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Sample records for metal clusters adequate

  1. Alkali Metal Cluster Theory.

    NASA Astrophysics Data System (ADS)

    Chen, Jian

    Available from UMI in association with The British Library. Requires signed TDF. In this thesis, we apply the tight-binding Hubbard model to alkali metal clusters with Hartree-Fock self-consistent methods and perturbation methods for the numerical calculations. We have studied the relation between the equilibrium structures and the range of the hopping matrix elements in the Hubbard Hamiltonian. The results show that the structures are not sensitive to the interaction range but are determined by the number of valence electrons each atom has. Inertia tensors are used to analyse the symmetries of the clusters. The principal axes of the clusters are determined and they are the axes of rotational symmetries of clusters if the clusters have any. The eigenvalues of inertia tensors which are the indication of the deformation of clusters are compared between our model and the ellipsoidal jellium model. The agreement is good for large clusters. At a finite temperature, the thermal motion fluctuates the structures. We defined a fluctuation function with the distance matrix of a cluster. The fluctuation has been studied with the Monte-Carlo simulation method. Our studies show that the clusters remain in the solid state when temperature is low. The small values of fluctuation functions indicates the thermal vibration of atoms around their equilibrium positions. If the temperature is high, the atoms are delocalized. The cluster melts and enters the liquid region. The cluster melting is simulated by the Monte-Carlo simulation with the fluctuation function we defined. Energy levels of clusters are calculated from the Hubbard model. Ionization potentials and magic numbers are also obtained from these energy levels. The results confirm that the Hubbard model is a good approximation for a small cluster. The excitation energy is presented by the difference between the original level and excited level, and the electron-hole interactions. We also have studied cooling of clusters

  2. Internal gettering by metal alloy clusters

    DOEpatents

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

    2010-07-27

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

  3. Metallic bonding and cluster structure

    SciTech Connect

    Soler, Jose M.; Beltran, Marcela R.; Michaelian, Karo; Garzon, Ignacio L.; Ordejon, Pablo; Sanchez-Portal, Daniel

    2000-02-15

    Knowledge of the structure of clusters is essential to predict many of their physical and chemical properties. Using a many-body semiempirical Gupta potential (to perform global minimizations), and first-principles density functional calculations (to confirm the energy ordering of the local minima), we have recently found [Phys. Rev. Lett. 81, 1600 (1998)] that there are many intermediate-size disordered gold nanoclusters with energy near or below the lowest-energy ordered structure. This is especially surprising because we studied ''magic'' cluster sizes, for which very compact-ordered structures exist. Here, we show how the analysis of the local stress can be used to understand the physical origin of this amorphization. We find that the compact ordered structures, which are very stable for pair potentials, are destabilized by the tendency of metallic bonds to contract at the surface, because of the decreased coordination. The amorphization is also favored by the relatively low energy associated to bondlength and coordination disorder in metals. Although these are very general properties of metallic bonding, we find that they are especially important in the case of gold, and we predict some general trends in the tendency of metallic clusters towards amorphous structures. (c) 2000 The American Physical Society.

  4. Structure stability and spectroscopy of metal clusters

    SciTech Connect

    Not Available

    1993-01-01

    Theory based on self-consistent field-linear combinations of atomic orbitals-molecular orbital theory was applied to clusters. Four areas were covered: electronic structure, equilibrium geometries, and stability of charged clusters, interaction of metal clusters with H and halogen atoms, thermal stability of isolated clusters, and stability and optical properties of hetero-atomic clusters. (DLC)

  5. Reactive cluster model of metallic glasses

    SciTech Connect

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

    2014-02-28

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

  6. Surface deposition and encapsulation of metallic clusters

    NASA Astrophysics Data System (ADS)

    Hund, Jared Franklin

    In this work metallic clusters are produced by both encapsulation in an aerogel matrix and deposition on a surface. Entrapment of metal clusters inside aerogels is accomplished though synthesis of a hydrogel precursor, washing it with an aqueous metal salt solution, and controlled reduction of the metal. Although the aerogel matrix stabilizes and prevents subsequent loss or aggregation of the clusters once they are produced, controlling the rate of reduction is key to the size and morphology of the clusters. In order to do this, both radiolytic and chemical reduction methods are used. The radiolytic technique for the formation of metal cluster aerogel composites utilizes gamma radiation to reduce the solution of Ag+ or [AuCl 4]- ions inside of the hydrogel precursor. After exposure to gamma rays, the previously colorless gels have the coloration typical of colloids of Au (pink) and Ag (yellow/brown) clusters. Typical gamma doses are between 2 to 3.5 kGy for hydrogels containing 10-4 to 10-3 mol·L-1 metal solutions. Subsequent characterization confirmed the presence of metal clusters with a fcc structure. The cluster diameters varied between 10 and 200nm, depending on the synthesis parameters. More conventional chemical reduction is also employed in this work to produce noble metal clusters in an aerogel matrix. Hydrogels were washed in a basic solution of Ag+ or [AuCl4]- ions, and formaldehyde was added to the solution. The reduction proceeded relatively slowly, allowing the formaldehyde to diffuse into the hydrogel before complete reduction took place. This procedure was also used to produce alloys of gold and silver clusters embedded in silica aerogels. Also included in this dissertation is the surface deposition of metallic clusters on a silicon surface. The apparatus built produces a cold beam of gas droplets that pick up evaporated metal clusters and deposit them on a surface. The gas clusters are produced by supersonic expansion of a gas (Ar, He, or N2

  7. A Simple MO Treatment of Metal Clusters.

    ERIC Educational Resources Information Center

    Sahyun, M. R. V.

    1980-01-01

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

  8. Structural evolution and metallicity of lead clusters

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

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

  9. Supersonic Bare Metal Cluster Beams. Final Report

    DOE R&D Accomplishments Database

    Smalley, R. E.

    1997-10-14

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

  10. (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.

  11. Novel Metal Encapsulated Silicon Cage Clusters

    NASA Astrophysics Data System (ADS)

    Kawazoe, Yoshiyuki

    2002-03-01

    The discovery of novel nano-forms of carbon such as fullerenes and nanotubes created much interest in the search for similar novel structures of silicon for applications in nano-devices. However, these cage structures are not stable for silicon. Small silicon clusters having upto about 20 atoms are found to have prolate structures in which a 10-atom unit plays an important role. Here we report results of new findings(Vijay Kumar and Yoshiyuki Kawazoe, ``Metal-Encapsulated Fullerenelike and Cubic Caged Clusters of Silicon", Phys. Rev. Lett., 87[4] (2001), 045503-1-045503-4.) on a rich variety of caged silicon clusters that are realized by encapsulating a metal atom. The shape and size of these new clusters depend upon the metal atom which also determines their properties. As silicon is the most important material for devices, these findings offer new opportunities to design novel nano-silicon based devices. The results have been obtained by performing computer experiments using ab initio calculations in an effort to stabilize a silicon cage of 20 atoms. We have tried several metal atoms and used a cage shrinking approach. These led to the findings of fullerene and cubic type stable symmetric clusters in the range of 14 to 16 silicon atoms, depending on the encapsulated metal atom. A Frank-Kasper polyhedron, M@Si16 is found to be of lowest energy for M = Ti and Hf with exceptionally large gaps of about 2.35 eV that lie in the optical region. Further studies have been done to stabilize the smallest fullerene shape of 20 silicon atoms and to develop assemblies of clusters to form more interesting nano-scale structures like wires, which might be useful industrially to realize conducting atomic lines covered by semiconductor tubes.

  12. Electrophobic interaction induced impurity clustering in metals

    SciTech Connect

    Zhou, Hong-Bo; Wang, Jin-Long; Jiang, W.; Lu, Guang-Hong; Aguiar, J. A.; Liu, Feng

    2016-10-01

    We introduce the concept of electrophobic interaction, analogous to hydrophobic interaction, for describing the behavior of impurity atoms in a metal, a 'solvent of electrons'. We demonstrate that there exists a form of electrophobic interaction between impurities with closed electron shell structure, which governs their dissolution behavior in a metal. Using He, Be and Ar as examples, we predict by first-principles calculations that the electrophobic interaction drives He, Be or Ar to form a close-packed cluster with a clustering energy that follows a universal power-law scaling with the number of atoms (N) dissolved in a free electron gas, as well as W or Al lattice, as Ec is proportional to (N2/3-N). This new concept unifies the explanation for a series of experimental observations of close-packed inert-gas bubble formation in metals, and significantly advances our fundamental understanding and capacity to predict the solute behavior of impurities in metals, a useful contribution to be considered in future material design of metals for nuclear, metallurgical, and energy applications.

  13. 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.

  14. Magnetic impurities in small metal clusters

    NASA Astrophysics Data System (ADS)

    Pastor, G. M.

    2005-09-01

    [Dedicated to Bernhard Mühlschlegel on the occasion of his 80th birthday]Magnetic impurities in small metallic clusters are investigated in the framework of the Anderson model by using exact diagonalization and geometry optimization methods.The singlet-triplet spin gap E shows a remarkable dependence as a function of band-filling, cluster structure, and impurity position that can be interpreted in terms of the environment-specific conduction-electron spectrum. The low-energy spin excitations involve similar energies as isomerizations. Interesting correlations between cluster structure and magnetic behavior are revealed. Finite-temperature properties such as specific heat, effective impurity moment, and magnetic susceptibility are calculated exactly in the canonical ensemble. A finite-size equivalent of the Kondo effect is identified and its structural dependence is discussed.

  15. Structure stability and spectroscopy of metal clusters. Progress report

    SciTech Connect

    Not Available

    1993-06-01

    Theory based on self-consistent field-linear combinations of atomic orbitals-molecular orbital theory was applied to clusters. Four areas were covered: electronic structure, equilibrium geometries, and stability of charged clusters, interaction of metal clusters with H and halogen atoms, thermal stability of isolated clusters, and stability and optical properties of hetero-atomic clusters. (DLC)

  16. The chemistry and physics of transition metal clusters

    SciTech Connect

    Parks, E.K.; Jellinek, J.; Knickelbein, M.B.; Riley, S.J.

    1994-06-01

    In this program the authors study the fundamental properties of isolated clusters of transition metal atoms. Experimental studies of cluster chemistry include determination of cluster structure, reactivity, and the nature of cluster-adsorbate interactions. Studies of physical properties include measurements of cluster ionization potentials and photoabsorption cross sections. Theoretical studies focus on the structure and dynamics of clusters, including isomers, phases and phase changes, interactions with molecules, and fragmentation process.

  17. 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

  18. 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.

  19. Gas phase metal cluster model systems for heterogeneous catalysis.

    PubMed

    Lang, Sandra M; Bernhardt, Thorsten M

    2012-07-14

    Since the advent of intense cluster sources, physical and chemical properties of isolated metal clusters are an active field of research. In particular, gas phase metal clusters represent ideal model systems to gain molecular level insight into the energetics and kinetics of metal-mediated catalytic reactions. Here we summarize experimental reactivity studies as well as investigations of thermal catalytic reaction cycles on small gas phase metal clusters, mostly in relation to the surprising catalytic activity of nanoscale gold particles. A particular emphasis is put on the importance of conceptual insights gained through the study of gas phase model systems. Based on these concepts future perspectives are formulated in terms of variation and optimization of catalytic materials e.g. by utilization of bimetals and metal oxides. Furthermore, the future potential of bio-inspired catalytic material systems are highlighted and technical developments are discussed.

  20. 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.

  1. 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.

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

    NASA Astrophysics Data System (ADS)

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

    1987-01-01

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

  3. 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.

  4. Properties and Chemisorptive Reactivity of Transition Metal Clusters

    DTIC Science & Technology

    1991-12-14

    structure of metal complexes that go beyond ligand field theory ideas, and of practical importance, in that it is crucial to understand how magnetic...aggregates or clusters of these metals with quntum mechanics, we will be able to develop a detailed understanding of metallic bonding. So far, we have...interactions between early and late TM’s in these so-called Engel-Brewer intermetallic compounds. The only theory that has attempted to explain the high

  5. 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

  6. Metallic clusters on a model surface: Quantum versus geometric effects

    NASA Astrophysics Data System (ADS)

    Blundell, S. A.; Haldar, Soumyajyoti; Kanhere, D. G.

    2011-08-01

    We determine the structure and melting behavior of supported metallic clusters using an ab initio density-functional-based treatment of intracluster interactions and an approximate treatment of the surface as an idealized smooth plane yielding an effective Lennard-Jones interaction with the ions of the cluster. We apply this model to determine the structure of sodium clusters containing from 4 to 22 atoms, treating the cluster-surface interaction strength as a variable parameter. For a strong cluster-surface interaction, the clusters form two-dimensional (2D) monolayer structures; comparisons with calculations of structure and dissociation energy performed with a classical Gupta interatomic potential show clearly the role of quantum shell effects in the metallic binding in this case, and evidence is presented that these shell effects correspond to those for a confined 2D electron gas. The thermodynamics and melting behavior of a supported Na20 cluster is considered in detail using the model for several cluster-surface interaction strengths. We find quantitative differences in the melting temperatures and caloric curve from density-functional and Gupta treatments of the valence electrons. A clear dimensional effect on the melting behavior is also demonstrated, with 2D structures showing melting temperatures above those of the bulk or (at very strong cluster-surface interactions) no clear meltinglike transition.

  7. Probing Metal Cluster and Metal Oxide Cluster Interactions with Organo-Sulfur and Organo-Phosphorous Molecules using Mass Spectrometry and Anion PES

    DTIC Science & Technology

    2007-11-02

    DATES COVERED Final 01 Dec 02 – 30 Nov 03 4. TITLE AND SUBTITLE Probing metal cluster and metal oxide cluster interactions with organo -sulfur and... Organo -phosphorous molecules using mass spectrometry and anion PES 5. FUNDING NUMBERS DAAD19-03-1-0009 6. AUTHOR(S) Caroline...298-102 Probing metal cluster and metal oxide cluster interactions with organo -sulfur and organo

  8. Metallic Clusters in Strong Femtosecond Laser Pulses

    NASA Astrophysics Data System (ADS)

    Suraud, Eric; Reinhard, P.-G.; Ullrich, Carsten A.

    1998-03-01

    We present a theoretical study of the electron response of a Na_9^+ cluster excited by strong femtosecond laser pulses.(C. A. Ullrich, P.-G. Reinhard, and E. Suraud, J. Phys. B 30), 5043 (1997) Our approach is based on time-dependent density functional theory within the adiabatic local density approximation, including a recently developed self-interaction correction scheme. We investigate numerically the full electronic dipolar response and multiphoton ionization of the cluster and discuss the ionization mechanism. A strong correlation between induced electronic dipole oscillations and electron emission is observed, leading to a pronounced resonant enhancement of ionization at the frequency of the Mie plasmon.

  9. 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.

  10. Size to density coupling of supported metallic clusters.

    PubMed

    Gross, Elad; Asscher, Micha

    2009-01-28

    One of the difficulties in standard growth of metallic nano-clusters on oxide substrates as model catalysts is the strong coupling between clusters size and density. Employing multiple cycles, amorphous solid water-buffer layer assisted growth (ASW-BLAG) procedure, we demonstrate how the size to density coupling can be eliminated under certain conditions. In this study, gold clusters were deposited on a SiO2/Si(100) substrate in UHV, using ASW as a buffer layer assisting aggregation and growth. The clusters were imaged ex situ by tapping mode atomic force microscope (AFM) and high-resolution scanning electron microscope (HR-SEM). In situ Auger electron spectroscopy (AES) measurements have led to independent evaluation of the gold covered area. In order to increase the clusters density we have introduced a multiple BLAG procedure, in which, a BALG cycle is repeated up to 10 times. The cluster density can be increased this way by more than five fold without changing their size. Above a specific number of cycles, however, the cluster density reaches saturation and a gradual increase in clusters size is observed. Larger clusters correlate with lower saturation density following multiple BLAG cycles. This observation is explained in terms of long range cluster-cluster attraction between clusters already on the substrate and those approaching in the next BLAG cycle. This attraction is more pronounced as the clusters become larger. We have shown that at saturation density, inter-cluster distance can not be smaller than 20 nm for clusters 4 nm in diameter or larger. Employing two consecutive BLAG cycles, characterized by different parameters (metal dosage and buffer layer thickness) result in a bi-modal size distribution. Moreover, it is demonstrated that one can prepare this way co-adsorbed bi-metallic film of e.g. Au and Pd clusters, with specific density and size on the same substrate. The ASW-BLAG procedure is thus expected to introduce a new pathway for tailor made

  11. 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.

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

    DOEpatents

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

    2017-01-24

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

  13. Nonlinear plasmon response in highly excited metallic clusters

    SciTech Connect

    Calvayrac, F.; Reinhard, P.G.; Suraud, E.

    1995-12-15

    We present a dynamical study of the electron response of metallic clusters in the nonlinear regime, as excited, e.g., in ion-cluster interactions or with intense laser beams. We use a quantal time-dependent local-density approximation in axial symmetry to describe the electron dynamics. Ions are either treated in a jellium approximation or explicitly. We find different dynamical regimes depending on the symmetries of the ionic background.

  14. Abundances for globular cluster giants. I. Homogeneous metallicities for 24 clusters

    NASA Astrophysics Data System (ADS)

    Carretta, E.; Gratton, R. G.

    1997-01-01

    We have obtained high resolution, high signal-to-noise ratio CCD echelle spectra of 10 bright red giants in 3 globular clusters (47 Tuc, NGC 6752 and NGC 6397) roughly spanning the whole range of metallicities of the galactic globular cluster system. The analysis of this newly acquired material reveals no significant evidence of star-to-star variation of the [Fe/H] ratio in these three clusters. Moreover, a large set of high quality literature data (equivalent widths from high dispersion CCD spectra) was re-analyzed in an homogeneous and self-consistent way to integrate our observations and derive new metal abundances for more than 160 bright red giants in 24 globular clusters (i.e. about 16% of the known population of galactic globulars). This set was then used to define a new metallicity scale for globular clusters which is the result of high quality, direct spectroscopic data, of new and updated model atmospheres from the grid of \\cite[Kurucz (1992)]{\\ref41}, and of a careful fine abundance analysis; this last, in turn, is based on a common set of both atomic and atmospheric parameters for all the stars examined. Given the very high degree of internal homogeneity, our new scale supersedes the offsets and discrepancies existing in previous attempts to obtain a metallicity scale. The internal uncertainty in [Fe/H] is very small: 0.06 dex (24 clusters) on average, and can be interpreted also as the mean precision of the c luster ranking. Compared to our system, metallicities on the widely used Zinn and West's scale are about 0.10 dex higher for [Fe/H]>-1, 0.23 dex lower for -1<[Fe/H]<-1.9 and 0.11 dex too high for [Fe/H]<-1.9. The non-linearity of the Zinn and West's scale is significant even at 3 sigma level. A quadratic transformation is given to correct older values to the new scale in the range of our calibrating clusters (-2.24 <= [Fe/H]ZW <= -0.51). A minor disagreement is found at low metallicities between the metallicity scale based on field and cluster

  15. STEM characterization of metal clusters in/on oxides

    NASA Astrophysics Data System (ADS)

    Mehraeen, Shareghe

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

  16. Scattering of electrons on metal clusters and fullerenes

    NASA Astrophysics Data System (ADS)

    Gerchikov, Leonid G.; Solov'yov, Andrey V.; Connerade, Jean-Patrick; Greiner, Walter

    1997-09-01

    It is shown that the main contribution to the elastic cross section of fast electrons on metal clusters and fullerenes results from scattering on the frozen cluster potential, which is determined by the electron density distribution of the ground state of the target cluster. The specific shape of the electron distribution in fullerenes and metal clusters manifests itself in the diffraction behaviour of the elastic differential cross section. The analysis of the total elastic cross section dependence upon projectile velocity, the number of atoms in the cluster and its size is provided. The cross section of elastic scattering on a cluster surpasses the sum of the individual scattering cross sections on the equivalent number of isolated atoms. This occurs because of the coherent interaction of the projectile electron with electrons delocalized in the cluster volume. We have demonstrated that collective electron excitations sensitive to the many-electron correlations dominate inelastic scattering. The surface plasmon resonances can be observed in the differential cross section for inelastic scattering. We found a condition for the quadrupole and higher multipole plasmon excitations to contribute relatively little to the electron energy loss spectrum. The results obtained have been compared with experimental data for the electron - fullerene 0953-4075/30/18/013/img7 collision. Reasonable agreement between theoretical and experimental results is reported. We have also demonstrated that plasmon excitations provide the main contribution to the total inelastic cross section over a wide energy range. We have calculated the dependence of the total inelastic cross section on collision energy and compared the result obtained with the experimental data available, giving an interpretation for the plateau region in the cross section as caused by plasmon excitations rather than the cluster fragmentation process. We have shown that the single-particle jellium approximation fails to

  17. 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.

  18. 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.

  19. Reactivity of small transition-metal clusters with CO

    NASA Astrophysics Data System (ADS)

    Andersson, Mats T.; Gronbeck, H.; Holmgren, L.; Rosen, Arne

    1995-09-01

    The size-dependent reactivity of several transition-metal clusters: Con, Nbn, Rhn, and Wn with CO has been investigated in a cluster beam experiment. The reactions occur at single-collision-like conditions and the results are evaluated in terms of the reaction probability (S) in a collision. For all the four metals, clusters with more than 10 - 15 atoms show a high reaction probability, S >= 0.4, rather independent of size. For smaller Nbn and Wn, the reaction probability is lower, and for Nbn, large variations in the CO reactivity are observed in the n equals 8 - 13 range with a distinct minimum at Nb10. Using an LCAO approach within the local spin density approximation (LSDA) the adsorption of molecular CO on Nbn has also been investigated theoretically. The geometries of the bare clusters were optimized and two different sites for CO were investigated. The discussion is based on a detailed analysis of Nb4. The calculations show that compact structures with high coordination numbers are the most stable ones for the bare Nb clusters and hollow sites, also maximizing the coordination, are preferred for CO adsorption. The calculations indicate that a high CO-Nbn bond strength is obtained for clusters with a high density of states close to the Fermi level and for which the HOMO level has a symmetry that allows for an efficient back-donation of electrons to the 2(pi) *-orbital of CO. A particularly low chemisorption energy was calculated for the Nb10 cluster.

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. Metallicity in the Galactic Center: The Arches Cluster

    NASA Astrophysics Data System (ADS)

    Najarro, Francisco; Figer, Donald F.; Hillier, D. John; Kudritzki, Rolf P.

    2004-04-01

    We present a quantitative spectral analysis of five very massive stars in the Arches cluster, located near the Galactic center, to determine stellar parameters, stellar wind properties, and, most importantly, metallicity content. The analysis uses a new technique, presented here for the first time, and uses line-blanketed non-LTE wind/atmosphere models fitted to high-resolution near-infrared spectra of late-type nitrogen-rich Wolf-Rayet stars and OfI+ stars in the cluster. It relies on the fact that massive stars reach a maximum nitrogen abundance that is related to initial metallicity when they are in the WNL phase. We determine the present-day nitrogen abundance of the WNL stars in the Arches cluster to be 1.6% (mass fraction) and constrain the stellar metallicity in the cluster to be solar. This result is invariant to assumptions about the mass-luminosity relationship, the mass-loss rates, and rotation speeds. In addition, from this analysis, we find the age of the Arches cluster to be 2-2.5 Myr, assuming coeval formation.

  5. Hydride encapsulation by molecular alkali-metal clusters.

    PubMed

    Haywood, Joanna; Wheatley, Andrew E H

    2008-07-14

    The sequential treatment of group 12 and 13 Lewis acids with alkali-metal organometallics is well established to yield so-called ''ate' complexes, whereby the Lewis-acid metal undergoes nucleophilic attack to give an anion, at least one group 1 metal acting to counter this charge. However, an alternative, less well recognised, reaction pathway involves the Lewis acid abstracting hydride from the organolithium reagent via a beta-elimination mechanism. It has recently been shown that in the presence of N,N'-bidentate ligands this chemistry can be harnessed to yield a new type of molecular main-group metal cluster in which the abstracted LiH is effectively trapped, with the hydride ion occupying an interstitial site in the cluster core. Discussion focuses on the development of this field, detailing advances in our understanding of the roles of Lewis acid, organolithium, and amine substrates in the syntheses of these compounds. Structure-types are discussed, as are efforts to manipulate cluster geometry and composition as well as hydride-coordination. Embryonic mechanistic studies are reported, as well as attempts to generate hydride-encapsulation clusters under catalytic control.

  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. Atomic resolution electron microscopy of small metal clusters

    NASA Astrophysics Data System (ADS)

    Bovin, J.-O.; Malm, J.-O.

    1991-03-01

    Atomic resolution imaging of cluster structures has been performed with high resolution transmission electron microscopy (HRTEM). Metal particles of the sizes 1 nanometer to tens of nanometers have been surface profile imaged on different supports; like zeolites, cordierite and amorphous carbon. It is shown that organic ligands in Schmid-clusters coordinated to the metal surface are desorbed or destroyed by the electron beam. Dynamic events on the surfaces and in the bulk of small metal particles have been recorded for small crystals of Au, Pt, Rh and Pb and can be classified under three headings; The smaller the crystals are the faster rearrangements of the crystal structure; “clouds” of atoms existing outside some surfaces are involved in extensive structural rearrangements of the surface or crystal surface growth; localized atom hopping on surfaces during crystal growth and desorption also occurs.

  8. Characterization of oxide supported metal carbonyl clusters

    NASA Astrophysics Data System (ADS)

    Evans, John

    The chemisorption of [Ma 3(CO) 1 2] on silica (M = Ru and Os) and alumina (M = Os) has been studied by vibrational and X-ray absorption spectroscopies making close comparisons with model compounds. The results indicate that the first chemisorption species observed has the form [M 3H(CO) 10(O---O)]; the bridging hydride was observed directly for the silica systems as evidenced by the M-H-M bending vibration in the i.r. Also consistent with this structure are the EXAFS analysis of the Ru/SiOz material. This indicated an essentially equilateral ruthenium triangle and coordination to oxygen. The published low frequency Raman data on the Os/Al2Oa product was shown to match most closely with that of model compounds with a bidentate oxygen donor ligand (acac or O2CR). The tethered cluster [O s3H 2(CO) 9(PPh 2C 2H 4SIL)] was found to be a relatively short lived species on a silica surface. Under ambient conditions it reacts further and the i.r., EXAFS and 31P NMR data of this species suggest that the two osmium atoms not coordinated to the tethering phosphine become involved with a bidentate site from the surface.

  9. Spectroscopy at metal cluster surfaces. Final report, September 15, 1993--September 14, 1996

    SciTech Connect

    Duncan, M.A.

    1998-06-01

    The focus of this research program is the study of gas phase metal clusters to evaluate their potential as models for the fundamental interactions present in catalysis. To do this, the authors characterize the chemical bonding present between the component atoms in metal clusters as well as the bonding exhibited by {open_quotes}physisorption{close_quotes} on metal atom or metal cluster surfaces. Electronic spectra, vibrational frequencies and bond dissociation energies are measured for both neutral and ionized clusters with a variety of laser/mass spectrometry techniques. The authors are particularly interested in bimetallic cluster systems, and how their properties compare to those of corresponding pure metal clusters.

  10. Si clusters are more metallic than bulk Si

    NASA Astrophysics Data System (ADS)

    Jackson, Koblar; Jellinek, Julius

    2016-12-01

    Dipole polarizabilities were computed using density functional theory for silicon clusters over a broad range of sizes up to N = 147 atoms. The calculated total effective polarizabilities, which include contributions from permanent dipole moments of the clusters, are in very good agreement with recently measured values. We show that the permanent dipole contributions are most important for clusters in the intermediate size range and that the measured polarizabilities can be used to distinguish between energetically nearly degenerate cluster isomers at these sizes. We decompose the computed total polarizabilities α into the so-called dipole and charge transfer contributions, αp and αq, using a site-specific analysis. When the per-atom values of these quantities are plotted against N-1 /3, clear linear trends emerge that can be extrapolated to the large size limit (N-1 /3→0 ), resulting in a value for α/N of 30.5 bohrs3/atom that is significantly larger than the per-atom polarizability of semiconducting bulk Si, 25.04 bohrs3/atom. This indicates that Si clusters possess a higher degree of metallicity than bulk Si, a conclusion that is consistent with the strong electrostatic screening of the cluster interiors made evident by the analysis of the calculated atomic polarizabilities.

  11. The lifetime of electronic excitations in metal clusters

    NASA Astrophysics Data System (ADS)

    Quijada, M.; Díez Muiño, R.; Echenique, P. M.

    2005-05-01

    Density functional theory and the self-energy formalism are used to evaluate the lifetime of electronic excitations in metal clusters of nanometre size. The electronic structure of the cluster is obtained in the jellium model and spherical symmetry is assumed. Two effects that depend on the size of the clusters are discussed: the change in the number of final states to which the excitation can decay, and the modification in the screened interaction between electrons. For clusters with density parameter rs = 4 and diameter a few nanometres, a lifetime value of {\\approx }5 fs is reached for electronic excitations of {\\approx }1 eV. This value is of the same order of magnitude of that obtained in the bulk limit at the same level of approximation. For smaller clusters, a distinct non-monotonic behaviour of the lifetime as a function of the cluster size is found and the lifetime of excitations of {\\approx }1 eV can vary between 4 and 30 fs.

  12. Metallicity of Globular Cluster M13 from VI CCD Photometry

    NASA Astrophysics Data System (ADS)

    Shon, Young-Jong

    2000-12-01

    From the VI images of M13, obtained by using 2K CCD camera and the BOAO 1.8m telescope, we derive the (V-I)-V CMD of M13. From the shapes of red giant branch, the magnitude of horizontal branch, and the giant branch bump on the constructed CMD, we determined the metallicity of the globular cluster to be 1.74 ~<[Fe/H]~< -1.41. The good agreement between our determination of [Fe/H] and those determined by using other methods implies that the morphology of red giant and horizontal branches on (V-I)-V CMD's can be good indirect metallicity indicators of Galactic globular clusters.

  13. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2015-01-01

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

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

    NASA Astrophysics Data System (ADS)

    Abreu, Marissa Baddick

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

  16. 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

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

    NASA Astrophysics Data System (ADS)

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

    2015-08-01

    Stellar evolution and Galactic evolution have both been greatly advanced by the study of star clusters. In addition the elemental abundance results from clusters have revealed information about Galactic chemical evolution and nucleosynthesis. The cluster, NGC 6791, has a number of bizarre properties that make it especially interesting for comparative cluster studies. It is old (8.3 Gyr) yet metal-rich ([Fe/H] = +0.30). It has a heliocentric distance of 4 kpc and a galactic latitude of +11 degrees which makes it 1 kpc above the galactic plane. Its boxy orbit has a high eccentricity (~0.5) with a perigalactic distance of 3 kpc and an apogalactic distance of 10 kpc. The orbital period of ~130 Myr indicates that it has crossed the Galactic plane several times yet has remained as an intact cluster. We have determined abundances from high-resolution (R = 46,000) Keck/HIRES spectra of turn-off stars in this open cluster NGC 6791. We have a solid determination of [Fe/H] = +0.30 +/-0.02 from measurements of some 40 unblended, unsaturated lines of both Fe I and Fe II in eight turn-off stars. Our O abundances come from the O I triplet near 7774 Å and are corrected for small nLTE effects. We find consistent ratios of [O/Fe]n with a mean of -0.06 +/-0.02, indicating a single population of stars. Our results for the alpha elements [Mg/Fe], [Si/Fe], [Ca/Fe] and [Ti/Fe] are near solar and compare well with those of old, metal-rich field stars. The Fe-peak elements, Cr and Ni, have values of [Cr/Fe] = +0.05 +/-0.02 and [Ni/Fe] = +0.04 +/-0.01. Determinations of upper limits were found for Li by spectrum synthesis; this is consistent with the upper limits in this temperature range for turn-off/subgiant stars in the relatively old, super-metal-rich cluster NGC 6253. We speculate that no stars in NGC 6791 have retained the Li with which they formed.

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

    PubMed

    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.

  19. 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.

  20. 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

  1. 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.

  2. 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.

  3. 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.

  4. 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

  5. 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.

  6. Mixed-metal chalcogenide tetrahedral clusters with an exo-polyhedral metal fragment.

    PubMed

    Yuvaraj, K; Roy, Dipak Kumar; Anju, V P; Mondal, Bijnaneswar; Varghese, Babu; Ghosh, Sundargopal

    2014-12-07

    The reaction of metal carbonyl compounds with group 6 and 8 metallaboranes led us to report the synthesis and structural characterization of several novel mixed-metal chalcogenide tetrahedral clusters. Thermolysis of arachno-[(Cp*RuCO)2B2H6], 1, and [Os3(CO)12] in the presence of 2-methylthiophene yielded [Cp*Ru(CO)2(μ-H){Os3(CO)9}S], 3, and [Cp*Ru(μ-H){Os3(CO)11}], 4. In a similar fashion, the reaction of [(Cp*Mo)2B5H9], 2, with [Ru3(CO)12] and 2-methylthiophene yielded [Cp*Ru(CO)2(μ-H){Ru3(CO)9}S], 5, and conjuncto-[(Cp*Mo)2B5H8(μ-H){Ru3(CO)9}S], 6. Both compounds 3 and 5 can be described as 50-cve (cluster valence electron) mixed-metal chalcogenide clusters, in which a sulfur atom replaces one of the vertices of the tetrahedral core. Compounds 3 and 5 possess a [M3S] tetrahedral core, in which the sulfur is attached to an exo-metal fragment, unique in the [M3S] metal chalcogenide tetrahedral arrangements. All the compounds have been characterized by mass spectrometry, IR, and (1)H, (11)B and (13)C NMR spectroscopy in solution, and the solid state structures were unequivocally established by crystallographic analysis of compounds 3, 5 and 6.

  7. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2014-11-01

    Comproportionation reactions of rare-earth metal trihalides (RX3) 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 ({T3R11}X15-type, P63/m), tetramers ({T4R16}X28{R4} (P-43m), {T4R16}X20 (P42/nnm), {T4R16}X24(RX3)4 (I41/a) and {T4R16}X23 (C2/m) types of structure) and pentamers ({Ru5La14}2Br39, Cc) of {TRr}n (n=2-5) clusters. These oligomers are further enveloped by inner (Xi) as well as outer (Xa) 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 {TR6} octahedra via common edges are more frequent than trimers and pentamers, in which the {TRr} clusters share common faces.

  9. Search for a more adequate test to predict the long-term migration from the PVC gaskets of metal lids into oily foods in glass jars.

    PubMed

    Graubardt, Nadine; Biedermann, Maurus; Fiselier, Katell; Bolzoni, Luciana; Pedrelli, Turno; Cavalieri, Chiara; Simoneau, Cathérine; Grob, Koni

    2009-07-01

    As shown previously, the conventional testing procedure for simulating long-term migration from the gaskets of metal closures into oily foods does not adequately reflect reality. It appears to be impossible to accelerate migration to the extent that the situation at the end of the shelf life of a product can be anticipated in a few days or weeks. Therefore, we investigated whether long-term migration could be extrapolated from migration rates determined for new lids. Jars were kept in the normal upright position. Since heat treatment may have a strong temporary impact, migration during the initial heating for pasteurization or sterilization and storage at ambient temperature were determined using different lids. Commercial products were recalled from sales points throughout Europe to determine the real migration over extended periods of time and for jars with differing histories. This migration was compared with data from the short-term testing to investigate whether an empirical relationship could be derived. The results show that the short-term test enables the comparison of lids and plasticizers in the initial phase of migration, but that long-term extrapolation presupposes more complex kinetic modeling. The results also demonstrate that the legal relevance of "official" testing methods should be reconsidered to avoid conflict when food contact materials comply with migration limits in the test but not in actual application.

