Interatomic Coulombic decay (ICD) is an efficient electronic decay mechanism of electronically excited atoms and molecules embedded in an environment. For the series of isoelectronic Na+, Mg2+, and Al3+ ions in aqueous solution, ultrashort ICD lifetimes of 3.1 fs, 1.5 fs, and 0.9 fs, respectively, were observed experimentally. The magnitude of the ICD lifetimes and their variation within the series were qualitatively explained by shortening metal-oxygen equilibrium distances and the increasing polarization of the water molecules as the metal's charge grows. We carried out an extensive ab initio investigation of the variation of the ICD widths with the metal-oxygen distances and the number of water neighbors in Na+-(H2O)m (m = 1-4) and Mg2+-(H2O)n (n = 1-6) clusters including and excluding polarization effects in the decaying state. We demonstrated that the effect of the induced polarization of the water ligand and the equilibrium cation-oxygen distance are equally important in determining the ordering and ratios of the ICD lifetimes in the series. Moreover, we showed that the induced polarization of the water molecules leads to a slower than linear growth of ICD width with the number of equivalent water neighbors; the non-linearity is stronger for Mg2+. The ab initio ICD widths in microsolvated Na+-(H2O)4 and Mg2+-(H2O)6 clusters are found to be in good agreement with the experimental values.

  18. Impact of metal ion's charge on the interatomic Coulombic decay widths in microsolvated clusters.

    PubMed

    Stumpf, V; Brunken, C; Gokhberg, K

    2016-09-14

    Interatomic Coulombic decay (ICD) is an efficient electronic decay mechanism of electronically excited atoms and molecules embedded in an environment. For the series of isoelectronic Na(+), Mg(2+), and Al(3+) ions in aqueous solution, ultrashort ICD lifetimes of 3.1 fs, 1.5 fs, and 0.9 fs, respectively, were observed experimentally. The magnitude of the ICD lifetimes and their variation within the series were qualitatively explained by shortening metal-oxygen equilibrium distances and the increasing polarization of the water molecules as the metal's charge grows. We carried out an extensive ab initio investigation of the variation of the ICD widths with the metal-oxygen distances and the number of water neighbors in Na(+)-(H2O)m (m = 1-4) and Mg(2+)-(H2O)n (n = 1-6) clusters including and excluding polarization effects in the decaying state. We demonstrated that the effect of the induced polarization of the water ligand and the equilibrium cation-oxygen distance are equally important in determining the ordering and ratios of the ICD lifetimes in the series. Moreover, we showed that the induced polarization of the water molecules leads to a slower than linear growth of ICD width with the number of equivalent water neighbors; the non-linearity is stronger for Mg(2+). The ab initio ICD widths in microsolvated Na(+)-(H2O)4 and Mg(2+)-(H2O)6 clusters are found to be in good agreement with the experimental values. PMID:27634259

  19. Reactions of metal ions and their clusters in the gas phase using laser ionization--Fourier transform mass spectrometry

    SciTech Connect

    Freiser, B.S.

    1990-09-01

    Carbon clusters of the form C{sub N}{sup {minus}} are observed at least out to N = 30 confirming that cluster formation is occurring in the high pressure waiting room'' of the supersonic cluster source. This can be stated unequivocally, since only up to N = 13 is observed by direct laser desorption of a carbon target in the absence of supersonic expansion. Currently underway is a systematic investigation of a wide variety of M{sup +}-C{sub n}H{sub 2n} species with n = 2--10 and M = first and second row transition metal ions. In addition we will shortly apply this methodology to doubly charged ions and metal cluster ions. All indications are that this area will be highly productive.

  20. Limits to thermal transport in nanoscale metal bilayers due to weak electron-phonon coupling in Au and Cu.

    PubMed

    Wang, Wei; Cahill, David G

    2012-10-26

    Weak electron-phonon coupling in Au and Cu produces a significant thermal resistance when heat flows from a thin Pt layer into a thin Au or Cu layer on picosecond time scales. Metal bilayers (Pt/Au and Pt/Cu) were prepared by magnetron sputter deposition; thermal transport in the bilayers was studied by time domain thermoreflectance in the temperature range 38

  1. Synthesis Methods, Microscopy Characterization and Device Integration of Nanoscale Metal Oxide Semiconductors for Gas Sensing in Aerospace Applications

    NASA Technical Reports Server (NTRS)

    VanderWal, Randy L.; Berger, Gordon M.; Kulis, Michael J.; Hunter, Gary W.; Xu, Jennifer C.; Evans, Laura J.

    2009-01-01

    A comparison is made between SnO2, ZnO, and TiO2 single-crystal nanowires and SnO2 polycrystalline nanofibers for gas sensing. Both nanostructures possess a one-dimensional morphology. Different synthesis methods are used to produce these materials: thermal evaporation-condensation (TEC), controlled oxidation, and electrospinning. Advantages and limitations of each technique are listed. Practical issues associated with harvesting, purification, and integration of these materials into sensing devices are detailed. For comparison to the nascent form, these sensing materials are surface coated with Pd and Pt nanoparticles. Gas sensing tests, with respect to H2, are conducted at ambient and elevated temperatures. Comparative normalized responses and time constants for the catalyst and noncatalyst systems provide a basis for identification of the superior metal-oxide nanostructure and catalyst combination. With temperature-dependent data, Arrhenius analyses are made to determine an activation energy for the catalyst-assisted systems.

  2. Nanoscale Transformations in Covellite (CuS) Nanocrystals in the Presence of Divalent Metal Cations in a Mild Reducing Environment

    PubMed Central

    2015-01-01

    We studied the structural and compositional transformations of colloidal covellite (CuS) nanocrystals (and of djurleite (Cu1.94S) nanocrystals as a control) when exposed to divalent cations, as Cd2+ and Hg2+, at room temperature in organic solvents. All the experiments were run in the absence of phosphines, which are a necessary ingredient for cation exchange reactions involving copper chalcogenides, as they strongly bind to the expelled Cu+ ions. Under these experimental conditions, no remarkable reactivity was indeed seen for both CuS and Cu1.94S nanocrystals. On the other hand, in the covellite structure 2/3 of sulfur atoms form covalent S–S bonds. This peculiarity suggests that the combined presence of electron donors and of foreign metal cations can trigger the entry of both electrons and cations in the covellite lattice, causing reorganization of the anion framework due to the rupture of the S–S bonds. In Cu1.94S, which lacks S–S bonds, this mechanism should not be accessible. This hypothesis was proven by the experimental evidence that adding ascorbic acid increased the fraction of metal ions incorporated in the covellite nanocrystals, while it had no noticeable effect on the Cu1.94S ones. Once inside the covellite particles, Cd2+ and Hg2+ cations engaged in exchange reactions, pushing the expelled Cu+ ions toward the not-yet exchanged regions in the same particles, or out to the solution, from where they could be recaptured by other covellite nanoparticles/domains. Because no good solvating agent for Cu ions was present in solution, they essentially remained in the nanocrystals. PMID:26617434

  3. 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.

  4. Metallicities and radial velocities of two stellar clusters located in the outer regions of the Small Magellanic Cloud

    NASA Astrophysics Data System (ADS)

    Gramajo, L. V.; Parisi, M. C.; Clariá, J. J.; Geisler, D.; Vásquez, S.; Da Costa, G.; Grebel, E. K.

    2016-08-01

    We studied near-infrared spectra of red giant stars in two Small Magellanic Cloud (SMC) clusters. We used the Caii lines to measure radial velocities as well as the equivalent widths of these lines to determine metallicity. The two studied clusters (L32 and L38) are projected on the outer regions of the SMC so they are particularly interesting to examine the possible existence of a change of sign in the metallicity gradient in the outer regions, as suggested by a recent study.