  10. Antiferromagnetic resonance in alkali-metal clusters in sodalite

    NASA Astrophysics Data System (ADS)

    Nakano, Takehito; Tsugeno, Hajime; Hanazawa, Atsufumi; Kashiwagi, Takanari; Nozue, Yasuo; Hagiwara, Masayuki

    2013-11-01

    We have performed electron spin resonance (ESR) studies of K43+ and (K3Rb)3+ nanoclusters incorporated in powder specimens of aluminosilicate sodalite at several microwave frequencies between 9 and 34 GHz. The K43+ and (K3Rb)3+ clusters are arrayed in a bcc structure and are known to show antiferromagnetic ordering below the Néel temperatures of TN ≃72 and ≃80 K, respectively, due to the exchange coupling between s electrons confined in the clusters. We have found sudden broadenings of ESR spectra in both samples below TN. The line shape of the spectra below TN is analyzed by powder pattern simulations of antiferromagnetic resonance (AFMR) spectra. The calculated line shapes well reproduce the experimental ones at all the frequencies by assuming a biaxial magnetic anisotropy. We have evaluated extremely small anisotropy fields of approximately 1 Oe indicating that these materials are ideal Heisenberg antiferromagnets. We have also found that the magnetic anisotropy changes from easy-plane type to uniaxial type by changing into a heavier alkali-metal cluster and that the g value shifts to a large value beyond two below TN for K43+ and (K3Rb)3+ nanoclusters. These novel features of K43+ and (K3Rb)3+ nanoclusters incorporated in sodalite are discussed.

  11. 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

  12. Sulphur in the metal poor globular cluster NGC 6397

    NASA Astrophysics Data System (ADS)

    Koch, A.; Caffau, E.

    2011-10-01

    Sulphur (S) is a non-refractory α-element that is not locked into dust grains in the interstellar medium. Thus no correction to the measured, interstellar sulphur abundance is needed and it can be readily compared to the S content in stellar photospheres. Here we present the first measurement of sulphur in the metal poor globular cluster (GC) NGC 6397, as detected in a MIKE/Magellan high signal-to-noise, high-resolution spectrum of one red giant star. While abundance ratios of sulphur are available for a larger number of Galactic stars down to an [Fe/H] of ~ -3.5 dex, no measurements in globular clusters more metal poor than -1.5 dex have been reported so far. We find aNLTE, 3-D abundance ratio of [S/Fe] = +0.52 ± 0.20 (stat.) ± 0.08 (sys.), based on theS I, Multiplet 1 line at 9212.8 Å. This value is consistent with a Galactic halo plateau as typical of other α-elements in GCs and field stars, but we cannot rule out its membership with a second branch of increasing [S/Fe] with decreasing [Fe/H], claimed in the literature, which leads to a large scatter at metallicities around - 2 dex. The [S/Mg] and [S/Ca] ratios in this star are compatible with a Solar value to within the (large) uncertainties. Despite the very large scatter in these ratios across Galactic stars between literature samples, this indicates that sulphur traces the chemical imprints of the other α-elements in metal poor GCs. Combined with its moderate sodium abundance ([S/Na]NLTE = 0.48), the [S/Fe] ratio in this GC extends a global, positive S-Na correlation that is not seen in field stars and might indicate that proton-capture reactions contributed to the production of sulphur in the (metal poor) early GC environments. This paper includes data gathered with the 6.5 m Magellan Telescopes located at Las Campanas Observatory, Chile.

  13. 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)

  14. 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.

  15. Study of globular cluster M53: new variables, distance, metallicity

    NASA Astrophysics Data System (ADS)

    Dékány, I.; Kovács, G.

    2009-11-01

    Aims: We study the variable star content of the globular cluster M53 to compute the physical parameters of the constituting stars and the distance of the cluster. Methods: Covering two adjacent seasons in 2007 and 2008, new photometric data are gathered for 3048 objects in the field of M53. By using the OIS (optimal image subtraction) method and subsequently TFA (trend filtering algorithm), we search for variables in the full sample by using discrete Fourier transformation and box-fitting least squares methods. We select variables based on the statistics related to these methods combined with visual inspection. Results: We identified 12 new variables (2 RR Lyrae stars, 7 short periodic stars - 3 of them are SX Phe stars - and 3 long-period variables). No eclipsing binaries were found in the present sample. Except for the 3 (hitherto unknown) Blazhko RR Lyrae (two RRab and an RRc) stars, no multiperiodic variables were found. We showed that after proper period shift, the PLC (period-luminosity-color) relation for the first overtone RR Lyrae sample tightly follows the one spanned by the fundamental stars. Furthermore, the slope is in agreement with that derived from other clusters. Based on the earlier Baade-Wesselink calibration of the PLC relations, the derived reddening-free distance modulus of M53 is 16.31±0.04 mag, corresponding to a distance modulus of 18.5 mag for the Large Magellanic Cloud. From the Fourier parameters of the RRab stars we obtained an average iron abundance of -1.58± 0.03 (error of the mean). This is ~0.5 dex higher than the overall abundance of the giants as given in the literature and derived in this paper from the three-color photometry of giants. We suspect that the source of this discrepancy (observable also in other, low-metallicity clusters) is the lack of a sufficient number of low-metallicity objects in the calibrating sample of the Fourier method. Table 1 is only available in electronic form at http://www.aanda.org Photometric data

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

    PubMed

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

    2013-10-07

    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.

  17. 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.

  18. Observation of small metal clusters on graphite surface with scanning tunneling microscopy

    NASA Astrophysics Data System (ADS)

    Shen, Jian; Zhu, Changxin; Ma, Zili; Pang, Shijin; Xue, Zengquan

    The motivation for studying the dynamic behavior and morphology of small metal clusters on solid single crystal surface is the desire to understand the physical mechanisms evolving in the initial stages of thin-film growth. In the experiments we have used a scanning tunneling microscope to study the static morphology of small Pt and Ni clusters supported on clean graphite surfaces, as well as the dynamic behaviors of small Pt clusters in an ultrahigh vacuum chamber. The metal deposition was fulfilled by controllable evaporation from ultra-pure superfine metal wires at room temperature in UHV. The STM images of small Pt and Ni clusters on graphite substrates with atomic resolution, as well as a series of STM images reveal some transformation processes of small metal clusters on the solid crystal surfaces, which provide us a better understanding on the procedure of atomic diffusion of metal clusters. All the STM images have been performed at room temperature.

  19. 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.

  20. Monitoring the dissolution process of metals in the gas phase: reactions of nanoscale Al and Ga metal atom clusters and their relationship to similar metalloid clusters.

    PubMed

    Burgert, Ralf; Schnöckel, Hansgeorg

    2008-05-14

    Formation and dissolution of metals are two of the oldest technical chemical processes. On the atomic scale, these processes are based on the formation and cleavage of metal-metal bonds. During the past 15 years we have studied intensively the intermediates during the formation process of metals, i.e. the formation of compounds containing many metal-metal bonds between naked metal atoms in the center and ligand-bearing metal atoms at the surface. We have called the clusters metalloid or, more generally, elementoid clusters. Via a retrosynthetic route, the many different Al and Ga metalloid clusters which have been structurally characterized allow us to understand also the dissolution process; i.e. the cleavage of metal-metal (M-M) bonds. However, this process can be detected much more directly by the reaction of single metal atom clusters in the gas phase under high vacuum conditions. A suitable tool to monitor the dissolution process of a metal cluster in the gas phase is FT-ICR (Fourier transform ion cyclotron resonance) mass spectrometry. Snapshots during these cleavage processes are possible because only every 1-10 s is there a contact between a cluster molecule and an oxidizing molecule (e.g. Cl2). This period is long, i.e. the formation of the primary product (a smaller metal atom cluster) is finished before the next collision happens. We have studied three different types of reaction:(1) Step-by-step fragmentation of a structurally known metalloid cluster allows us to understand the bonding principle of these clusters because in every step only the weakest bond is broken.(2) There are three oxidation reactions of an Al13(-) cluster molecule with Cl2, HCl and O2 central to this review. These three reactions represent three different reaction types, (a) an exothermic reaction (Cl2), (b) an endothermic reaction (HCl), and (c) a kinetically limited reaction based on spin conservation rules (O2).(3) Finally, we present the reaction of a metalloid cluster with Cl2

  1. 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.

  2. Are the Effects of Structure Formation Seen in the Central Metallicity of Galaxy Clusters?

    NASA Astrophysics Data System (ADS)

    Elkholy, Tamer Y.; Bautz, Mark W.; Canizares, Claude R.

    2015-05-01

    A sample of 46 nearby clusters observed with Chandra is analyzed to produce radial density, temperature, entropy, and metallicity profiles, as well as other morphological measurements. The entropy profiles are computed to larger radii than in previous Chandra cluster sample analyses. We find that the iron mass fraction measured in the inner 0.15{{R}500} shows a larger dispersion across the sample of low-mass clusters than it does for the sample of high-mass clusters. We interpret this finding as the result of the mixing of more halos in large clusters than in small clusters, leading to an averaging of the metallicity in the large clusters, and thus less dispersion of metallicity. This interpretation lends support to the idea that the low-entropy, metal-rich gas of merging halos reaches the clusters’ centers, which explains observations of core-collapse supernova product metallicity peaks, and which is seen in hydrodynamical simulations. The gas in these merging halos would have to reach cluster centers without mixing in the outer regions. On the other hand, the metallicity dispersion does not change with mass in the outer regions of the clusters, suggesting that most of the outer metals originate from a source with a more uniform metallicity level, such as during pre-enrichment. We also measure a correlation between the metal content in low-mass clusters and the morphological disturbance of their intracluster medium, as measured by centroid shift. This suggests an alternative interpretation, whereby transitional metallicity boosts in the center of low-mass clusters account for the larger dispersion of their metallicities.

  3. Entrapment of Metal Clusters in MOF Channels by Extended Hooks Anchored at Open Metal Sites

    PubMed Central

    Zheng, Shou-Tian; Zhao, Xiang; Lau, Samuel; Fuhr, Addis; Feng, Pingyun; Bu, Xianhui

    2015-01-01

    Reported here is a new concept and its practical implementation that involves the novel utilization of open metal sites (OMS) for architectural pore design. Specifically, it is shown here that OMS can be used to run extended hooks (isonicotinate in this work) from the framework wall to channel centers to effect the capture of single metal ions or clusters, with the concurrent partition of the large channel space into multiple domains, alteration of host-guest charge relationship and associated guest-exchange properties, as well as the transfer of OMS from the wall to the channel centers. The concept of the extended hook, demonstrated here in the multi-component dual-metal and dual-ligand system, should be generally applicable to a range of framework types. PMID:23826752

  4. Structure and mobility of metal clusters in MOFs: Au, Pd, and AuPd clusters in MOF-74.

    PubMed

    Vilhelmsen, Lasse B; Walton, Krista S; Sholl, David S

    2012-08-01

    Understanding the adsorption and mobility of metal-organic framework (MOF)-supported metal nanoclusters is critical to the development of these catalytic materials. We present the first theoretical investigation of Au-, Pd-, and AuPd-supported clusters in a MOF, namely MOF-74. We combine density functional theory (DFT) calculations with a genetic algorithm (GA) to reliably predict the structure of the adsorbed clusters. This approach allows comparison of hundreds of adsorbed configurations for each cluster. From the investigation of Au(8), Pd(8), and Au(4)Pd(4) we find that the organic part of the MOF is just as important for nanocluster adsorption as open Zn or Mg metal sites. Using the large number of clusters generated by the GA, we developed a systematic method for predicting the mobility of adsorbed clusters. Through the investigation of diffusion paths a relationship between the cluster's adsorption energy and diffusion barrier is established, confirming that Au clusters are highly mobile in the MOF-74 framework and Pd clusters are less mobile.

  5. 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.

  6. Growth of Metal Nano-Clusters on Metal and Oxide Surfaces:. a Rheed Study

    NASA Astrophysics Data System (ADS)

    Zei, M. S.

    The powerful RHEED technique has been demonstrated for the structural determination of the nano-crystals grown on metal and oxide substrate surfaces. Pt was electrochemically deposited onto a Ru(10bar {1}0) electrode, while Pb and cobalt were vapor deposited onto Ag(111) and oxide film/NiAl(100), respectively under UHV conditions. At any Pt coverage, 3D-clusters develop for which the Pt clusters grow in (311) orientation on the Ru(10bar {1}0) substrate surface, where the [01bar {1}] atomic rows of the (311) facet are parallel to the [1bar {2}10] atomic rows of the Ru(10bar {1}0) surface. Due to the strong bonding at Pb/Ag(111) interface, the Pb deposit grows in 2D-islands with a (√ {3} × √ {3})R30o phase (Θ < 1 ML). On the other hand, the β-crystallites of ≈ 1 nm in diameter with inclusion of smaller-sized particles (D < 1 nm) are observed on Θ-Al2O3 after Co deposition at room temperature. Annealing at 900 K Co clusters (≈ 3 nm) grow larger at expense of small particles on thin oxide film on NiAl(100) and become better ordered, where the [110] axis of the Co(001) facet is parallel to the [100] direction of the (001)-oxide surface. The in-plane lattice constant of Co clusters is ca. 4 larger than that of bulk Co, yielding less strain at the (001)-oxide surface. These results demonstrate that both orientation and phase of metal nano-clusters are governed by surface structure of the substrate.

  7. Simulation studies of electroless metal deposition using gold nano-clusters on polymeric surfaces

    NASA Astrophysics Data System (ADS)

    Lively, Mike; Bhattacharya, Aniket; Grabill, Chris; Kuebler, Stephen M.; Dutta, Aniruddha; Heinrich, Helge

    2010-03-01

    We report lattice Monte Carlo (MC) simulation studies of deposition of metallic silver on randomly distributed gold nano clusters on a polymeric surface. The gold nano-clusters act as seeds for further deposition of silver atoms. We assume ballistic growth for the growth of metallic silver on gold clusters but treat the lateral growth (which eventually form bridges among original clusters) with different rules and study the evolving morphologies of the deposited silver atoms as a function of the surface density and the size distribution of gold nano-clusters and compare simulation results with those obtained from TEM studies of the prepared samples.

  8. Social Franchising and a Nationwide Mass Media Campaign Increased the Prevalence of Adequate Complementary Feeding in Vietnam: A Cluster-Randomized Program Evaluation.

    PubMed

    Rawat, Rahul; Nguyen, Phuong Hong; Tran, Lan Mai; Hajeebhoy, Nemat; Nguyen, Huan Van; Baker, Jean; Frongillo, Edward A; Ruel, Marie T; Menon, Purnima

    2017-02-08

    Background: Rigorous evaluations of health system-based interventions in large-scale programs to improve complementary feeding (CF) practices are limited. Alive & Thrive applied principles of social franchising within the government health system in Vietnam to improve the quality of interpersonal counseling (IPC) for infant and young child feeding combined with a national mass media (MM) campaign and community mobilization (CM). Objective: We evaluated the impact of enhanced IPC + MM + CM (intensive) compared with standard IPC + less-intensive MM and CM (nonintensive) on CF practices and anthropometric indicators.Methods: A cluster-randomized, nonblinded evaluation design with cross-sectional surveys (n = ∼500 children aged 6-23.9 mo and ∼1000 children aged 24-59.9 mo/group) implemented at baseline (2010) and endline (2014) was used. Difference-in-difference estimates (DDEs) of impact were calculated for intent-to-treat (ITT) analyses and modified per-protocol analyses (MPAs; mothers who attended the social franchising at least once: 62%).Results: Groups were similar at baseline. In ITT analyses, there were no significant differences between groups in changes in CF practices over time. In the MPAs, greater improvements in the intensive than in the nonintensive group were seen for minimum dietary diversity [DDE: 6.4 percentage points (pps); P < 0.05] and minimum acceptable diet (8.0 pps; P < 0.05). Significant stunting declines occurred in both intensive (7.1 pps) and nonintensive (5.4 pps) groups among children aged 24-59.9 mo, with no differential decline.Conclusions: When combined with MM and CM, an at-scale social franchising approach to improve IPC, delivered through the existing health care system, significantly improved CF practices, but not child growth, among mothers who used counseling services at least once. A greater impact may be achieved with strategies designed to increase service utilization. This trial was registered at clinicaltrials.gov as NCT

  9. 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.

  10. Formation of metallic magnetic clusters in a Kondo-lattice metal: evidence from an optical study.

    PubMed

    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, Tb(2)PdSi(3). 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.

  11. Formation of metallic magnetic clusters in a Kondo-lattice metal: Evidence from an optical study

    NASA Astrophysics Data System (ADS)

    Kovaleva, N. N.; Kugel, K. I.; Bazhenov, A. V.; Fursova, T. N.; Löser, W.; Xu, Y.; Behr, G.; Kusmartsev, F. V.

    2012-11-01

    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.

  12. 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

  13. Surface modification of metal and metal coated nanoparticles to induce clustering

    NASA Astrophysics Data System (ADS)

    Gowda, M. H.; Glembocki, O. J.; Geng, S.; Prokes, S. M.; Garces, N.; Caldwell, J. D.

    2010-08-01

    Surface enhanced Raman scattering (SERS) is a powerful technique for the detection of submonolayer coverage of gold or silver surfaces. The magnitude of the effect and the spectral wavelength of the peak depend on the metal nanoparticles used and its geometry. In this paper we show that the use of chemicals that bind to gold or silver can lead to the clustering of nanoparticles. We used well defined Au nanoparticles in our experiments and add cysteamine to solutions containing the nanoparticles. The plasmonic response of the nanoparticles is measured by transmission Surface Plasmon Resonance (SPR) spectroscopy. We observed significant changes to the SPR spectra that are characteristics of close coupled nanoparticles. The time evolution of these changes indicates the formation of gold nanoparticles clusters. The SERS response of these clustered nanoparticles is observed to red shift from the designed peak wavelength in the green to the red. In addition, the placement of these clusters on dielectric surfaces shifts the SPR even more into the red. The experimental results are supported by calculations of the electromagnetic fields using finite difference methods.

  14. Origin of Selective Adsorption for Metal Nano-clusters on Graphene/Ru(0001)

    NASA Astrophysics Data System (ADS)

    Zhang, Lizhi; Sun, Jiatao; Huang, Li; Pan, Lida; Du, Shixuan; Gao, Hongjun

    2013-03-01

    These years, metal nano-clusters have attracted many interests because of their exciting properties and the potential applications in the catalysis industries, the information storage and so on. Recently, many groups composed the homogenous and size-controlled metal nano-clusters on graphene/Ru(0001) moiré template (G/Ru(0001)). However, the growth modes of these nano-clusters are not very clear. Here, we investigated the mechanism of selective adsorption of some transition metal (TM) atoms on G/Ru(0001) by DFT calculations, and proposed a criterion to estimate the growth mode of TM atoms on G/Ru(0001). We found that both the intensity of sp3 hybridization of carbon atoms in different regions of G/Ru(0001) and the electronic structure of the transition metal atoms influence the adsorption site and the selectivity of metal atoms on G/Ru(0001) at initio stage. According to the electronic structures of some other different G/metal systems, we also predicted that some other G/metal templates can be used to grow the metal nano-clusters. The growth mechanism agrees well with the experimental observations, and provides a way to select suitable metal atoms to form dispersed metal nano-clusters on the G/metal template.

  15. The SLUGGS survey: calcium triplet-based spectroscopic metallicities for over 900 globular clusters

    NASA Astrophysics Data System (ADS)

    Usher, Christopher; Forbes, Duncan A.; Brodie, Jean P.; Foster, Caroline; Spitler, Lee R.; Arnold, Jacob A.; Romanowsky, Aaron J.; Strader, Jay; Pota, Vincenzo

    2012-10-01

    Although the colour distribution of globular clusters in massive galaxies is well known to be bimodal, the spectroscopic metallicity distribution has been measured in only a few galaxies. After redefining the calcium triplet index-metallicity relation, we use our relation to derive the metallicity of 903 globular clusters in 11 early-type galaxies. This is the largest sample of spectroscopic globular cluster metallicities yet assembled. We compare these metallicities with those derived from Lick indices finding good agreement. In six of the eight galaxies with sufficient numbers of high-quality spectra we find bimodality in the spectroscopic metallicity distribution. Our results imply that most massive early-type galaxies have bimodal metallicity as well as colour distributions. This bimodality suggests that most massive early-type galaxies experienced two periods of star formation.

  16. Metal clusters and nanoparticles in dielectric matrices: Formation and optical properties

    NASA Astrophysics Data System (ADS)

    Gladskikh, I. A.; Vartanyan, T. A.

    2016-12-01

    The optical properties of thin dielectric films with metal inclusions and their dependence on thermal and laser annealing are studied experimentally. Metal clusters (Ag, Au, and Cu) in dielectric materials (Al2O3 and SiO2) are obtained by simultaneous vacuum deposition of metal and dielectric on the surface of a corresponding dielectric substrate (sapphire and quartz). It is shown that, depending on the deposited dielectric material, on the weight ratio of deposited metal and dielectric, and on the subsequent thermal treatment, one can obtain different metal structures, from clusters with a small number of atoms to complex dendritic plasmonic structures.

  17. Composite Hybrid Cluster Built from the Integration of Polyoxometalate and a Metal Halide Cluster: Synthetic Strategy, Structure, and Properties.

    PubMed

    Li, Xin-Xiong; Ma, Xiang; Zheng, Wen-Xu; Qi, Yan-Jie; Zheng, Shou-Tian; Yang, Guo-Yu

    2016-09-06

    A step-by-step synthetic strategy, setting up a bridge between the polyoxometalate (POM) and metal halide cluster (MHC) systems, is demonstrated to construct an unprecedented composite hybrid cluster built up from one high-nuclearity cationic MHC [Cu8I6](2+) and eight Anderson-type anionic POMs [HCrMo6O18(OH)6](2-) cross-linked by a tripodal alcohol derivative.

  18. White Dwarfs in the Metal-Rich Open Cluster NGC 6253

    NASA Astrophysics Data System (ADS)

    Jeffery, E. J.; Campos, F.; Romero, A.; Kepler, S. O.

    2017-03-01

    We have obtained 53 images with the g filter and 19 images with the i filter, each with 600-second exposures of the super metal rich open cluster NGC 6253 with the Gemini-South telescope to create deep images of the cluster to observe the cluster white dwarfs for the first time. We will analyze the white dwarf luminosity function to measure the cluster's white dwarf age, search for any anomalous features (as has been seen in the similarly metal rich cluster NGC 6791), and constrain the initial-final mass relation at high metallicities. We present an update on these observations and our program to study the formation of white dwarfs in super high metallicity environments.

  19. 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.

  20. 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.

  1. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2012-11-01

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

  3. Carbon nanotube-metal cluster composites: a new road to chemical sensors?

    PubMed

    Zhao, Q; Buongiorno Nardelli, M; Lu, W; Bernholc, J

    2005-05-01

    Novel carbon nanotube-metal cluster structures are proposed as prototype systems for molecular recognition at the nanoscale. Ab initio calculations show that already the bare nanotube cluster system displays some specificity because the adsorption of ammonia on a carbon nanotube-Al cluster system is easily detected electrically, while diborane adsorption does not provide an electrical signature. Since there are well-established procedures for attaching molecular receptors to metal clusters, these results provide a "proof-of-principle" for the development of novel, high-specificity molecular sensors.

  4. Tetrahedral Clusters of GaMo 4S 8-Type Compounds: A Metal Bonding Analysis

    NASA Astrophysics Data System (ADS)

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

    1995-11-01

    Extended Hückel tight binding calculations have been performed on ligated as well as on ligand-free Mo4 and Mo6 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 M4 tetrahedral units contained in GaM4X8 (M = Mo, Nb, V, Ta; X = S, Se, Te), Mo4S4Y4 (Y = Cl, Br, I). A comparison with the M6 octahedral units of the M Mo6X8 (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 M4 and M6 differ: M-M bond lengths are unaffected by the VEC in the regular M4 cluster, whereas some M-M bond lengths undergo a significant change when the VEC increases in the distorded M6 clusters. Likewise, it is worthy to note that metal d orbitals have a more significant effect in M4 cluster series. In contrast, the metal-ligand covalency induces similar elongations of metal-metal bonds in the two series.

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

    SciTech Connect

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

    2012-11-01

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

  6. Self-Assembly of Silver Metal Clusters of Small Atomicity on Cyclic Peptide Nanotubes.

    PubMed

    Cuerva, Miguel; García-Fandiño, Rebeca; Vázquez-Vázquez, Carlos; López-Quintela, M Arturo; Montenegro, Javier; Granja, Juan R

    2015-11-24

    Subnanometric noble metal clusters, composed by only a few atoms, behave like molecular entities and display magnetic, luminescent and catalytic activities. However, noncovalent interactions of molecular metal clusters, lacking of any ligand or surfactant, have not been seen at work. Theoretically attractive and experimentally discernible, van der Waals forces and noncovalent interactions at the metal/organic interfaces will be crucial to understand and develop the next generation of hybrid nanomaterials. Here, we present experimental and theoretical evidence of noncovalent interactions between subnanometric metal (0) silver clusters and aromatic rings and their application in the preparation of 1D self-assembled hybrid architectures with ditopic peptide nanotubes. Atomic force microscopy, fluorescence experiments, circular dichroism and computational simulations verified the occurrence of these interactions in the clean and mild formation of a novel peptide nanotube and metal cluster hybrid material. The findings reported here confirmed the sensitivity of silver metal clusters of small atomicity toward noncovalent interactions, a concept that could find multiple applications in nanotechnology. We conclude that induced supramolecular forces are optimal candidates for the precise spatial positioning and properties modulation of molecular metal clusters. The reported results herein outline and generalize the possibilities that noncovalent interactions will have in this emerging field.

  7. Sub-nanometre sized metal clusters: from synthetic challenges to the unique property discoveries.

    PubMed

    Lu, Yizhong; Chen, Wei

    2012-05-07

    Sub-nanometre sized metal clusters, with dimensions between metal atoms and nanoparticles, have attracted more and more attention due to their unique electronic structures and the subsequent unusual physical and chemical properties. However, the tiny size of the metal clusters brings the difficulty of their synthesis compared to the easier preparation of large nanoparticles. Up to now various synthetic techniques and routes have been successfully applied to the preparation of sub-nanometre clusters. Among the metals, gold clusters, especially the alkanethiolate monolayer protected clusters (MPCs), have been extensively investigated during the past decades. In recent years, silver and copper nanoclusters have also attracted enormous interest mainly due to their excellent photoluminescent properties. Meanwhile, more structural characteristics, particular optical, catalytic, electronic and magnetic properties and the related technical applications of the metal nanoclusters have been discovered in recent years. In this critical review, recent advances in sub-nanometre sized metal clusters (Au, Ag, Cu, etc.) including the synthetic techniques, structural characterizations, novel physical, chemical and optical properties and their potential applications are discussed in detail. We finally give a brief outlook on the future development of metal nanoclusters from the viewpoint of controlled synthesis and their potential applications.

  8. VizieR Online Data Catalog: Metallicity estimates of M31 globular clusters (Galleti+, 2009)

    NASA Astrophysics Data System (ADS)

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

    2010-04-01

    New empirical relations of [Fe/H] as a function of [MgFe] and Mg2 indices are based on the well-studied galactic globular clusters, complemented with theoretical model predictions for -0.2<=[Fe/H]<=+0.5. Lick indices for M31 clusters from various literature sources (225 clusters) and from new observations by our team (71 clusters) have been transformed into the Trager et al. (2000AJ....119.1645T) system, yielding new metallicity estimates for 245 globular clusters of M31. (3 data files).

  9. 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.

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

    NASA Technical Reports Server (NTRS)

    Walch, Stephen P.

    1987-01-01

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

  11. Hard X-ray-induced optical luminescence via biomolecule-directed metal clusters.

    PubMed

    Osakada, Yasuko; Pratx, Guillem; Sun, Conroy; Sakamoto, Masanori; Ahmad, Moiz; Volotskova, Olga; Ong, Qunxiang; Teranishi, Toshiharu; Harada, Yoshie; Xing, Lei; Cui, Bianxiao

    2014-04-07

    Here, we demonstrate that biomolecule-directed metal clusters are applicable in the study of hard X-ray excited optical luminescence, promising a new direction in the development of novel X-ray-activated imaging probes.

  12. Chemical abundances in Virgo cluster spirals - what drives the environmental dependence of galaxy metallicity?

    NASA Astrophysics Data System (ADS)

    Ellison, Sara; Skillman, Evan; Chung, Aeree

    2009-08-01

    The Virgo cluster is not only our nearest massive cluster, but its dynamical infancy also renders it an ideal laboratory for studies of cluster formation and galaxy evolution. Given the intense interest in Virgo, it is astounding that only 9 out of over 100 spirals in its firmament have chemical abundance measurements. We propose to simultaneously address this gap in our fundamental knowledge of Virgo cluster spirals and investigate how the metallicity and abundance gradients of star forming galaxies are sensitive to environment. Our sample consists of 13 Virgo cluster spiral galaxies, preferentially gas-poor early types, which complement the existing metallicity measurements. We also sample a range of clustercentric distances (0.3 -- 3 Mpc from M87), local densities and include several galaxies which exhibit evidence for interactions with the intra-cluster medium.

  13. 24 electron cluster formulas as the 'molecular' units of ideal metallic glasses

    NASA Astrophysics Data System (ADS)

    Luo, L. J.; Chen, H.; Wang, Y. M.; Qiang, J. B.; Wang, Q.; Dong, C.; Häussler, P.

    2014-08-01

    It is known that ideal metallic glasses fully complying with the Hume-Rothery stabilization mechanism can be expressed by a universal cluster formula of the form [cluster](glue atom)1 or 3. In the present work, it is shown, after a re-examination of the cluster-resonance model, that the number of electrons per unit cluster formula, e/u, is universally 24. The cluster formulas are then the atomic as well as the electronic structural units, mimicking the 'molecular' formulas for chemical substances. The origin of different electron number per atom ratios e/a is related to the total number of atoms Z in unit cluster formula, e/a = 24/Z. The 24 electron formulas are well confirmed in typical binary and ternary bulk metallic glasses.

  14. 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.

  15. Infrared Probes of Metal Cluster Structure and Bonding

    DTIC Science & Technology

    2006-03-01

    corresponding niobium and tantalum analogues of these clusters. Preliminary attempts were conducted for the production of other ligand- coated ...interactions. Prospects are evaluated for macroscopic synthesis of cluster materials and synthesis experiments employing ligand- coating strategies have been...experiments that isolate ligand- coated nanoclusters in solution were conducted using a new laser ablation flowtube reactor. Graduate and undergraduate

  16. Metal Sulfide Cluster Complexes and their Biogeochemical Importance in the Environment

    NASA Astrophysics Data System (ADS)

    Luther, George W.; Rickard, David T.

    2005-10-01

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

  17. 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.

  18. Near-infrared photometry of globular clusters towards the Galactic bulge: observations and photometric metallicity indicators

    NASA Astrophysics Data System (ADS)

    Cohen, Roger E.; Moni Bidin, Christian; Mauro, Francesco; Bonatto, Charles; Geisler, Douglas

    2017-01-01

    We present wide-field JHKS photometry of 16 Galactic globular clusters located towards the Galactic bulge, calibrated on the Two Micron All-Sky Survey photometric system. Differential reddening corrections and statistical field star decontamination are employed for all of these clusters before fitting fiducial sequences to the cluster red giant branches (RGBs). Observed values and uncertainties are reported for several photometric features, including the magnitude of the RGB bump, tip, the horizontal branch (HB) and the slope of the upper RGB. The latest spectroscopically determined chemical abundances are used to build distance- and reddening-independent relations between observed photometric features and cluster metallicity, optimizing the sample size and metallicity baseline of these relations by supplementing our sample with results from the literature. We find that the magnitude difference between the HB and the RGB bump can be used to predict metallicities, in terms of both iron abundance [Fe/H] and global metallicity [M/H], with a precision of better than 0.1 dex in all three near-IR bandpasses for relatively metal-rich ([M/H] ≳ -1) clusters. Meanwhile, both the slope of the upper RGB and the magnitude difference between the RGB tip and bump are useful metallicity indicators over the entire sampled metallicity range (-2 ≲ [M/H] ≲ 0) with a precision of 0.2 dex or better, despite model predictions that the RGB slope may become unreliable at high (near-solar) metallicities. Our results agree with previous calibrations in light of the relevant uncertainties, and we discuss implications for clusters with controversial metallicities as well as directions for further investigation.

  19. 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.

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

    DOE PAGES

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

    2015-06-26

    The lowest-energy structures of neutral and cationic Ge nM (n = 9, 10; M = Si, Li, Mg, Al, Fe, Mn, Pb, Au, Ag, Yb, Pm and Dy) clusters were studied by genetic algorithm (GA) and first-principles calculations. The calculation results show that doping of the metal atoms and Si into 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

  1. 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.

  2. The Photo-Electric Effect in Metallic Clusters

    NASA Astrophysics Data System (ADS)

    Krc, Eugene

    Small clusters of Silver atoms have been observed to yield about 100 times more photo-electrons than crystalline Silver (per unit area of surface) for photons with energy up to 1.5 ev above threshold. I have calculated the yield from Silver and Sodium clusters of up to 55 atoms using a Green's function formalism. A method of successive approximations takes into account the scattering of the electrons by the ion-cores as well as by the surface. The formalism is applied to an independent-electron model with a muffin -tin potential. Each electron feels the incident light wave and the polarization field of all the other electrons computed with the bulk dielectric function. Scattering of the photo-excited electron is included as a final step in the photo-emission process. The cross-sections calculated for Silver clusters are in good agreement with experiment; for Sodium clusters, however, the relevant experimental data are incomplete.

  3. Nucleoside modification with boron clusters and their metal complexes.

    PubMed

    Wojtczak, Blazej A; Olejniczak, Agnieszka B; Lesnikowski, Zbigniew J

    2009-09-01

    General methods for the synthesis of nucleosides modified with borane clusters and metallacarborane complexes are presented. These include: (1) the click chemistry approach based on Huisgen 1,3-dipolar cycloaddition and (2) tethering of the metallacarborane group to the aglycone of a nucleoside via a dioxane ring opening in oxonium metallacarborane derivatives. The proposed methodologies broaden the availability of nucleoside-borane cluster conjugates and open up new areas for their applications.

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

    NASA Astrophysics Data System (ADS)

    Dias, B.; Coelho, P.; Barbuy, B.; Kerber, L.; Idiart, T.