  5. EDITORIAL: Nanoscale metrology Nanoscale metrology

    NASA Astrophysics Data System (ADS)

    Klapetek, P.; Koenders, L.

    2011-09-01

    This special issue of Measurement Science and Technology presents selected contributions from the NanoScale 2010 seminar held in Brno, Czech Republic. It was the 5th Seminar on Nanoscale Calibration Standards and Methods and the 9th Seminar on Quantitative Microscopy (the first being held in 1995). The seminar was jointly organized with the Czech Metrology Institute (CMI) and the Nanometrology Group of the Technical Committee-Length of EURAMET. There were two workshops that were integrated into NanoScale 2010: first a workshop presenting the results obtained in NANOTRACE, a European Metrology Research Project (EMRP) on displacement-measuring optical interferometers, and second a workshop about the European metrology landscape in nanometrology related to thin films, scanning probe microscopy and critical dimension. The aim of this workshop was to bring together developers, applicants and metrologists working in this field of nanometrology and to discuss future needs. For more information see www.co-nanomet.eu. The articles in this special issue of Measurement Science and Technology cover some novel scientific results. This issue can serve also as a representative selection of topics that are currently being investigated in the field of European and world-wide nanometrology. Besides traditional topics of dimensional metrology, like development of novel interferometers or laser stabilization techniques, some novel interesting trends in the field of nanometrology are observed. As metrology generally reflects the needs of scientific and industrial research, many research topics addressed refer to current trends in nanotechnology, too, focusing on traceability and improved measurement accuracy in this field. While historically the most studied standards in nanometrology were related to simple geometric structures like step heights or 1D or 2D gratings, now we are facing tasks to measure 3D structures and many unforeseen questions arising from interesting physical

  6. 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

  7. 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

  8. 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.

  9. Tuning the redox activity of encapsulated metal clusters via the metallic and semiconducting character of carbon nanotubes

    PubMed Central

    Zhang, Fan; Pan, Xiulian; Hu, Yongfeng; Yu, Liang; Chen, Xiaoqi; Jiang, Peng; Zhang, Hongbo; Deng, Shibin; Zhang, Jin; Bolin, Trudy B.; Zhang, Shuo; Huang, Yuying; Bao, Xinhe

    2013-01-01

    We demonstrate that reactions confined within single-walled carbon nanotube (SWCNT) channels are modulated by the metallic and semiconducting character of the hosts. In situ Raman and X-ray absorption near-edge structure spectroscopies provide complementary information about the electronic state of carbon nanotubes and the encapsulated rhenium species, which reveal electronic interactions between encapsulated species and nanotubes. More electrons are transferred from metallic tubes (m-SWCNTs) to oxidic rhenium clusters, leading to a lower valence state rhenium oxide than that in semiconducting tubes (s-SWCNTs). Reduction in 3.5% (vol/vol) H2/Ar leads to weakened host–guest electronic interaction. The high valence state Re within s-SWCNTs is more readily reduced when raising the temperature, whereas only a sluggish change is observed for Re within m-SWCNTs. Only at 400 °C does Re reach a similar electronic state (mixture of Re0 and Re4+) in both types of tubes. Subsequent oxidation in 1% O2/Ar does not show changes for Re in s-SWCNTs up to 200 °C. In comparison, m-SWCNTs facilitate the oxidation of reduced rhenium (160 °C). This can be exploited for rational design of active catalysts with stable species as a desired valence state can be obtained by selecting specific-type SWCNTs and a controlled thermal treatment. These results also provide a chemical approach to modulate reversibly the electronic structure of SWCNTs without damaging the sidewalls of SWCNTs. PMID:23980145

  10. Simulation studies of the structural and dynamic properties of atomic and molecular clusters: Transition metals and fullerenes

    NASA Astrophysics Data System (ADS)

    Gayoso, Juan Garcia-Rodeja

    1997-12-01

    Using molecular dynamics (MD) simulations, the binding energies and melting behaviour of clusters NiN PdN, PtN, CuN, AgN, AuN with N2 23 were obtained on the basis of several models of metallic cohesion widely used in the study of bulk and surface systems. The results show that the use of dimer molecule properties in fitting the model parameters reduces the predicted cluster binding energies. The Voter and Chen version of the embedded atom method (V-EAM) predict icosahedral cluster grown sequences for every metal. The appearance of a premelting state in clusters with icosahedral magic sizes plus a few atoms was observed whenever such magic sizes were obtained. V-EAM has also been employed in obtaining the ground- state atomic configurations of Ni-Al clusters with 13, 19 and 55 atoms for all the range of concentrations. All cluster structures are found to be based on icosahedral packing. The interplay between the tendencies to surface segregation of Al atoms and heterocoordination was analysed in detail. The ground-state structures of (C60)N clusters with N2 20 were calculated using a pairwise additive atom-atom intermolecular potential, and the Girifalco's spherical potential. Both potentials agree in predicting a change from icosahedral to decahedral structures, but at slightly different sizes. The structures and thermal behaviour of(C60)N clusters supported on a graphite substrate were studied by means of MD and Monte Carlo simulations, using Girifalco's and Ruof-Hickman's potentials to model the C60-C60 and C60-graphite interactions, respectively. The ground-state structures of the supported clusters consists in monolayer-like hexagonal arrangements. The short range of the interactions causes the absence of a liquidlike state prior to cluster fragmentation.

  11. Cluster Synthesis and Direct Ordering of Rare-Earth Transition-Metal Nanomagnets

    SciTech Connect

    Balasubramanian, B; Skomski, R; Li, XZ; Valloppilly, SR; Shield, JE; Hadjipanayis, GC; Sellmyer, DJ

    2011-04-01

    Rare-earth transition-metal (R-TM) alloys show superior permanent magnetic properties in the bulk, but the synthesis and application of R-TM nanoparticles remains a challenge due to the requirement of high-temperature annealing above about 800 degrees C for alloy formation and subsequent crystalline ordering. Here we report a single-step method to produce highly ordered R-TM nanoparticles such as YCo(5) and Y(2)Co(17), without high-temperature thermal annealing, by employing a cluster-deposition system and investigate their structural and magnetic properties. The direct ordering is highly desirable to create and assemble R-TM nanoparticle building blocks for future permanent-magnet and other significant applications.

  12. Folate-targeted pH-responsive calcium zoledronate nanoscale metal-organic frameworks: Turning a bone antiresorptive agent into an anticancer therapeutic.

    PubMed

    Au, Kin Man; Satterlee, Andrew; Min, Yuanzeng; Tian, Xi; Kim, Young Seok; Caster, Joseph M; Zhang, Longzhen; Zhang, Tian; Huang, Leaf; Wang, Andrew Z

    2016-03-01

    Zoledronate (Zol) is a third-generation bisphosphonate that is widely used as an anti-resorptive agent for the treatment of cancer bone metastasis. While there is preclinical data indicating that bisphosphonates such as Zol have direct cytotoxic effects on cancer cells, such effect has not been firmly established in the clinical setting. This is likely due to the rapid absorption of bisphosphonates by the skeleton after intravenous (i.v.) administration. Herein, we report the reformulation of Zol using nanotechnology and evaluation of this novel nanoscale metal-organic frameworks (nMOFs) formulation of Zol as an anticancer agent. The nMOF formulation is comprised of a calcium zoledronate (CaZol) core and a polyethylene glycol (PEG) surface. To preferentially deliver CaZol nMOFs to tumors as well as facilitate cellular uptake of Zol, we incorporated folate (Fol)-targeted ligands on the nMOFs. The folate receptor (FR) is known to be overexpressed in several tumor types, including head-and-neck, prostate, and non-small cell lung cancers. We demonstrated that these targeted CaZol nMOFs possess excellent chemical and colloidal stability in physiological conditions. The release of encapsulated Zol from the nMOFs occurs in the mid-endosomes during nMOF endocytosis. In vitro toxicity studies demonstrated that Fol-targeted CaZol nMOFs are more efficient than small molecule Zol in inhibiting cell proliferation and inducing apoptosis in FR-overexpressing H460 non-small cell lung and PC3 prostate cancer cells. Our findings were further validated in vivo using mouse xenograft models of H460 and PC3. We demonstrated that Fol-targeted CaZol nMOFs are effective anticancer agents and increase the direct antitumor activity of Zol by 80-85% in vivo through inhibition of tumor neovasculature, and inhibiting cell proliferation and inducing apoptosis.