    2010-09-01

    Context. Analysis of ages and metallicities of star clusters in the Magellanic Clouds provide information for studies on the chemical evolution of the Clouds and other dwarf irregular galaxies. Aims: The aim is to derive ages and metallicities from integrated spectra of 14 star clusters in the Small Magellanic Cloud, including a few intermediate/old age star clusters. Methods: Making use of a full-spectrum fitting technique, we compared the integrated spectra of the sample clusters to three different sets of single stellar population models, using two fitting codes available in the literature. Results: We derive the ages and metallicities of 9 intermediate/old age clusters, some of them previously unstudied, and 5 young clusters. Conclusions: We point out the interest of the newly identified as intermediate/old age clusters HW1, NGC 152, Lindsay 3, Lindsay 11, and Lindsay 113. We also confirm the old ages of NGC 361, NGC 419, Kron 3, and of the very well-known oldest SMC cluster, NGC 121. Appendix A is only available in electronic form at http://www.aanda.org

  5. Bonding study in all-metal clusters containing Al4 units.

    PubMed

    Mandado, Marcos; Krishtal, Alisa; Van Alsenoy, Christian; Bultinck, Patrick; Hermida-Ramón, J M

    2007-11-22

    The nature of the bonding of a series of gas-phase all-metal clusters containing the Al4 unit attached to an alkaline, alkaline earth, or transition metal is investigated at the DFT level using Mulliken, quantum theory of atoms in molecules (QTAIM), and Hirshfeld iterative (Hirshfeld-I) atomic partitionings. The characterization of ionic, covalent, and metallic bonds is done by means of charge polarization and multicenter electron delocalization. This Article uses for the first time Hirshfeld-I multicenter indices as well as Hirshfeld-I based atomic energy calculations. The QTAIM charges are in line with the electronegativity scale, whereas Hirshfeld-I calculations display deviations for transition metal clusters. The Mulliken charges fail to represent the charge polarization in alkaline metal clusters. The large ionic character of Li-Al and Na-Al bonds results in weak covalent bonds. On the contrary, scarcely ionic bonds (Be-Al, Cu-Al and Zn-Al) display stronger covalent bonds. These findings are in line with the topology of the electron density. The metallic character of these clusters is reflected in large 3-, 4- and 5-center electron delocalization, which is found for all the molecular fragments using the three atomic definitions. The previously reported magnetic inactivity (based on means of magnetic ring currents) of the pi system in the Al42- cluster contrasts with its large pi electron delocalization. However, it is shown that the different results not necessary contradict each other.

  6. 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)

  7. 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

  8. Generation and characterization of alkali metal clusters in Y-FAU zeolites. An ESR and MAS NMR spectroscopic study

    NASA Astrophysics Data System (ADS)

    Hannus, István; Béres, Attila; Nagy, János B.; Halász, János; Kiricsi, Imre

    1997-06-01

    Charged and neutral metal clusters of various compositions and sizes can be prepared by controlling the alkali metal content by the decomposition of alkali azides and the composition of the host zeolite by ion-exchange. ESR signals show that electron transfer from alkali metal atoms to alkali metal cations does occur, but in a direction opposite to that predicted by the gas-phase thermochemistry. Alkali metal clusters proved to be very active basic catalytic centers.

  9. Ligand-modified metal clusters for gas separation and purification

    DOEpatents

    Okrut, Alexander; Ouyang, Xiaoying; Runnebaum, Ron; Gates, Bruce C.; Katz, Alexander

    2017-02-21

    Provided is an organic ligand-bound metal surface that selects one gaseous species over another. The species can be closely sized molecular species having less than 1 Angstrom difference in kinetic diameter. In one embodiment, the species comprise carbon monoxide and ethylene. Such organic ligand-bound metal surfaces can be successfully used in gas phase separations or purifications, sensing, and in catalysis.

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

    NASA Astrophysics Data System (ADS)

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

    2010-04-01

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

  11. 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.

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

    PubMed

    Staikov, Georgi

    2016-08-07

    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.

  13. 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.

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

    NASA Astrophysics Data System (ADS)

    Wang, La-Mei; Fan, Yong; Wang, Yan; Xiao, Li-Na; Hu, Yang-Yang; Peng, Yu; Wang, Tie-Gang; Gao, Zhong-Min; Zheng, Da-Fang; Cui, Xiao-Bing; Xu, Ji-Qing

    2012-07-01

    Two new organic-inorganic compounds based on polyoxometalates, metal halide clusters and organic ligands: [BW12O40]2[Cu2(Phen)4Cl](H24, 4'-bpy)4·H3O·5H2O (1) and [HPW12O40][Cd2(Phen)4Cl2](4, 4'-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 [BW12O40]5-, metal halide clusters [Cu2(Phen)4Cl]+and 4, 4'-bpy ligands, while compound 2 is constructed from [PW12O40]3-, metal halide cluster [Cd2(Phen)4Cl2]2+ and 4, 4'-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.

  15. Electrochemical Synthesis and Catalytic Properties of Encapsulated Metal Clusters within Zeolitic Imidazolate Frameworks.

    PubMed

    Wang, Pengyuan; Liu, Jia; Liu, Chuanfang; Zheng, Bin; Zou, Xiaoqin; Jia, Mingjun; Zhu, Guangshan

    2016-11-07

    It is very interesting and also a big challenge to encapsulate metal clusters within microporous solids to expand their application diversity. For this target, herein, we present an electrochemical synthesis strategy for the encapsulation of noble metals (Au, Pd, Pt) within ZIF-8 cavities. In this method, metal precursors of AuCl4(2-) , PtCl6(2-) , and PdCl4(2-) are introduced into ZIF-8 crystals during the concurrent crystallization of ZIF-8 at the anode. As a consequence, very small metal clusters with sizes around 1.2 nm are obtained within ZIF-8 crystals after hydrogen reduction; these clusters exhibit high thermal stability, as evident from the good maintenance of their original sizes after a high-temperature test. The catalytic properties of the encapsulated metal clusters within ZIF-8 are evaluated for CO oxidations. Because of the small pore window of ZIF-8 (0.34 nm) and the confinement effect of small pores, about 80 % of the metal clusters (fractions of 0.74, 0.77, and 0.75 for Au, Pt, and Pd in ZIF-8, respectively) retain their catalytic activity after exposure to the organosulfur poison thiophene (0.46 nm), which is in contrast to their counterparts (fractions of 0.22, 0.25, and 0.20 for Au, Pt, and Pd on the SiO2 support). The excellent performances of metal clusters encapsulated within ZIF-8 crystals give new opportunities for catalytic reactions.

  16. Structure and Dynamics in Metal-Containing Clusters

    DTIC Science & Technology

    2010-03-11

    increases but the basic nature of the vibration remains constant. A surprising development followed from this new spectroscopic study of titanium ...establishes that titanium -carbide nanocrystals are seeds present in the early phases of the formation of stardust. Titanium -carbide crystallites are actually...multi-metal sandwiches (M3-coronene2). In some species (e.g., iron with C6o or niobium with coronene), the metal inserts into the organic ring system

  17. Spherical Clusters of Simple Metals: Madelung Energies and Structure.

    DTIC Science & Technology

    1986-06-01

    crystalline structures remain lower than those of the optimal structures even at cluster sizes of more than 90 atoms. Also the calculations of the...differ from crystalline structures up to clus- ter sizes of hundreds of atoms. Acknowledgements - The author would like to thank N.W. Ashcroft, J.W

  18. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

    We obtained deep near-infrared images of Sh 2-208, one of the lowest-metallicity H ii regions in the Galaxy, [O/H] = -0.8 dex. We detected a young cluster in the center of the H ii region with a limiting magnitude of K = 18.0 mag (10σ), which corresponds to a mass detection limit of ˜0.2 M⊙. This enables the comparison of star-forming properties under low metallicity with those of the solar neighborhood. We identified 89 cluster members. From the fitting of the K-band luminosity function (KLF), the age and distance of the cluster are estimated to be ˜0.5 Myr and ˜4 kpc, respectively. The estimated young age is consistent with the detection of strong CO emission in the cluster region and the estimated large extinction of cluster members (AV ˜ 4-25 mag). The observed KLF suggests that the underlying initial mass function (IMF) of the low-metallicity cluster is not significantly different from canonical IMFs in the solar neighborhood in terms of both high-mass slope and IMF peak (characteristic mass). Despite the very young age, the disk fraction of the cluster is estimated at only 27% ± 6%, which is significantly lower than those in the solar metallicity. Those results are similar to Sh 2-207, which is another star-forming region close to Sh 2-208 with a separation of 12 pc, suggesting that their star-forming activities in low-metallicity environments are essentially identical to those in the solar neighborhood, except for the disk dispersal timescale. From large-scale mid-infrared images, we suggest that sequential star formation is taking place in Sh 2-207, Sh 2-208, and the surrounding region, triggered by an expanding bubble with a ˜30 pc radius.

  20. 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.

  1. Size and Charge Distributions of Stable Clusters Formed in Ion Sputtering of Metals

    NASA Astrophysics Data System (ADS)

    Matveev, V. I.; Kapustin, S. N.

    2016-10-01

    A theory of ion sputtering of metals in the form of neutral and charged clusters with their subsequent fragmentation into the stable state is developed. The theory is based on simple physical assumptions and is in good agreement with experiment. Results are presented in the form of formulas convenient for practical application. As an example, calculations of the total yield of stable neutral and charged clusters of silver, indium, and niobium are carried out.

  2. METAL DEFICIENCY IN CLUSTER STAR-FORMING GALAXIES AT Z = 2

    SciTech Connect

    Valentino, F.; Daddi, E.; Strazzullo, V.; Gobat, R.; Bournaud, F.; Juneau, S.; Zanella, A.; Renzini, A.; Arimoto, N.

    2015-03-10

    We investigate the environmental effect on the metal enrichment of star-forming galaxies (SFGs) in the farthest spectroscopically confirmed and X-ray-detected cluster, CL J1449+0856 at z = 1.99. We combined Hubble Space Telescope/WFC3 G141 slitless spectroscopic data, our thirteen-band photometry, and a recent Subaru/Multi-object InfraRed Camera and Spectrograph (MOIRCS) near-infrared spectroscopic follow-up to constrain the physical properties of SFGs in CL J1449+0856 and in a mass-matched field sample. After a conservative removal of active galactic nuclei, stacking individual MOIRCS spectra of 6 (31) sources in the cluster (field) in the mass range 10 ≤ log(M/M{sub ⊙}) ≤ 11, we find a ∼4σ lower [N ii]/Hα ratio in the cluster than in the field. Stacking a subsample of 16 field galaxies with Hβ and [O iii] in the observed range, we measure an [O iii]/Hβ ratio fully compatible with the cluster value. Converting these ratios into metallicities, we find that the cluster SFGs are up to 0.25 dex poorer in metals than their field counterparts, depending on the adopted calibration. The low metallicity in cluster sources is confirmed using alternative indicators. Furthermore, we observe a significantly higher Hα luminosity and equivalent width in the average cluster spectrum than in the field. This is likely due to the enhanced specific star formation rate; even if lower dust reddening and/or an uncertain environmental dependence on the continuum-to-nebular emission differential reddening may play a role. Our findings might be explained by the accretion of pristine gas around galaxies at z = 2 and from cluster-scale reservoirs, possibly connected with a phase of rapid halo mass assembly at z > 2 and of a high galaxy merging rate.

  3. 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.

  4. CO adsorption on transition metal clusters: Trends from density functional theory

    NASA Astrophysics Data System (ADS)

    Zeinalipour-Yazdi, Constantinos D.; Cooksy, Andrew L.; Efstathiou, Angelos M.

    2008-05-01

    This work reports for the first time the trends for carbon monoxide (CO) chemisorption on transition metal clusters present in supported metal catalysts. In particular, the energetic, structural and infrared adsorption characteristics of linearly (atop) CO adsorbed on transition metal nano-clusters of less than 10 Å in size were explored. Spin-unrestricted density functional theory (DFT) calculations were employed to explore the trends of CO adsorption energy (AM-CO) and C-O vibrational frequency (νCO) for clusters composed of Ni, Cu, Ru, Rh, Pd, Ag, Ir, Pt and Au. The effects of the transition metal electronic structure onto the adsorption energy of CO and the vibrational stretching frequency of C-O, and how these chemical parameters can be correlated to the catalytic activity of transition supported metal catalysts that involve the adsorption, surface diffusion, and C-O bond dissociation elementary steps in heterogeneous catalytic surface reactions, are discussed. Our findings show that an increase of the electronic d-shell occupancy and the principal quantum number (n) in transition metals causes an increase in the vibrational stretching frequency of the C-O bond. This trend is inconsistent with the classical Blyholder model for the metal-carbonyl bond.

  5. 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.

  6. 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.

  7. 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

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

    NASA Astrophysics Data System (ADS)

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

    2007-02-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2013-02-01

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

  10. Energies, charges, and sizes of clusters under ion sputtering of a metal

    SciTech Connect

    Matveev, V. I. Kochkin, S. A.

    2010-04-15

    A theory of ion sputtering of a metal in the form of neutral and singly charged clusters with a number of atoms of N {>=} 5 has been developed. This theory is based on simple physical assumptions and agrees well with experiment. The results are presented in the form of expressions convenient for practical use. The energy spectra of clusters, charge distributions, ionization coefficients, and total yields of neutral and singly charged clusters at different target temperatures are calculated in terms of the proposed theory as an example.

  11. Heating and ionization of metal clusters in the field of an intense femtosecond laser pulse

    NASA Astrophysics Data System (ADS)

    Kostenko, O. F.; Andreev, N. E.

    2007-06-01

    Inverse bremsstrahlung heating and thermal electron-impact ionization of a metal cluster are analyzed with account for the spatial structure of the electromagnetic field. It is shown that, for a femtosecond IR radiation pulse with an intensity of ˜1018 W/cm2 and for an iron cluster with an optimum radius of ˜25 nm, the electron temperature is higher than 1 keV. In this case, the L shell of the ions is highly stripped. The X-ray bremsstrahlung yield from clusters with a radius greater than the skin depth is estimated.

  12. The N-heterocyclic carbene chemistry of transition-metal carbonyl clusters.

    PubMed

    Cabeza, Javier A; García-Álvarez, Pablo

    2011-11-01

    In the last decade, chemists have dedicated many efforts to investigate the coordination chemistry of N-heterocyclic carbenes (NHCs). Although most of that research activity has been devoted to mononuclear complexes, transition-metal carbonyl clusters have not escaped from these investigations. This critical review, which is focussed on the reactivity of NHCs (or their precursors) with transition-metal carbonyl clusters (mostly are of ruthenium and osmium) and on the transformations underwent by the NHC-containing species initially formed in those reactions, shows that the polynuclear character of these metallic compounds or, more precisely, the close proximity of one or more metal atoms to that which is or can be attached to the NHC ligand, is responsible for reactivity patterns that have no parallel in the NHC chemistry of mononuclear complexes (74 references).

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

    SciTech Connect

    Wang, Zhe; Daemen, Luke L.; Cheng, Yongqiang; Mamontov, Eugene; Bonnesen, Peter V.; Hong, Kunlun; Ramirez-Cuesta, Anibal J.; Yin, Panchao

    2016-08-19

    Encapsulation behavior, as well as the presence of internal catalytically-active sites, has been spurring the applications of a 3 nm hollow spherical metal oxide cluster {Mo132} as an encapsulation host and a nano-reactor. Due to its well-defined and tunable cluster structures, and nano-scaled internal void space comparable to the volumes of small molecules, this cluster provides a good model to study the dynamics of materials under ultra-confinement. Neutron scattering studies suggest that bulky internal ligands inside the cluster show slower and limited dynamics compared to their counterparts in the bulk state, revealing the rigid nature of the skeleton of the internal ligands. Furthermore, NMR studies indicate that the rigid internal ligands that partially cover the interfacial pore on the molybdenum oxide shells are able to block some large guest molecules from going inside the capsule cluster, which provides a convincing protocol for size-selective encapsulation and separation.

  14. S-P coupling induced unusual open-shell metal clusters.

    PubMed

    Cheng, Shi-Bo; Berkdemir, Cuneyt; Melko, Joshua J; Castleman, A W

    2014-04-02

    Metal clusters featuring closed supershells or aromatic character usually exhibit remarkably enhanced stability in their cluster series. However, not all stable clusters are subject to these fundamental constraints. Here, by employing photoelectron imaging spectroscopy and ab initio calculations, we present experimental and theoretical evidence on the existence of unexpectedly stable open-shell clusters, which are more stable than their closed-shell and aromatic counterparts. The stabilization of these open-shell Al-Mg clusters is proposed to originate from the S-P molecular orbital coupling, leading to highly stable species with increased HOMO-LUMO gaps, akin to s-p hybridization in an organic carbon atom that is beneficial to form stable species. Introduction of the coupling effect highlighted here not only shows the limitations of the conventional closed-shell model and aromaticity but also provides the possibility to design valuable building blocks.

  15. 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

  16. 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.

  17. 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.

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

    PubMed

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

    2014-07-21

    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.

  19. The Effect of Metallicity on Surface Lithium Abundance in Hyades-Aged Open Clusters

    NASA Astrophysics Data System (ADS)

    Gayetsky, Lisa; Cummings, J.; Deliyannis, C. P.; Steinhauer, A.; James, D.; Sarajedini, A.

    2007-12-01

    Two of the most important predictions from standard stellar evolution theory about the lithium depletion of solar-type F and G dwarfs are that it occurs primarily during the pre-main sequence and that it depends on metallicity. Abundant evidence from star clusters shows that Li depletion does indeed occur during the pre-main sequence, but then also continues during the main sequence, perhaps due to the effects of (non-standard) rotationally-induced or wave-induced mixing. However, little is known about whether Li depletion depends on metallicity. To test the predicted dependence of standard Li depletion on metallicity, a program has begun that compares the Li-Teff relation in Hyades-aged clusters of different metallicities. Here, we present high resolution results from WIYN/Hydra observations of IC 4756. We find, first, that our data qualitatively support the prediction that stars with higher metallicity have depleted more Li. Second, if a reasonable adjustment is made to the (unknown) initial cluster Li abundances that is consistent with knowledge of Galactic Li production from the field dwarf Li-Fe relation, then our data are also in good quantitative agreement with the metallicity-dependence of the Li depletion from standard theory. This work has been supported by the National Science Foundation under grants AST-0452975 and AST-0206202.

  20. Negative ion photoelectron spectroscopic studies of transition metal cluster

    NASA Astrophysics Data System (ADS)

    Marcy, Timothy Paul

    The studies reported in this thesis were performed using a negative ion photoelectron spectrometer consisting of a cold cathode DC discharge ion source, a flowing afterglow ion-molecule reactor, a magnetic sector mass analyzer, an argon ion laser for photodetachment and a hemispherical electron kinetic energy analyzer and microchannel plate detector for photoelectron spectrum generation. The 476.5 nm (2.601 eV), 488.0 nm (2.540 eV) and 514.5 nm (2.410 eV) negative ion photoelectron spectra of VMn are reported and compared to the previously studied spectra of isoelectronic Cr2.1 The photoelectron spectra are remarkably similar to those of Cr2 in electron affinity and vibrational frequencies. The 488.0 nm photoelectron spectra and electron affinities of Nb n- (n = 1 - 9) are reported with discussion of observed vibrational structure. There are transitions to several electronic states of Nb2 in the reported spectra with overlapping vibrational progressions. The spectra of Nb3, Nb4 and Nb6 show partially resolved vibrational structure in the transitions to the lowest observed electronic state of each cluster. There is a single distinct active vibrational mode in the transition to the ground state of Nb8. Spin-orbit energies of Nb- are also reported. The 488.0 nm negative ion photoelectron spectra of Nb3H(D) are reported and compared to those of Nb3. There is a single vibrational mode active in the spectra of Nb3H(D) which is very similar to the most distinct mode active in the spectrum of Nb3. The 488.0 nm photoelectron spectra of the NbxCyH(D) y- (x = 1, 2, 3, y = 2, 4, 6) dehydrogenated products of the reactions of ethylene with niobium cluster anions are reported. Temperature studies of some of these species give evidence for the presence of multiple isomers of each molecule in the ion beam. The spectra of NbC6H(D) 6 are identical to those obtained from the reactions of benzene with niobium clusters and indicate that benzene is being formed from ethylene in the flow

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

    PubMed

    Chakraborty, Debdutta; Chattaraj, Pratim Kumar

    2016-07-28

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

  2. 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.

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

    SciTech Connect

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

    1995-05-01

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

  4. 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.

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

    PubMed

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

    2013-02-28

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

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

    SciTech Connect

    Hsieh, H.; Averback, R.S. ); Sellers, H. ); Flynn, C.P. )

    1992-02-15

    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 {approx}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.

  7. Hydration process of alkaline-earth metal atoms in water clusters

    NASA Astrophysics Data System (ADS)

    Okai, Nobuhiro; Ishikawa, Haruki; Fuke, Kiyokazu

    2005-10-01

    Ionization potentials (IPs) of water clusters containing alkaline-earth metal atoms are measured by a photoionization threshold method to examine the hydration process of the metal atoms in clusters. IPs of Mg(H 2O) n and Ca(H 2O) n are found to decrease with increasing n and become constant at 3.18 eV for n ⩾ 9 and n ⩾ 8, respectively. The observed constant IP agrees with an estimated photoelectric threshold (3.2 eV) of bulk ice. From the comparison with the results on the theoretical calculations as well as the IPs for alkali atom-water clusters, the anomalous size dependence of IPs is ascribed to the formation of an ion-pair state.

  8. 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.

  9. 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.

  10. Metal Chalcogenide Clusters with Closed Electronic Shells and the Electronic Properties of Alkalis and Halogens.

    PubMed

    Chauhan, Vikas; Reber, Arthur C; Khanna, Shiv N

    2017-02-08

    Clusters with filled electronic shells and a large gap between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) are generally energetically and chemically stable. Enabling clusters to become electron donors with low ionization energies or electron acceptors with high electron affinities usually requires changing the valence electron count. Here we demonstrate that a metal cluster may be transformed from an electron donor to an acceptor by exchanging ligands while the neutral form of the clusters has closed electronic shells. Our studies on Co6Te8(PEt3)m(CO)n (m + n = 6) clusters show that Co6Te8(PEt3)6 has a closed electronic shell and a low ionization energy of 4.74 eV, and the successive replacement of PEt3 by CO ligands ends with Co6Te8(CO)6 exhibiting halogen-like behavior. Both the low ionization energy Co6Te8(PEt3)6 and high electron affinity Co6Te8(CO)6 have closed electronic shells marked by high HOMO-LUMO gaps of 1.24 and 1.39 eV, respectively. Further, the clusters with an even number of ligands favor a symmetrical placement of ligands around the metal core.

  11. 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.

  12. 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.

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

    NASA Astrophysics Data System (ADS)

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

    1991-04-01

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

  14. 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.

  15. Electronic charging of non-metallic clusters: size-selected Mo(x)S(y) clusters supported on an ultrathin alumina film on NiAl(110).

    PubMed

    Zhou, Jing; Zhou, Jia; Camillone, Nicholas; White, Michael G

    2012-06-14

    Two photon photoemission was used to investigate the interfacial charge transfer for size-selected Mo(x)S(y) (x/y: 2/6, 4/6, 6/8, 7/10) clusters deposited on an ultrathin alumina film prepared on a NiAl(110) surface. The local work function of the surface increases with increasing cluster coverage, which is unexpected for charge transfer resulting from the formation of Mo-O bonds between the clusters and the alumina surface. By analogy with Au atoms and clusters on metal-supported ultrathin oxide films, we invoke electron tunneling from the NiAl substrate to explain the charge transfer to the Mo(x)S(y) clusters. Electron tunneling is favored by the large electron affinities of the Mo(x)S(y) clusters and the relatively low work function induced by the presence of the alumina film. The interfacial dipole moments derived from coverage-dependent measurements are cluster dependent and reflect differences in Mo(x)S(y) cluster structure and surface bonding. These results extend previous observations of electronic charging to non-metallic clusters, specifically, metal sulfides, and suggest a novel way to modify the electronic structure and reactivity of nanocatalysts for heterogeneous chemistry.

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

    PubMed

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

    2016-11-15

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

  17. 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.

  18. 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).

  19. 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.

  20. Cluster chemical reactions at mineral–liquid interface in metal leaching by photo-electroactive water-and-gas emulsions

    NASA Astrophysics Data System (ADS)

    Sekisov, AG

    2017-02-01

    Possibility of cluster (inter-cluster) reactions at the interface of mineral and liquid phases in leaching of metals mainly in dispersed cluster form by photo-electrically activated water-and-gas emulsions is theoretically evaluated. The governing role of active clusters of water and clustered hydrate envelopes generated under dissolution of active oxygen forms is determined. The scope of the study covers possible processes of transformation of clustered gold in mineral substance under direct interaction with the components of the active water-and-gas emulsions.

  1. LOW-METALLICITY YOUNG CLUSTERS IN THE OUTER GALAXY. I. Sh 2-207

    SciTech Connect

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

    2016-03-15

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

  2. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2002-02-01

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

  4. 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.

  5. Catalytic dehydrogenation of alcohol over solid-state molybdenum sulfide clusters with an octahedral metal framework

    SciTech Connect

    Kamiguchi, Satoshi; Okumura, Kazu; Nagashima, Sayoko; Chihara, Teiji

    2015-12-15

    Graphical abstract: - Highlights: • Solid-state molybdenum sulfide clusters catalyzed the dehydrogenation of alcohol. • The dehydrogenation proceeded without the addition of any oxidants. • The catalytic activity developed when the cluster was activated at 300–500 °C in H{sub 2}. • The Lewis-acidic molybdenum atom and basic sulfur ligand were catalytically active. • The clusters function as bifunctional acid–base catalysts. - Abstract: Solid-state molybdenum sulfide clusters with an octahedral metal framework, the superconducting Chevrel phases, are applied to catalysis. A copper salt of a nonstoichiometric sulfur-deficient cluster, Cu{sub x}Mo{sub 6}S{sub 8–δ} (x = 2.94 and δ ≈ 0.3), is stored in air for more than 90 days. When the oxygenated cluster is thermally activated in a hydrogen stream above 300 °C, catalytic activity for the dehydrogenation of primary alcohols to aldehydes and secondary alcohols to ketones develops. The addition of pyridine or benzoic acid decreases the dehydrogenation activity, indicating that both a Lewis-acidic coordinatively unsaturated molybdenum atom and a basic sulfur ligand synergistically act as the catalytic active sites.

  6. MD simulation of cluster-surface impacts for metallic phases: soft landing, droplet spreading and implantation

    NASA Astrophysics Data System (ADS)

    Kholmurodov, Kholmirzo; Puzynin, Igor; Smith, William; Yasuoka, Kenji; Ebisuzaki, Toshikazu

    2001-11-01

    An optimized version of the DL_POLY molecular dynamics simulation code [K. Kholmurodov, W. Smith, K. Yasuoka, T. Ebisuzaki, Comput. Phys. Commun. 125 (2000) 167-192] has been used to study the cluster-surface impact processes for metallic phases. The interaction of an energetic cluster of atoms with a solid surface has been investigated using the Finnis-Sinclair many-body potential. The characteristics of the cluster-surface collisions were studied in a wide range of the cluster impact energies ( Einc=0.035-3.5 eV/atom). Modification of the surface, exposed to the cluster-beams, was studied by monitoring the molecular dynamics configurations of the system in real time. The density and temperature distributions in the system under the energetic irradiations has been investigated in detail. The three major channels of the impact yield (viz., soft landing, droplet spreading and implantation) were distinguished and estimated. Based on the density and temperature distributions data the low energy cluster-surface impact has been analyzed and a novel interpretation of droplet spreading process is given.

  7. 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.

  8. 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.

  9. 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

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

    NASA Astrophysics Data System (ADS)

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

    2014-05-01

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

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

    SciTech Connect

    Lentz, Nicholas B.

    2007-01-01

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

  12. Thermal Stabilization of Metal-Organic Framework-Derived Single-Site Catalytic Clusters through Nanocasting.

    PubMed

    Malonzo, Camille D; Shaker, Sammy M; Ren, Limin; Prinslow, Steven D; Platero-Prats, Ana E; Gallington, Leighanne C; Borycz, Joshua; Thompson, Anthony B; Wang, Timothy C; Farha, Omar K; Hupp, Joseph T; Lu, Connie C; Chapman, Karena W; Myers, Jason C; Penn, R Lee; Gagliardi, Laura; Tsapatsis, Michael; Stein, Andreas

    2016-03-02

    Metal-organic frameworks (MOFs) provide convenient systems for organizing high concentrations of single catalytic sites derived from metallic or oxo-metallic nodes. However, high-temperature processes cause agglomeration of these nodes, so that the single-site character and catalytic activity are lost. In this work, we present a simple nanocasting approach to provide a thermally stable secondary scaffold for MOF-based catalytic single sites, preventing their aggregation even after exposure to air at 600 °C. We describe the nanocasting of NU-1000, a MOF with 3 nm channels and Lewis-acidic oxozirconium clusters, with silica. By condensing tetramethylorthosilicate within the NU-1000 pores via a vapor-phase HCl treatment, a silica layer is created on the inner walls of NU-1000. This silica layer provides anchoring sites for the oxozirconium clusters in NU-1000 after the organic linkers are removed at high temperatures. Differential pair distribution functions obtained from synchrotron X-ray scattering confirmed that isolated oxozirconium clusters are maintained in the heated nanocast materials. Pyridine adsorption experiments and a glucose isomerization reaction demonstrate that the clusters remain accessible to reagents and maintain their acidic character and catalytic activity even after the nanocast materials have been heated to 500-600 °C in air. Density functional theory calculations show a correlation between the Lewis acidity of the oxozirconium clusters and their catalytic activity. The ability to produce MOF-derived materials that retain their catalytic properties after exposure to high temperatures makes nanocasting a useful technique for obtaining single-site catalysts suitable for high-temperature reactions.

  13. A Search For Planets in the Metal-Rich Open Cluster Praesepe

    NASA Astrophysics Data System (ADS)

    White, Russel

    The most promising way to distinguish between competing theories of planet formation and subsequent migration is to find and determine the basic properties of short period (< 1 yr) planets with well-determined ages younger than 1 billion years. Open clusters are the most promising locations to do this, but disappointingly no main sequence open cluster stars are known to harbor planets. This is primarily a consequence of most clusters being too distant for precise radial velocity measurements at visual wavelength. A better determined frequency of planets within open clusters would also clarify if this environment inhibits their formation, as has recently been suggested. If confirmed, that would imply that most stars will not have planets since most stars are believed to form in dense clusters. Here we request funding to support a 2-year program to search for radial velocity planets in the 600 Myr Praesepe open cluster. Praesepe is the most metal rich open cluster within 1000 pc of the sun. Based on known planet frequency - metallicity correlations, its high metallicity suggests a planet frequency enhanced by nearly a factor of 4 relative to sun- like stars; approximately 1 in 20 of its members should harbor a short period (3-10 day) hot Jupiter-like planet, and 1 in 400 of its members should have a transiting planet. The observations will be carried out using the Mayall 4-m/Echelle and Keck/HIRES facilities; nearly 100 Praesepe FGK stars will be surveyed over a 1+ year baseline. Precise radial velocities will be obtained using telluric features as a wavelength reference. We have demonstrated this technique achieves a precision of at least 50 m/s, and anticipate a final precision of 10 m/s, similar to what has been previously achieved. This precision and proposed temporal sampling will enable us to confidently identify nearly all Jupiter-sized planets with periods less than ~1 yr. The discovery of the first planets orbiting dwarf stars within an open cluster with a

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

    NASA Astrophysics Data System (ADS)

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

    2017-03-01

    We report on the composition of turn-off stars in the intriguing open cluster, NGC 6791, which is old, but super-metal-rich using Keck/HIRES spectra. We find [Fe/H] = +0.30 +/-0.02[O/Fe]n -0.06 +/-0.02,[Mg/Fe], [Si/Fe], [Ca/Fe], and [Ti/Fe] near solar and the two Fe-peak elements, Cr and Ni, are consistent with Fe.

  15. Precipitation of Ordered Phases in Metallic Solid Solutions: A Synergistic Clustering and Ordering Process (Preprint)

    DTIC Science & Technology

    2011-07-01

    of such concurrent clustering and ordering processes in metallic solid solutions including Fe-Al [4], Ni-Al [5,6], Ni-Ti [7,8], and Cu -Ti [9,10...ordering reaction to take place. The proposition is that since the Cu -15Ni-8Sn alloy composition cannot undergo congruent ordering, spinodal...interpretation of their results. For example, Wendt and Hassan noted from [14] that in samples of the quenched alloy that have been briefly aged

  16. 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.

  17. 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.

  18. 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.

  19. Electronic structure and stability of clusters, especially of alkali metals and carbon

    NASA Astrophysics Data System (ADS)

    March, N. H.

    1993-12-01

    The electronic structure of alkali metal atom clusters of various sizes is first discussed, using a spherically averaged pseudopotential model. The main technique employed is density functional theory, and a connection is established with predictions about dissociation energy from the theory of the inhomogeneous electron gas. This latter theory is then invoked explicitly to discuss the barrier to fission for doubly charged alkali metal atom clusters. In the case of asymmetric fission, comparison is made with experiment following the study of Garcias [F. Garcias, J.A. Alonso, J.M. Lopez and M. Barranco, Phys. Rev. B, 43 (1991) 9459], while for symmetric fission a connection is again made between fission barrier and concepts which follow from the general theory of the inhomogeneous electron gas. Finally, and more briefly, both density functional calculations and quantum-chemical studies of carbon clusters are referred to. After a summary of the work of Adamowicz on small linear C clusters [L. Adamowicz, J. Chem. Phys., 94 (1991) 1241], results on C 60 and its singly and doubly charged anions, and on (C 60) 2, are summarized, the potential relevance to alkali doped buckminsterfullerene superconductivity being emphasized as an important direction for future work.

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

    SciTech Connect

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

    2011-04-20

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

  1. 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.

  2. Cluster synthesis via ligand-arrested solid growth: triethylphosphine-capped fragments of binary metal chalcogenides.

    PubMed

    Crawford, Nathan R M; Hee, Allan G; Long, Jeffrey R

    2002-12-18

    A new and potentially highly generalizable technique for synthesizing molecular fragments of binary solids is demonstrated through application to selected transition metal chalcogenides. Employing a metal atom reactor, the solids are evaporated with a tungsten heating boat, and the resulting vapor is co-condensed with triethylphosphine. Major cluster products identified from a survey of first-row transition metal sulfides include the known species Cr6S8(PEt3)6, Co6S8(PEt3)6, and Cu12S6(PEt3)8, as well as the unprecedented species Fe4S4(PBun3)4, Ni4S4(PEt3)8, and Cu6S4(PEt3)4. Reactions utilizing Cu2Se resulted in the much larger clusters Cu26Se13(PEt3)14 and Cu70Se35(PEt3)21. The core of the former has a Th-symmetry structure featuring a body-centered icosahedron of Se2- anions, while the latter adopts a triangular structure based on three hexagonal closest packed layers of Se2- anions. In both cases, the Cu+ cations occupy distorted tetrahedral or trigonal planar sites similar to those encountered in Cu2Se; however, emergence of the face-centered cubic anion lattice of the bulk solid is not yet apparent at these cluster sizes.

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

    PubMed

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

    2014-09-01

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

  4. First Detection of a Cluster-scale Gradient in the ISM metallicity of the Star-forming Galaxies

    NASA Astrophysics Data System (ADS)

    Gupta, Anshu; Yuan, Tiantian; Tran, Kim-Vy; Martizzi, Davide; Taylor, Philip; Kewley, Lisa J.