  13. Nanoscale 2013

    NASA Astrophysics Data System (ADS)

    Koenders, Ludger; Ducourtieux, Sebastien

    2014-04-01

    The accurate determination of the properties of micro- and nano-structures is essential in research and development. It is also a prerequisite in process control and quality assurance in industry. In most cases, especially at the nanometer range, knowledge of the dimensional properties of structures is the fundamental base, to which further physical properties are linked. Quantitative measurements presuppose reliable and stable instruments, suitable measurement procedures as well as calibration artifacts and methods. This special issue of Measurement Science and Technology presents selected contributions from the NanoScale 2013 seminar held in Paris, France, on 25 and 26 April. It was the 6th Seminar on NanoScale Calibration Standards and Methods and the 10th Seminar on Quantitative Microscopy (the first being held in 1995). The seminar was jointly organized with the Nanometrology Group of the Technical Committee-Length of EURAMET, the Physikalisch-Technische Bundesanstalt and the Laboratoire National de Métrologie et d'Essais. Three satellite meetings related to nanometrology were coupled to the seminar. The first one was an open Symposium on Scanning Probe Microscopy Standardization organized by the ISO/TC 201/SC9 technical committee. The two others were specific meetings focused on two European Metrology Research Projects funded by the European Association of National Metrology Institutes (EURAMET) (see www.euramet.org), the first one focused on the improvement of the traceability for high accuracy devices dealing with sub-nm length measurement and implementing optical interferometers or capacitive sensors (JRP SIB08 subnano), the second one aiming to develop a new metrological traceability for the measurement of the mechanical properties of nano-objects (JRP NEW05 MechProNo). More than 100 experts from industry, calibration laboratories and metrology institutes from around the world joined the NanoScale 2013 Seminar to attend 23 oral and 64 poster

  14. 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

  15. 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

  16. 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.

  17. Fabrication of Nanoscale Circuits on Inkjet-Printing Patterned Substrates.

    PubMed

    Chen, Shuoran; Su, Meng; Zhang, Cong; Gao, Meng; Bao, Bin; Yang, Qiang; Su, Bin; Song, Yanlin

    2015-07-01

    Nanoscale circuits are fabricated by assembling different conducting materials (e.g., metal nanoparticles, metal nano-wires, graphene, carbon nanotubes, and conducting polymers) on inkjet-printing patterned substrates. This non-litho-graphy strategy opens a new avenue for integrating conducting building blocks into nanoscale devices in a cost-efficient manner. PMID:26011403

  18. EDITORIAL: Nanoscale metrology Nanoscale metrology

    NASA Astrophysics Data System (ADS)

    Picotto, G. B.; Koenders, L.; Wilkening, G.

    2009-08-01

    Instrumentation and measurement techniques at the nanoscale play a crucial role not only in extending our knowledge of the properties of matter and processes in nanosciences, but also in addressing new measurement needs in process control and quality assurance in industry. Micro- and nanotechnologies are now facing a growing demand for quantitative measurements to support the reliability, safety and competitiveness of products and services. Quantitative measurements presuppose reliable and stable instruments and measurement procedures as well as suitable calibration artefacts to ensure the quality of measurements and traceability to standards. This special issue of Measurement Science and Technology presents selected contributions from the Nanoscale 2008 seminar held at the Istituto Nazionale di Ricerca Metrologica (INRIM), Torino, in September 2008. This was the 4th Seminar on Nanoscale Calibration Standards and Methods and the 8th Seminar on Quantitative Microscopy (the first being held in 1995). The seminar was jointly organized by the Nanometrology Group within EUROMET (The European Collaboration in Measurement Standards), the German Nanotechnology Competence Centre 'Ultraprecise Surface Figuring' (CC-UPOB), the Physikalisch-Technische Bundesanstalt (PTB) and INRIM. A special event during the seminar was the 'knighting' of Günter Wilkening from PTB, Braunschweig, Germany, as the 1st Knight of Dimensional Nanometrology. Günter Wilkening received the NanoKnight Award for his outstanding work in the field of dimensional nanometrology over the last 20 years. The contributions in this special issue deal with the developments and improvements of instrumentation and measurement methods for scanning force microscopy (SFM), electron and optical microscopy, high-resolution interferometry, calibration of instruments and new standards, new facilities and applications including critical dimension (CD) measurements on small and medium structures and nanoparticle

  19. 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.

  20. Ab initio study of neutral (TiO2)n clusters and their interactions with water and transition metal atoms.

    PubMed

    Cakır, D; Gülseren, O

    2012-08-01

    We have systematically investigated the growth behavior and stability of small stoichiometric (TiO(2))(n) (n = 1-10) clusters as well as their structural, electronic and magnetic properties by using the first-principles plane wave pseudopotential method within density functional theory. In order to find out the ground state geometries, a large number of initial cluster structures for each n has been searched via total energy calculations. Generally, the ground state structures for the case of n = 1-9 clusters have at least one monovalent O atom, which only binds to a single Ti atom. However, the most stable structure of the n = 10 cluster does not have any monovalent O atom. On the other hand, Ti atoms are at least fourfold coordinated for the ground state structures for n ≥ 4 clusters. Our calculations have revealed that clusters prefer to form three-dimensional structures. Furthermore, all these stoichiometric clusters have nonmagnetic ground state. The formation energy and the highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) gap for the most stable structure of (TiO(2))(n) clusters for each n have also been calculated. The formation energy and hence the stability increases as the cluster size grows. In addition, the interactions between the ground state structure of the (TiO(2))(n) cluster and a single water molecule have been studied. The binding energy (E(b)) of the H(2)O molecule exhibits an oscillatory behavior with the size of the clusters. A single water molecule preferably binds to the cluster Ti atom through its oxygen atom, resulting an average binding energy of 1.1 eV. We have also reported the interaction of the selected clusters (n = 3, 4, 10) with multiple water molecules. We have found that additional water molecules lead to a decrease in the binding energy of these molecules to the (TiO(2))(n) clusters. Finally, the adsorption of transition metal (TM) atoms (V, Co and Pt) on the n = 10 cluster has been

  1. Reactions of metal ions and their clusters in the gas phase using laser ionization: Fourier transform mass spectrometry

    SciTech Connect

    Freiser, B.S.

    1992-11-01

    This report focuses on three areas we have made substantial new progress in over the past several months: (1) Infrared multiphoton photoinduced ion molecule reactions; (2) The use of SF[sub 6] to detect excited state metal ion behavior; and (3) Cluster ion chemistry.

  2. The Development of a Model for Estimating the Costs Associated with the Delivery of a Metals Cluster Program.

    ERIC Educational Resources Information Center

    Hunt, Charles R.

    A study developed a model to assist school administrators to estimate costs associated with the delivery of a metals cluster program at Norfolk State College, Virginia. It sought to construct the model so that costs could be explained as a function of enrollment levels. Data were collected through a literature review, computer searches of the…

  3. Layer-by-layer growth of metal-metal bonded supramolecular thin films and its use in the fabrication of lateral nanoscale devices.