    2017-01-01

    Understanding the effect of cluster environment on galaxy formation and evolution is a central topic in extragalactic astronomy. The interstellar medium (ISM) metallicity provides a powerful constraint on the complex interplay of star formation and the galactic inflow/outflow. Disentangling the effect of internal (stellar mass) and external (environment) processes on galaxy evolution is difficult because high mass galaxies tend to exist in dense environments. For the past decade, the difference between mass-metallicity relations in the cluster and field environment have been used to disentangle the effect of internal/external processes. Current observations of the mass-metallicity relation show minimal dependence on the large-scale environment. In this talk, I will present the radial distribution of ISM metallicity in galaxy clusters as an alternative method to study the impact of environment on galaxy evolution. I will present the first observation of cluster-scale negative abundance gradients in two CLASH clusters at z~0.35: MACS1115+0129 and RXJ1532+3021. Our observation presents the highest metallicity enhancement observed in a galaxy cluster on the mass-metallicity relation to date. Most strikingly, we discover that neither the radial metallicity gradient nor the offset on the mass-metallicity relation show any obvious dependence on the stellar mass of cluster members. I will discuss the different physical processes in the cluster environment such as disk truncation due to ram-pressure stripping and self-enrichment due to strangulation that can lead to the observed cluster-scale negative abundance gradient in ISM metallicity.In our follow-up work, we have performed simulations of the disk-truncation in cluster environment using a sample of CALIFA galaxies. Our analytical model of disk-truncation is based on the ram-pressure stripping of the cold gas component of the infalling galaxy in the cluster environment. I will present the simulated radial metallicity

  5. 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

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. 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.

  11. Bonding with parallel spins: high-spin clusters of monovalent metal atoms.

    PubMed

    Danovich, David; Shaik, Sason

    2014-02-18

    Bonding is a glue of chemical matter and is also a useful concept for designing new molecules. Despite the fact that electron pairing remains the bonding mechanism in the great majority of molecules, in the past few decades scientists have had a growing interest in discovering novel bonding motifs. As this Account shows, monovalent metallic atoms having exclusively parallel spins, such as (11)Li10, (11)Au10, and (11)Cu10, can nevertheless form strongly bound clusters, without having even one traditional bond due to electron pairing. These clusters, which also can be made chiral, have high magnetic moments. We refer to this type as no-pair ferromagnetic (NPFM) bonding, which characterizes the (n+1)Mn clusters, which were all predicted by theoretical computations. The small NPFM alkali clusters that have been "synthesized" to date, using cold-atom techniques, support the computational predictions. In this Account, we describe the origins of NPFM bonding using a valence bond (VB) analysis, which shows that this bonding motif arises from bound triplet electron pairs that spread over all the close neighbors of a given atom in the cluster. The bound triplet pair owes its stabilization to the resonance energy provided by the mixing of the local ionic configurations, [(3)M(↑↑)(-)]M(+) and M(+)[(3)M(↑↑)(-)], and the various excited covalent configurations (involving pz and dz(2) atomic orbitals) into the repulsive covalent structure (3)(M↑↑M) with the s(1)s(1) electronic configuration. The NPFM bond of the bound triplet is described by a resonating wave function with "in-out" and "out-in" pointing hybrids. The VB model accounts for the tendency of NPFM clusters to assume polyhedral shapes with rather high symmetry. In addition, this model explains the very steep rise of the bonding energy per atom (De/n), which starts out small in the (3)M2 dimer (<1 kcal/mol) and reaches 12-19 kcal/mol for clusters with 10 atoms. The model further predicts that usage of

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

    DOE PAGES

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

    2016-08-19

    Encapsulation behavior, as well as the presence of internal catalytically-active sites, has been spurring the applications of a 3 nm hollow spherical metal oxide cluster {Mo132} as an encapsulation host and a nano-reactor. Due to its well-defined and tunable cluster structures, and nano-scaled internal void space comparable to the volumes of small molecules, this cluster provides a good model to study the dynamics of materials under ultra-confinement. Neutron scattering studies suggest that bulky internal ligands inside the cluster show slower and limited dynamics compared to their counterparts in the bulk state, revealing the rigid nature of the skeleton of themore » internal ligands. Furthermore, NMR studies indicate that the rigid internal ligands that partially cover the interfacial pore on the molybdenum oxide shells are able to block some large guest molecules from going inside the capsule cluster, which provides a convincing protocol for size-selective encapsulation and separation.« less

  13. Orbitals in inorganic chemistry: metal rings and clusters, hydronitrogens, and heterocyles.

    PubMed

    Inagaki, Satoshi

    2010-01-01

    A chemical orbital theory is useful in inorganic chemistry. Some applications are described for understanding and designing of inorganic molecules. Among the topics included are: (1) valence electron rules to predict stabilities of three- and four-membered ring metals and for those of regular octahedral M(6) metal clusters solely by counting the number of valence electrons; (2) pentagon stability (stability of five- relative to six-membered rings in some classes of molecules), predicted and applied for understanding and designing saturated molecules of group XV elements; (3) properties of unsaturated hydronitrogens N( m )H( n ) in contrast to those of hydrocarbons C( m )H( n ); (4) unusually short nonbonded distances between metal atoms in cyclic molecules.

  14. 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.

  15. 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

  16. Chemical Abundances in NGC 5053: A Very Metal Poor and Dynamically Complex Globular Cluster

    NASA Astrophysics Data System (ADS)

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

    2015-01-01

    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 spherical distribution expected from GCs. These features include a ˜6° tidal stream (Lauchner et al. 2006), and a possible, but still debated, bridge-like structure between it and its nearby neighbor NGC 5024 (Chun et al. 2010). These features suggest that the evolution of these clusters has not only been greatly affected by their gravitational interaction with the Galaxy, but possibly each other. Additionally, simulations have shown that NGC 5053 could be a likely candidate to belong to the Sgr dSph stream (Law & Majewski 2010). Using the WIYN-Hydra multi-object spectrograph, we have collected high quality (S/N ˜75-90), medium-resolution spectra for red giant branch (RGB) 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 -2.46 with a standard deviation of 0.05 dex, making NGC 5053 one of the most metal poor GCs in the Milky Way. The [Ca/Fe], [Ti/Fe], and [Ba/Fe] we measure are consistent with the abundances of Milky Way halo stars at a similar metallicity, with high alpha values 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 Milky Way. This does not, however, rule out NGC 5053 being a member of the Sgr dSph stream.

  17. 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.

  18. 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).

  19. Finite-difference analysis of plasmon-induced forces of metal nano-clusters by the Lorentz force formulation.

    PubMed

    Fujii, Masafumi

    2010-12-20

    We analyze light-induced forces on metal nano-spheres by using the three-dimensional finite-difference time-domain method with the Lorentz force formulation. Convergent analysis of the force on metal nano-particle clusters has been achieved by integrating the Lorentz and the Coulomb forces over the volume of the metal particles. Comparison to the Mie theory of radiation pressure on metal spheres under a plane wave illumination has verified rigorously the accuracy of the numerical method. We also analyze separate two metal spheres in close proximity and the results of the induced forces are compared to those in previous publications. The present method allows analysis of forces on various irregular structures; we apply the method to touching metal spheres, forming a simple cluster with a slight deformation at the contact point, to analyze the forces induced by the plasmonic resonance of the clusters. We show that the fundamental resonance modes, which newly appear in an infrared range when spheres are touching, exhibit strong binding forces within the clusters. Based on the numerical analyses we identify the resonance modes and evaluate quantitatively the infrared-induced forces on metal nano-sphere clusters.

  20. Silver cluster formation, dynamics, and chemistry in metal-organic frameworks.

    PubMed

    Houk, Ronald J T; Jacobs, Benjamin W; El Gabaly, Farid; Chang, Noel N; Talin, A Alec; Graham, Dennis D; House, Stephen D; Robertson, Ian M; Allendorf, Mark D

    2009-10-01

    Synthetic methods used to produce metal nanoparticles typically lead to a distribution of particle sizes. In addition, creation of the smallest clusters, with sizes of a few to tens of atoms, remains very challenging. Nanoporous metal-organic frameworks (MOFs) are a promising solution to these problems, since their long-range crystalline order creates completely uniform pore sizes with the potential for both steric and chemical stabilization. We report a systematic investigation of silver nanocluster formation within MOFs using three representative MOF templates. The as-synthesized clusters are spectroscopically consistent with dimensions < or =1 nm, with a significant fraction existing as Ag(3) clusters, as shown by electron paramagnetic resonance. Importantly, we show conclusively that very rapid TEM-induced MOF degradation leads to agglomeration and stable, easily imaged particles, explaining prior reports of particles larger than MOF pores. These results solve an important riddle concerning MOF-based templates and suggest that heterostructures composed of highly uniform arrays of nanoparticles within MOFs are feasible.

  1. Infrared Array Photometry of Metal-Rich Globular Clusters.III.Two More Clusters and an Analysis of V-K Colors

    NASA Astrophysics Data System (ADS)

    Kuchinski, Leslie E.; Frogel, Jay A.

    1995-12-01

    We present new JHK photometry for the disk globular clusters NGC 6440 and NUC 6624. These data are initially used to confirm and refine several important results from Kuchinski et al. [AJ, 109, 1131(1995)] for other disk globulars. First, we again demonstrate the ability to derive a reddening-independent estimate for the [Fe/H] of a cluster from the slope if its giant branch (GB) in a K, J - K color-magnitude diagram (CMD). Second, the reddening corrected J- K color and K magnitude of the center of the horizontal branch (HB) and the J - K color of its red edge are confirmed to be independent of [Fe/H] for these clusters. Thus these parameters can be used to estimate E(J - K) of metal-rich clusters with no knowledge of distance or [Fe/H] and to estimate (m - M) if one can first estimate the reddening. We also confirm that the reddening-independent quantities, the half width of a cluster's horizontal branch (HB), and the color difference between the center of the HB and the GB at the level of the HB, both appear to be insensitive to metallicity. The JHK colors of NGC 6440 are similar to those of Liller 1; in both cases these colors are unlike those seen for other globular clusters, field giants, or bulge giants. We have not been able to identify any other cluster parameter that would help to explain these anomalous colors. We have assembled V photometry from the literature for the clusters in our sample and VK photometry for two additional disk globular clusters from Davidge et al. [ApJS, 81, 251(1992)]. We conclude that K, J - K CMDs are preferable to K, V- K CMDs as tools to study basic cluster properties. Finally, we compare our data with theoretical isochrones for metal-rich clusters and present observational evidence that the dependence of the V- K color of the GB on [Fe/H] may be different for halo and disk globular clusters. This difference may be related to differences in the [0/Fe] values for the two cluster systems.

  2. 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).

  3. Redox-Inactive Metals Modulate the Reduction Potential in Heterometallic Manganese-Oxido Clusters

    PubMed Central

    Tsui, Emily Y.; Tran, Rosalie; Yano, Junko; Agapie, Theodor

    2013-01-01

    Redox-inactive metals are found in biological and heterogeneous water oxidation catalysts, but their roles in catalysis are currently not well understood. A series of high oxidation state tetranuclear-dioxido clusters comprised of three manganese centers and a redox-inactive metal (M) of various charge is reported. Crystallographic studies show an unprecedented Mn3M(μ4-O)(μ2-O) core that remains intact upon changing M or the manganese oxidation state. Electrochemical studies reveal that the reduction potentials span a window of 700 mV, dependent upon the Lewis acidity of the second metal. With the pKa of the redox-inactive metal-aqua complex as a measure of Lewis acidity, these compounds display a linear dependence between reduction potential and acidity with a slope of ca. 100 mV per pKa unit. The Sr2+ and Ca2+ compounds show similar potentials, an observation that correlates with the behavior of the OEC, which is active only in the presence of one of these two metals. PMID:23511417

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

    NASA Astrophysics Data System (ADS)

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

    2009-12-01

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

  5. 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.

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

    NASA Astrophysics Data System (ADS)

    Goel, Sarika

    The selective encapsulation of metal clusters within zeolites can be used to prepare clusters that are uniform in diameter and to protect them against sintering and contact with feed impurities, while concurrently allowing active sites to select reactants based on their molecular size, thus conferring enzyme-like specificity to chemical catalysis. The apertures in small and medium-pore zeolites preclude the use of post-synthetic protocols to encapsulate the relevant metal precursors because cationic or anionic precursors with their charge-balancing double layer and gaseous complexes cannot diffuse through their windows or channels. We have developed general strategies to encapsulate metal clusters within small-pore zeolites by using metal precursors stabilized by ammonia or organic amine ligands, which stabilize metal precursors against their premature precipitation at the high temperature and pH conditions required for the hydrothermal synthesis of the target zeolite structures and favor interactions between metal precursors and incipient aluminosilicate nuclei during the self-assembly of microporous frameworks. When synthesis temperatures were higher than 400 K, available ligands were unable to prevent the premature precipitation of the metal precursors. In such cases, encapsulation was achieved instead via interzeolite transformations after successfully encapsulating metal precursors or clusters via post-synthesis exchange or ligand protection into parent zeolites and subsequently converting them into the target structures while retaining the encapsulated clusters or precursors. Such strategies led to the successful selective encapsulation of a wide range of metal clusters (Pt, Pd, Ru, Rh, Ir, Re, and Ag) within small-pore (SOD (sodalite), LTA (Linde type A (zeolite A)), GIS (gismondine), and ANA (analcime)) and medium-pore (MFI (ZSM-5)) zeolites. These protocols provide novel and diverse mechanism-based strategies for the design of catalysts with protected

  7. The chiroptical signature of achiral metal clusters induced by dissymmetric adsorbates.

    PubMed

    Goldsmith, Michael-Rock; George, Christopher B; Zuber, Gérard; Naaman, Ron; Waldeck, David H; Wipf, Peter; Beratan, David N

    2006-01-07

    Using a dissymmetrically-perturbed particle-in-a-box model, we demonstrate that the induced optical activity of chiral monolayer protected clusters, such as Whetten's Au28(SG)16 glutathione-passivated gold nanoclusters (J. Phys. Chem. B, 2000, 104, 2630-2641), could arise from symmetric metal cores perturbed by a dissymmetric or chiral field originating from the adsorbates. This finding implies that the electronic states of the nanocluster core are chiral, yet the lattice geometries of these cores need not be geometrically distorted by the chiral adsorbates. Based on simple chiral monolayer protected cluster models, we rationalize how the adsorption pattern of the tethering sulfur atoms has a substantial effect on the induced CD in the NIR spectral region, and we show how the chiral image charge produced in the core provides a convenient means of visualizing dissymmetric perturbations to the achiral gold nanocluster core.

  8. The manufacturing of a metallic nano-cluster at a tip apex for field-sensitive microscopy applications.

    PubMed

    Lin, Hung-Min; Chang, Mao-Nan; Lin, Yue-Sheng; Cheng, Chao-Chia

    2010-07-01

    Using a conductive atomic force microscopic setup, a metallic nano-cluster at a tip apex was successfully manufactured by an electrochemical redox process from an anodic aluminum oxide template. The diameter of the metallic nano-clusters ranged from 15 nm to 200 nm. The diameters of the nano-clusters could be well-controlled by adjusting the pore size of the templates. The formation of a variety of metallic nano-clusters at the tip apex was accomplished by preparing the electrolyte solution from different metallic salts. The formation mechanism for the nano-cluster is outlined and discussed. Moreover, we were able to enhance the performance of the nano-cluster tips for field-sensitive scanning probe microscopy, including electrostatic force microscopy and scanning Kelvin probe microscopy by laser annealing. Our experimental results indicated that for applications in field-sensitive scanning probe microscopy the stray field effect was significantly suppressed by the nano-cluster tip and hence the spatial resolution was improved.

  9. 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.

  10. 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.

  11. CHEMICAL ABUNDANCES IN NGC 5053: A VERY METAL-POOR AND DYNAMICALLY COMPLEX GLOBULAR CLUSTER

    SciTech Connect

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

    2015-05-10

    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.

  12. 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

  13. 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.

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

    NASA Astrophysics Data System (ADS)

    Baishya, Kopinjol

    Clusters are metastable structures that form a bridge between the atomic and the bulk phase. Due to their small size, quantum confinement effects are very important in clusters. They also have large surface to volume ratio, and as such, surface effects are also important. Due to these effects the properties of clusters are quite different from those of the bulk. When the size of a cluster is increased, its properties change from atomic to bulk values usually in nontrivial ways, often displaying interesting effects. By studying the evolution of cluster properties as a function of size one can try to understand the evolution and origin of bulk properties. This thesis concentrates on two main topics, noble-metal clusters of Ag and Cu, and TiO2 nanocrystals. I present my study of the optical properties of these systems calculated using first principles methods. Noble metal clusters have intriguing physical and chemical properties due to their electronic structure that contains a fully filled and localized d orbital energetically and spatially very close to the half filled s orbital. In Chapters 3 and 4 of this thesis, I present a detailed study of the role of d electrons on the optical properties of Ag and Cu clusters. I also show that the optical spectra of these clusters can be explained remarkably well by the classical Mie-Gans theory which uses the bulk dielectric constant of the material to predict their optical absorption spectra. The fact that the concept of the bulk dielectric constant survives up to the sub-nanometer size range is one of the main findings of this thesis. TiO2 is arguably the most studied single-crystalline material in the field of surface science of metal oxides. In chapter 5 of this thesis I present results and analyses on the electronic and optical excitations in rutile TiO2 nanocrystals. The motivation for this study stems from the following observation: In modeling optical prooperties of DSSC configurations with various organic molecules

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

    SciTech Connect

    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.

  16. Capturing local atomic environment dependence of activation barriers in metals using cluster expansion models

    NASA Astrophysics Data System (ADS)

    Kulkarni, Nimish; Chatterjee, Abhijit

    2016-10-01

    It is well known that surface diffusion in metals can proceed via multiple mechanisms, such as hop, exchange and other types of concerted moves. However, the manner in which kinetic rates associated with a mechanism can depend sensitively on local atomic environment is relatively less understood. We describe recent attempts in our research group to capture the atomic environment dependence using the cluster expansion model (CEM). In particular, we focus on hop and exchange moves at the (001) surface in homoepitaxy, and show that while CEM can work remarkably well in most cases, it can sometimes provide inaccurate predictions for concerted moves.

  17. 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.; ...

    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.

  18. Hydrogen activation by unsaturated mixed-metal cluster complexes: new directions.

    PubMed

    Adams, Richard D; Captain, Burjor

    2008-01-01

    There has been a renewed interest in the chemistry of hydrogen as a result of the ever-increasing global demands for energy. Recent studies have revealed new electronically unsaturated polynuclear metal complexes containing bulky ligands that exhibit a variety of reactions with hydrogen, including facile addition and elimination under mild conditions. Materials and molecules that can reversibly absorb large quantities of hydrogen are very attractive for hydrogen storage and hydrogenation catalysis. This Minireview summarizes recent studies of reactions of hydrogen with unsaturated mixed-metal cluster complexes containing platinum and bulky phosphine ligands. Some related studies on bimetallic cooperativity and the synthesis of trimetallic nanoparticles on mesoporous supports that exhibit high activity and selectivity for catalytic hydrogenations are also discussed.

  19. 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.

  20. 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.

  1. Globular Cluster Abundances from High-resolution, Integrated-light Spectroscopy. II. Expanding the Metallicity Range for Old Clusters and Updated Analysis Techniques

    NASA Astrophysics Data System (ADS)

    Colucci, Janet E.; Bernstein, Rebecca A.; McWilliam, Andrew

    2017-01-01

    We present abundances of globular clusters (GCs) in the Milky Way and Fornax from integrated-light (IL) spectra. Our goal is to evaluate the consistency of the IL analysis relative to standard abundance analysis for individual stars in those same clusters. This sample includes an updated analysis of seven clusters from our previous publications and results for five new clusters that expand the metallicity range over which our technique has been tested. We find that the [Fe/H] measured from IL spectra agrees to ∼0.1 dex for GCs with metallicities as high as [Fe/H] = ‑0.3, but the abundances measured for more metal-rich clusters may be underestimated. In addition we systematically evaluate the accuracy of abundance ratios, [X/Fe], for Na i, Mg i, Al i, Si i, Ca i, Ti i, Ti ii, Sc ii, V i, Cr i, Mn i, Co i, Ni i, Cu i, Y ii, Zr i, Ba ii, La ii, Nd ii, and Eu ii. The elements for which the IL analysis gives results that are most similar to analysis of individual stellar spectra are Fe i, Ca i, Si i, Ni i, and Ba ii. The elements that show the greatest differences include Mg i and Zr i. Some elements show good agreement only over a limited range in metallicity. More stellar abundance data in these clusters would enable more complete evaluation of the IL results for other important elements. This paper includes data gathered with the 6.5 m Magellan Telescopes located at Las Campanas Observatory, Chile.

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

    SciTech Connect

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

    2014-06-01

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

  3. 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 −})

  4. Detection of second-generation asymptotic giant branch stars in metal-poor globular clusters

    NASA Astrophysics Data System (ADS)

    García-Hernández, D. A.

    2017-03-01

    Multiple stellar populations are actually known to be present in Galactic globular clusters (GCs). The first generation (FG) displays a halo-like chemical pattern, while the second generation (SG) one is enriched in Al and Na (depleted in Mg and O).Both generations of stars are found at different evolutionary stages like the main-sequence turnoff, the subgiant branch, and the red giant branch (RGB), but the SG seems to be absent - especially in metal-poor ([Fe/H] < -1) GCs - in more evolved evolutionary stages such as the asymptotic giant branch (AGB) phase. This suggests that not all SG stars experience the AGB phase and that AGB-manqué stars may be quite common in metal-poor GCs, which represents a fundamental problem for the theories of GC formation and evolution and stellar evolution. Very recently, we have combined the H-band Al abundances obtained by the APOGEE survey with ground-based optical photometry, reporting the first detection of SG Al-rich AGB stars in several metal-poor GCs with different observational properties such as horizontal branch (HB) morphology, metallicity, and age. The APOGEE observations thus resolve the apparent problem for stellar evolution, supporting the existing horizontal branch star canonical models, and may help to discern the nature of the GC polluters.

  5. 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.

  6. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2015-08-01

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

  8. Prediction of the lowest-energy structures of rare-earth metallic clusters with a Moebius inversion pair potential

    SciTech Connect

    Luo, You-Hua; Wang, Yuzhu

    2001-07-01

    The Moebius inversion pair potential has been employed, in combination with genetic algorithms, to predict the lowest-energy structures of the rare-earth metallic clusters La{sub N}, Ce{sub N}, and Pr{sub N} (N=3--20). Results are given for the symmetries, binding energies, nearest-neighbor distances of these clusters, and lowest-energy configurations of Ce{sub N} clusters. Also, the calculated second finite difference of the total energy shows that for three species elements, the 13-atom clusters with I{sub d} symmetry are particularly stable. Some minor peaks are also found at size N=4, 6, 11, and 15, which indicates that the corresponding clusters are relatively stable in structure. Present work points out a route to studying clusters.

  9. 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.

  10. 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.

  11. Atomic clusters triggering nucleation and solidification of the metallic glass melt

    NASA Astrophysics Data System (ADS)

    Li, Gong; Zhang, Lijun; Zhan, Zaiji; Yu, Pengfei; Liaw, Peter K.; Liu, Riping

    2017-03-01

    The Zr41Ti14Cu12.5Ni10Be22.5 (atomic percent, at. %) melts embedded in a flux of the dehydrated B2O3 were under cooled by the repeated treatment of melting. The maximum melt undercooling of ΔT = 145 K achieved for this melt corresponds to a comparatively large relative undercooling of 0.15 times the melting-point temperature of Tm˜ about 953 K(ΔT/Tm = 0.15). The solidification and nucleation behaviors of the Zr41Ti14Cu12.5Ni10Be22.5 undercooled melts triggered by Ni, Ti, Cu, and Zr clusters introduced by sputtering these pure metal targets are studied. An anomalous solidification triggered by Zr-atomic clusters above the Zr41Ti14Cu12.5Ni10Be22.5 melting temperature of 140 K is observed. The instability of a metallic-glass (MG) liquid near the thermodynamic critical temperature is present. The nucleation in the undercooled Zr41Ti14Cu12.5Ni10Be22.5 is investigated by Monte Carlo simulations and analyzed by the classical nucleation theory. This letter reveals an effective research method on investigating the instability of a MG liquid near the thermodynamic critical temperature.

  12. Method/basis set dependence of NICS values among metallic nano-clusters and hydrocarbons.

    PubMed

    Badri, Zahra; Foroutan-Nejad, Cina; Rashidi-Ranjbar, Parviz

    2012-03-14

    The influence of various all-electron basis sets and effective core potentials employed along with several DFT functionals (B3LYP, B3PW91, BLYP, BP86 and M06) on the magnitude of nucleus independent chemical shift (NICS) values in different metallic nano-clusters and hydrocarbons is studied. In general, it is demonstrated that the NICS values are very sensitive to the applied method/basis set; however, the method/basis set dependence is more prominent for computed NICS values in transition metal clusters. In hydrocarbons, medium-size basis sets perform roughly similar to large basis sets in most cases. It is also found that NICS(0) values are more sensitive to the method/basis set variation compared to the NICS values computed at 1 or 2 Å above the ring plane. However, in many cases, no broad-spectrum regulation is found for the effect of basis set/method on the magnitude of NICS values. A detailed study showed that bond length alternation in a molecule has an insignificant effect on the magnitude of NICS values so the influence of method/basis sets on the magnitude of NICS values mostly arises from the different predicted ring current intensities at various computational levels.

  13. 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.

  14. Ages and metallicities of LMC and SMC red clusters through H-beta and G band photometry

    NASA Astrophysics Data System (ADS)

    Bica, E.; Dottori, H.; Pastoriza, M.

    1986-02-01

    The authors present narrow band integrated photometry of the Hβ and G band absorption features for 41 LMC and 10 SMC red star clusters. An age-metallicity calibration is provided for the color-color diagram. SWB types are derived between IV and VII for 23 unclassified clusters and their distribution in the ages vs metallicity plane is discussed. The authors study the chemical evolution of the Magellanic Clouds: the LMC presents a steeper chemical enrichment slope. An intrinsic metallicity dispersion is found in the LMC chemical evolution, indicating that the gas has been inhomogeneous at any time, prevailing a local enrichment over a global one. One zone models describe the evolution of both Clouds, being the efficiency of star cluster formation larger in the LMC. The LMC presents a burst of star cluster formation at t = 4.5×109yr. The authors also present new B-V data for fainter SMC clusters, providing an essentially complete color histogram for clusters with globular cluster appearance.

  15. Faujasite-supported Ir{sub 4} clusters: A density functional model study of metal-zeolite interactions

    SciTech Connect

    Ferrari, A.M. |; Neyman, K.M.; Mayer, M.; Staufer, M.; Roesch, N.; Gates, B.C.

    1999-06-24

    The interaction of a metal cluster, Ir{sub 4}, and a zeolite support was investigated computationally with the aid of a density functional method and a cluster model of a zeolite, i.e., a six-ring consisting of six O atoms and six T (Si or Al) atoms facing a supercage of a faujasite framework. Structural parameters are reported for an Ir{sub 4} tetrahedron interacting with the zeolite six-ring. The calculations indicate two Ir-O distances, which match those reported on the basis of EXAFS spectroscopy at about 2.1--2.2 and 2.5--2.7 {angstrom} for various transition and noble metal clusters on zeolite (and metal oxide) supports, including Ir{sub 4} in the supercages of zeolite NaY. The calculations indicate an Ir-Ir distance of about 2.5 {angstrom}, only a few hundredths of an Angstrom more than the value calculated for the free Ir{sub 4} cluster, but about 0.2 {angstrom} less than the values observed repeatedly by EXAFS spectroscopy for zeolite-supported clusters approximated as Ir{sub 4}. The experimental distances characterizing the zeolite-supported clusters are in close agreement with the crystallographic and calculated value reported for the coordinatively saturated cluster Ir{sub 4}(CO){sub 12} and favor the suggestion that the supported clusters investigated with EXAFS spectroscopy were not entirely ligand free (i.e., that their formation by decarbonylation of the parent Ir{sub 4}(CO){sub 12} did not proceed by simple, complete removal of CO ligands). Consequently, calculations were performed for unsupported model clusters Ir{sub 4} with single H or C atoms as ligands; the results match the EXAFS data characterizing the Ir-Ir distance and favor the suggestion of carbon on the zeolite-supported clusters. The bonding of a single CO molecule to the supported Ir{sub 4} at the on-top site was also modeled to probe changes in the electronic structure of the metal cluster in comparison with an unsupported metal cluster. The results show that the interaction of the

  16. OPTICAL AND INFRARED PHOTOMETRY OF GLOBULAR CLUSTERS IN NGC 1399: EVIDENCE FOR COLOR-METALLICITY NONLINEARITY

    SciTech Connect

    Blakeslee, John P.; Ferrarese, Laura; Martel, Andre R.; Cho, Hyejeon; Peng, Eric W.; Jordan, Andres

    2012-02-10

    We combine new Wide Field Camera 3 IR Channel (WFC3/IR) F160W (H{sub 160}) imaging data for NGC 1399, the central galaxy in the Fornax cluster, with archival F475W (g{sub 475}), F606W (V{sub 606}), F814W (I{sub 814}), and F850LP (z{sub 850}) optical data from the Advanced Camera for Surveys (ACS). The purely optical g{sub 475} - I{sub 814}, V{sub 606} - I{sub 814}, and g{sub 475} - z{sub 850} colors of NGC 1399's rich globular cluster (GC) system exhibit clear bimodality, at least for magnitudes I{sub 814} > 21.5. The optical-IR I{sub 814} - H{sub 160} color distribution appears unimodal, and this impression is confirmed by mixture modeling analysis. The V{sub 606} - H{sub 160} colors show marginal evidence for bimodality, consistent with bimodality in V{sub 606} - I{sub 814} and unimodality in I{sub 814} - H{sub 160}. If bimodality is imposed for I{sub 814} - H{sub 160} with a double Gaussian model, the preferred blue/red split differs from that for optical colors; these 'differing bimodalities' mean that the optical and optical-IR colors cannot both be linearly proportional to metallicity. Consistent with the differing color distributions, the dependence of I{sub 814} - H{sub 160} on g{sub 475} - I{sub 814} for the matched GC sample is significantly nonlinear, with an inflection point near the trough in the g{sub 475} - I{sub 814} color distribution; the result is similar for the I{sub 814} - H{sub 160} dependence on g{sub 475} - z{sub 850} colors taken from the ACS Fornax Cluster Survey. These g{sub 475} - z{sub 850} colors have been calibrated empirically against metallicity; applying this calibration yields a continuous, skewed, but single-peaked metallicity distribution. Taken together, these results indicate that nonlinear color-metallicity relations play an important role in shaping the observed bimodal distributions of optical colors in extragalactic GC systems.

  17. WIYN Open Cluster Study. LXXV. Testing the Metallicity Dependence of Stellar Lithium Depletion Using Hyades-aged Clusters. I. Hyades and Praesepe

    NASA Astrophysics Data System (ADS)

    Cummings, Jeffrey D.; Deliyannis, Constantine P.; Maderak, Ryan M.; Steinhauer, Aaron

    2017-03-01

    WIYN/Hydra spectroscopy (at R ∼ 15,000) of the moderately metal-rich Praesepe and Hyades open clusters was used to study their main-sequence (MS) iron ([Fe/H]) and lithium (A(Li)) abundances. Self-consistent [Fe/H] and Li analyses of these clusters of consistent age, which we re-evaluate, confirms that they have consistent [Fe/H] and provides a foundation to investigate the poorly understood G-dwarf and F-dwarf Li-depletions. Neither phenomenon agrees with standard stellar evolution theory, but possible explanations abound. We supplement our A(Li) with previously published results placed on a uniform abundance scale. This creates the largest self-consistently analyzed sample of A(Li) in both the Hyades (90) and Praesepe (110). For each star, high-precision UBVRI photometry was used to determine a 10-color-based {T}{eff} and then to test for photometric peculiarities indicated by a large {σ }{Teff} (>75 K). The stars that have large {σ }{Teff} were predominantly found to be binaries or stars with peculiar (apparent) A(Li). When considering only proper-motion members that have low {σ }{Teff} and are also photometrically consistent with the cluster MS fiducial, each cluster has a more tightly defined Li morphology than previously observed and the two clusters’ A(Li) are indistinguishable. This suggests that clusters of consistent age and metallicity may have consistent Li-depletion trends across a broad range of {T}{eff}; no additional major parameters are required, at least for these two clusters. We propose that the combined Hyades and Praesepe data offer more rigorous constraints than does either cluster alone, and we discuss newly revealed features of the combined Li–{T}{eff} trend.

  18. 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.

  19. Reducing Capsule Based on Electron Programming: Versatile Synthesizer for Size-Controlled Ultra-Small Metal Clusters.

    PubMed

    Kambe, Tetsuya; Imaoka, Takane; Yamamoto, Kimihisa

    2016-11-07

    Controlled reducing capsules with a specific number of reducing electrons were achieved by appropriately placed BH3 units in the dendritic polyphenylazomethines (DPAs). Using the 1:1 coordination fashion on their basic branches with radius affinity gradient, the 4th generation DPA (DPAG4) possessing four BH3 units in the central positions was prepared as a template synthesizer for size-controlled ultra-small metal clusters. This was well-demonstrated by reduction of Ag, Pt, and other metal ions resulting in monodispersed ultra-small clusters.

  20. 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

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

    SciTech Connect

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

    2008-03-12

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

  2. Gas-phase catalysis by atomic and cluster metal ions: the ultimate single-site catalysts.

    PubMed

    Böhme, Diethard K; Schwarz, Helmut

    2005-04-15

    Gas-phase experiments with state-of-the-art techniques of mass spectrometry provide detailed insights into numerous elementary processes. The focus of this Review is on elementary reactions of ions that achieve complete catalytic cycles under thermal conditions. The examples chosen cover aspects of catalysis pertinent to areas as diverse as atmospheric chemistry and surface chemistry. We describe how transfer of oxygen atoms, bond activation, and coupling of fragments can be mediated by atomic or cluster metal ions. In some cases truly unexpected analogies of the idealized gas-phase ion catalysis can be drawn with related chemical transformations in solution or the solid state, and so improve our understanding of the intrinsic operation of a practical catalyst at a strictly molecular level.

  3. WIYN Open Cluster Study. LXXII. A uvbyCaHβ CCD Analysis of the Metal-deficient Open Cluster NGC 2506

    NASA Astrophysics Data System (ADS)

    Anthony-Twarog, Barbara J.; Deliyannis, Constantine P.; Twarog, Bruce A.

    2016-12-01

    Precision uvbyCaHβ photometry of the metal-deficient, old open cluster NGC 2506 is presented. The survey covers an area of 20\\prime × 20\\prime and extends to V˜ 18 for b - y and Hβ and to V˜ 17.0 for c 1 and hk. For V brighter than 16.0, photometric scatter among the indices leads to the recovery of six known variables within the cluster core and five new variables in the outer 5\\prime of the survey field. Proper motions, radial velocities, and precise multicolor indices are used to isolate a highly probable sample of cluster members from the very rich color-magnitude diagram. From 257 highly probable members at the cluster turnoff, we derive a reddening estimate of E(b-y)=0.042+/- 0.001 (E(B-V)=0.058+/- 0.001), where the errors refer to the internal standard errors of the mean. [Fe/H] is derived from the A/F dwarf members using both m 1 and hk, leading to [Fe/H] = -0.296 ± 0.011 (sem) and -0.317 ± 0.004 (sem), respectively. The weighted average, heavily dominated by hk, is [Fe/H] = -0.316 ± 0.033. Based on red giant members, we place an upper limit of ±0.010 on the variation in the reddening across the face of the cluster. We also identify two dozen potential red giant cluster members outside the cluster core. Victoria-Regina isochrones on the Strömgren system produce an excellent match to the cluster for an apparent modulus of (m-M)=12.75+/- 0.1 and an age of 1.85 ± 0.05 Gyr.