    PubMed

    Lin, Chun; Kagan, Cherie R

    2003-01-15

    Layer-by-layer self-assembly of metal-metal bonded supramolecules is demonstrated and utilized to fabricate lateral nanoelectronic devices. Mercaptoethylpyridine is used to bind to Au substrates and to template the sequential assembly of alternating layers of redox active dirhodium complexes [Rh2(DAniF)2]2(O2CCH2CO2)2 (DAniF = N,N'-di-p-anisylformamidinate) and conjugated organic ligands trans-1,2-bis(4-pyridyl)ethylene. Optical spectroscopy and atomic force microscopy show that the structure and composition of these thin films are similar to those found in tightly packed single crystals. Electrochemical studies of these films grown on Au substrates reveal a reversible oxidation wave at approximately 406 mV, corresponding to the one electron oxidation of the Rh24+ center. This directed assembly technique has been used to fabricate lateral nano-electronic devices in which the supramolecules span the channels. Tailoring the chemistry of the templating ligand enables assembly on desired surfaces and engineering the chemistry of the supramolecules' dimetal units and coordinating ligands may tune the device characteristics.

  4. Matrix isolation FTIR spectroscopic and DFT studies of metal-carbide clusters

    NASA Astrophysics Data System (ADS)

    Bejjani, Micheline

    2011-01-01

    Several metal containing molecules, including MgCN, NaCN, KCl, AlOH, and AlF have been observed in the interstellar medium. Additionally, transition metals have been observed. Many carbon containing molecules have also been observed in astrophysical sources. The purpose of the present research is to provide information on the spectral properties of metal carbide molecules that are potentially observable in space. Additional interest for studying small metal carbide molecules is the understanding of larger clusters including metallofullerenes and metallocarbohedrenes, and the catalytic growth of carbon nanotubes. FTIR spectra were obtained by condensing the vapor produced by dual laser ablation of metal and carbon rods in an argon matrix at ˜12K. Comparison of the observed 13C enriched vibrational spectra to the DFT simulated isotopic spectra has enabled the identification of vibrational fundamentals of linear MnC3, linear MgC3-, and chain ZnC3. The linear MnC3 has been detected for the first time. Its nu 1(sigma) vibrational fundamental has been observed at 1846.9 cm -1. Although previous photoelectron studies by Wang and Li have reported evidence for the cyclic isomer of MnC3, their assignment was inconclusive since the linear and fanlike structures have been found to lie very close in energy, and the observed PE frequency matched the frequencies predicted for the vibrational fundamentals of both the linear and the fanlike isomers of MnC3. Theoretical investigations of MgC3 - have indicated that the bent, linear, fan and kite structures are close in energy, and thus are potentially observables. In the present work, the nu1(sigma) asymmetric carbon stretching mode of linear MgC3- has been observed at 1797.5 cm-1. A second absorption at 1190.1 cm-1 which is correlated in intensity to the nu1(sigma) has tentatively been assigned to the nu2(sigma) vibrational fundamental. Although DFT calculations on ZnC3 have indicated that the linear, bent and kite structures are

  5. UB CCD PHOTOMETRY OF THE OLD, METAL-RICH, OPEN CLUSTERS NGC 6791, NGC 6819, AND NGC 7142

    SciTech Connect

    Carraro, G.; Buzzoni, A.; Bertone, E.; Buson, L. E-mail: alberto.buzzoni@oabo.inaf.it E-mail: lucio.buson@oapd.inaf.it

    2013-11-01

    We report on a UV-oriented imaging survey in the fields of the old, metal-rich open clusters NGC 6791, NGC 6819, and NGC 7142. With their super-solar metallicity and ages ∼> 3-8 Gyr, these three clusters represent both very near and ideal stellar aggregates to match the distinctive properties of the evolved stellar populations, as in elliptical galaxies and bulges of spirals. Following a first discussion of NGC 6791 observations in an accompanying paper, here we complete our analysis, also presenting for NGC 6819 and NGC 7142 the first-ever U CCD photometry. The color-magnitude diagram of the three clusters is analyzed in detail, with special emphasis on the hot stellar component. We report, in this regard, one new extreme horizontal-branch star candidate in NGC 6791. For NGC 6819 and 7142, the stellar luminosity function clearly points to a looser radial distribution of faint lower main sequence stars, either as a consequence of cluster dynamical interaction with the Galaxy or as an effect of an increasing fraction of binary stars toward the cluster core, as also observed in NGC 6791. Compared to a reference theoretical model for the Galaxy disk, the analysis of the stellar field along the line of sight of each cluster indicates that a more centrally concentrated thick disk, on a scale length shorter than ∼2.8 kpc, might better reconcile the lower observed fraction of bright field stars and their white-dwarf progeny.

  6. UB CCD Photometry of the Old, Metal-rich, Open Clusters NGC 6791, NGC 6819, and NGC 7142

    NASA Astrophysics Data System (ADS)

    Carraro, G.; Buzzoni, A.; Bertone, E.; Buson, L.

    2013-11-01

    We report on a UV-oriented imaging survey in the fields of the old, metal-rich open clusters NGC 6791, NGC 6819, and NGC 7142. With their super-solar metallicity and ages >~ 3-8 Gyr, these three clusters represent both very near and ideal stellar aggregates to match the distinctive properties of the evolved stellar populations, as in elliptical galaxies and bulges of spirals. Following a first discussion of NGC 6791 observations in an accompanying paper, here we complete our analysis, also presenting for NGC 6819 and NGC 7142 the first-ever U CCD photometry. The color-magnitude diagram of the three clusters is analyzed in detail, with special emphasis on the hot stellar component. We report, in this regard, one new extreme horizontal-branch star candidate in NGC 6791. For NGC 6819 and 7142, the stellar luminosity function clearly points to a looser radial distribution of faint lower main sequence stars, either as a consequence of cluster dynamical interaction with the Galaxy or as an effect of an increasing fraction of binary stars toward the cluster core, as also observed in NGC 6791. Compared to a reference theoretical model for the Galaxy disk, the analysis of the stellar field along the line of sight of each cluster indicates that a more centrally concentrated thick disk, on a scale length shorter than ~2.8 kpc, might better reconcile the lower observed fraction of bright field stars and their white-dwarf progeny.

  7. Transition Metal Nitride Clusters and Solid State Materials via Alkyl Ammonolyses of Molecular Precursors.

    NASA Astrophysics Data System (ADS)

    Banaszak Holl, Mark Monroe

    A research program designed to synthesize new types of metal nitride clusters and apply them to the syntheses of solids resulted in several new cluster compounds and low temperature routes to binary transition metal nitrides. The reaction of Cp*TaMe_4 (1) with excess ammonia generates yellow (Cp*(Me)TaN) _3 (2). 2 has equivalent bond lengths about the ring of 1.886 (17)_{rm av} A. EHMO calculations predicted that a non-bonding metal centered LUMO should be ~ 1.2 eV above the HOMO. Cyclic voltammetry and coulometry demonstrated the existence of a reversible one-electron reduction at -2.5 V vs SSCE. Chemical reduction of 2 with NaK amalgam generated purple (K cdotn Et_2O) ^+ ({Cp*(Me)TaN }_3^-) (3, 83%). Treatment of (^{rm t }BuCH_2)_3TaCH ^{rm t}Bu (4) with ammonia generated orange to green-orange precipitates (17, 17^'), which upon annealing at 820^circC formed metastable Fm3m TaN. Yellow ((^{rm t} BuCH_2)_2TaN) _5 (7) could be isolated in 42% yield if the reaction was protected from exposure to light. The geometrical similarity between 7 and Fm3m TaN prompted mechanistic experiments to determine if 7 dictated the formation of the Fm3m phase. The results of a variety of experiments involving electron microscopy, FAB and high resolution mass spectrometry, MAS and Spin-Echo NMR were inconclusive. Treatment of (tritox)ZrBz_3 (8) with 1.8 equivalents of ammonia generated a white, square-pyramidal cluster, (tritoxZr)_5( mu_5-N)(mu_3 -NH)_4(mu_2-NH _2)_4 (10) in 32% yield. Treatment of 8 or 10 with excess ammonia resulted in the formation of (tritoxZr)_5(mu_5 -N)(mu_2-NH_2) _8(NH_2)_4 (11) (56% from 8). Upon treating 8 with one equivalent of NH_3, crystals containing (tritoxZr) _6(mu_6-N)( mu_3-NH)_6(mu _2-NH_2)_3 (12) formed. The crystals were determined to contain a 0.6:1 ratio of 12:10 via ^{15} N CPMAS solid state NMR. A system to model the reaction of ammonia with metal alkyls was developed. The reaction of (silox) _2TaBz_3 (13) with one and two equivalents of