  4. Alkali metal-cationized serine clusters studied by sonic spray ionization tandem mass spectrometry.

    PubMed

    Nanita, Sergio C; Sokol, Ewa; Cooks, R Graham

    2007-05-01

    Serine solutions containing salts of alkali metals yield magic number clusters of the type (Ser(4)+C)(+), (Ser(8)+C)(+), (Ser(12)+C)(+), and (Ser(17)+2C)(+2) (where C = Li(+), Na(+), K(+), Rb(+), or Cs(+)), in relative abundances which are strongly dependent on the cation size. Strong selectivity for homochirality is involved in the formation of serine tetramers cationized by K(+), Rb(+), and Cs(+). This is also the case for the octamers cationized by the smaller alkalis but there is a strong preference for heterochirality in the octamers cationized by the larger alkali cations. Tandem mass spectrometry shows that the octamers and dodecamers cationized by K(+), Rb(+), and Cs(+) dissociate mainly by the loss of Ser(4) units, suggesting that the neutral tetramers are the stable building blocks of the observed larger aggregates, (Ser(8)+C)(+) and (Ser(12)+C)(+). Remarkably, although the Ser(4) units are formed with a strong preference for homochirality, they aggregate further regardless of their handedness and, therefore, with a preference for the nominally racemic 4D:4L structure and an overall strong heterochiral preference. The octamers cationized by K(+), Rb(+), or Cs(+) therefore represent a new type of cluster ion that is homochiral in its internal subunits, which then assemble in a random fashion to form octamers. We tentatively interpret the homochirality of these tetramers as a consequence of assembly of the serine molecules around a central metal ion. The data provide additional evidence that the neutral serine octamer is homochiral and is readily cationized by smaller ions.

  5. 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.

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

    SciTech Connect

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

    1995-09-01

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

  7. 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.

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

    PubMed

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

    2014-08-14

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

  9. New Insights in Catalytic Sites: Characterization of Spectroscopy and Reactivity of Metal Oxide Clusters with Anion Slow Electron Velocity-Map Imaging

    DTIC Science & Technology

    2016-06-08

    in heterogeneous catalysts , many of which comprise complex transition metal oxides. Size-selected transition metal oxide clusters can serve as...tractable model systems for the analogous bulk catalyst . This research program has focused on developing novel spectroscopic probes of such clusters...materials, with extensive applications as catalysts , catalyst supports, photocatalysts, dielectric materials, and corrosion resistant materials

  10. 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…

  11. Unusual structures and reactivity of mixed metal cluster complexes containing the palladium/platinum tri-t-butylphosphine grouping.

    PubMed

    Adams, Richard D; Captain, Burjor

    2009-03-17

    Polynuclear metal carbonyl complexes have a range of applications in chemical research: for example, they can serve as surface models to probe features of heterogeneous catalysis and can perform novel transformations of organic molecules in solutions. Mixed metal complexes can demonstrate bimetallic cooperativity and synergism and can also serve as precursors to multimetallic heterogeneous catalysts that have superior activities and selectivities. This Account describes the results of our recent comprehensive study of the chemistry of mixed metal cluster complexes containing the sterically encumbered M(PBu(t)(3)), M = Pd or Pt, group. This grouping readily adds to the metal-metal bonds of metal carbonyl cluster complexes and modifies their reactivity. We have prepared new, highly electronically unsaturated mixed metal complexes that exhibit unusually high reactivity toward hydrogen. The platinum atom of the Pt(PBu(t)(3)) grouping can bond to as many as five metal atoms, and it can interconvert, sometimes rapidly, between the different bonding modes. The large steric effects of the PBu(t)(3) ligand allowed us to prepare highly unsaturated, stable, mixed-metal complexes, and these complexes react with hydrogen, sometimes reversibly, under very mild conditions to yield polyhydride complexes. Strong evidence suggests that the Pt(PBu(t)(3)) group can also activate metal-hydrogen bonds in other complexes. In the future, we expect that researchers will prepare a greater variety of mixed metal complexes containing the Pd/Pt(PBu(t)(3)) group or other similar bulky groups, and that some of these complexes will exhibit even more unusual chemistry than what we have observed so far.

  12. Exciton-plasmon interaction in hybrid quantum dot/metal cluster structures fabricated by molecular-beam epitaxy

    NASA Astrophysics Data System (ADS)

    Lyamkina, A. A.; Moshchenko, S. P.; Dmitriev, D. V.; Toropov, A. I.; Shamirzaev, T. S.

    2014-04-01

    Hybrid structures consisting of InAs/AlGaAs quantum dots and In clusters on the surface separated by an AlGaAs spacer with a specified thickness are investigated. The enhancement of the photoluminescence signal in the long-wavelength region manifesting itself in the appearance of a new narrow emission line is observed. This line is absent in the control structure with a quantum-dot array and no metal clusters. It also disappears with increasing thickness of the dielectric spacer between the layers. These results are explained in terms of a model taking into account the resonance interaction of excitons in quantum dots with localized surface plasmons in metal clusters.

  13. 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.

  14. 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.

  15. 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

  16. 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

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

    NASA Astrophysics Data System (ADS)

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

    2014-04-01

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

  18. 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

  19. Selective electrodesorption based atomic layer deposition (SEBALD): a novel electrochemical route to deposit metal clusters on Ag(111).

    PubMed

    Innocenti, M; Bellandi, S; Lastraioli, E; Loglio, F; Foresti, M L

    2011-09-20

    The possibility of synergic effects of some metals on the catalytic activity of silver led us to study the way to perform controlled deposition on silver. In fact, many metals of technological interest such as Co, Ni, and Fe cannot be deposited at underpotential on silver, and any attempt to control the deposition at overpotential, even at potentials slightly negative of the Nernst value, did not allow an effective control. However, due to the favorable energy gain involved in the formation of the corresponding sulfides, these metals can be deposited at underpotential on sulfur covered silver. The deposition is surface limited and the successive electrodesorption of sulfur leaves confined clusters of metals. The method can also be used to obtain metal clusters of different size. In fact, the alternate underpotential deposition of elements that form a compound is the basis of the electrochemical atomic layer epitaxy (ECALE), and the reiteration of the basic cycle allows us to obtain sulfide deposits whose thickness increases with the number of cycles. Therefore, the successive selective desorption of sulfur leaves increasing amounts of metals.

  20. Robust MOFs of 'tsg' Topology Based on Trigonal Prismatic Organic and Metal Cluster SBUs: Single Crystal-to-Single Crystal Postsynthetic Metal Exchange and Selective CO2 Capture.

    PubMed

    Moorthy, Narasimha Jarugu; Chandrasekhar, Pujari; Savitha, Govardhan

    2017-04-03

    The self-assembly of a rigid and trigonal prismatic triptycene-hexaacid H6THA with Co(NO3)2 and Mn(NO3)2 leads to isostructural MOFs that are sustained by 6-c metal cluster [M3(μ3-O)(COO)6] SBUs. The Co- and Mn-MOFs, constructed from organic and metal-cluster building blocks that are both trigonal prismatic, correspond to the heretofore unknown 'tsg' topology. Due to the rigidity and concave attributes of H6THA, the networks in Co- and Mn-MOFs are highly porous and undergo 3-fold interpenetration. The interpenetration imparts permanent microporosity and high thermal stability to the MOFs to permit postsynthetic metal exchange (PSME) and gas sorption. The PSME occurs in a SC-SC fashion when the crystals of Co- and Mn-MOFs are immersed in a solution of Cu(NO3)2 in MeOH/H2O. Further, the isostructural robust MOFs exhibit significant gas sorption and remarkable selectivity for CO2 over N2 (ca. 100 fold) at ambient conditions. In fact, the postsynthetically-engineered Cu-THA exhibits better CO2 sorption than Co-THA and Mn-THA. A composite of effects that include pore dimensions (ca. 0.7 nm), unsaturated metal centers and basic environments conferred by the quinoxaline nitrogen atoms appears to be responsible for the observed high CO2 capture and selectivity. The high-symmetry and structural attributes of the organic linker seemingly dictate adoption of the trigonal-prismatic metal cluster SBU by the metal ions in the MOFs.

  1. Novel linear transition metal clusters of a heptadentate bis-beta-diketone ligand.

    PubMed

    Aromí, Guillem; Gamez, Patrick; Krzystek, J; Kooijman, Huub; Spek, Anthony L; MacLean, Elizabeth J; Teat, Simon J; Nowell, Harriott

    2007-04-02

    The synthesis and the structure of the new potentially heptadentate ligand 1,3-bis-(3-oxo-3-(2-hydroxyphenyl)-propionyl)-2-methoxybenzene (H5L) is described. The reaction in pyridine or DMF of this ligand with various M(AcO)2 salts (M = NiII, CoII, MnII) leads to very different products depending on the metal. Thus, the dinuclear complexes [M2(H3L)2(py)4] (M = NiII, 1; CoII, 2) or the linear zigzag tetranuclear clusters [Mn4(H2L)2(AcO)2(py)5] (3) and [Mn4(H2L)2(AcO)2(dmf)4] (4) have been synthesized and characterized crystallographically. Slow oxidation of complex 3 leads to the formation of the novel mixed-valence linear complex [Mn3(HL)2(py)6] (5), displaying an unprecedented asymmetric MnIIIMnIIIMnII topology. The coordination geometry of complexes 1 to 5 has been analyzed and discussed by means of continuous shape measures. Magnetic measurements of 3 and 5 demonstrate that the metals within these complexes weakly interact magnetically with coupling constants of J1 = -1.13 cm-1 and J2 = -0.43 cm-1 (S = 0) for complex 3 and J1 = -5.4 cm-1 and J2 = -0.4 cm-1 (S = 5/2) for complex 5 (using the H = -Sigma2JijSiSj convention). These results are consistent with X-band EPR measurements on these compounds.

  2. 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.

  3. A Differential Chemical Element Analysis of the Metal-poor Globular Cluster NGC 6397

    NASA Astrophysics Data System (ADS)

    Koch, Andreas; McWilliam, Andrew

    2011-08-01

    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 ~0.1 dex, with opposite signs for the red giant branch (RGB) and TO stars. The α-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. This paper includes data gathered with the 6.5 m Magellan Telescopes located at Las Campanas Observatory, Chile.

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. 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

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

    NASA Astrophysics Data System (ADS)

    Baksi, Ananya; Pradeep, T.

    2013-11-01

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

  11. 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.

  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. 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.

  14. Effects of charging and tunnelling in a structure based on magic and non-magic metal clusters.

    PubMed

    Pogosov, V V; Vasyutin, E V

    2006-07-28

    The effects of charging and single-electron tunnelling in a metal cluster structure are investigated theoretically. In the framework of the particle-in-a-box model for spherical and disc-shaped gold clusters, the electron spectrum and the temperature dependence of the electron chemical potential are calculated. The difference between the electron chemical potentials of massive electrodes and islands leads to the noticeable charging of the electrode. We show that the effective residual charge is equal to the non-integer value of the elementary charge e and depends on the shape of the cluster. The equations for the analysis of the current-voltage characteristic are used under the conditions of conservation of the total energy of the structure, taking into account the contact potential difference. Restrictions associated with the Coulomb instability of a cluster are introduced into the theory in a simple way. It is shown that the critical charge of the cluster in an open electron system is close to the effective residual charge. For single-electron molecular transistors based on small gold clusters the current gap and its voltage asymmetry are computed. We demonstrate that the current gap exhibits non-monotonic size dependences which are related to the quantization of the electron spectrum and the Coulomb blockade.

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

    NASA Astrophysics Data System (ADS)

    Borisova, Svetlana D.; Rusina, Galina G.

    2015-10-01

    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 Co4 cluster on the surface the high frequency modes remain strongly localized and mixed with the nearest neighbor atoms vibrations.

  16. 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.

  17. Influence of 3 d metal atoms on the geometry, electronic structure, and stability of a Mg13H26 cluster

    NASA Astrophysics Data System (ADS)

    Shelyapina, M. G.; Siretskiy, M. Yu.

    2010-09-01

    This paper reports on the results of the theoretical investigation of magnesium hydride nanoclusters doped with 3 d metals (from Sc to Zn). The influence of transition metal atoms on the geometry, electronic structure, and energy characteristics of the clusters has been analyzed. The results of the performed calculations have been compared with the available experimental data. This comparison has made it possible to predict which 3 d transition elements can serve as the most effective catalysts for the improvement of the thermodynamic characteristics of MgH2.

  18. 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.

  19. 21 CFR 1404.900 - Adequate evidence.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 9 2012-04-01 2012-04-01 false Adequate evidence. 1404.900 Section 1404.900 Food and Drugs OFFICE OF NATIONAL DRUG CONTROL POLICY GOVERNMENTWIDE DEBARMENT AND SUSPENSION (NONPROCUREMENT) Definitions § 1404.900 Adequate evidence. Adequate evidence means information sufficient...

  20. 21 CFR 1404.900 - Adequate evidence.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

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

  1. 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.

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

    SciTech Connect

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

    1997-02-01

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

  3. Mixed-metal cluster chemistry. 28. Core enlargement of tungsten-iridium clusters with alkynyl, ethyndiyl, and butadiyndiyl reagents.

    PubMed

    Dalton, Gulliver T; Viau, Lydie; Waterman, Susan M; Humphrey, Mark G; Bruce, Michael I; Low, Paul J; Roberts, Rachel L; Willis, Anthony C; Koutsantonis, George A; Skelton, Brian W; White, Allan H

    2005-05-02

    Reaction of [WIr3(mu-CO)3(CO)8(eta-C5Me5)] (1c) with [W(C[triple bond]CPh)(CO)3(eta-C5H5)] afforded the edge-bridged tetrahedral cluster [W2Ir3(mu4-eta2-C2Ph)(mu-CO)(CO)9(eta-C5H5)(eta-C5Me5)] (3) and the edge-bridged trigonal-bipyramidal cluster [W3Ir3(mu4-eta2-C2Ph)(mu-eta2-C=CHPh)(Cl)(CO)8(eta-C5Me5)(eta-C5H5)2] (4) in poor to fair yield. Cluster 3 forms by insertion of [W(C[triple bond]CPh)(CO)3(eta-C5H5)] into Ir-Ir and W-Ir bonds, accompanied by a change in coordination mode from a terminally bonded alkynyl to a mu4-eta2 alkynyl ligand. Cluster 4 contains an alkynyl ligand interacting with two iridium atoms and two tungsten atoms in a mu4-eta2 fashion, as well as a vinylidene ligand bridging a W-W bond. Reaction of [WIr3(CO)11(eta-C5H5)] (1a) or 1c with [(eta-C5H5)(CO)2 Ru(C[triple bond]C)Ru(CO)2(eta-C5H5)] afforded [Ru2WIr3(mu5-eta2-C2)(mu-CO)3(CO)7(eta-C5H5)2(eta-C5R5)] [R = H (5a), Me (5c)] in low yield, a structural study of 5a revealing a WIr3 butterfly core capped and spiked by Ru atoms; the diruthenium ethyndiyl precursor has undergone Ru-C scission, with insertion of the C2 unit into a W-Ir bond of the cluster precursor. Reaction of [W2Ir2(CO)10(eta-C5H5)2] with the diruthenium ethyndiyl reagent gave [RuW2Ir2{mu4-eta2-(C2C[triple bond]C)Ru(CO)2(eta-C5H5)}(mu-CO)2(CO)6(eta-C5H5)3] (6) in low yield, a structural study of 6 revealing a butterfly W2Ir2 unit capped by a Ru(eta-C5H5) group resulting from Ru-C scission; the terminal C2 of a new ruthenium-bound butadiyndiyl ligand has been inserted into the W-Ir bond. Reaction between 1a, [WIr3(CO)11(eta-C5H4Me)] (1b), or 1c and [(eta-C5H5)(CO)3W(C[triple bond]CC[triple bond]C)W(CO)3(eta-C5H5)] afforded [W2Ir3{mu4-eta2-(C2C[triple bond]C)W(CO)3(eta-C5H5)}(mu-CO)2(CO)2(eta-C5H5)(eta-C5R5)] [R = H (7a), Me (7c); R5 = H4Me (7b)] in good yield, a structural study of 7c revealing it to be a metallaethynyl analogue of 3.

  4. 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

  5. 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

  6. Covalent Metal-Metal-Bonded Mn4 Tetrahedron Inscribed within a Four-Coordinate Manganese Cubane Cluster, As Evidenced by Unexpected Temperature-Independent Diamagnetism.

    PubMed

    Vaddypally, Shivaiah; Jovinelli, Daniel J; McKendry, Ian G; Zdilla, Michael J

    2017-03-17

    The electronic structures of the manganese(IV) cubane cluster Mn(μ3-N(t)Bu)4(N(t)Bu)4 (1) and its one-electron-oxidized analogue, the 3:1 Mn(IV)/Mn(V) cluster [Mn(μ3-N(t)Bu)4(N(t)Bu)4](+)[PF6](-) (1(+)[PF6]), are described. The S = 0 spin quantum number of 1 is explained by a diamagnetic electronic structure where all metal-based d electrons are paired in Mn-Mn bonding orbitals. Temperature- and power-dependent studies of the S = (1)/2 electron paramagnetic resonance signal of 1(+) are consistent with an electronic structure described as a delocalized one-electron radical.

  7. Star-to-Star Abundance Variations among Bright Giants in the Mildly Metal-poor Globular Cluster M4

    NASA Astrophysics Data System (ADS)

    Ivans, Inese I.; Sneden, Christopher; Kraft, Robert P.; Suntzeff, Nicholas B.; Smith, Verne V.; Langer, G. Edward; Fulbright, Jon P.

    1999-09-01

    We present a chemical composition analysis of 36 giants in the nearby mildly metal-poor (<[Fe/H]>=-1.18) ``CN-bimodal'' globular cluster M4. The stars were observed at the Lick and McDonald Observatories using high-resolution échelle spectrographs and at the Cerro Tololo Inter-American Observatory using the multiobject spectrometer. Confronted with a cluster having interstellar extinction that is large and variable across the cluster face, we combined traditional spectroscopic abundance methods with modifications to the line depth ratio technique pioneered by Gray to determine the atmospheric parameters of our stars. We derive a total-to-selective extinction ratio of 3.4+/-0.4 and an average reddening of 0.33+/-0.01, which is significantly lower than that estimated by using the dust maps made by Schlegel and coworkers. We determine abundance ratios typical of halo field and cluster stars for scandium, titanium, vanadium, nickel, and europium with star-to-star variations in these elements of less than +/-0.1. Silicon, aluminum, barium, and lanthanum are overabundant with respect to what is seen in other globular clusters of similar metallicity. These overabundances confirm the results of an earlier study by Brown & Wallerstein based on a much smaller sample of M4 giants. Superposed on the primordial abundance distribution is evidence for the existence of proton capture synthesis of carbon, oxygen, neon, and magnesium. We recover some of the C, N, O, Na, Mg, and Al abundance swings and correlations found in other more metal-poor globular clusters, but the range of variation is muted. In the case of Mg and Al, this is compatible with the idea that the Al enhancements are derived from the destruction of ^25,26Mg, not ^24Mg. We determine that the C+N+O abundance sum is constant to within the observational errors and agrees with the C+N+O total that might be expected for M4 stars at birth. The asymptotic giant branch (AGB) stars in M4 have C, N, and O

  8. [Electronic and structural properties of individual nanometer-size supported metallic clusters]. Final performance report

    SciTech Connect

    Reifenberger, R.

    1993-09-01

    This report summarizes the work performed under contract DOE-FCO2-84ER45162. During the past ten years, our study of electron emission from laser-illuminated field emission tips has taken on a broader scope by addressing problems of direct interest to those concerned with the unique physical and chemical properties of nanometer-size clusters. The work performed has demonstrated that much needed data can be obtained on individual nanometer-size clusters supported on a wide-variety of different substrates. The work was performed in collaboration with R.P. Andres in the School of Chemical Engineering at Purdue University. The Multiple Expansion Cluster Source developed by Andres and his students was essential for producing the nanometer-size clusters studied. The following report features a discussion of these results. This report provides a motivation for studying the properties of nanometer-size clusters and summarizes the results obtained.

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

    PubMed

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

    2012-01-01

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

  10. 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

  11. 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.

  12. Quantum-chemical modeling of gas-phase adsorption of the hydroxyl radical on IB metal clusters Me n ( n = 2-8)

    NASA Astrophysics Data System (ADS)

    Doroshenko, A. A.; Nechaev, I. V.; Vvedenskii, A. V.

    2014-09-01

    The structure of the most stable Me n clusters and Me n OH complexes (Me = Cu, Ag, Au; n = 2-8) was calculated using the density functional theory. The enthalpy and Gibbs energy of the interaction of OH· with metal clusters were calculated. It was shown that the hydroxyl radical is predominantly adsorbed into the bridge position on the metal IB clusters. During the adsorption of the hydroxyl radical, the frequency and intensity of the stretching vibrations of the O-H bond increased relative to the corresponding values for the isolated state; the frequency shift changed in the series Ag < Cu < Au.

  13. 5 CFR 919.900 - Adequate evidence.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 5 Administrative Personnel 2 2010-01-01 2010-01-01 false Adequate evidence. 919.900 Section 919.900 Administrative Personnel OFFICE OF PERSONNEL MANAGEMENT (CONTINUED) CIVIL SERVICE REGULATIONS (CONTINUED) GOVERNMENTWIDE DEBARMENT AND SUSPENSION (NONPROCUREMENT) Definitions § 919.900 Adequate...

  14. 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.

  15. 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.

  16. Switching Plasmons: Gold Nanorod-Copper Chalcogenide Core-Shell Nanoparticle Clusters with Selectable Metal/Semiconductor NIR Plasmon Resonances.

    PubMed

    Muhammed, Madathumpady Abubaker Habeeb; Döblinger, Markus; Rodríguez-Fernández, Jessica

    2015-09-16

    Exerting control over the near-infrared (NIR) plasmonic response of nanosized metals and semiconductors can facilitate access to unexplored phenomena and applications. Here we combine electrostatic self-assembly and Cd(2+)/Cu(+) cation exchange to obtain an anisotropic core-shell nanoparticle cluster (NPC) whose optical properties stem from two dissimilar plasmonic materials: a gold nanorod (AuNR) core and a copper selenide (Cu(2-x)Se, x ≥ 0) supraparticle shell. The spectral response of the AuNR@Cu2Se NPCs is governed by the transverse and longitudinal plasmon bands (LPB) of the anisotropic metallic core, since the Cu2Se shell is nonplasmonic. Under aerobic conditions the shell undergoes vacancy doping (x > 0), leading to the plasmon-rich NIR spectrum of the AuNR@Cu(2-x)Se NPCs. For low vacancy doping levels the NIR optical properties of the dually plasmonic NPCs are determined by the LPBs of the semiconductor shell (along its major longitudinal axis) and of the metal core. Conversely, for high vacancy doping levels their NIR optical response is dominated by the two most intense plasmon modes from the shell: the transverse (along the shortest transversal axis) and longitudinal (along the major longitudinal axis) modes. The optical properties of the NPCs can be reversibly switched back to a purely metallic plasmonic character upon reversible conversion of AuNR@Cu(2-x)Se into AuNR@Cu2Se. Such well-defined nanosized colloidal assemblies feature the unique ability of holding an all-metallic, a metallic/semiconductor, or an all-semiconductor plasmonic response in the NIR. Therefore, they can serve as an ideal platform to evaluate the crosstalk between plasmonic metals and plasmonic semiconductors at the nanoscale. Furthermore, their versatility to display plasmon modes in the first, second, or both NIR windows is particularly advantageous for bioapplications, especially considering their strong absorbing and near-field enhancing properties.

  17. 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.

  18. 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.

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

    SciTech Connect

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

    2007-07-01

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

  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

  1. Insights into the chemical composition of the metal-poor Milky Way halo globular cluster NGC 6426

    NASA Astrophysics Data System (ADS)

    Hanke, M.; Koch, A.; Hansen, C. J.; McWilliam, A.

    2017-03-01

    We present our detailed spectroscopic analysis of the chemical composition of four red giant stars in the halo globular cluster NGC 6426. We obtained high-resolution spectra using the Magellan2/MIKE spectrograph, from which we derived equivalent widths and subsequently computed abundances of 24 species of 22 chemical elements. For the purpose of measuring equivalent widths, we developed a new semi-automated tool, called EWCODE. We report a mean Fe content of [Fe/H] =-2.34 ± 0.05 dex (stat.) in accordance with previous studies. At a mean α-abundance of [(Mg, Si, Ca)/3 Fe] = 0.39 ± 0.03 dex, NGC 6426 falls on the trend drawn by the Milky Way halo and other globular clusters at comparably low metallicities. The distribution of the lighter α-elements as well as the enhanced ratio [Zn/Fe] = 0.39 dex could originate from hypernova enrichment of the pre-cluster medium. We find tentative evidence for a spread in the elements Mg, Si, and Zn, indicating an enrichment scenario, where ejecta of evolved massive stars of a slightly older population have polluted a newly born younger one. The heavy element abundances in this cluster fit well into the picture of metal-poor globular clusters, which in that respect appear to be remarkably homogeneous. The pattern of the neutron-capture elements heavier than Zn points toward an enrichment history governed by the r-process with little, if any, sign of s-process contributions. This finding is supported by the striking similarity of our program stars to the metal-poor field star HD 108317. This paper includes data gathered with the 6.5-m Magellan Telescopes located at Las Campanas Observatory, Chile.Equivalent widths and full Table 2 are only available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (http://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/599/A97

  2. Preparation and hydriding behavior of magnesium metal clusters formed in low-temperature cocondensation: application of magnesium for hydrogen storage

    SciTech Connect

    Imamura, H.; Nobunaga, T.; Kawahigashi, M.; Tsuchiya, S.

    1984-08-01

    Magnesium metal clusters formed in low-temperature matrices were investigated with a view to forming the metal hydride. In practice, magnesium readily absorbed large amounts of hydrogen under more moderate conditions (P/sub H/sub 2// = 460 torr, T = 200-250/sup 0/C) when it had been transformed into tetrahydrofuran- (THF-) solvated small particles formed by the cocondensation reaction of magnesium atoms with THF molecules at -196/sup 0/C. To elucidate the characteristics of hydrogen sorption of Mg-THF, a comparative study with pure magnesium powder was carried out. It is believed from the H/sub 2/-D/sub 2/ isotope scrambling measurements that the high activity of the present Mg-THF system for hydrogen absorption is due to a rapid surface process in comparison with the case of the pure magnesium. This identification is reinforced by the employment of surface modification. 19 references, 2 figures, 1 table.

  3. Coordination structure and charge transfer in microsolvated transition metal hydroxide clusters [MOH](+)(H2O)1-4.

    PubMed

    Marsh, Brett M; Voss, Jonathan M; Zhou, Jia; Garand, Etienne

    2015-09-21

    Infrared vibrational predissociation spectra of transition metal hydroxide clusters, [MOH](+)(H2O)1-4·D2 with M = Mn, Fe, Co, Ni, Cu, and Zn, are presented and analyzed with the aid of density functional theory calculations. For the [MnOH](+), [FeOH](+), [CoOH](+) and [ZnOH](+) species, we find that the first coordination shell contains three water molecules and the four ligands are arranged in a distorted tetrahedral geometry. [CuOH](+) can have either two or three water molecules in the first shell arranged in a planar arrangement, while [NiOH](+) has an octahedral ligand geometry with the first shell likely closed with five water molecules. Upon closure of the first coordination shell, characteristic stretch frequencies of hydrogen-bonded OH in the 2500-3500 cm(-1) region are used to pinpoint the location of the water molecule in the second shell. The relative energetics of different binding sites are found to be metal dependent, dictated by the first-shell coordination geometry and the charge transfer between the hydroxide and the metal center. Finally, the frequency of the hydroxide stretch is found to be sensitive to the vibrational Stark shift induced by the charged metal center, as observed previously for the smaller [MOH](+)(H2O) species. Increasing solvation modulates this frequency by reducing the extent of the charge transfer while elongating the M-OH bond.

  4. THE X-RAY LUMINOSITY FUNCTION OF LOW MASS X-RAY BINARIES IN EARLY-TYPE GALAXIES, THEIR METAL-RICH, AND METAL-POOR GLOBULAR CLUSTERS

    SciTech Connect

    Peacock, Mark B.; Zepf, Stephen E.

    2016-02-10

    We present the X-ray luminosity function (XLF) of low-mass X-ray binaries (LMXBs) in the globular clusters (GCs) and fields of seven early-type galaxies. These galaxies are selected to have both deep Chandra observations, which allow their LMXB populations to be observed to X-ray luminosities of 10{sup 37}–10{sup 38} erg s{sup −1}, and Hubble Space Telescope optical mosaics that enable the X-ray sources to be separated into field LMXBs, GC LMXBs, and contaminating background and foreground sources. We find that at all luminosities the number of field LMXBs per stellar mass is similar in these galaxies. This suggests that the field LMXB populations in these galaxies are not effected by the GC specific frequency, and that properties such as binary fraction and the stellar initial mass function are either similar across the sample or change in a way that does not affect the number of LMXBs. We compare the XLF of the field LMXBs to that of the GC LMXBs and find that they are significantly different with a p-value of 3 × 10{sup −6} (equivalent to 4.7σ for a normal distribution). The difference is such that the XLF of the GC LMXBs is flatter than that of the field LMXBs, with the GCs hosting relatively more bright sources and fewer faint sources. A comparison of the XLF of the metal-rich and metal-poor GCs hints that the metal-poor clusters may have more bright LMXBs, but the difference is not statistically significant.

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

    PubMed Central

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

    2011-01-01

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

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

    NASA Technical Reports Server (NTRS)

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

    1986-01-01

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

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

    SciTech Connect

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

    2007-04-06

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

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

    NASA Astrophysics Data System (ADS)

    Jaiswal, Abhishek; Egami, Takeshi; Zhang, Yang

    2015-04-01

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

  9. Visible tunable lighting system based on polymer composites embedding ZnO and metallic clusters: from colloids to thin films

    PubMed Central

    Truong, Thai Giang; Dierre, Benjamin; Grasset, Fabien; Saito, Noriko; Saito, Norio; Nguyen, Thi Kim Ngan; Takahashi, Kohsei; Uchikoshi, Tetsuo; Amela-Cortes, Marian; Molard, Yann; Cordier, Stéphane; Ohashi, Naoki

    2016-01-01

    Abstract The development of phosphor devices free of heavy metal or rare earth elements is an important issue for environmental reasons and energy efficiency. Different mixtures of ZnO nanocrystals with Cs2Mo6I8(OOC2F5)6 cluster compound (CMIF) dispersed into polyvinylpyrrolidone matrix have been prepared by very simple and low cost solution chemistry. The resulting solutions have been used to fabricate highly transparent and luminescent films by dip coating free of heavy metal or rare earth elements. The luminescence properties of solution and dip-coated films were investigated. The luminescence of such a system is strongly dependent on the ratios between ZnO and CMIF amounts, the excitation wavelength and the nature of the system. By varying these two parameters (ratio and wavelength), a large variety of colors, from blue to red as well as white, can be achieved. In addition, differences in the luminescence properties have been observed between solutions and thin films as well as changes of CMIF emission band maximum wavelength. This may suggest some possible interactions between the different luminophore centers, such as energy transfer or ligands exchange on the Mo6 clusters. PMID:27877895

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

    DOE PAGES

    Jaiswal, Abhishek; Egami, Takeshi; Zhang, Yang

    2015-04-01

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

  11. On the Question of Site-Selective Ligand Exchange in Carboxylate-Substituted Metal Oxo Clusters

    PubMed Central

    Kreutzer, Johannes; Czakler, Matthias; Puchberger, Michael; Pittenauer, Ernst; Schubert, Ulrich

    2015-01-01

    Reaction of [Ti4Zr4O6(OBu)4(OMc)16] (OMc = methacrylate) with acetylacetone (acacH) resulted in dissection of the cluster and formation of [Ti(OBu)2(acac)2] and the smaller cluster [Ti2Zr4O4(OMc)16]. In contrast, the same reaction with [Zr6O4(OH)4(OOCR)12]2·6RCOOH (R = Et, CH2CH=CH2) led to site-selective substitution of two carboxylate ligands and formation of isostructural [Zr6O4(OH)4(OOCR)12–x(acac)x]2·6RCOOH (x ≤ 1). PMID:26300687

  12. Mononuclear Clusterfullerene Single‐Molecule Magnet Containing Strained Fused‐Pentagons Stabilized by a Nearly Linear Metal Cyanide Cluster

    PubMed Central

    Liu, Fupin; Wang, Song; Gao, Cong‐Li; Deng, Qingming; Zhu, Xianjun; Kostanyan, Aram; Westerström, Rasmus; Jin, Fei

    2017-01-01

    Abstract Fused‐pentagons results in an increase of local steric strain according to the isolated pentagon rule (IPR), and for all reported non‐IPR clusterfullerenes multiple (two or three) metals are required to stabilize the strained fused‐pentagons, making it difficult to access the single‐atom properties. Herein, we report the syntheses and isolations of novel non‐IPR mononuclear clusterfullerenes MNC@C76 (M=Tb, Y), in which one pair of strained fused‐pentagon is stabilized by a mononuclear cluster. The molecular structures of MNC@C76 (M=Tb, Y) were determined unambiguously by single‐crystal X‐ray diffraction, featuring a non‐IPR C 2v(19138)‐C76 cage entrapping a nearly linear MNC cluster, which is remarkably different from the triangular MNC cluster within the reported analogous clusterfullerenes based on IPR‐obeying C82 cages. The TbNC@C76 molecule is found to be a field‐induced single‐molecule magnet (SMM). PMID:28079303

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

    NASA Astrophysics Data System (ADS)

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

    2015-06-01

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

  14. CO(v=1) population lifetimes of metal-carbonyl cluster compounds in dilute CHCl3 solution

    NASA Astrophysics Data System (ADS)

    Heilweil, E. J.; Cavanagh, R. R.; Stephenson, J. C.

    1988-07-01

    Tunable infrared picosecond pulses in the 5 μ region have been used for time-resolved pump-probe measurements of the population relaxation lifetime (T1) of CO(v=1) stretching vibrations in a series of metal-carbonyl cluster compounds in room temperature chloroform solution. T1 was the same for symmetric (ν=2084 cm-1, 90±10 ps) and antisymmetric (2014 cm-1, 87±10 ps) modes of the dicarbonyl Rh(CO)2(C5H7O2); T1 was the same for the B1 (2092 cm-1, 710±130 ps) and B2 (2036 cm-1, 750±90 ps) modes of Rh2(CO)4Cl2. Similarly long T1 times were found for Rh4(CO)12 (2075 cm-1, 610±65 ps) and Rh6(CO)16 (2077 cm-1, 700±100 ps). The molecule Co4(CO)12 has also been compared to the corresponding rhodium analog and it exhibits an initially fast relaxation of 47±5 ps followed by a slower 396±70 ps decay. The transient response of the more complex systems to the single frequency experiment is found to be sensitive to frequency and can exhibit bleaching, absorption, and a combination of these effects. Such behavior is attributed to overlap of the IR pulse with v=1 to v=2 and higher transitions in the M4(CO)12 (M=Rh or Co) and Rh6(CO)16 molecules. The long CO(v=1) T1 values for the metal cluster molecules suggest relaxation via multiquantum transfer of vibrational energy to adjacent M-C stretch and M-C-O bend vibrations; energy transfer to vibrational or electronic states of the central metal core seems unimportant in determining T1 for these systems.