  8. Nanoscale relaxation oscillator

    DOEpatents

    Zettl, Alexander K.; Regan, Brian C.; Aloni, Shaul

    2009-04-07

    A nanoscale oscillation device is disclosed, wherein two nanoscale droplets are altered in size by mass transport, then contact each other and merge through surface tension. The device may also comprise a channel having an actuator responsive to mechanical oscillation caused by expansion and contraction of the droplets. It further has a structure for delivering atoms between droplets, wherein the droplets are nanoparticles. Provided are a first particle and a second particle on the channel member, both being made of a chargeable material, the second particle contacting the actuator portion; and electrodes connected to the channel member for delivering a potential gradient across the channel and traversing the first and second particles. The particles are spaced apart a specified distance so that atoms from one particle are delivered to the other particle by mass transport in response to the potential (e.g. voltage potential) and the first and second particles are liquid and touch at a predetermined point of growth, thereby causing merging of the second particle into the first particle by surface tension forces and reverse movement of the actuator. In a preferred embodiment, the channel comprises a carbon nanotube and the droplets comprise metal nanoparticles, e.g. indium, which is readily made liquid.

  9. A Wide-Field Photometric Survey for Extratidal Tails Around Five Metal-Poor Globular Clusters in the Galactic Halo

    NASA Astrophysics Data System (ADS)

    Chun, Sang-Hyun; Kim, Jae-Woo; Sohn, Sangmo T.; Park, Jang-Hyun; Han, Wonyong; Kim, Ho-Il; Lee, Young-Wook; Lee, Myung Gyoon; Lee, Sang-Gak; Sohn, Young-Jong

    2010-02-01

    Wide-field deep g'r'i' images obtained with the Megacam of the Canada-France-Hawaii Telescope are used to investigate the spatial configuration of stars around five metal-poor globular clusters M15, M30, M53, NGC 5053, and NGC 5466, in a field-of-view ~3°. Applying a mask filtering algorithm to the color-magnitude diagrams of the observed stars, we sorted cluster's member star candidates that are used to examine the characteristics of the spatial stellar distribution surrounding the target clusters. The smoothed surface density maps and the overlaid isodensity contours indicate that all of the five metal-poor globular clusters exhibit strong evidence of extratidal overdensity features over their tidal radii, in the form of extended tidal tails around the clusters. The orientations of the observed extratidal features show signatures of tidal tails tracing the clusters' orbits, inferred from their proper motions, and effects of dynamical interactions with the Galaxy. Our findings include detections of a tidal bridge-like feature and an envelope structure around the pair of globular clusters M53 and NGC 5053. The observed radial surface density profiles of target clusters have a deviation from theoretical King models, for which the profiles show a break at 0.5-0.7rt , extending the overdensity features out to 1.5-2rt . Both radial surface density profiles for different angular sections and azimuthal number density profiles confirm the overdensity features of tidal tails around the five metal-poor globular clusters. Our results add further observational evidence that the observed metal-poor halo globular clusters originate from an accreted satellite system, indicative of the merging scenario of the formation of the Galactic halo. Based on observations carried out at the Canada-France-Hawaii Telescope, operated by the National Research Council of Canada, the Centre National de la Recherche Scientifique de France, and the University of Hawaii. This is part of the

  10. 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).

  11. Pure carbon nanoscale devices: Nanotube heterojunctions

    SciTech Connect

    Chico, L.; Crespi, V.H.; Benedict, L.X.; Louie, S.G.; Cohen, M.L. |

    1996-02-01

    Introduction of pentagon-heptagon pair defects into the hexagonal network of a single carbon nanotube can change the helicity of the tube and alter its electronic structure. Using a tight-binding method to calculate the electronic structure of such systems we show that they behave as nanoscale metal/semiconductor or semiconductor/semiconductor junctions. These junctions could be the building blocks of nanoscale electronic devices made entirely of carbon. {copyright} {ital 1996 The American Physical Society.}

  12. Nanoscale Thermal Imaging

    NASA Astrophysics Data System (ADS)

    Baloch, Kamal; Brintlinger, Todd; Qi, Yi; Goldhaber-Gordon, David; Cumings, John

    2007-03-01

    We present real time, in-situ, high resolution thermal imaging of metallic nanowires. The nanowires are grown on the front-side of silicon nitride membranes. Resistive heating along the wires produces thermal gradients which melt/freeze 20-200nm diameter indium islands deposited by thermal evaporation on the back-side of the membrane. These transitions can be imaged using a transmission electron microscope operating in dark-field mode such that contrast corresponds to the phase of an individual island. Global changes in temperature can be used to calibrate the melting point of individual islands and to account for the presence of the ˜100nm thick silicon nitride membrane. Thermal modeling confirms the imaged thermal behavior. This technique could be generally employed for thermal imaging of nanowires and nanotubes, wherein the nanoscale systems are imaged in-situ and under electrical bias. Results of local resistive heating in a carbon nanotube device will also be shown

  13. Nanoscale waveguiding methods.

    PubMed

    Wang, Chia-Jean; Lin, Lih Y

    2007-05-01

    While 32 nm lithography technology is on the horizon for integrated circuit (IC) fabrication, matching the pace for miniaturization with optics has been hampered by the diffraction limit. However, development of nanoscale components and guiding methods is burgeoning through advances in fabrication techniques and materials processing. As waveguiding presents the fundamental issue and cornerstone for ultra-high density photonic ICs, we examine the current state of methods in the field. Namely, plasmonic, metal slot and negative dielectric based waveguides as well as a few sub-micrometer techniques such as nanoribbons, high-index contrast and photonic crystals waveguides are investigated in terms of construction, transmission, and limitations. Furthermore, we discuss in detail quantum dot (QD) arrays as a gain-enabled and flexible means to transmit energy through straight paths and sharp bends. Modeling, fabrication and test results are provided and show that the QD waveguide may be effective as an alternate means to transfer light on sub-diffraction dimensions.

  14. Nanoscale waveguiding methods

    NASA Astrophysics Data System (ADS)

    Wang, Chia-Jean; Lin, Lih Y.

    2007-05-01

    While 32 nm lithography technology is on the horizon for integrated circuit (IC) fabrication, matching the pace for miniaturization with optics has been hampered by the diffraction limit. However, development of nanoscale components and guiding methods is burgeoning through advances in fabrication techniques and materials processing. As waveguiding presents the fundamental issue and cornerstone for ultra-high density photonic ICs, we examine the current state of methods in the field. Namely, plasmonic, metal slot and negative dielectric based waveguides as well as a few sub-micrometer techniques such as nanoribbons, high-index contrast and photonic crystals waveguides are investigated in terms of construction, transmission, and limitations. Furthermore, we discuss in detail quantum dot (QD) arrays as a gain-enabled and flexible means to transmit energy through straight paths and sharp bends. Modeling, fabrication and test results are provided and show that the QD waveguide may be effective as an alternate means to transfer light on sub-diffraction dimensions.

  15. 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

  16. 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.

  17. Prediction of structural and metal-to-semiconductor phase transitions in nanoscale MoS2, WS2, and other transition metal dichalcogenide zigzag ribbons

    NASA Astrophysics Data System (ADS)

    Güller, F.; Llois, A. M.; Goniakowski, J.; Noguera, C.

    2015-02-01

    While MoS2 and WS2 nanostructures gain an increasing importance in a number of recent technological applications, the control of their structure as a function of their size and their environment appears of prominent importance. In the present study which relies on first-principles simulations, we predict the dimerized 1T ' structural phase to be the actual ground state of MoS2, WS2, and MoSe2 zigzag nanoribbons of small width and monolayer thickness. We assign this result to the competition between edge energy—which favors the nonpolar 1T ' edges over the polar 1H edges—and the energy of atoms in the center of the ribbons—which favors the 1H ground state of the infinite monolayers. A metal-to-semiconductor transition accompanies the structural transition. At variance, ZrS2 zigzag ribbons are predicted to display the 1T structure whatever their width. In compounds of major technological importance, such structural and electronic flexibility associated with polarity effects opens the possibility for controlling the ribbon type during synthesis.

  18. 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

  19. Nanosolids, slushes, and nanoliquids: characterization of nanophases in metal clusters and nanoparticles.

    PubMed

    Li, Zhen Hua; Truhlar, Donald G

    2008-09-24

    One of the keys to understanding the emergent behavior of complex materials and nanoparticles is understanding their phases. Understanding the phases of nanomaterials involves new concepts not present in bulk materials; for example, the phases of nanoparticles are quantum mechanical even when no hydrogen or helium is present. To understand these phases better, molecular dynamics (MD) simulations on size-selected particles employing a realistic analytic many-body potential based on quantum mechanical nanoparticle calculations have been performed to study the temperature-dependent properties and melting transitions of free Al n clusters and nanoparticles with n = 10-300 from 200 to 1700 K. By analyzing properties of the particles such as specific heat capacity (c), radius of gyration, volume, coefficient of thermal expansion (beta), and isothermal compressibility (kappa), we developed operational definitions of the solid, slush, and liquid states of metal clusters and nanoparticles. Applying the definitions, which are based on the temperature dependences of c, beta, and ln kappa, we determined the temperature domains of the solid, slush, and liquid states of the Al n particles. The results show that Al n clusters ( n or= 19, diameter of more than 1 nm) do have a melting transition and are in the liquid state above 900-1000 K. However, all aluminum nanoparticles have a wide temperature interval corresponding to the slush state in which the solid and liquid states coexist in equilibrium, unlike a bulk material where coexistence occurs only at a single temperature (for a given pressure). The commonly accepted operational marker of the melting temperature, namely, the peak position of c, is not unambiguous and not appropriate for characterizing the melting transition for aluminum particles with the exception of

  20. 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

  1. Laser ablation source for formation and deposition of size-selected metal clusters.

    PubMed

    Vucković, S; Svanqvist, M; Popok, V N

    2008-07-01

    This work describes construction of a source and optimisation of its parameters for production of cluster ion beams using material ablation by the second harmonic of a Nd:YAG laser (532 nm). The influence of different source parameters such as carrier gas pressure, laser power, delay time between gas, and laser pulses as well as nozzle configuration on the cluster formation are studied. For the current experiments the laser ablation cluster source was optimized for production of Con+ cluster ions. Clusters with n up to 150 atoms are registered by a time-of-flight mass spectrometer. Deposition of size-selected Co50+ clusters with kinetic energies in the interval of 250-4850 eV/cluster on highly ordered pyrolytic graphite is studied. At the highest impact energies the clusters are implanted. Craters and well-like structures can be seen by scanning tunneling microscopy at impact spots. A decrease in cluster kinetic energy leads to formation of bumplike structures which probably represent damaged graphite areas with incorporated Co atoms. Further decrease in the cluster impact energy to the level of 450-250 eV/cluster creates condition for so-called cluster pinning when the cluster constituents are intact but the energy transferred to the graphite is still enough to produce radiation defects to which the cluster is bound. PMID:18681696

  2. Nature of the interaction between rare gas atoms and transition metal doped silicon clusters: the role of shielding effects.

    PubMed

    Ngan, Vu Thi; Janssens, Ewald; Claes, Pieterjan; Fielicke, André; Nguyen, Minh Tho; Lievens, Peter

    2015-07-21

    Mass spectrometry experiments show an exceptionally weak bonding between Si7Mn(+) and rare gas atoms as compared to other exohedrally transition metal (TM) doped silicon clusters and other SinMn(+) (n = 5-10) sizes. The Si7Mn(+) cluster does not form Ar complexes and the observed fraction of Xe complexes is low. The interaction of two cluster series, SinMn(+) (n = 6-10) and Si7TM(+) (TM = Cr, Mn, Cu, and Zn), with Ar and Xe is investigated by density functional theory calculations. The cluster-rare gas binding is for all clusters, except Si7Mn(+) and Si7Zn(+), predominantly driven by short-range interaction between the TM dopant and the rare gas atoms. A high s-character electron density on the metal atoms in Si7Mn(+) and Si7Zn(+) shields the polarization toward the rare gas atoms and thereby hinders formation of short-range complexes. Overall, both Ar and Xe complexes are similar except that the larger polarizability of Xe leads to larger binding energies.

  3. 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.

  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. 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

  6. Mass-loss on the red giant branch: the value and metallicity dependence of Reimers' η in globular clusters

    NASA Astrophysics Data System (ADS)

    McDonald, I.; Zijlstra, A. A.

    2015-03-01

    The impact of metallicity on the mass-loss rate from red giant branch (RGB) stars is studied through its effect on the parameters of horizontal branch (HB) stars. The scaling factors from Reimers and Schröder and Cuntz are used to measure the efficiency of RGB mass-loss for typical stars in 56 well-studied Galactic globular clusters (GCs). The median values among clusters are, respectively, η _R = 0.477 ± 0.070 ^{+0.050}_{-0.062} and η _SC = 0.172 ± 0.024 ^{+0.018}_{-0.023} (standard deviation and systematic uncertainties, respectively). Over a factor of 200 in iron abundance, η varies by ≲30 per cent, thus mass-loss mechanisms on the RGB have very little metallicity dependence. Any remaining dependence is within the current systematic uncertainties on cluster ages and evolution models. The low standard deviation of η among clusters (≈14 per cent) contrasts with the variety of HB morphologies. Since η incorporates cluster age, this suggests that age accounts for the majority of the `second parameter problem', and that a Reimers-like law provides a good mass-loss model. The remaining spread in η correlates with cluster mass and density, suggesting helium enrichment provides the third parameter explaining HB morphology of GCs. We close by discussing asymptotic giant branch (AGB) mass-loss, finding that the AGB tip luminosity is better reproduced and η has less metallicity dependence if GCs are more co-eval than generally thought.

  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. 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.

  9. THE MASS-METALLICITY RELATION OF GLOBULAR CLUSTERS IN THE CONTEXT OF NONLINEAR COLOR-METALLICTY RELATIONS

    SciTech Connect

    Blakeslee, John P.; Cantiello, Michele; Peng, Eric W.