  15. [Study on the infrared spectra of metallic clusters containing R2dtc ligand and V = O group].

    PubMed

    Zhu, H; Chen, C; Yang, Y; Deng, Y; Zhang, Y; Liu, Q

    2000-12-01

    This paper reports the features and regularities of the infrared spectra for two kinds of complexes containing R2dtc ligand. The cubane-like clusters containing R2dtc ligand possess weak and wide peaks at 400-500 cm-1 assigned to M-mu 3S vibration, while the peaks at 330-380 cm-1 and 1,470-1,510 cm-1 can be assigned to M-Sdtc and C-N vibrations, respectively. The nu(C-N) and nu(C = S) vibrations for Me2dtc-cubane cluster exhibit blue shift and red shift, respectively, when compared with those of other R2dtc ones. This would be attributed to the strong super-conjugation of the methyl group. The M-mu 3S vibrations for both types of complexes [V2Cu2S4(R2dtc)2(PhS)2]2- and [VCu4S4(R2dtc)n(PhS)4-n]3- (n = 0, 1, 2) occur at 480 and 465 cm-1, respectively. This small difference becomes a useful indication to distinguish the two types of clusters. Cluster complexes containing (R2dtc)2V2O2(mu-S)2 structural unit show the V = O vibration in the range of 844-970 cm-1. It is noted that (Et4N)[V3S2O3(Et2dtc)3] contains two sets of the V = O bonds corresponding to two sets of V = O vibrations at 970 and 844 cm-1. An additional coordination of the V = O bond to another metal atom obviously weakens the V = O bond to give rise to the red shift of the infrared frequency. Similar red shifts were also observed for other complexes and were discussed.

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

    NASA Astrophysics Data System (ADS)

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

    2016-08-01

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

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

    DOE PAGES

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

    2016-07-27

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

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

    SciTech Connect

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

    2016-07-27

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

  19. Noble metal-titania hybrid nanoparticle clusters and the interaction to proteins for photo-catalysis in aqueous environments.

    PubMed

    Tsai, Tung-Yu; Wang, Hong-Li; Chen, Yi-Chen; Chang, Wei-Chang; Chang, Je-Wei; Lu, Shih-Yuan; Tsai, De-Hao

    2017-03-15

    We report a systematic study of the controlled synthesis of new hybrid spherical TiO2 nanoparticle cluster (TiO2-NPC) homogeneously decorated with noble metal nanoparticles (NPs) by gas-phase evaporation-induced self-assembly. Silver NP (AgNP) was used as the representative noble metal NP. The degradation of methyl blue (MB) in the aqueous solution was chosen as the representative system for the study of photocatalysis, which were tested and evaluated with respect to irradiation conditions and the presence of bovine serum albumin (BSA). The results show that particle size and chemical composition of the hybrid nanostructure were tunable by choosing the suitable concentration of precursors. The photocatalytic activity of AgNP-decorated TiO2-NPC was strongly affected by the light irradiation and the ligand-nanoparticle interfacial interaction. The presence of BSA influenced molecular conjugation to the surface of the hybrid nanostructure. Under conditions of simultaneous competitive adsorption of MB and BSA, the combination of AgNPs improved the photocatalytic activity of the TiO2-NPC-based catalysts. Our work describes a prototype methodology to fabricate TiO2-NPC homogeneously decorated with noble metal NPs with well-controlled material properties. The mechanistic understanding developed in this study can be useful for the future optimization of material properties of hybrid nanostructures versus interfacial interactions with the surrounding molecules.

  20. Ceci N'est Pas a globular cluster: the metallicity distribution of the stellar system Terzan 5

    SciTech Connect

    Massari, D.; Mucciarelli, A.; Ferraro, F. R.; Lanzoni, B.; Dalessandro, E.; Lovisi, L.; Rich, R. M.; Reitzel, D.; Valenti, E.; Ibata, R.

    2014-11-01

    We present new determinations of the iron abundance for 220 stars belonging to the stellar system Terzan 5 in the Galactic bulge. The spectra have been acquired with FLAMES at the Very Large Telescope of the European Southern Observatory and DEIMOS at the Keck II Telescope. This is by far the largest spectroscopic sample of stars ever observed in this stellar system. From this data set, a subsample of targets with spectra unaffected by TiO bands was extracted and statistically decontaminated from field stars. Once combined with 34 additional stars previously published by our group, a total sample of 135 member stars covering the entire radial extent of the system has been used to determine the metallicity distribution function of Terzan 5. The iron distribution clearly shows three peaks: a super-solar component at [Fe/H] ≅ 0.25 dex, accounting for ∼29% of the sample, a dominant sub-solar population at [Fe/H] ≅ –0.30 dex, corresponding to ∼62% of the total, and a minor (6%) metal-poor component at [Fe/H] ≅ –0.8 dex. Such a broad, multi-modal metallicity distribution demonstrates that Terzan 5 is not a genuine globular cluster but the remnant of a much more complex stellar system.

  1. Spectroscopic study of globular clusters in the halo of M31 with the Xinglong 2.16 m telescope II: dynamics, metallicity and age

    NASA Astrophysics Data System (ADS)

    Fan, Zhou; Huang, Ya-Fang; Li, Jin-Zeng; Zhou, Xu; Ma, Jun; Zhao, Yong-Heng

    2012-07-01

    In Paper I, we performed spectroscopic observations on 11 confirmed globular clusters (GCs) in M31 with the Xinglong 2.16 m telescope. We mainly focused on the fitting method and the metallicity gradient for the M31 GC sample. Here, we analyze and further discuss the dynamics, metallicity and age, and their distributions, as well as the relationships between these parameters. In our work, eight more confirmed GCs in the halo of M31 were observed, most of which lack previous spectroscopic information. These star clusters are located far from the galactic center at a projected radius of ~ 14 to ~ 117 kpc, which is more spatially extended than that in the previous work. Firstly, we measured the Lick absorption-line indices and the radial velocities. Then the ages and metallicity values of [Fe/H] and [α/Fe] were fitted by comparing the observed spectral feature indices and the Single Stellar Population model of Thomas et al. in the Cassisi and Padova stellar evolutionary tracks, respectively. Our results show that most of the star clusters in our sample are older than 10 Gyr except B290, which is ~ 5.5 Gyr, and most of them are metal-poor with metallicity [Fe/H] < -1, suggesting that these clusters were born at the early stage of the galaxy's formation. We find that the metallicity gradient for the outer halo clusters with rp > 25 kpc may have an insignificant slope of -0.005 ± 0.005 dex kpc-1 and if the outliers G001 and H11 are excluded, the slope does not change significantly, with a value of -0.002 ± 0.003 dex kpc-1. We also find that the metallicity is not a function of age for the GCs with age < 7 Gyr, but for the old GCs with age > 7 Gyr, there seems to be a trend that the older ones have lower metallicity. Additionally, we plot metallicity distributions with the largest sample of M31 GCs so far and show the bimodality is not significant, and the number of metal-poor and metal-rich groups becomes comparable. The spatial distributions show that the metal

  2. Chemical reactivity on gas-phase metal clusters driven by blackbody infrared radiation.

    PubMed

    Parry, Imogen S; Kartouzian, Aras; Hamilton, Suzanne M; Balaj, O Petru; Beyer, Martin K; Mackenzie, Stuart R

    2015-01-19

    We report the observation of chemical reactions in gas-phase Rh(n)(N2O)m(+) complexes driven by absorption of blackbody radiation. The experiments are performed under collision-free conditions in a Fourier transform ion cyclotron resonance mass spectrometer. Mid-infrared absorption by the molecularly adsorbed N2O moieties promotes a small fraction of the cluster distribution sufficiently to drive the N2O decomposition reaction, leading to the production of cluster oxides and the release of molecular nitrogen. N2O decomposition competes with molecular desorption and the branching ratios for the two processes show marked size effects, reflecting variations in the relative barriers. The rate of decay is shown to scale approximately linearly with the number of infrared chromophores. The experimental findings are interpreted in terms of calculated infrared absorption rates assuming a sudden-death limit.

  3. Controllable Encapsulation of "Clean" Metal Clusters within MOFs through Kinetic Modulation: Towards Advanced Heterogeneous Nanocatalysts.

    PubMed

    Liu, Hongli; Chang, Lina; Bai, Cuihua; Chen, Liyu; Luque, Rafael; Li, Yingwei

    2016-04-11

    Surfactant-free tiny Pt clusters were successfully encapsulated within MOFs with controllable size and spatial distribution by a novel kinetically modulated one-step strategy. Our synthesis relies on the rational manipulation of the reduction rate of Pt ions and/or the growth rate of MOFs by using H2 as assistant reducing agent and/or acetic acid as MOF-formation modulator. The as-prepared Pt@MOF core-shell composites exhibited exceedingly high activity and excellent selectivity in the oxidation of alcohols as a result of the ultrafine "clean" Pt clusters, as well as interesting molecular-sieving effects derived from the outer platinum-free MOF shell.

  4. Asbestos/NESHAP adequately wet guidance

    SciTech Connect

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

    1990-12-01

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

  5. THE PREPARATION OF CURRICULUM MATERIALS AND THE DEVELOPMENT OF TEACHERS FOR AN EXPERIMENTAL APPLICATION OF THE CLUSTER CONCEPT OF VOCATIONAL EDUCATION AT THE SECONDARY SCHOOL LEVEL. VOLUME III, INSTRUCTIONAL PLANS FOR THE METAL FORMING AND FABRICATION CLUSTER.

    ERIC Educational Resources Information Center

    MALEY, DONALD

    DESIGNED FOR USE WITH 11TH AND 12TH GRADE STUDENTS, THIS CURRICULUM GUIDE FOR THE OCCUPATIONAL CLUSTER IN METAL FORMING AND FABRICATION WAS DEVELOPED BY PARTICIPATING TEACHERS FROM RESULTS OF THE RESEARCH PROCEDURES DESCRIBED IN VOLUME I (VT 004 162). THE COURSE DESCRIPTION, NEED FOR THE COURSE, COURSE OBJECTIVES, PROCEDURES AND INSTRUCTIONAL PLAN…

  6. Radial Distribution of ISM Gas-phase Metallicity in CLASH Clusters at z ~ 0.35: A New Outlook on Environmental Impact on Galaxy Evolution

    NASA Astrophysics Data System (ADS)

    Gupta, Anshu; Yuan, Tiantian; Tran, Kim-Vy H.; Martizzi, Davide; Taylor, Philip; Kewley, Lisa J.

    2016-11-01

    We present the first observation of cluster-scale radial metallicity gradients from star-forming galaxies. We use DEIMOS on the Keck II telescope to observe two CLASH clusters at z ˜ 0.35: MACS J1115+0129 and RX J1532+3021. Based on our measured interstellar medium properties of star-forming galaxies out to a radius of 2.5 Mpc from the cluster center, we find that the galaxy metallicity decreases as a function of projected cluster-centric distance (-0.15 ± 0.08 dex/Mpc) in MACS 1115+01. On the mass-metallicity relation (MZR), star-forming galaxies in MACS J1115+01 are offset to higher metallicity (˜0.2 dex) than the local Sloan Digital Sky Survey galaxies at a fixed mass range. In contrast, the MZR of RX J1532+30 is consistent with the local comparison sample. RX J1532+30 exhibits a bimodal radial metallicity distribution, with one branch showing a similar negative gradient to MACS J1115+01 (-0.14 ± 0.05 dex/Mpc) and the other branch showing a positive radial gradient. The positive gradient branch in RX J1532+30 is likely caused by either interloper galaxies or an in-plane merger, indicating that cluster-scale abundance gradients probe cluster substructures and thus the dynamical state of a cluster. Most strikingly, we discover that neither the radial metallicity gradient nor the offset from the MZR is driven by the stellar mass. We compare our observations with Rhapsody-G cosmological hydrodynamical zoom-in simulations of relaxed galaxy clusters and find that the simulated galaxy cluster also exhibits a negative abundance gradient, albeit with a shallower slope (-0.04 ± 0.03 dex/Mpc). Our observations suggest that the negative radial gradient originates from ram pressure stripping and/or strangulation processes in the cluster environments.

  7. Structural, electronic and magnetic properties of 3d metal trioxide clusters-doped monolayer graphene: A first-principles study

    NASA Astrophysics Data System (ADS)

    Rafique, Muhammad; Shuai, Yong; Tan, He-Ping; Hassan, Muhammad

    2017-03-01

    We present first-principles density-functional calculations for the structural, electronic and magnetic properties of monolayer graphene doped with 3d (Ti, V, Cr, Fe, Co, Mn and Ni) metal trioxide TMO3 halogen clusters. In this paper we used two approaches for 3d metal trioxide clusters (i) TMO3 halogen cluster was embedded in monolayer graphene substituting four carbon (C) atoms (ii) three C atoms were substituted by three oxygen (O) atoms in one graphene ring and TM atom was adsorbed at the hollow site of O atoms substituted graphene ring. All the impurities were tightly bonded in the graphene ring. In first case of TMO3 doped graphene layer, the bond length between Csbnd O atom was reduced and bond length between TM-O atom was increased. In case of Cr, Fe, Co and Ni atoms substitution in between the O atoms, leads to Fermi level shifting to conduction band thereby causing the Dirac cone to move into valence band, however a band gap appears at high symmetric K-point. In case of TiO3 and VO3 substitution, system exhibits semiconductor properties. Interestingly, TiO3-substituted system shows dilute magnetic semiconductor behavior with 2.00 μB magnetic moment. On the other hand, the substitution of CoO3, CrO3, FeO3 and MnO3 induced 1.015 μB, 2.347 μB, 2.084 μB and 3.584 μB magnetic moment, respectively. In second case of O atoms doped in graphene and TM atoms adsorbed at the hollow site, the O atom bulges out of graphene plane and bond length between TM-O atom is increased. After TM atoms adsorption at the O substituted graphene ring the Fermi level (EF) shifts into conduction band. In case of Cr and Ni adsorption, system displays indirect band gap semiconductor properties with 0.0 μB magnetic moment. Co adsorption exhibits dilute magnetic semiconductor behavior producing 0.916 μB magnetic moment. Fe, Mn, Ti and V adsorption introduces band gap at high symmetric K-point also inducing 1.54 μB, 0.9909 μB, 1.912 μB, and 0.98 μB magnetic moments, respectively

  8. Expansion flow and cluster distributions originating from ultrafast-laser-induced fragmentation of thin metal films: A molecular-dynamics study

    SciTech Connect

    Upadhyay, Arun K.; Urbassek, Herbert M.

    2006-01-15

    Using molecular-dynamics simulation, we study the fragmentation patterns of ultrathin metal films as a function of the initial energization. The energization is assumed to occur instantaneously. Above the threshold for fragmentation, a homogeneous expansion of the exploding film is observed, in which a mixture of clusters of all sizes is found. The internal temperature of the clusters is constant, independent of space, time, and cluster size. The cluster size distribution can be characterized for small energizations as a biexponential distribution, but is better represented for larger energizations by a power law in cluster size m,{proportional_to}m{sup -{alpha}}, with an exponent {alpha} congruent with 2.8-3.1.

  9. Clear Evidence for the Presence of Second-generation Asymptotic Giant Branch Stars in Metal-poor Galactic Globular Clusters

    NASA Astrophysics Data System (ADS)

    García-Hernández, D. A.; Mészáros, Sz.; Monelli, M.; Cassisi, S.; Stetson, P. B.; Zamora, O.; Shetrone, M.; Lucatello, S.

    2015-12-01

    Galactic globular clusters (GCs) are known to host multiple stellar populations: a first generation (FG) with a chemical pattern typical of halo field stars and a second generation (SG) enriched in Na and Al and depleted in O and Mg. Both stellar generations are found at different evolutionary stages (e.g., the main-sequence turnoff, the subgiant branch, and the red giant branch (RGB)). The non detection of SG asymptotic giant branch (AGB) stars in several metal-poor ([Fe/H] < -1) GCs suggests that not all SG stars ascend the AGB phase, and that failed AGB stars may be very common in metal-poor GCs. This observation represents a serious problem for stellar evolution and GC formation/evolution theories. We report fourteen SG-AGB stars in four metal-poor GCs (M13, M5, M3, and M2) with different observational properties: horizontal branch (HB) morphology, metallicity, and age. By combining the H-band Al abundances obtained by the Apache Point Observatory Galactic Evolution Experiment survey with ground-based optical photometry, we identify SG Al-rich AGB stars in these four GCs and show that Al-rich RGB/AGB GC stars should be Na-rich. Our observations provide strong support for present, standard stellar models, i.e., without including a strong mass-loss efficiency, for low-mass HB stars. In fact, current empirical evidence is in agreement with the predicted distribution of FG and SG stars during the He-burning stages based on these standard stellar models.

  10. Funding the Formula Adequately in Oklahoma

    ERIC Educational Resources Information Center

    Hancock, Kenneth

    2015-01-01

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

  11. In search for new bonding modes of the methylenedithiolato ligand: novel tri- and tetra-metallic clusters.

    PubMed

    Anju, R S; Saha, Koushik; Mondal, Bijan; Roisnel, Thierry; Halet, Jean-François; Ghosh, Sundargopal

    2015-07-07

    Building upon our earlier results on the chemistry of diruthenium analogue of pentaborane (9) with heterocumulenes, we continued to investigate the reactivity of arachno-[(Cp*Ru)2(B3H8)(CS2H)], 1, (Cp* = η(5)-C5Me5) towards group 7 and 8 transition metal carbonyl compounds under photolytic and thermolytic conditions. The metal carbonyl compounds show diverse reactivity pattern with arachno-1. For example, the photolysis of arachno-1 with [Re2(CO)10] yielded [(Cp*Ru)2B3H5(CH2S2){Re(CO)4}2], 2, [(Cp*RuCO)2(μ-H)2(CH2S2){Re(CO)4}{Re(CO)3}], 3 and [(Cp*Ru)2(μ-CO)(μ-H)(CH2S2){Re(CO)3}], 4. The geometry of 2 with a nearly planar eight-membered ring containing heavier transition metals rhenium, ruthenium is unprecedented. Compounds 3 and 4 can be considered as M4-quadrilateral and M3-triangle with a methylenedithiolato ligand attached to the metal centres, respectively. [Mn2(CO)10], on the other hand, reacts with arachno-1 to yield heterometallic binuclear [(Cp*RuCO){Mn(CO)4}(μ-H)(SCH3)], 5 and homocubane [(Cp*Ru)2{Mn(CO)3}-(CS2H2)B3H4], 6. In an attempt to generate group 8 analogues of 2-5, we performed the reaction of arachno-1 with [Fe2(CO)9] and [Ru3(CO)12]. Although, the objective of isolating analogous compounds was not achieved, the reaction with [Fe2(CO)9] led to novel tetrahedral cluster [(Cp*RuCO){(Fe(CO)3}2S(μ-H)], 7. [Ru3(CO)12], in contrast, yielded known compounds [{Cp*Ru(CO)}2B2H6], 9 and [Cp*Ru(CO)2]2, 10. All the cluster compounds have been characterized by mass spectrometry, IR, and (1)H, (11)B, and (13)C NMR spectroscopy, and the geometric structures were unequivocally established by crystallographic analysis of 2-5 and 7.

  12. CCD time-series photometry of variable stars in globular clusters and the metallicity dependence of the horizontal branch luminosity

    NASA Astrophysics Data System (ADS)

    Arellano Ferro, A.; Bramich, D. M.; Giridhar, S.

    2017-04-01

    We describe and summarize the findings from our CCD time-series photometry of globular clusters (GCs) program and the use of difference image analysis (DIA) in the extraction of precise light curves down to V≍19 mag in crowded regions. We have discovered approximately 250 variable stars in a sample of 23 selected GCs. The absolute magnitude and [Fe/H] for each individual RR Lyrae is obtained via the Fourier decomposition of the light curve. An average of these parameters leads to the distance and metallicity of the host GCs. We present the mean [Fe/H], MV and distance for 26 GCs based exclusively on the RR Lyrae light curve Fourier decomposition technique on an unprecedented homogeneous scale. We also discuss the luminosity dependence of the horizontal branch (HB) via the MV-[Fe/H] relation. We find that this relation should be considered separately for the RRab and RRc stars.

  13. METAL-MASS-TO-LIGHT RATIOS OF THE PERSEUS CLUSTER OUT TO THE VIRIAL RADIUS

    SciTech Connect

    Matsushita, K.; Sakuma, E.; Sasaki, T.; Sato, K.; Simionescu, A.

    2013-02-20

    We analyzed XMM-Newton data of the Perseus cluster out to {approx}1 Mpc, or approximately half the virial radius. Using the flux ratios of Ly{alpha} lines of H-like Si and S to K{alpha} line of He-like Fe, the abundance ratios of Si/Fe and S/Fe of the intracluster medium (ICM) were derived using the APEC plasma code v2.0.1. The temperature dependence of the line ratio limits the systematic uncertainty in the derived abundance ratio. The Si/Fe and S/Fe in the ICM of the Perseus cluster show no radial gradient. The emission-weighted averages of the Si/Fe and S/Fe ratios outside the cool core are 0.91 {+-} 0.08 and 0.93 {+-} 0.10, respectively, in solar units according to the solar abundance table of Lodders. These ratios indicate that most Fe was synthesized by supernovae Ia. We collected K-band luminosities of galaxies and calculated the ratio of Fe and Si mass in the ICM to K-band luminosity, iron-mass-to-light ratio (IMLR), and silicon-mass-to-light ratio (SMLR). Within {approx}1 Mpc, the cumulative IMLR and SMLR increase with radius. Using Suzaku data for the northwest and east directions, we also calculated the IMLR out to {approx}1.8 Mpc, or about the virial radius. We constrained the SMLR out to this radius and discussed the slope of the initial mass function of stars in the cluster. Using the cumulative IMLR profile, we discuss the past supernova Ia rate.

  14. VizieR Online Data Catalog: On the metallicity of open clusters. III. (Netopil+, 2016)

    NASA Astrophysics Data System (ADS)

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

    2016-03-01

    In Paper II (Heiter et al., Paper II 2014A&A...561A..93H) we have evaluated available spectroscopic iron abundance determinations of open cluster stars and presented mean values for 78 open clusters. The results are based on high-resolution data (R>=25000) with high signal-to-noise ratios (S/N>=50). Furthermore, quality criteria were introduced by adopting only [Fe/H] measurements of stars with Teff=4400-6500K and logg>=2.0dex. We have to note that the mean iron abundance for Berkeley 29, listed in Paper II, also incorporates some measurements based upon lower S/N data. In the present paper we therefore list the correct values for the higher and lower quality data. Since publication of Paper II, some new studies were made (Boesgaard et al., 2013ApJ...775...58B; Bocek Topcu et al., 2015, Cat. J/MNRAS/446/3562; Carraro et al., 2014A&A...568A..86C; Donati et al., 2015, Cat. J/MNRAS/446/1411; Magrini et al.. 2014A&A...563A..44M, 2015A&A...580A..85M; Molenda-Zakowicz et al., 2014MNRAS.445.2446M; Monaco et al., 2014A&A...564L...6M; Reddy et al., 2015MNRAS.450.4301R), which we examined the same way as described in Paper II. This adds ten open clusters to our list (Berkeley 81, NGC 1342, NGC 1662, NGC 1912, NGC 2354, NGC 4337, NGC 4815, NGC 6811, Trumpler 5, and Trumpler 20) and supplementary data for NGC 752, NGC 2447, NGC 2632, and NGC 6705. (1 data file).

  15. Metal-mass-to-light Ratios of the Perseus Cluster Out to the Virial Radius

    NASA Astrophysics Data System (ADS)

    Matsushita, K.; Sakuma, E.; Sasaki, T.; Sato, K.; Simionescu, A.

    2013-02-01

    We analyzed XMM-Newton data of the Perseus cluster out to ~1 Mpc, or approximately half the virial radius. Using the flux ratios of Lyα lines of H-like Si and S to Kα line of He-like Fe, the abundance ratios of Si/Fe and S/Fe of the intracluster medium (ICM) were derived using the APEC plasma code v2.0.1. The temperature dependence of the line ratio limits the systematic uncertainty in the derived abundance ratio. The Si/Fe and S/Fe in the ICM of the Perseus cluster show no radial gradient. The emission-weighted averages of the Si/Fe and S/Fe ratios outside the cool core are 0.91 ± 0.08 and 0.93 ± 0.10, respectively, in solar units according to the solar abundance table of Lodders. These ratios indicate that most Fe was synthesized by supernovae Ia. We collected K-band luminosities of galaxies and calculated the ratio of Fe and Si mass in the ICM to K-band luminosity, iron-mass-to-light ratio (IMLR), and silicon-mass-to-light ratio (SMLR). Within ~1 Mpc, the cumulative IMLR and SMLR increase with radius. Using Suzaku data for the northwest and east directions, we also calculated the IMLR out to ~1.8 Mpc, or about the virial radius. We constrained the SMLR out to this radius and discussed the slope of the initial mass function of stars in the cluster. Using the cumulative IMLR profile, we discuss the past supernova Ia rate.

  16. Structure and Energetics of Macromolecular Systems: POSS, Metal Clusters and other Oligomeric Molecules

    DTIC Science & Technology

    2006-03-31

    n = 2 to 13). These systems have been shown to have size-dependent catalytic behavior for double bond oxidation in small alkenes when dispersed on...Dunbar, 227, 205 (2003). 4. Bonding Interactions in Ag+(O 2)n and Ag2+(0 2). Clusters: Experiment and Theory, M. J. Manard, P. R. Kemper, and M. T. Bowers...G. P. Bartholomew , G. C. Bazan, and M. T. Bowers, J. Am. Chem. Soc. 126, 6255 (2004). 7. The Determination of Cis-Trans Conformations in Tetrahedral

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

    SciTech Connect

    Jaiswal, Abhishek; Egami, Takeshi; Zhang, Yang

    2015-04-01

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

  18. The Herschel Virgo Cluster Survey. V. Star-forming dwarf galaxies - dust in metal-poor environments

    NASA Astrophysics Data System (ADS)

    Grossi, M.; Hunt, L. K.; Madden, S.; Vlahakis, C.; Bomans, D. J.; Baes, M.; Bendo, G. J.; Bianchi, S.; Boselli, A.; Clemens, M.; Corbelli, E.; Cortese, L.; Dariush, A.; Davies, J. I.; De Looze, I.; di Serego Alighieri, S.; Fadda, D.; Fritz, J.; Garcia-Appadoo, D. A.; Gavazzi, G.; Giovanardi, C.; Hughes, T. M.; Jones, A. P.; Pierini, D.; Pohlen, M.; Sabatini, S.; Smith, M. W. L.; Verstappen, J.; Xilouris, E. M.; Zibetti, S.

    2010-07-01

    We present the dust properties of a small sample of Virgo cluster dwarf galaxies drawn from the science demonstration phase data set of the Herschel Virgo Cluster Survey. These galaxies have low metallicities (7.8 < 12 + log(O/H) < 8.3) and star-formation rates ≲10-1 M⊙ yr-1. We measure the spectral energy distribution (SED) from 100 to 500 μm and derive dust temperatures and dust masses. The SEDs are fitted by a cool component of temperature T ≲ 20 K, implying dust masses around 105 M⊙ and dust-to-gas ratios D within the range 10-3-10-2. The completion of the full survey will yield a larger set of galaxies, which will provide more stringent constraints on the dust content of star-forming dwarf galaxies. Herschel is an ESA space observatory with science instruments provided by European-led Principal Investigator consortia and with important participation from NASA.

  19. Ion channel clustering by membrane-associated guanylate kinases. Differential regulation by N-terminal lipid and metal binding motifs.

    PubMed

    El-Husseini, A E; Topinka, J R; Lehrer-Graiwer, J E; Firestein, B L; Craven, S E; Aoki, C; Bredt, D S

    2000-08-04

    The postsynaptic density protein PSD-95 and related membrane-associated guanylate kinase (MAGUK) proteins assemble signal transduction complexes at sites of cell-cell contact including synapses. Whereas PSD-95 and PSD-93 occur only at postsynaptic sites in hippocampal neurons, SAP-102 also occurs in axons. In heterologous cells, PSD-95 and PSD-93 mediate cell surface ion channel clustering, but SAP-102 and SAP-97 do not. This selective ion channel clustering activity by MAGUKs is explained by differential palmitoylation, as PSD-93 and PSD-95 are palmitoylated though SAP-97, and SAP-102 are not. Rather than being palmitoylated, we find that N-terminal cysteines from SAP-102 tightly bind to zinc. And, appending the N terminus of SAP-102 to PSD-95 results in localization of the chimera to both axons and dendrites. These data suggest that lipid modifications and heavy metal associations with the N termini of MAGUKs mediate differential functions and subcellular localizations of these synaptic scaffolds.

  20. Bistable regulation of integrin adhesiveness by a bipolar metal ion cluster.

    PubMed

    Chen, JianFeng; Salas, Azucena; Springer, Timothy A

    2003-12-01

    Integrin alpha(4)beta(7) mediates rolling adhesion in Ca(2+) and Ca(2+) + Mg(2+), and firm adhesion in Mg(2+) and Mn(2+), mimicking the two key steps in leukocyte accumulation in inflamed vasculature. We mutated an interlinked linear array of three divalent cation-binding sites present in integrin beta-subunit I-like domains. The middle, metal ion-dependent adhesion site (MIDAS) is required for both rolling and firm adhesion. One polar site, that adjacent to MIDAS (ADMIDAS), is required for rolling because its mutation results in firm adhesion. The other polar site, the ligand-induced metal binding site (LIMBS), is required for firm adhesion because its mutation results in rolling. The LIMBS mediates the positive regulatory effects of low Ca(2+) concentrations, whereas the ADMIDAS mediates the negative regulatory effects of higher Ca(2+) concentrations, which are competed by Mn(2+). The bipolar sites thus stabilize two alternative phases of adhesion.

  1. Novel polymerization catalysts and hydride clusters from rare-earth metal dialkyls.

    PubMed

    Nishiura, Masayoshi; Hou, Zhaomin

    2010-04-01

    This Review gives an overview on recent progress in the synthesis and chemistry of rare-earth metal dialkyl complexes bearing monoanionic ancillary ligands, with an emphasis on novel polymerization catalysts. These structurally well-defined and highly reactive compounds are prepared either by alkane elimination reactions between trialkyl rare-earth complexes and acidic neutral ligands, or by the metathetical reactions of rare-earth trihalides with the alkali metal salts of the corresponding ligands. On treatment with an appropriate borate compound, the dialkyl complexes are converted into the corresponding cationic monoalkyl species, which serve as excellent catalysts for the polymerization and copolymerization of a variety of olefins to yield a series of new polymer materials that exhibit novel properties. Alternatively, hydrogenation of the dialkyl rare-earth complexes with H(2) affords a new class of rare-earth polyhydride complexes with unique features in terms of both their structure and reactivity.

  2. Preparing transition-metal clusters in known structural forms: The mass-analyzed threshold ionization spectrum of V3

    NASA Astrophysics Data System (ADS)

    Ford, Mark S.; Mackenzie, Stuart R.

    2005-08-01

    The first results are presented of a new experiment designed both to generate and characterize spectroscopically individual isomers of transition-metal cluster cations. As a proof of concept the one-photon mass-analyzed threshold ionization (MATI) spectrum of V3 has been recorded in the region of 44000-45000cm-1. This study extends the range of a previous zero-kinetic-energy (ZEKE) photoelectron study of Yang et al. [Chem. Phys. Lett. 231, 177 (1994)] with which the current results are compared. The MATI spectra reported here exhibit surprisingly high resolution (0.2cm-1) for this technique despite the use of large discrimination and extraction fields. Analysis of the rotational profile of the origin band allows assignment of the V3 ground state as A1'2 and the V3+ ground state as A2'3, both with D3h geometry, in agreement with the density-functional theory study of the V3 ZEKE spectrum by Calaminici et al. [J. Chem. Phys. 114, 4036 (2001)]. There is also some evidence in the spectrum of transitions to the low-lying A1'1 excited state of the ion. The vibrational structure observed in the MATI spectrum is, however, significantly different to and less extensive than that predicted in the density-functional theory study. Possible reasons for the discrepancies are discussed and an alternative assignment is proposed which results in revised values for the vibrational wave numbers of both the neutral and ionic states. These studies demonstrate the efficient generation of cluster ions in known structural (isomeric) forms and pave the way for the study of cluster reactivity as a function of geometrical structure.

  3. The Electronic Structure of Metallic and Bimetallic Clusters of IRON-57 with Chromium, TIN-119 and Platinum.

    NASA Astrophysics Data System (ADS)

    Nagarathna, H. M.

    Rare gas matrix isolation techniques have been used in conjunction with Mossbauer spectroscopy to study the bimetallic clusters of ('57)Fe with Cr, ('119)Sn and Pt. Various molecules have been identified by concentration and temperature dependence studies and also with the aid of Monte Carlo calculations. The iron-tin system is studied using both ('57)Fe and ('119)Sn Mossbauer isotopes. The Mossbauer parameters of FeCr, FeSn and FePt heteronuclear diatomic molecules and Sn(,2) homonuclear diatomic molecules isolated in argon at 4.2 K are obtained very accurately and used to determine their electronic ground states. In addition to diatomic molecules, the larger clusters have also been characterized using Mossbauer spectroscopy and their relevance to bulk alloys is discussed. SCF-X(alpha)-SW molecular orbital calculations are performed on Fe(,2), FeCr, Sn(,2), FeSn and FePt diatomic molecules to determine their electronic ground states by looking at the calculations which agreed with the measured Mossbauer hyperfine parameters. The most probable electronic ground state for Fe(,2) is determined to be a ('7)(SIGMA)(,g) and for FeCr a ('7)(SIGMA) or ('7)(DELTA) indicating a ferromagnetic coupling between the atoms. The calculations indicated a need for a smaller value of the quadrupole moment of the ('57)Fe nucleus. For Sn(,2) a ('3)(SIGMA)(,g) is the most probable ground state and for FeSn a ('7)(DELTA). The calculations showed a ('5)(SIGMA) state as the most probable electronic ground state for FePt. The X(alpha)-SW calculations are found to be very useful in understanding the nature of chemical bonding between the atoms in the above molecules. Antimony metal clusters are also studied using ('121)Sb Mossbauer spectroscopy and extended Huckel molecular orbital calculations. A good correlation is observed between the experimental and calculated data.

  4. Quest for highly connected metal-organic framework platforms: rare-earth polynuclear clusters versatility meets net topology needs.

    PubMed

    Alezi, Dalal; Peedikakkal, Abdul Malik P; Weseliński, Łukasz J; Guillerm, Vincent; Belmabkhout, Youssef; Cairns, Amy J; Chen, Zhijie; Wojtas, Łukasz; Eddaoudi, Mohamed

    2015-04-29

    Gaining control over the assembly of highly porous rare-earth (RE) based metal-organic frameworks (MOFs) remains challenging. Here we report the latest discoveries on our continuous quest for highly connected nets. The topological exploration based on the noncompatibility of a 12-connected RE polynuclear carboxylate-based cluster, points of extension matching the 12 vertices of the cuboctahedron (cuo), with 3-connected organic ligands led to the discovery of two fascinating and highly connected minimal edge-transitive nets, pek and aea. The reduced symmetry of the employed triangular tricarboxylate ligand, as compared to the prototype highly symmetrical 1,3,5-benzene(tris)benzoic acid guided the concurrent occurrence of nonanuclear [RE9(μ3-OH)12(μ3-O)2(O2C-)12] and hexanuclear [RE6(OH)8(O2C-)8] carboxylate-based clusters as 12-connected and 8-connected molecular building blocks in the structure of a 3-periodic pek-MOF based on a novel (3,8,12)-c trinodal net. The use of a tricarboxylate ligand with modified angles between carboxylate moieties led to the formation of a second MOF containing solely nonanuclear clusters and exhibiting once more a novel and a highly connected (3,12,12)-c trinodal net with aea topology. Notably, it is the first time that RE-MOFs with double six-membered ring (d6R) secondary building units are isolated, representing therefore a critical step forward toward the design of novel and highly coordinated materials using the supermolecular building layer approach while considering the d6Rs as building pillars. Lastly, the potential of these new MOFs for gas separation/storage was investigated by performing gas adsorption studies of various probe gas molecules over a wide range of pressures. Noticeably, pek-MOF-1 showed excellent volumetric CO2 and CH4 uptakes at high pressures.

  5. Electronic Structure of Transition Metal Clusters and Actinide Complexes and Their Reactivity

    SciTech Connect

    Balasubramanian, K

    2008-10-06

    Our research in this area since October 2007 has resulted in seven completed publications and more papers of the completed work are in progress. Our work during this period principally focused on actinide complexes with secondary emphasis on spectroscopic properties and electronic structure of metal complexes. As the publications are available online with all of the details of the results, tables and figures, we are providing here only a brief summary of major highlights, in each of the categories.

  6. High-resolution abundance analysis of red giants in the metal-poor bulge globular cluster HP 1

    NASA Astrophysics Data System (ADS)

    Barbuy, B.; Cantelli, E.; Vemado, A.; Ernandes, H.; Ortolani, S.; Saviane, I.; Bica, E.; Minniti, D.; Dias, B.; Momany, Y.; Hill, V.; Zoccali, M.; Siqueira-Mello, C.

    2016-06-01

    Context. The globular cluster HP 1 is projected at only 3.̊33 from the Galactic center. Together with its distance, this makes it one of the most central globular clusters in the Milky Way. It has a blue horizontal branch (BHB) and a metallicity of [Fe/H] ≈ -1.0. This means that it probably is one of the oldest objects in the Galaxy. Abundance ratios can reveal the nucleosynthesis pattern of the first stars as well as the early chemical enrichment and early formation of stellar populations. Aims: High-resolution spectra obtained for six stars were analyzed to derive the abundances of the light elements C, N, O, Na, and Al, the alpha-elements Mg, Si, Ca, and Ti, and the heavy elements Sr, Y, Zr, Ba, La, and Eu. Methods: High-resolution spectra of six red giants that are confirmed members of the bulge globular cluster HP 1 were obtained with the 8 m VLT UT2-Kueyen telescope with the UVES spectrograph in FLAMES-UVES configuration. The spectroscopic parameter derivation was based on the excitation and ionization equilibrium of Fe i and Fe ii. Results: We confirm a mean metallicity of [Fe/H] = -1.06 ± 0.10, by adding the two stars that were previously analyzed in HP 1. The alpha-elements O and Mg are enhanced by about +0.3 ≲ [O,Mg/Fe] ≲ +0.5 dex, Si is moderately enhanced with +0.15 ≲ [Si/Fe] ≲ +0.35 dex, while Ca and Ti show lower values of -0.04 ≲ [Ca,Ti/Fe] ≲ +0.28 dex. The r-element Eu is also enhanced with [Eu/Fe] ≈ +0.4, which together with O and Mg is indicative of early enrichment by type II supernovae. Na and Al are low, but it is unclear if Na-O are anticorrelated. The heavy elements are moderately enhanced, with -0.20 < [La/Fe] < +0.43 dex and 0.0 < [Ba/Fe] < +0.75 dex, which is compatible with r-process formation. The spread in Y, Zr, Ba, and La abundances, on the other hand, appears to be compatible with the spinstar scenario or other additional mechanisms such as the weak r-process. Observations collected at the European Southern

  7. Effect of interaction between AC electric field and phonon oscillation of metal cluster on tip-growth of carbon nanotube

    NASA Astrophysics Data System (ADS)

    Saeidi, Mohammadreza

    2015-06-01

    The paper reports effect of interaction between AC electric field and metal cluster sitting at tip end of the carbon nanotube (CNT) on CNT tip-growth in CVD theoretically. For this purpose, a theoretical model based on phonon oscillations of the metal catalyst and influence of AC electric field on these oscillations is presented. Results show that there is an optimum AC electric field which optimizes growth of ultra-long CNTs. Then it is demonstrated that, in comparison with CNTs in the absence of field, CNTs under optimum electric field grow more. In addition, relation between optimum temperature and amplitude of AC electric field is investigated and it is shown that increasing electric field leads to higher optimum temperature. Finally, Investigation of effect of catalyst type on optimum electric field demonstrates the optimum field for various catalysts is different due to their different characteristics including van der Waals interaction with carbon, atomic mass and number of free charge carriers per each atom. All results are discussed and interpreted.

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

    NASA Technical Reports Server (NTRS)

    Scott, Carl D.; Smalley, Richard E.

    2003-01-01

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

  9. Electronic states of linear Au clusters supported on metal surfaces: why are they like those of a particle in a box?

    PubMed

    Mills, Greg; Wang, Bing; Ho, Wilson; Metiu, Horia

    2004-04-22

    Scanning tunneling spectroscopy and microscopy show that the empty states of linear Au clusters supported on a metal surface behave as if they are the states of an electron in an empty one-dimensional box. We show here that certain difficulties of this description are removed by a particle-in-a-cylinder model. This interpretation is supported by density functional calculations.

  10. CURiuos Variables Experiment (CURVE): Variable Stars in the Metal-Poor Globular Cluster M56

    NASA Astrophysics Data System (ADS)

    Pietrukowicz, P.; Olech, A.; Kedzierski, P.; Zloczewski, K.; Wisniewski, M.; Mularczyk, K.

    2008-06-01

    We surveyed a 6.5'x6.5' field centered on the globular cluster M56 (NGC 6779) in a search for variable stars detecting seven variables, among which two objects are new identifications. One of the new variables is an RR Lyrae star, the third star of that type in M56. Comparison of the new observations and old photometric data for an RVTauri variable V6 indicates a likely period change in the star. Its slow and negative rate of -0.005+/-0.003 d/yr would disagree with post-AGB evolution, however this could be a result of blue-loop evolution and/or random fluctuations of the period.

  11. Monte-Carlo simulation of defect-cluster nucleation in metals during irradiation

    NASA Astrophysics Data System (ADS)

    Nakasuji, Toshiki; Morishita, Kazunori; Ruan, Xiaoyong

    2017-02-01

    A multiscale modeling approach was applied to investigate the nucleation process of CRPs (copper rich precipitates, i.e., copper-vacancy clusters) in α-Fe containing 1 at.% Cu during irradiation. Monte-Carlo simulations were performed to investigate the nucleation process, with the rate theory equation analysis to evaluate the concentration of displacement defects, along with the molecular dynamics technique to know CRP thermal stabilities in advance. Our MC simulations showed that there is long incubation period at first, followed by a rapid growth of CRPs. The incubation period depends on irradiation conditions such as the damage rate and temperature. CRP's composition during nucleation varies with time. The copper content of CRPs shows relatively rich at first, and then becomes poorer as the precipitate size increases. A widely-accepted model of CRP nucleation process is finally proposed.

  12. The Herschel Virgo Cluster Survey. IX. Dust-to-gas mass ratio and metallicity gradients in four Virgo spiral galaxies

    NASA Astrophysics Data System (ADS)

    Magrini, L.; Bianchi, S.; Corbelli, E.; Cortese, L.; Hunt, L.; Smith, M.; Vlahakis, C.; Davies, J.; Bendo, G. J.; Baes, M.; Boselli, A.; Clemens, M.; Casasola, V.; De Looze, I.; Fritz, J.; Giovanardi, C.; Grossi, M.; Hughes, T.; Madden, S.; Pappalardo, C.; Pohlen, M.; di Serego Alighieri, S.; Verstappen, J.

    2011-11-01

    Context. Using Herschel data from the open time key project the Herschel Virgo Cluster Survey (HeViCS), we investigated the relationship between the metallicity gradients expressed by metal abundances in the gas phase as traced by the chemical composition of HII regions, and in the solid phase, as traced by the dust-to-gas mass ratio. Aims: We derived the radial gradient of the dust-to-gas mass ratio for all galaxies observed by HeViCS whose metallicity gradients are available in the literature. They are all late type Sbc galaxies, namely NGC 4254, NGC 4303, NGC 4321, and NGC 4501. Methods: We fitted PACS and SPIRE observations with a single-temperature modified blackbody, inferred the dust mass, and calculated two dimensional maps of the dust-to-gas mass ratio, with the total mass of gas from available HI and CO maps. HI moment-1 maps were used to derive the geometric parameters of the galaxies and extract the radial profiles. We examined different dependencies on metallicity of the CO-to-H2 conversion factor (XCO), used to transform the 12CO observations into the amount of molecular hydrogen. Results: We found that in these galaxies the dust-to-gas mass ratio radial profile is extremely sensitive to choice of the XCO value, since the molecular gas is the dominant component in the inner parts. We found that for three galaxies of our sample, namely NGC 4254, NGC 4321, and NGC 4501, the slopes of the oxygen and of the dust-to-gas radial gradients agree up to ~0.6-0.7 R25 using XCO values in the range 1/3-1/2 Galactic XCO. For NGC 4303 a lower value of XCO ~ 0.1 × 1020 is necessary. Conclusions: We suggest that such low XCO values might be due to a metallicity dependence of XCO (from close to linear for NGC 4254, NGC 4321, and NGC 4501 to superlinear for NGC 4303), especially in the radial regions RG < 0.6-0.7 R25 where the molecular gas dominates. On the other hand, the outer regions, where the atomic gas component is dominant, are less affected by the choice of

  13. Star formation in the first galaxies - III. Formation, evolution, and characteristics of the first metal-enriched stellar cluster

    NASA Astrophysics Data System (ADS)

    Safranek-Shrader, Chalence; Montgomery, Michael H.; Milosavljević, Miloš; Bromm, Volker

    2016-01-01

    We simulate the formation of a low-metallicity (10-2 Z⊙) stellar cluster at redshift z ˜ 14. Beginning with cosmological initial conditions, the simulation utilizes adaptive mesh refinement and sink particles to follow the collapse and evolution of gas past the opacity limit for fragmentation, thus resolving the formation of individual protostellar cores. A time- and location-dependent protostellar radiation field, which heats the gas by absorption on dust, is computed by integration of protostellar evolutionary tracks. The simulation also includes a robust non-equilibrium chemical network that self-consistently treats gas thermodynamics and dust-gas coupling. The system is evolved for 18 kyr after the first protostellar source has formed. In this time span, 30 sink particles representing protostellar cores form with a total mass of 81 M⊙. Their masses range from ˜0.1 to 14.4 M⊙ with a median mass ˜0.5-1 M⊙. Massive protostars grow by competitive accretion while lower mass protostars are stunted in growth by close encounters and many-body ejections. In the regime explored here, the characteristic mass scale is determined by the cosmic microwave background temperature floor and the onset of efficient dust-gas coupling. It seems unlikely that host galaxies of the first bursts of metal-enriched star formation will be detectable with the James Webb Space Telescope or other next-generation infrared observatories. Instead, the most promising access route to the dawn of cosmic star formation may lie in the scrutiny of metal-poor, ancient stellar populations in the Galactic neighbourhood. The observable targets corresponding to the system simulated here are ultra-faint dwarf satellite galaxies such as Boötes II and Willman I.

  14. Gold clusters on Nb-doped SrTiO3: effects of metal-insulator transition on heterogeneous Au nanocatalysis.

    PubMed

    Zhou, Miao; Feng, Yuan Ping; Zhang, Chun

    2012-07-21

    Doping induced metal-insulator transition (MIT) in transition-metal (TM) oxides has been the topic of continued interest outside the field of catalysis chemistry. In this paper, via ab initio (GGA+U) calculations, we show that Nb-doping induced MIT in SrTiO(3) causes a dimensionality crossover of supported Au clusters, and at the same time, greatly enhances the stability and catalytic activity of these clusters. Underlying the predicted high catalytic activity of Au clusters towards the CO oxidation is the MIT induced interaction between the O(2) antibonding 2π* orbital and Au conduction bands, leading to a shift in the population of electrons from Au to the antibonding orbital and the activation of the O(2) molecule. We expect these results to provide a new methodology for the control of catalytic performance of TM-oxide supported Au nanoclusters.

  15. Aromatic pi-pi interaction mediated by a metal atom: structure and ionization of the bis(eta(6)-benzene)chromium-benzene cluster.

    PubMed

    Han, Songhee; Singh, N Jiten; Kang, Tae Yeon; Choi, Kyo-Won; Choi, Sunyoung; Baek, Sun Jong; Kim, Kwang S; Kim, Sang Kyu

    2010-07-21

    Aromatic pi-pi interaction in the presence of a metal atom has been investigated experimentally and theoretically with the model system of bis(eta(6)-benzene)chromium-benzene cluster (Cr(Bz)(2)-Bz) in which a free solvating benzene is non-covalently attached to the benzene moiety of Cr(Bz)(2). One-photon mass-analyzed threshold ionization (MATI) spectroscopy and first principles calculations are employed to identify the structure of Cr(Bz)(2)-Bz which adopts the parallel-displaced configuration. The decrease in ionization potential for Cr(Bz)(2)-Bz compared with Cr(Bz)(2), resulting from the increase of the cation-pi stabilization energy upon ionization, is consistent with the parallel-displaced structure of the cluster. Theoretical calculations give the detailed cluster structures with associated energetics, thus revealing the nature of pi-pi-metal or pi-pi-cation interactions at the molecular level.

  16. A Chandra Archival Study of the Temperature and Metal Abundance Profiles in Hot Galaxy Clusters at 0.1 <~ z <~ 0.3

    NASA Astrophysics Data System (ADS)

    Baldi, A.; Ettori, S.; Mazzotta, P.; Tozzi, P.; Borgani, S.

    2007-09-01

    We present an analysis of the temperature and metallicity profiles of 12 galaxy clusters in the redshift range 0.1-0.3 selected from the Chandra archive with at least ~20,000 net ACIS counts and kT>6 keV. We divide the sample between seven cooling-core (CC) and five non-cooling-core (NCC) clusters according to their central cooling time. We find that single power laws can properly describe both the temperature and metallicity profiles at radii larger than 0.1r180 in both CC and NCC systems, with NCC objects showing steeper profiles outward. A significant deviation is present only in the inner 0.1r180. We perform a comparison of our sample with the De Grandi & Molendi BeppoSAX sample of local CC and NCC clusters, finding a complete agreement in the CC cluster profile and a marginally higher value (at ~1 σ) in the inner regions of the NCC clusters. The slope of the power law describing kT(r) within 0.1r180 correlates strongly with the ratio between the cooling time and the age of the universe at the cluster redshift, with a slope >0 and τc/τage<~0.6 in CC systems.

  17. Cage-Core Interactions in Fullerenes Enclosing Metal Clusters with Multiple Scandium and Yttrium Atoms.

    NASA Astrophysics Data System (ADS)

    Dan, Liu; Hagelberg, Frank

    2007-03-01

    Pronounced stability has been reported for metallofullerenes of the form NSc3@CN (N = 68, 78) /1/. In response of these and related findings, Density Functional Theory studies have been performed on the relation between cage-core interactions and the geometry as well as stability of endofullerenes with metal impurities containing Sc and Y. Substantial electron transfer from the metal core to the fullerene cage combines with electron backdonation, involving the interaction between the occupied orbitals of the negatively charged cage and the unoccupied d orbitals of the positively charged core. The Hueckel 4n+2 rule, well established in organic chemistry, is shown to provide a valuable heuristic tool for understanding the intramolecular electron transfer and the related stability gain /1/. The usefulness of the aromaticity concept for explaining and predicting the architecture of metallofullerenes is further exemplified by the units Sc2@C84 and Y2@C84 which were analyzed in spin triplet and singlet conditions. The Sc2 core turns out to be realized by two separated ions, while Y2 forms a bound subunit. These findings are in agreement with conclusions based on the 4n + 2 rule, assisted by Nucleus Independent Chemical Shift (NICS) calculations. /1/ Stevenson, S.; Fowler, P.W.; Heine, T.; Duchamp, J.C.; Rice, G.; Glass, T.; Harich, K.; Hadju, F.; Bible, R.; Dorn, H.C. Nature, 2000, 408, 427, /2/ S. S. Park, D. Liu, F. Hagelberg, J. Phys. Chem. A 109, 8865 (2005).

  18. Atomistic mechanisms of intermittent plasticity in metals: Dislocation avalanches and defect cluster pinning

    NASA Astrophysics Data System (ADS)

    Niiyama, Tomoaki; Shimokawa, Tomotsugu

    2015-02-01

    Intermittent plastic deformation in crystals with power-law behaviors has been reported in previous experimental studies. The power-law behavior is reminiscent of self-organized criticality, and mesoscopic models have been proposed that describe this behavior in crystals. In this paper, we show that intermittent plasticity in metals under tensile deformation can be observed in molecular dynamics models, using embedded atom method potentials for Ni, Cu, and Al. Power-law behaviors of stress drop and waiting time of plastic deformation events are observed. It is shown that power-law behavior is due to dislocation avalanche motions in Cu and Ni. A different mechanism of dislocation pinning is found in Al. These different stress relaxation mechanisms give different power-law exponents. We propose a probabilistic model to describe the novel dislocation motion in Al and analytically deduce the power-law behavior.

  19. Atomistic mechanisms of intermittent plasticity in metals: dislocation avalanches and defect cluster pinning.

    PubMed

    Niiyama, Tomoaki; Shimokawa, Tomotsugu

    2015-02-01

    Intermittent plastic deformation in crystals with power-law behaviors has been reported in previous experimental studies. The power-law behavior is reminiscent of self-organized criticality, and mesoscopic models have been proposed that describe this behavior in crystals. In this paper, we show that intermittent plasticity in metals under tensile deformation can be observed in molecular dynamics models, using embedded atom method potentials for Ni, Cu, and Al. Power-law behaviors of stress drop and waiting time of plastic deformation events are observed. It is shown that power-law behavior is due to dislocation avalanche motions in Cu and Ni. A different mechanism of dislocation pinning is found in Al. These different stress relaxation mechanisms give different power-law exponents. We propose a probabilistic model to describe the novel dislocation motion in Al and analytically deduce the power-law behavior.

  20. DFT based study of transition metal nano-clusters for electrochemical NH3 production.

    PubMed

    Howalt, J G; Bligaard, T; Rossmeisl, J; Vegge, T

    2013-05-28

    Theoretical studies of the possibility of producing ammonia electrochemically at ambient temperature and pressure without direct N2 dissociation are presented. Density functional theory calculations were used in combination with the computational standard hydrogen electrode to calculate the free energy profile for the reduction of N2 admolecules and N adatoms on transition metal nanoclusters in contact with an acidic electrolyte. This work has established linear scaling relations for the dissociative reaction intermediates NH, NH2, and NH3. In addition, linear scaling relations for the associative reaction intermediates N2H, N2H2, and N2H3 have been determined. Furthermore, correlations between the adsorption energies of N, N2, and H have been established. These scaling relations and the free energy corrections are used to establish volcanoes describing the onset potential for electrochemical ammonia production and hence describe the potential determining steps for the electrochemical ammonia production. The competing hydrogen evolution reaction has also been analyzed for comparison.

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

    SciTech Connect

    Lopez, M.J.; Jellinek, J.

    1995-12-31

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

  2. Clustering dynamics of the metal-benzene sandwich complex: the role of microscopic structure of the solute in the bis(eta6-benzene)chromium .Arn Clusters (n = 1-15).

    PubMed

    Choi, Kyo-Won; Choi, Sunyoung; Ahn, Doo-Sik; Han, Songhee; Kang, Tae Yeon; Baek, Sun Jong; Kim, Sang Kyu

    2008-08-07

    Ar clustering dynamics around the metal-benzene sandwich complex, bis(eta (6)-benzene)chromium: Cr(Bz) 2, is found to occur in two distinct regimes. The shift of the ionization potential (IP) upon the addition of Ar is measured to be 151 cm (-1), and it is constant until the number of Ar solvents ( n) becomes 6. The IP shift per Ar is found to be suddenly decreased to 82 cm (-1) for the clusters of n = 7-12. The cluster distribution indicates that the n = 6 cluster is most populated in the molecular beam. These experimental findings with the aid of ab initio calculation indicate that the first six Ar solvent molecules are attached to top and bottom of Cr(Bz) 2 to give the robust structure for the Cr(Bz) 2-Ar 6 cluster whereas the next six Ar molecules are gathered on the side of the solute core to give the highly symmetric structure of the Cr(Bz) 2-Ar 12 cluster.

  3. A coupled-cluster study on the noble gas binding ability of metal cyanides versus metal halides (metal = Cu, Ag, Au).

    PubMed

    Pan, Sudip; Gupta, Ashutosh; Saha, Ranajit; Merino, Gabriel; Chattaraj, Pratim K

    2015-11-05

    A coupled-cluster study is carried out to investigate the efficacy of metal(I) cyanide (MCN; M = Cu, Ag, Au) compounds to bind with noble gas (Ng) atoms. The M-Ng bond dissociation energy, enthalpy change, and Gibbs free energy change for the dissociation processes producing Ng and MCN are computed to assess the stability of NgMCN compounds. The Ng binding ability of MCN is then compared with the experimentally detected NgMX (X = F, Cl, Br) compounds. While CuCN and AgCN have larger Ng binding ability than those of MCl and MBr (M = Cu, Ag), AuCN shows larger efficacy toward bond formation with Ng than that of AuBr. Natural bond orbital analysis, energy decomposition analysis in conjunction with the natural orbital for chemical valence theory, and the topological analysis of the electron density are performed to understand the nature of interaction occurring in between Ng and MCN. The Ng-M bonds in NgMCN are found comprise an almost equal contribution from covalent and electrostatic types of interactions. The different electron density descriptors also reveal the partial covalent character in the concerned bonds.

  4. Discovery of a Metal-poor Field Giant with a Globular Cluster Second-generation Abundance Pattern

    NASA Astrophysics Data System (ADS)

    Fernández-Trincado, J. G.; Robin, A. C.; Moreno, E.; Schiavon, R. P.; García Pérez, A. E.; Vieira, K.; Cunha, K.; Zamora, O.; Sneden, C.; Souto, Diogo; Carrera, R.; Johnson, J. A.; Shetrone, M.; Zasowski, G.; García-Hernández, D. A.; Majewski, S. R.; Reylé, C.; Blanco-Cuaresma, S.; Martinez-Medina, L. A.; Pérez-Villegas, A.; Valenzuela, O.; Pichardo, B.; Meza, A.; Mészáros, Sz.; Sobeck, J.; Geisler, D.; Anders, F.; Schultheis, M.; Tang, B.; Roman-Lopes, A.; Mennickent, R. E.; Pan, K.; Nitschelm, C.; Allard, F.

    2016-12-01

    We report on the detection, from observations obtained with the Apache Point Observatory Galactic Evolution Experiment spectroscopic survey, of a metal-poor ([Fe/H] = -1.3 dex) field giant star with an extreme Mg-Al abundance ratio ([Mg/Fe] = -0.31 dex; [Al/Fe] = 1.49 dex). Such low Mg/Al ratios are seen only among the second-generation population of globular clusters (GCs) and are not present among Galactic disk field stars. The light-element abundances of this star, 2M16011638-1201525, suggest that it could have been born in a GC. We explore several origin scenarios, studying the orbit of the star in particular to check the probability of its being kinematically related to known GCs. We performed simple orbital integrations assuming the estimated distance of 2M16011638-1201525 and the available six-dimensional phase-space coordinates of 63 GCs, looking for close encounters in the past with a minimum distance approach within the tidal radius of each cluster. We found a very low probability that 2M16011638-1201525 was ejected from most GCs; however, we note that the best progenitor candidate to host this star is GC ω Centauri (NGC 5139). Our dynamical investigation demonstrates that 2M16011638-1201525 reaches a distance | {Z}\\max | \\lt 3 {kpc} from the Galactic plane and minimum and maximum approaches to the Galactic center of R min < 0.62 kpc and R max < 7.26 kpc in an eccentric (e ˜ 0.53) and retrograde orbit. Since the extreme chemical anomaly of 2M16011638-1201525 has also been observed in halo field stars, this object could also be considered a halo contaminant, likely to have been ejected into the Milky Way disk from the halo. We conclude that 2M16011638-20152 is also kinematically consistent with the disk but chemically consistent with halo field stars.

  5. Relative Age Difference Between the Metal-Poor Globular Clusters M53 and M92

    NASA Astrophysics Data System (ADS)

    Cho, Dong-Hwan; Sung, Hyun-Il; Lee, Sang-Gak; Yoon, Tae Seog

    2016-10-01

    CCD photometric observations of the globular cluster (GC), M53 (NGC 5024), are performed using the 1.8 m telescope at the Bohyunsan Optical Astronomy Observatory in Korea on the same nights (2002 April and 2003 May) as the observations of the GC M92 (NGC 6341) reported by Cho and Lee using the same instrumental setup. The data for M53 is reduced using the same method as used for M92 by Cho and Lee, including preprocessing, point-spread function fitting photometry, and standardization etc. Therefore, M53 and M92 are on the same photometric system defined by Landolt, and the photometry of M53 and M92 is tied together as closely as possible. After complete photometric reduction, the V versus B-V, V versus V-I, and V versus B-I color-magnitude diagrams (CMDs) of M53 are produced to derive the relative ages of M53 and M92 and derive the various characteristics of its CMDs in future analysis. From the present analysis, the relative ages of M53 and M92 are derived using the Δ(B-V) method reported by VandenBerg et al. The relative age of M53 is found to be 1.6 ± 0.85 Gyr younger than that of M92 if the absolute age of M92 is taken to be 14 Gyr. This relative age difference between M53 and M92 causes slight differences in the horizontal-branch morphology of these two GCs.

  6. Hybrid magnetic nanoparticle/nanogold clusters and their distance-dependent metal-enhanced fluorescence effect via DNA hybridization

    NASA Astrophysics Data System (ADS)

    GuThese Authors Contributed Equally To This Study., Xuefan; Wu, Youshen; Zhang, Lingze; Liu, Yongchun; Li, Yan; Yan, Yongli; Wu, Daocheng

    2014-07-01

    To improve the metal-enhanced fluorescence (MEF) effect of nanogolds (AuNPs) and accurately detect specific DNA sequences via DNA hybridization, novel hybrid magnetic nanoparticles/nanogold clusters (HMNCs) were designed based on finite-difference time-domain simulation results and prepared by using Fe3O4 and nanogolds. The nanogolds outside the HMNC were then conjugated with thiol-terminated DNA molecules, thus DNA modified-HMNCs (DNA-HMNCs) were obtained. The size distributions of these nanostructures were measured by a Malvern size analyzer, and their morphology was observed via transmission electron microscopy (TEM). The ultraviolet (UV)-visible (vis) absorption spectra of the samples were recorded with a UV-2600 spectrophotometer. Fluorescence spectra and the MEF effect were recorded using a spectrophotofluorometer, and lifetimes were determined using a time-correlated single photon counting apparatus. The prepared HMNCs were stable in aqueous solutions and had an average diameter of 87 +/- 3.2 nm, with six to eight AuNPs around a single Fe3O4 nanoparticle. Fluorescein isothiocyanate (FITC) tagged DNA-HMNC conjugates exhibited a significant MEF effect and could accurately detect specific DNA sequences after DNA hybridization. This result indicates their various potential applications in sensors and biomedical fields.To improve the metal-enhanced fluorescence (MEF) effect of nanogolds (AuNPs) and accurately detect specific DNA sequences via DNA hybridization, novel hybrid magnetic nanoparticles/nanogold clusters (HMNCs) were designed based on finite-difference time-domain simulation results and prepared by using Fe3O4 and nanogolds. The nanogolds outside the HMNC were then conjugated with thiol-terminated DNA molecules, thus DNA modified-HMNCs (DNA-HMNCs) were obtained. The size distributions of these nanostructures were measured by a Malvern size analyzer, and their morphology was observed via transmission electron microscopy (TEM). The ultraviolet (UV

  7. What determines catalyst functionality in molecular water oxidation? Dependence on ligands and metal nuclearity in cobalt clusters.

    PubMed

    Smith, Paul F; Kaplan, Christopher; Sheats, John E; Robinson, David M; McCool, Nicholas S; Mezle, Nicholas; Dismukes, G Charles

    2014-02-17

    The metal-oxo M4O4 "cubane" topology is of special significance to the field of water oxidation as it represents the merging of bioinspired structural principles derived from natural photosynthesis with successful artificial catalysts known to date. Herein, we directly compare the rates of water oxidation/O2 evolution catalyzed by six cobalt-oxo clusters including the Co4O4 cubanes, Co4O4(OAc)4(py)4 and [Co4O4(OAc)2(bpy)4](2+), using the common Ru(bpy)3(2+)/S2O8(2-) photo-oxidant assay. At pH 8, the first-order rate constants for these cubanes differ by 2-fold, 0.030 and 0.015 s(-1), respectively, reflecting the number of labile carboxylate sites that allow substrate water binding in a pre-equilibrium step before O2 release. Kinetic results reveal a deprotonation step occurs on this pathway and that two electrons are removed before O2 evolution occurs. The Co4O4 cubane core is shown to be the smallest catalytic unit for the intramolecular water oxidation pathway, as neither "incomplete cubane" trimers [Co3O(OH)3(OAc)2(bpy)3](2+) and [Co3O(OH)2(OAc)3(py)5](2+) nor "half cubane" dimers [Co2(OH)2(OAc)3(bpy)2](+) and [Co2(OH)2(OAc)3(py)4](+) were found capable of evolving O2, despite having the same ligand sets as their cubane counterparts. Electrochemical studies reveal that oxidation of both cubanes to formally Co4(3III,IV) (0.7 V vs Ag/AgCl) occurs readily, while neither dimers nor trimers are oxidized below 1.5 V, pointing to appreciably greater charge delocalization in the [Co4O4](5+) core. The origin of catalytic activity by Co4O4 cubanes illustrates three key features for water oxidation: (1) four one-electron redox metals, (2) efficient charge delocalization of the first oxidation step across the Co4O4 cluster, allowing for stabilization of higher oxidizing equivalents, and (3) terminal coordination site for substrate aquo/oxo formation.

  8. Influence of electronic stopping on sputtering induced by cluster impact on metallic targets

    SciTech Connect

    Sandoval, Luis; Urbassek, Herbert M.

    2009-04-01

    Using molecular-dynamics simulation, we model the sputtering of a Au (111) crystallite induced by the impact of Au{sub 13} projectiles with total energies up to 500 keV. Due to the uncertainty of the electronic stopping of Au moving in particular at small velocities, we performed several simulations, in which the electronic stopping parameters are systematically changed. Our results demonstrate the dominating influence of the cut-off energy E{sub c}, below which the high-velocity electronic stopping of atoms is switched off in the simulation. If E{sub c} is smaller than roughly one half the cohesive energy of the target, sputtering ceases after a few ps; the spike contribution to sputtering (also called phase explosion or gas-flow contribution) is entirely quenched and the sputtering yield is up to an order of magnitude smaller than when electronic stopping is taken into account only at higher atom energies. Our results demonstrate the importance of a careful modeling of electronic stopping in simulations of spike sputtering from metals.

  9. Thermochromic and mechanochromic luminescence umpolung in isostructural metal-organic frameworks based on Cu6I6 clusters.

    PubMed

    Deshmukh, Mahesh S; Yadav, Ashok; Pant, Rakesh; Boomishankar, Ramamoorthy

    2015-02-16

    Two isostructural metal-organic framework (MOF) materials, namely, {[MeSi((3)Py)3]6(Cu6I6)}n (1) and {[ MeSi((3)Qy)3]6(Cu6I6)}n (2), featuring Cu6I6 clusters were synthesized from tridentate arylsilane ligands of the type MeSi((3)Py)3 ((3)Py = 3-pyridyl) and MeSi((3)Qy)3 ((3)Qy = 3-quinolyl), respectively. While the MOF 1 displays the usual thermochromism associated with traditional Cu4I4Py4 clusters, the MOF 2 shows (3)XLCT/(3)MLCT emission due to the Cu6I6 cluster core at both 298 and 77 K, albeit with some marginal variations in its emission wavelengths. Interestingly, an unusual reversal in the mechanochromic luminescent behavior was observed for these isostructural MOFs at 298 K wherein a pronounced blue-shifted high energy emission for 1 (from orange to yellowish-orange) and a red-shifted low-energy emission for 2 (from green to orange) were obtained upon grinding these samples. This is primarily due to the variations in their cuprophilic interactions as 1 displays shorter Cu···Cu distances (2.745(1) Å) in comparison with those present in 2 (3.148(0) Å). As a result, the ground sample of 2 exhibits a prominent red shift in luminescence owing to the reduction of its Cu···Cu distances to an unknown value closer to the sum of van der Waals radii between two Cu(I) atoms (2.80 Å). However, the blue-shifted emission in 1 is presumably attributed to the rise in its lowest unoccupied molecular orbital energy levels caused by changes in the secondary packing forces. Furthermore, the absorption and emission characteristics of 1 and 2 were substantiated by time-dependent density functional theory calculations on their discrete-model compounds. In addition, the syntheses, reactivity studies, and photophysical properties of two one-dimensional MOFs, namely, {[MeSi((3)Qy)3]2(Cu2I2)}n (3) and {[MeSi((3)Qy)3](CuI)}n (4), having dimeric Cu2I2 and monomeric CuI moieties, respectively, were examined.

  10. High-resolution CCD spectra of stars in globular clusters. II - Metals and CNO in M71

    NASA Technical Reports Server (NTRS)

    Leep, E. Myckky; Wallerstein, George; Oke, J. B.

    1987-01-01

    Palomar coude CCD spectra of resolution 0.3 and 0.6 has been used to redetermine abundances in five stars of the relatively metal rich globular cluster M71. The (Fe/H) value is restricted to the limits of -0.6 to -1.0. The largest source of uncertainty is a systematic difference in f-values between those derived via the Holweger-Muller (1974) solar model and the Bell et al. (1976) solar model. If we use absolute f-values measured by the Oxford group (Blackwell et al. 1982) we find Fe/H to lie in the range of -0.6 to -0.75, i.e., as given by using the Bell et al. solar model. The relative abundances of the light elements, i.e., Na through Ca and probably including Ti show an average excess relative to iron of 0.4-dex. The effect of this difference on metal indices derived from broad- and narrow- band photometry is discussed. For three stars we find O/H = -0.6 using absolute f-values. For CN an analysis of individual rotational lines of the 2-0 band of the red system yields lines in the (C/H, N/H) plane that are consistent with either an original C/Fe = N/Fe = 0 or a modest increase in N relative to C due to CN burning and mixing. A search for C-13N was not successful and an uncertain lower limit of C-12/C-13 near 10 was obtained.