    2010-02-10

    Two recent empirical developments in the study of extragalactic globular cluster (GC) populations are the color-magnitude relation of the blue GCs (the 'blue tilt') and the nonlinearity of the dependence of optical GC colors on metallicity. The color-magnitude relation, interpreted as a mass-metallicity relation, is thought to be a consequence of self-enrichment. Nonlinear color-metallicity relations have been shown to produce bimodal color distributions from unimodal metallicity distributions. We simulate GC populations including both a mass-metallicity scaling relation and nonlinear color-metallicity relations motivated by theory and observations. Depending on the assumed range of metallicities and the width of the GC luminosity function (GCLF), we find that the simulated populations can have bimodal color distributions with a 'blue tilt' similar to observations, even though the metallicity distribution appears unimodal. The models that produce these features have the relatively high mean GC metallicities and nearly equal blue and red peaks characteristic of giant elliptical galaxies. The blue tilt is less apparent in the models with metallicities typical of dwarf ellipticals; the narrower GCLF in these galaxies has an even bigger effect in reducing the significance of their color-magnitude slopes. We critically examine the evidence for nonlinearity versus bimodal metallicities as explanations for the characteristic double-peaked color histograms of giant ellipticals and conclude that the question remains open. We discuss the prospects for further theoretical and observational progress in constraining the models presented here and for uncovering the true metallicity distributions of extragalactic GC systems.

  10. Trimetallic nitride endohedral metallofullerenes: reactivity dictated by the encapsulated metal cluster.

    PubMed

    Cardona, Claudia M; Kitaygorodskiy, Alex; Echegoyen, Luis

    2005-07-27

    The first derivatives of Y(3)N@C(80) have been synthesized and fully characterized. 1,3-Dipolar cycloaddition of N-ethylazomethine ylide yielded mainly the pyrrolidine monoadduct of the icosahedral (I(h)()) symmetry cage exclusively at a [6,6] double bond. The same regioselectivity on a [6,6] double bond was observed when the endohedral compound was cyclopropanated with diethyl bromomalonate. These results are in pronounced contrast to those observed for icosahedral symmetry Sc(3)N@C(80), for which all reported derivatives add completely regioselectively to [5,6] double bonds. (1)H NMR, (13)C NMR, and HMQC spectroscopy revealed that the addition pattern on Y(3)N@C(80) resulted in a pyrrolidinofullerene derivative with unsymmetric pyrrolidine carbons and symmetric geminal protons. The cyclopropanated monoadduct exhibited symmetric ethyl groups on the malonate, consistent with regioselective addition at a [6,6] double bond. Attempts to perform the same cyclopropanation reaction on (I(h)()) Sc(3)N@C(80) failed to yield any identifiable products. These observations clearly indicate that the reactivity of trimetallic nitride endohedral metallofullerenes toward exohedral chemical functionalization is profoundly affected and effectively controlled by the nature of the endohedral metal cluster.

  11. 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.

  12. 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.

  13. 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.

  14. 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.

  15. Auger electron nanoscale mapping and x-ray photoelectron spectroscopy combined with gas cluster ion beam sputtering to study an organic bulk heterojunction

    SciTech Connect

    Heon Kim, Seong; Heo, Sung; Ihn, Soo-Ghang; Yun, Sungyoung; Hwan Park, Jong; Chung, Yeonji; Lee, Eunha; Park, Gyeongsu; Yun, Dong-Jin

    2014-06-16

    The lateral and vertical distributions of organic p/n bulk heterojunctions for an organic solar cell device are, respectively, investigated using nanometer-scale Auger electron mapping and using X-ray photoelectron spectroscopy (XPS) with Ar gas cluster ion beam (GCIB) sputtering. The concentration of sulfur, present only in the p-type material, is traced to verify the distribution of p-type (donor) and n-type (acceptor) materials in the blended structure. In the vertical direction, a considerable change in atomic sulfur concentration is observed using XPS depth profiling with Ar GCIB sputtering. In addition, Auger electron mapping of sulfur reveals the lateral 2-dimensional distribution of p- and n-type materials. The combination of Auger electron mapping with Ar GCIB sputtering should thereby allow the construction of 3-dimensional distributions of p- and n-type materials in organic photovoltaic cells.

  16. 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.

  17. 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.

  18. Optical antennas as nanoscale resonators.

    PubMed

    Agio, Mario

    2012-02-01

    Recent progress in nanotechnology has enabled us to fabricate sub-wavelength architectures that function as antennas for improving the exchange of optical energy with nanoscale matter. We describe the main features of optical antennas for enhancing quantum emitters and review the designs that increase the spontaneous emission rate by orders of magnitude from the ultraviolet up to the near-infrared spectral range. To further explore how optical antennas may lead to unprecedented regimes of light-matter interactions, we draw a relationship between metal nanoparticles, radio-wave antennas and optical resonators. Our analysis points out how optical antennas may function as nanoscale resonators and how these may offer unique opportunities with respect to state-of-the-art microcavities.

  19. Low-temperature electronic transport in one-dimensional hybrid systems: Metal cluster embedded carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Soldano, Caterina

    The investigation of the electronic and magnetotransport properties at low temperature in individual MWNT with embedded clusters are here presented. The majority of studies of transport in MWNT reported in literature has been carried out on arc-discharge grown tubes, generally considered "clean" and defect-free. In this project, individual MWNT grown in alumina template are used; these tubes are highly disordered compared for example to arc-discharge ones, conditions that dramatically will impact the charge transport. As-fabricated devices are in general highly resistive. A large decrease in the value of the device resistance can be achieved through a controlled and fast high-bias sweep method (HBT) across the sample. Scanning electron microscopy analysis shows that this method induces a metal (platinum) decoration of the MWNT surface as a consequence of the large amount of Joule heating developed during the sweep. Temperature dependence study (5

  20. Template synthesis of nanoscale materials using the membrane porosity

    NASA Astrophysics Data System (ADS)

    Piraux, L.; Dubois, S.; Demoustier-Champagne, S.

    1997-08-01

    The template strategy combined with electrodeposition techniques have been successfully used to produce nanoscale objects in the cylindrical pores of track-etched polycarbonate membranes. Using this method, nanometer-size metallic wires, conductive polymer nanotubules, superconducting nanowires and quasi-one-dimensional magnetic multilayers have been fabricated. These nanoscale materials exhibit physical properties different from those found in the bulk.

  1. 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

  2. Synthesis of Nanometer-Sized (bi)metallic Clusters with a Nuclear Reactor

    NASA Astrophysics Data System (ADS)

    Doudna, C. M.; Hund, J. F.; Bertino, M. F.

    Mono- and heteronuclear clusters were synthesized by irradiating with gamma rays from a nuclear reactor aqueous solutions containing ionic precursors. Ag, Au/Ag and Ag/Pd clusters were produced and characterized by optical absorption and transmission electron microscopy measurements. Electron diffraction measurements show that the clusters have a crystalline fcc structure. Ag and Au/Ag clusters have a lattice parameter which coincides with the bulk. In the case of Ag/Pd clusters, a homogeneous alloy is formed whose lattice parameter closely follows Vegard's law. The cluster size distribution is in the nanometer range, although coalescence processes lead often to large aggregates. Optical absorption spectra are in agreement with previously reported results, when the presence of large aggregates is taken into account.

  3. 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.

  4. Dynamic structural disorder in supported nanoscale catalysts

    SciTech Connect

    Rehr, J. J.; Vila, F. D.

    2014-04-07

    We investigate the origin and physical effects of “dynamic structural disorder” (DSD) in supported nano-scale catalysts. DSD refers to the intrinsic fluctuating, inhomogeneous structure of such nano-scale systems. In contrast to bulk materials, nano-scale systems exhibit substantial fluctuations in structure, charge, temperature, and other quantities, as well as large surface effects. The DSD is driven largely by the stochastic librational motion of the center of mass and fluxional bonding at the nanoparticle surface due to thermal coupling with the substrate. Our approach for calculating and understanding DSD is based on a combination of real-time density functional theory/molecular dynamics simulations, transient coupled-oscillator models, and statistical mechanics. This approach treats thermal and dynamic effects over multiple time-scales, and includes bond-stretching and -bending vibrations, and transient tethering to the substrate at longer ps time-scales. Potential effects on the catalytic properties of these clusters are briefly explored. Model calculations of molecule-cluster interactions and molecular dissociation reaction paths are presented in which the reactant molecules are adsorbed on the surface of dynamically sampled clusters. This model suggests that DSD can affect both the prefactors and distribution of energy barriers in reaction rates, and thus can significantly affect catalytic activity at the nano-scale.

  5. Nanoscale thermal probing

    PubMed Central

    Yue, Yanan; Wang, Xinwei

    2012-01-01

    Nanoscale novel devices have raised the demand for nanoscale thermal characterization that is critical for evaluating the device performance and durability. Achieving nanoscale spatial resolution and high accuracy in temperature measurement is very challenging due to the limitation of measurement pathways. In this review, we discuss four methodologies currently developed in nanoscale surface imaging and temperature measurement. To overcome the restriction of the conventional methods, the scanning thermal microscopy technique is widely used. From the perspective of measuring target, the optical feature size method can be applied by using either Raman or fluorescence thermometry. The near-field optical method that measures nanoscale temperature by focusing the optical field to a nano-sized region provides a non-contact and non-destructive way for nanoscale thermal probing. Although the resistance thermometry based on nano-sized thermal sensors is possible for nanoscale thermal probing, significant effort is still needed to reduce the size of the current sensors by using advanced fabrication techniques. At the same time, the development of nanoscale imaging techniques, such as fluorescence imaging, provides a great potential solution to resolve the nanoscale thermal probing problem. PMID:22419968

  6. The horizontal branch luminosity vs. metallicity in M 31 globular clusters

    NASA Astrophysics Data System (ADS)

    Federici, L.; Cacciari, C.; Bellazzini, M.; Fusi Pecci, F.; Galleti, S.; Perina, S.

    2012-08-01

    Context. Thanks to the outstanding capabilites of the HST, our current knowledge about the M 31 globular clusters (GCs) is similar to our knowledge of the Milky Way GCs in the 1960s - 1970s, which set the basis for studying the halo and galaxy formation using these objects as tracers, and established their importance in defining the cosmic distance scale. Aims: We intend to derive a new calibration of the MV(HB)-[Fe/H] relation by exploiting the large photometric database of old GCs in M 31 in the HST archive. Methods: We collected the BVI data for 48 old GCs in M 31 and analysed them by applying the same methods and procedures to all objects. We obtained a set of homogeneous colour-magnitude diagrams (CMDs) that were best-fitted with the fiducial CMD ridge lines of selected Milky Way template GCs. Reddening, metallicity, horizontal branch (HB) luminosity and distance were determined self-consistently for each cluster. Results: There are three main results of this study: i) the relation MV(HB) = 0.25( ± 0.02)[Fe/H] + 0.89( ± 0.03), which is obtained from the above parameters and is calibrated on the distances of the template Galactic GCs; ii) the distance modulus to M 31 of (m - M)0 = 24.42 ± 0.06 mag, obtained by normalising this relation at the reference value of [Fe/H] = -1.5 to a similar relation using V0(HB). This is the first determination of the distance to M 31 based on the characteristics of its GC system, which is calibrated on Galactic GCs, iii) the distance to the Large Magellanic Cloud (LMC), which is estimated to be 18.54 ± 0.07 mag as a consequence of the previous results. These values agree excellently with the most recent estimate based on HST parallaxes of Galactic Cepheid and RR Lyrae stars, as well as with recent methods. Based on observations made with the NASA/ESA Hubble Space Telescope, obtained from the Hubble Legacy Archive, which is a collaboration between the Space Telescope Science Institute (STScI/NASA), the Space Telescope European

  7. 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.

  8. Correlation between the latent heats and cohesive energies of metal clusters

    NASA Astrophysics Data System (ADS)

    Starace, Anne K.; Neal, Colleen M.; Cao, Baopeng; Jarrold, Martin F.; Aguado, Andrés; López, José M.

    2008-10-01

    Dissociation energies have been determined for Aln+ clusters (n=25-83) using a new experimental approach that takes into account the latent heat of melting. According to the arguments presented here, the cohesive energies of the solidlike clusters are made up of contributions from the dissociation energies of the liquidlike clusters and the latent heats for melting. The size-dependent variations in the measured dissociation energies of the liquidlike clusters are small and the variations in the cohesive energies of solidlike clusters result almost entirely from variations in the latent heats for melting. To compare with the measured cohesive energies, density-functional theory has been used to search for the global minimum energy structures. Four groups of low energy structures were found: Distorted decahedral fragments, fcc fragments, fcc fragments with stacking faults, and "disordered." For most cluster sizes, the measured and calculated cohesive energies are strongly correlated. The calculations show that the variations in the cohesive energies (and the latent heats) result from a combination of geometric and electronic shell effects. For some clusters an electronic shell closing is responsible for the enhanced cohesive energy and latent heat (e.g., n =37), while for others (e.g., n =44) a structural shell closing is the cause.

  9. 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

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

    NASA Astrophysics Data System (ADS)

    Hirai, Kenji; Isobe, Shigehito; Sada, Kazuki

    2015-12-01

    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.

  11. 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

  12. 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.

  13. 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.

  14. 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.

  15. 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.

  16. 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

  17. Electron counting rules for transition metal-doped Si12 clusters

    NASA Astrophysics Data System (ADS)

    Phi, Nguyen Duy; Trung, Nguyen Tien; Janssens, Ewald; Ngan, Vu Thi

    2016-01-01

    Application of the phenomenological shell model (PSM) provides an explanation for the enhanced stability of Si12Cr and Si12Fe clusters and relative cluster stability along the Si12M (M = Scsbnd Ni) series. Sequence of orbital shells in PSM is mostly determined by the confining potential, which depends on the cluster shape. In D6h hexagonal prism geometry, degenerate 2P and 2D shells undergo splitting, and the energy levels of 2Pz and 2Dz2 orbitals become higher than those of (2Px, 2Py) and (2Dxy , 2Dyz , 2Dxz , 2Dx2 -y2), respectively. Therefore, stability of the most stable Si12Cr and Si12Fe clusters is attributed to the filling of the 2S22P62D8 and 2S22P62D10 closed shells.

  18. Many-body forces and electron correlation in small metal clusters

    NASA Astrophysics Data System (ADS)

    Kaplan, Ilya G.; Hernández-Cobos, Jorge; Ortega-Blake, Iván; Novaro, Octavio

    1996-04-01

    The many-body decomposition of the interaction energy for BeN and LiN (N=2 to 4) clusters is calculated in two approximations: the self-consistent-field method and the Mo/ller-Plesset perturbation theory up to the fourth order. This allows us to estimate the electron-correlation contributions to the many-body forces. The explicit expressions for these contributions in the perturbation theory formalism are obtained. We present a comparative analysis of the role of electron correlations in the BeN and LiN cluster formations and in the many-body interactions in these clusters. As follows from our results, the contribution of electron correlation to many-body interactions is essential for both the BeN and LiN clusters, especially for the latter ones, where nonadditivities are surprisingly large.

  19. Nanoscale photonics using coupled hybrid plasmonic architectures

    NASA Astrophysics Data System (ADS)

    Lin, Charles; Su, Yiwen; Helmy, Amr S.

    2016-04-01

    Plasmonic waveguides, which support surface plasmon polaritons (SPP) propagating along metal-dielectric interfaces, offer strong field confinement and are ideal for the design of integrated nano-scale photonic devices. However, due to free-carrier absorption in the metal, the enhanced mode confinement inevitably entails an increase in the waveguide loss. This lowers the device figure-of-merit achievable with passive plasmonic components and in turn hinders the performance of active plasmonic components such as optical modulators.

  20. 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