  11. High resolution CCD spectra of stars in globular clusters. Part 2: Metals and CNO in M71

    NASA Technical Reports Server (NTRS)

    Leep, E. M.; Oke, J. B.; Wallerstein, G.

    1986-01-01

    Palomar coude CCD spectra of resolution 0.3 and 0.6 has been used to redetermine abundances in five stars of the relatively metal rich globular cluster M71. The (Fe/H) value is restricted to the limits of -0.6 to -1.0. The largest source of uncertainty is a systematic difference in f-values between those derived via the Holweger-Muller (1974) solar model and the Bell et al. (1976) solar model. If we use absolute f-values measured by the Oxford group (Blackwell et al. 1982) we find Fe/H to lie in the range of -0.6 to -0.75, i.e., as given by using the Bell et al. solar model. The relative abundances of the light elements, i.e., Na through Ca and probably including Ti show an average excess relative to iron of 0.4 dex. The effect of this difference on metal indices derived from broad- and narrow- band photometry is discussed. For three stars we find O/H = -0.6 using absolute f-values. For CN an analysis of individual rotational lines of the 2-0 band of the red system yields lines in the (C/H,N/H) plane that are consistent with either an original C/Fe = N/Fe = 0 or a modest increase in N relative to C due to CN burning and mixing. A search for C-13N was not successful and an uncertain lower limit of C-12/C-13 near 10 was obtained.

  12. The Distances to Open Clusters from Main-sequence Fitting. V. Extension of Color Calibration and Test Using Cool and Metal-rich Stars in NGC 6791

    NASA Astrophysics Data System (ADS)

    An, Deokkeun; Terndrup, Donald M.; Pinsonneault, Marc H.; Lee, Jae-Woo

    2015-09-01

    We extend our effort to calibrate stellar isochrones in the Johnson-Cousins ({{BVI}}C) and the 2MASS ({{JHK}}s) filter systems based on observations of well-studied open clusters. Using cool main-sequence (MS) stars in Praesepe, we define empirical corrections to the Lejeune et al. color-effective temperature ({T}{eff}) relations down to {T}{eff}˜ 3600 {{K}}, complementing our previous work based on the Hyades and the Pleiades. We apply empirically corrected isochrones to existing optical and near-infrared photometry of cool ({T}{eff}≲ 5500 {{K}}) and metal-rich ([{Fe}/{{H}}]= +0.37) MS stars in NGC 6791. The current methodology relies on an assumption that color-{T}{eff} corrections are independent of metallicity, but we find that estimates of color excess and distance from color-magnitude diagrams with different color indices converge on each other at the precisely known metallicity of the cluster. Along with a satisfactory agreement with eclipsing binary data in the cluster, we view the improved internal consistency as a validation of our calibrated isochrones at super-solar metallicities. For very cool stars ({T}{eff}≲ 4800 {{K}}), however, we find that B - V colors of our models are systematically redder than the cluster photometry by ˜0.02 mag. We use color-{T}{eff} transformations from the infrared flux method and alternative photometry to examine a potential color-scale error in the input cluster photometry. After excluding B - V photometry of these cool MS stars, we derive E(B\\-\\V)=0.105+/- 0.014, [M/H]\\=\\+0.42+/- 0.07, {(m\\-\\M)}0=13.04+/- 0.08, and the age of 9.5 ± 0.3 Gyr for NGC 6791.

  13. Electronic properties of embedded MnAs nano-clusters in a GaAs matrix and (Ga,Mn)As films: Evidence of distinct metallic character

    NASA Astrophysics Data System (ADS)

    Rache Salles, B.; Girard, J. C.; David, C.; Offi, F.; Borgatti, F.; Eddrief, M.; Etgens, V. H.; Simonelli, L.; Marangolo, M.; Panaccione, G.

    2012-05-01

    We investigated the electronic properties of MnAs nano-clusters embedded in GaAs by bulk sensitive photoemission spectroscopy and cross-sectional scanning tunneling microscopy/spectroscopy. We report experimental evidences that the clusters are metallic MnAs, in close resemblance to MnAs thin films, and display a sharp interface with the surrounding GaAs. These results are supported by the comparison with GaMnAs and MnAs film in the same experimental condition. Furthermore, we observe a clear Coulomb blockade effect, as due to confinement and their nanometric size.

  14. A structure-based analysis of the vibrational spectra of nitrosyl ligands in transition-metal coordination complexes and clusters

    NASA Astrophysics Data System (ADS)

    De La Cruz, Carlos; Sheppard, Norman

    2011-01-01

    The vibrational spectra of nitrogen monoxide or nitric oxide (NO) bonded to one or to several transition-metal (M) atom(s) in coordination and cluster compounds are analyzed in relation to the various types of such structures identified by diffraction methods. These structures are classified in: (a) terminal (linear and bent) nitrosyls, [M(σ-NO)] or [M(NO)]; (b) twofold nitrosyl bridges, [M 2(μ 2-NO)]; (c) threefold nitrosyl bridges, [M 3(μ 3-NO)]; (d) σ/π-dihaptonitrosyls or " side-on" nitrosyls; and (e) isonitrosyls (oxygen-bonded nitrosyls). Typical ranges for the values of internuclear N-O and M-N bond-distances and M-N-O bond-angles for linear nitrosyls are: 1.14-1.20 Å/1.60-1.90 Å/180-160° and for bent nitrosyls are 1.16-1.22 Å/1.80-2.00 Å/140-110°. The [M 2(μ 2-NO)] bridges have been divided into those that contain one or several metal-metal bonds and those without a formal metal/metal bond (M⋯M). Typical ranges for the M-M, N-O, M-N bond distances and M-N-M bond angles for the normal twofold NO bridges are: 2.30-3.00 Å/1.18-1.22 Å/1.80-2.00 Å/90-70°, whereas for the analogous ranges of the long twofold NO bridges these are 3.10-3.40 Å/1.20-1.24 Å/1.90-2.10 Å/130-110°. In both situations the N-O vector is approximately at right angle to the M-M (or M⋯M) vector within the experimental error; i.e. the NO group is symmetrical bonded to the two metal atoms. In contrast the threefold NO bridges can be symmetrically or unsymmetrically bonded to an M 3-plane of a cluster compound. Characteristic values for the N-O and M-N bond-distances of these NO bridges are: 1.24-1.28 Å/1.80-1.90 Å, respectively. As few dihaptonitrosyl and isonitrosyl complexes are known, the structural features of these are discussed on an individual basis. The very extensive vibrational spectroscopy literature considered gives emphasis to the data from linearly bonded NO ligands in stable closed-shell metal complexes; i.e. those which are consistent with the

  15. A structure-based analysis of the vibrational spectra of nitrosyl ligands in transition-metal coordination complexes and clusters.

    PubMed

    De La Cruz, Carlos; Sheppard, Norman

    2011-01-01

    The vibrational spectra of nitrogen monoxide or nitric oxide (NO) bonded to one or to several transition-metal (M) atom(s) in coordination and cluster compounds are analyzed in relation to the various types of such structures identified by diffraction methods. These structures are classified in: (a) terminal (linear and bent) nitrosyls, [M(σ-NO)] or [M(NO)]; (b) twofold nitrosyl bridges, [M2(μ2-NO)]; (c) threefold nitrosyl bridges, [M3(μ3-NO)]; (d) σ/π-dihaptonitrosyls or "side-on" nitrosyls; and (e) isonitrosyls (oxygen-bonded nitrosyls). Typical ranges for the values of internuclear N-O and M-N bond-distances and M-N-O bond-angles for linear nitrosyls are: 1.14-1.20 Å/1.60-1.90 Å/180-160° and for bent nitrosyls are 1.16-1.22 Å/1.80-2.00 Å/140-110°. The [M2(μ2-NO)] bridges have been divided into those that contain one or several metal-metal bonds and those without a formal metal/metal bond (M⋯M). Typical ranges for the M-M, N-O, M-N bond distances and M-N-M bond angles for the normal twofold NO bridges are: 2.30-3.00 Å/1.18-1.22 Å/1.80-2.00 Å/90-70°, whereas for the analogous ranges of the long twofold NO bridges these are 3.10-3.40 Å/1.20-1.24 Å/1.90-2.10 Å/130-110°. In both situations the N-O vector is approximately at right angle to the M-M (or M⋯M) vector within the experimental error; i.e. the NO group is symmetrical bonded to the two metal atoms. In contrast the threefold NO bridges can be symmetrically or unsymmetrically bonded to an M3-plane of a cluster compound. Characteristic values for the N-O and M-N bond-distances of these NO bridges are: 1.24-1.28 Å/1.80-1.90 Å, respectively. As few dihaptonitrosyl and isonitrosyl complexes are known, the structural features of these are discussed on an individual basis. The very extensive vibrational spectroscopy literature considered gives emphasis to the data from linearly bonded NO ligands in stable closed-shell metal complexes; i.e. those which are consistent with the

  16. Discovery of a Super-Li-rich Turnoff Star in the Metal-poor Globular Cluster NGC 6397

    NASA Astrophysics Data System (ADS)

    Koch, Andreas; Lind, Karin; Rich, R. Michael

    2011-09-01

    We report on the discovery of a super-Li-rich turnoff (TO) star in the old (12 Gyr), metal-poor ([Fe/H] = -2.1 dex) globular cluster (GC) NGC 6397, based on high-resolution MIKE/Magellan spectra. This star shows an unusually high lithium abundance of A(Li)NLTE = 4.03 ± 0.06 ± 0.14 dex (or, 4.21, accounting for possible contamination from a binary companion) that lies above the canonical Li-plateau by a factor of 100. This is the highest Li enhancement found in a Galactic GC dwarf star to date. We discuss several enhancement mechanisms, but none can unambiguously explain such a high overabundance. The spectrum of the star shows a possible indication of binarity, but its line strengths and chemical element abundance ratios are fully compatible with other TO stars in this GC, seemingly ruling out mass transfer from an asymptotic giant branch companion as origin of the high A(Li). A possible cause is an interaction with a red giant that has undergone cool bottom processing. This paper includes data gathered with the 6.5 m Magellan Telescopes located at Las Campanas Observatory, Chile.

  17. Self-assembled monolayer of organic iodine on a Au surface for attachment of redox-active metal clusters.

    PubMed

    Yu, Ying; Dubey, Manish; Bernasek, Steven L; Dismukes, G Charles

    2007-07-17

    The attachment of a bifunctional iodo-organo-phosphinate compound to gold (Au) surfaces via chemisorption of the iodine atom is described and used to chelate a redox-active metal cluster via the phosphinate group. XPS, AFM, and electrochemical measurements show that (4-iodo-phenyl)phenyl phosphinic acid (IPPA) forms a tightly bound self-assembled monolayer (SAM) on Au surfaces. The surface coverage of an IPPA monolayer on Au was quantified by an electrochemical method and found to be 0.40 +/- 0.03 nmol/cm2, roughly corresponding to 0.4 monolayers. We show that the Au/IPPA SAM, but not the underivatized Au, adsorbs Mn4O4(Ph2PO2)6 from solution by a phosphinate exchange reaction to yield Au/IPPA/Mn4O4(Ph2PO2)5 SAM. The resulting SAM is firmly bound and not removed by sonication, as confirmed by manganese XPS (Mn 2p1/2) and by AFM. Electrochemistry confirms that Mn4O4(Ph2PO2)6 is anchored on the Au/IPPA surface and that redox chemistry can be mediated between the electrode and the surface-attached complex. Mn4O4(Ph2PO2)6 contains the reactive Mn4O46+ cubane core, a redox-active bioinspired catalyst.

  18. The integrated calcium II triplet as a metallicity indicator: comparisons with high-resolution [Fe/H] in M31 globular clusters

    NASA Astrophysics Data System (ADS)

    Sakari, Charli M.; Wallerstein, George

    2016-02-01

    Medium resolution (R = 4000-9000) spectra of the near infrared Ca II lines (at 8498, 8542, and 8662 Å) in M31 globular cluster (GC) integrated light spectra are presented. In individual stars the Ca II triplet (CaT) traces stellar metallicity; this paper compares integrated CaT strengths to well determined, high-precision [Fe/H] values from high-resolution integrated light spectra. The target GCs cover a wide range in metallicity (from [Fe/H] ˜ -2.1 to -0.2). While most are older than ˜10 Gyr, some may be of intermediate age (2-6 Gyr). A handful (3-6) have detailed abundances (e.g. low [Ca/Fe]) that indicate they may have been accreted from dwarf galaxies. Using various measurements and definitions of CaT strength, it is confirmed that for GCs with [Fe/H] ≲ -0.4 and older than ˜2 Gyr the integrated CaT traces cluster [Fe/H] to within ˜0.2 dex, independent of age. CaT lines in metal-rich GCs are very sensitive to nearby atomic lines (and TiO molecular lines in the most metal-rich GCs), largely due to line blanketing in continuum regions. The [Ca/Fe] ratio has a mild effect on the integrated CaT strength in metal poor GCs. The integrated CaT can therefore be safely used to determine rough metallicities for distant, unresolved clusters, provided that attention is paid to the limits of the measurement techniques.

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

    NASA Astrophysics Data System (ADS)

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

    2016-08-01

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

  20. Cluster model of amorphized particles formation by plasma spraying of metallic powder

    NASA Astrophysics Data System (ADS)

    Barakhtin, Boris K.; Nesterova, E. V.

    1999-05-01

    Multifunctional coatings from materials with amorphized microcrystalline or nano-phase structure cause a considerable scientific and practical interest. With their help it is to manufacture heat resistant neutralizers of harmful ejections, to produce ecologically clean sources of electric current, to design electromagnetic protective shields and to fabricate a lot of other technical products. The variety of application and a unique complex of operating characteristics (ductility, strength, magnetic and chemical properties) are governed by the basic peculiarity of material in amorphized state - its thermodynamic instability. In comparison with traditional thermodynamically equilibrium metallic alloys, the kinetics of structure changes in amorphous materials is quite different. Thus, it is suggested, that they have peculiar defects (phasonics) which are not typical of materials in crystalline state, they have no translational symmetry and elementary cells. In the process of coatings forming with non-equilibrium structure states can be realized in them, which are characterized by a fluctuation type of origin, entropy export, appearance of space or temporary symmetry uncertainty of the transition direction 'order $ARLR disorder' in bifurcation points. The aforesaid explains a great scientific (not only practical) interest in the structure study of disordered medium. Functional coatings with amorphized, nano- and microcrystalline structure components formed on copper substrate by plasma spraying of dispersed (to 50 mcm) Ni-Al powder. According to the constitutional diagram it was expected to obtain a mixture from equilibrium intermetallide phases NiAl3 + Ni2Al3. The experimental results and investigations performed by X-ray structure, X-ray spectrum and electron microscopy techniques have shown it is possible to obtain phases of variable composition (Ni)m(Al)n with Ni content from 25 to 75 vol.%, including NiAl. It turned out that in the process of spraying the

  1. Serum thyroglobulin reference intervals in regions with adequate and more than adequate iodine intake.

    PubMed

    Wang, Zhaojun; Zhang, Hanyi; Zhang, Xiaowen; Sun, Jie; Han, Cheng; Li, Chenyan; Li, Yongze; Teng, Xiaochun; Fan, Chenling; Liu, Aihua; Shan, Zhongyan; Liu, Chao; Weng, Jianping; Teng, Weiping

    2016-11-01

    The purpose of this study was to establish normal thyroglobulin (Tg) reference intervals (RIs) in regions with adequate and more than adequate iodine intake according to the National Academy of Clinical Biochemistry (NACB) guidelines and to investigate the relationships between Tg and other factors.A total of 1317 thyroid disease-free adult subjects (578 men, 739 nonpregnant women) from 2 cities (Guangzhou and Nanjing) were enrolled in this retrospective, observational study. Each subject completed a questionnaire and underwent physical and ultrasonic examination. Serum Tg, thyroid-stimulating hormone (TSH), thyroid peroxidase antibody (TPOAb), Tg antibody (TgAb), and urinary iodine concentration (UIC) were measured. Reference groups were established on the basis of TSH levels: 0.5 to 2.0 and 0.27 to 4.2 mIU/L.The Tg RIs for Guangzhou and Nanjing were 1.6 to 30.0 and 1.9 to 25.8 ng/mL, respectively. No significant differences in Tg were found between genders or among different reference groups. Stepwise linear regression analyses showed that TgAb, thyroid volume, goiter, gender, age, and TSH levels were correlated with Tg.In adults from regions with adequate and more than adequate iodine intake, we found that Tg may be a suitable marker of iodine status; gender-specific Tg RI was unnecessary; there was no difference between Tg RIs in regions with adequate and more than adequate iodine intake; and the TSH criterion for selecting the Tg reference population could follow the local TSH reference rather than 0.5 to 2.0 mIU/L.

  2. Serum thyroglobulin reference intervals in regions with adequate and more than adequate iodine intake

    PubMed Central

    Wang, Zhaojun; Zhang, Hanyi; Zhang, Xiaowen; Sun, Jie; Han, Cheng; Li, Chenyan; Li, Yongze; Teng, Xiaochun; Fan, Chenling; Liu, Aihua; Shan, Zhongyan; Liu, Chao; Weng, Jianping; Teng, Weiping

    2016-01-01

    Abstract The purpose of this study was to establish normal thyroglobulin (Tg) reference intervals (RIs) in regions with adequate and more than adequate iodine intake according to the National Academy of Clinical Biochemistry (NACB) guidelines and to investigate the relationships between Tg and other factors. A total of 1317 thyroid disease-free adult subjects (578 men, 739 nonpregnant women) from 2 cities (Guangzhou and Nanjing) were enrolled in this retrospective, observational study. Each subject completed a questionnaire and underwent physical and ultrasonic examination. Serum Tg, thyroid-stimulating hormone (TSH), thyroid peroxidase antibody (TPOAb), Tg antibody (TgAb), and urinary iodine concentration (UIC) were measured. Reference groups were established on the basis of TSH levels: 0.5 to 2.0 and 0.27 to 4.2 mIU/L. The Tg RIs for Guangzhou and Nanjing were 1.6 to 30.0 and 1.9 to 25.8 ng/mL, respectively. No significant differences in Tg were found between genders or among different reference groups. Stepwise linear regression analyses showed that TgAb, thyroid volume, goiter, gender, age, and TSH levels were correlated with Tg. In adults from regions with adequate and more than adequate iodine intake, we found that Tg may be a suitable marker of iodine status; gender-specific Tg RI was unnecessary; there was no difference between Tg RIs in regions with adequate and more than adequate iodine intake; and the TSH criterion for selecting the Tg reference population could follow the local TSH reference rather than 0.5 to 2.0 mIU/L. PMID:27902589

  3. Observations of the Hot Horizontal Branch Stars in the Metal-Rich Bulge Globular Cluster NGC 6388

    NASA Technical Reports Server (NTRS)

    Moehler, S.; Sweigart, A. V.

    2006-01-01

    The metal-rich bulge globular cluster NGC 6388 shows a distinct blue horizontal-branch tail in its colour-magnitude diagram (Rich et al. 1997) and is thus a strong case of the well-known 2nd Parameter Problem. In addition, its horizontal branch (HB) shows an upward tilt toward bluer colours, which cannot be explained by canonical evolutionary models. Several non-canonical scenarios have been proposed to explain these puzzling observations. In order to test the predictions of these scenarios, we have obtained medium resolution spectra to determine the atmospheric parameters of a sample of the blue HB stars in NGC 6388.Using the medium resolution spectra, we determine effective temperatures, surface gravities and helium abundances by fitting the observed Balmer and helium lines with appropriate theoretical stellar spectra. As we know the distance to the cluster, we can verify our results by determining masses for the stars. During the data reduction we took special care to correctly subtract the background, which is dominated by the overlapping spectra of cool stars. The cool blue tail stars in our sample with T(sub eff) approximately 10000 K have lower than canonical surface gravities, suggesting that these stars are, on average, approximately equal to 0.4 mag brighter than canonical HB stars in agreement with the observed upward slope of the HB in NGC 6388. Moreover, the mean mass of these stars agrees well with theoretical predictions. In contrast, the hot blue tail stars in our sample with T(sub eff) greater than or equal to 12000 K show significantly lower surface gravities than predicted by any scenario, which can reproduce the photometric observations. Their masses are also too low by about a factor of 2 compared to theoretical predictions. The physical parameters of the blue HB stars at about 10,000 K support the helium pollution scenario. The low gravities and masses of the hot blue tail stars, however, are probably caused by problems with the data reduction

  4. Formation of Metal Clusters or Nitrogen-Bridged Adducts by Reaction of a Bis(amino)stannylene with Halides of Two-Valent Transition Metals.

    PubMed

    Veith, Michael; Müller, Alice; Stahl, Lothar; Nötzel, Martin; Jarczyk, Maria; Huch, Volker

    1996-06-19

    be isostructural. The molecules have an inner Sn(4)M pentametallic core (mean distances: Sn-Ni 2.463 Å, Sn-Pd 2.544 Å) with the transition metal in the center of a slightly distorted square formed by the four tin atoms, the distortion from planarity resulting in a weak paramagnetism of 0.2 &mgr;(B) for the nickel compound. The halogen atoms form bridges between two of the tin atoms and have no bonding interaction with the transition metal. The nickel compound has also been prepared by direct interaction of Br(2) or NR(4)Br(3) with [Me(2)Si(NtBu)(2)Sn](4)Ni as a minor product, the main products being Me(2)Si(NtBu)(2)Sn(NtBu)(2)SiMe(2,) Me(2)Si(NtBu)(2)SnBr(2), NiBr(2) and SnBr(2). Other metal clusters have been obtained by the reaction of Me(2)Si(NtBu)(2)Sn with tetrakis(triphenyphosphine)palladium or by the reaction of Me(2)Si(NtBu)(2)Ge with RhCl(PPh(3))(3). In the first case Ph(3)PPd[Sn(NtBu)(2)SiMe(2)](3)PdPPh(3) (rhombohedral, space group R3c, a = b = 21.397(12) Å, c = 57.01(5) Å, alpha = beta = 90 degrees, gamma = 120 degrees, Z = 12) is formed and is characterized by X-ray techniques to be composed of a central PdSn(3)Pd trigonal bipyramid with the tin atoms occupying the equatorial positions (Pd-Sn = 2.702(5) Å). In the second reaction all the triphenylphosphine ligands are replaced from rhodium and Rh[Ge(NtBu)(2)SiMe(2)](4)Cl is formed (monoclinic, space group P2(1)/n, a = 12.164(2) Å, b = 23.625(5) Å, c = 24.128(5) Å, beta = 102.74(3) degrees, Z = 4). The central core of this molecule is made up of a rhodium atom which is almost square planarly coordinated by the germanium atoms, two of which are bridged by chlorine (mean Ge-Rh = 2.355 Å).

  5. A series of 3D metal organic frameworks based on [24-MC-6] metallacrown clusters: structure, magnetic and luminescence properties.

    PubMed

    Wang, Kai; Zou, Hua-Hong; Chen, Zi-Lu; Zhang, Zhong; Sun, Wei-Yin; Liang, Fu-Pei

    2014-09-14

    Four isostructural metal organic frameworks (MOFs), namely [Co6(HipO)6]·6H2O (1), [Mn6(HipO)6]·6H2O (2), [Cd6(HipO)6]·6H2O (3) and [Zn6(HipO)6]·7H2O (4) (H3ipO = 2-hydroxyisophthalic acid), were synthesized and structurally characterized. They have a 3D (4,6)-connected framework based on [24-MC-6] metallacrown clusters ([24-MC-6]-based MOFs). The arrangements of the 24-MC-6 metallacrown SBUs show a regular change indicated by the orientation of their symmetry axes, resulting in a special dense packing mode different from other [24-MC-6]-based MOFs. The analysis of SQUID measurements reveal that compound 1 displays the dominant antiferromagnetic exchanges in 300-10 K between the adjacent Co(II) ions and a ferromagnetic-like behavior at lower temperatures, whereas compound 2 shows an antiferromagnetic interaction between the adjacent Mn(II) ions. Compound 1 exhibits a magnetocaloric effect (MCE) with the resulting entropy change (-ΔS(m)) of 15.20 J kg(-1) K(-1) for ΔH = 50 kG at 6 K, which is the highest value among the cobalt-based MOFs with MCE reported so far. The luminescence properties of compounds 3 and 4 were studied, both of them exhibit photoluminescence in the solid state at room temperature which can be ascribed to intraligand π→π* transitions.

  6. Barrierless growth of precursor-free, ultrafast laser-fragmented noble metal nanoparticles by colloidal atom clusters - A kinetic in situ study.

    PubMed

    Jendrzej, Sandra; Gökce, Bilal; Amendola, Vincenzo; Barcikowski, Stephan

    2016-02-01

    Unintended post-synthesis growth of noble metal colloids caused by excess amounts of reactants or highly reactive atom clusters represents a fundamental problem in colloidal chemistry, affecting product stability or purity. Hence, quantified kinetics could allow defining nanoparticle size determination in dependence of the time. Here, we investigate in situ the growth kinetics of ps pulsed laser-fragmented platinum nanoparticles in presence of naked atom clusters in water without any influence of reducing agents or surfactants. The nanoparticle growth is investigated for platinum covering a time scale of minutes to 50days after nanoparticle generation, it is also supplemented by results obtained from gold and palladium. Since a minimum atom cluster concentration is exceeded, a significant growth is determined by time resolved UV/Vis spectroscopy, analytical disc centrifugation, zeta potential measurement and transmission electron microscopy. We suggest a decrease of atom cluster concentration over time, since nanoparticles grow at the expense of atom clusters. The growth mechanism during early phase (<1day) of laser-synthesized colloid is kinetically modeled by rapid barrierless coalescence. The prolonged slow nanoparticle growth is kinetically modeled by a combination of coalescence and Lifshitz-Slyozov-Wagner kinetic for Ostwald ripening, validated experimentally by the temperature dependence of Pt nanoparticle size and growth quenching by Iodide anions.

  7. Comparative study of energy of particles ejected from coulomb explosion of rare gas and metallic clusters irradiated by intense femtosecond laser field

    NASA Astrophysics Data System (ADS)

    Boucerredj, N.; Beggas, K.

    2016-10-01

    We present our study of high intensity femtosecond laser field interaction with large cluster of Kr and Na (contained 2.103 to 2.107 atoms). When laser intensity is above a critical value, it blows off all of electrons from the cluster and forms a non neutral ion cloud. The irradiation of these clusters by the intense laser field leads to highly excitation energy which can be the source of energetic electrons, electronic emission, highly charge, energetic ions and fragmentation process. During the Coulomb explosion of the resulting highly ionized, high temperature nanoplasma, ions acquire again their energy. It is shown that ultra fast ions are produced. The goal of our study is to investigate in detail a comparative study of the expansion and explosion then the ion energy of metallic and rare gas clusters irradiated by an intense femtosecond laser field. We have found that ions have a kinetic energy up to 105 eV and the Coulomb pressure is little than the hydrodynamic pressure. The Coulomb explosion of a cluster may provide a new high energy ion source.

  8. A quantum Monte Carlo study on electron correlation in all-metal aromatic clusters MAl4(-) (M = Li, Na, K, Rb, Cu, Ag and Au).

    PubMed

    Brito, Bráulio Gabriel A; Hai, G-Q; Teixeira Rabelo, J N; Cândido, Ladir

    2014-05-14

    Using fixed-node diffusion quantum Monte Carlo (FN-DMC) simulation we investigate the electron correlation in all-metal aromatic clusters MAl4(-) (with M = Li, Na, K, Rb, Cu, Ag and Au). The electron detachment energies and electron affinities of the clusters are obtained. The vertical electron detachment energies obtained from the FN-DMC calculations are in very good agreement with the available experimental results. Calculations are also performed within the Hartree-Fock approximation, density-functional theory (DFT), and the couple-cluster (CCSD(T)) method. From the obtained results, we analyse the impact of the electron correlation effects in these bimetallic clusters and find that the correlation of the valence electrons contributes significantly to the detachment energies and electron affinities, varying between 20% and 50% of their total values. Furthermore, we discuss the electron correlation effects on the stability of the clusters as well as the accuracy of the DFT and CCSD(T) calculations in the present systems.

  9. Adequate mathematical modelling of environmental processes

    NASA Astrophysics Data System (ADS)

    Chashechkin, Yu. D.

    2012-04-01

    In environmental observations and laboratory visualization both large scale flow components like currents, jets, vortices, waves and a fine structure are registered (different examples are given). The conventional mathematical modeling both analytical and numerical is directed mostly on description of energetically important flow components. The role of a fine structures is still remains obscured. A variety of existing models makes it difficult to choose the most adequate and to estimate mutual assessment of their degree of correspondence. The goal of the talk is to give scrutiny analysis of kinematics and dynamics of flows. A difference between the concept of "motion" as transformation of vector space into itself with a distance conservation and the concept of "flow" as displacement and rotation of deformable "fluid particles" is underlined. Basic physical quantities of the flow that are density, momentum, energy (entropy) and admixture concentration are selected as physical parameters defined by the fundamental set which includes differential D'Alembert, Navier-Stokes, Fourier's and/or Fick's equations and closing equation of state. All of them are observable and independent. Calculations of continuous Lie groups shown that only the fundamental set is characterized by the ten-parametric Galilelian groups reflecting based principles of mechanics. Presented analysis demonstrates that conventionally used approximations dramatically change the symmetries of the governing equations sets which leads to their incompatibility or even degeneration. The fundamental set is analyzed taking into account condition of compatibility. A high order of the set indicated on complex structure of complete solutions corresponding to physical structure of real flows. Analytical solutions of a number problems including flows induced by diffusion on topography, generation of the periodic internal waves a compact sources in week-dissipative media as well as numerical solutions of the same

  10. STELLAR LIFETIME AND ULTRAVIOLET PROPERTIES OF THE OLD METAL-RICH GALACTIC OPEN CLUSTER NGC 6791: A PATHWAY TO UNDERSTAND THE ULTRAVIOLET UPTURN OF ELLIPTICAL GALAXIES

    SciTech Connect

    Buzzoni, Alberto; Bertone, Emanuele; Carraro, Giovanni; Buson, Lucio

    2012-04-10

    The evolutionary properties of the old metal-rich Galactic open cluster NGC 6791 are assessed based on deep UB photometry and Two Micron All Sky Survey JK data. For the 4739 stars in the cluster, bolometric luminosity and effective temperature have been derived from theoretical (U - B) and (J - K) color fitting. The derived H-R diagram has been matched with the UVBLUE grid of synthetic stellar spectra to obtain the integrated spectral energy distribution (SED) of the system, together with a full set of UV (Fanelli) and optical (Lick) narrowband indices. The total bolometric magnitude of NGC 6791 is M{sup bol}{sub 6791} = -6.29, with a color (B - V){sub 6791} = 0.97. The cluster appears to be a fairly good proxy of standard elliptical galaxies, although with significantly bluer infrared colors, a shallower 4000 A Balmer break, and a lower Mg{sub 2} index. The confirmed presence of a dozen hot stars along their extreme horizontal-branch evolution leads the cluster SED to consistently match the properties of the most active UV-upturn galaxies, with 1.7% {+-} 0.4% of the total bolometric luminosity emitted shortward of 2500 Angstrom-Sign . The cluster helium abundance results in Y{sub 6791} = 0.30 {+-} 0.04, while the post-main-sequence (PMS) implied stellar lifetime from star number counts fairly agrees with the theoretical expectations from both the PADOVA and BASTI stellar tracks. A PMS fuel consumption of 0.43 {+-} 0.01 M{sub Sun} is found for NGC 6791 stars, in close agreement with the estimated mass of cluster He-rich white dwarfs. Such a tight figure may lead one to suspect that a fraction of the cluster stellar population does not actually reach the minimum mass required to effectively ignite He in the stellar core.

  11. Stellar Lifetime and Ultraviolet Properties of the Old Metal-rich Galactic Open Cluster NGC 6791: A Pathway to Understand the Ultraviolet Upturn of Elliptical Galaxies

    NASA Astrophysics Data System (ADS)

    Buzzoni, Alberto; Bertone, Emanuele; Carraro, Giovanni; Buson, Lucio

    2012-04-01

    The evolutionary properties of the old metal-rich Galactic open cluster NGC 6791 are assessed based on deep UB photometry and Two Micron All Sky Survey JK data. For the 4739 stars in the cluster, bolometric luminosity and effective temperature have been derived from theoretical (U - B) and (J - K) color fitting. The derived H-R diagram has been matched with the UVBLUE grid of synthetic stellar spectra to obtain the integrated spectral energy distribution (SED) of the system, together with a full set of UV (Fanelli) and optical (Lick) narrowband indices. The total bolometric magnitude of NGC 6791 is M bol 6791 = -6.29, with a color (B - V)6791 = 0.97. The cluster appears to be a fairly good proxy of standard elliptical galaxies, although with significantly bluer infrared colors, a shallower 4000 Å Balmer break, and a lower Mg2 index. The confirmed presence of a dozen hot stars along their extreme horizontal-branch evolution leads the cluster SED to consistently match the properties of the most active UV-upturn galaxies, with 1.7% ± 0.4% of the total bolometric luminosity emitted shortward of 2500 Å. The cluster helium abundance results in Y 6791 = 0.30 ± 0.04, while the post-main-sequence (PMS) implied stellar lifetime from star number counts fairly agrees with the theoretical expectations from both the PADOVA and BASTI stellar tracks. A PMS fuel consumption of 0.43 ± 0.01 M ⊙ is found for NGC 6791 stars, in close agreement with the estimated mass of cluster He-rich white dwarfs. Such a tight figure may lead one to suspect that a fraction of the cluster stellar population does not actually reach the minimum mass required to effectively ignite He in the stellar core. Based on observations carried out at the Italian Telescopio Nazionale Galileo, operated by INAF at the Roque de los Muchachos Observatory (La Palma, Spain).

  12. Au25 cluster functionalized metal-organic nanostructures for magnetically targeted photodynamic/photothermal therapy triggered by single wavelength 808 nm near-infrared light

    NASA Astrophysics Data System (ADS)

    Yang, Dan; Yang, Guixin; Gai, Shili; He, Fei; An, Guanghui; Dai, Yunlu; Lv, Ruichan; Yang, Piaoping

    2015-11-01

    Near-infrared (NIR) light-induced cancer therapy has gained considerable interest, but pure inorganic anti-cancer platforms usually suffer from degradation issues. Here, we designed metal-organic frameworks (MOFs) of Fe3O4/ZIF-8-Au25 (IZA) nanospheres through a green and economic procedure. The encapsulated Fe3O4 nanocrystals not only produce hyperthemal effects upon NIR light irradiation to effectively kill tumor cells, but also present targeting and MRI imaging capability. More importantly, the attached ultrasmall Au25(SR)18- clusters (about 2.5 nm) produce highly reactive singlet oxygen (1O2) to cause photodynamic effects through direct sensitization under NIR light irradiation. Furthermore, the Au25(SR)18- clusters also give a hand to the hyperthemal effect as photothermal fortifiers. This nanoplatform exhibits high biocompatibility and an enhanced synergistic therapeutic effect superior to any single therapy, as verified by in vitro and in vivo assay. This image-guided therapy based on a metal-organic framework may stimulate interest in developing other kinds of metal-organic materials with multifunctionality for tumor diagnosis and therapy.Near-infrared (NIR) light-induced cancer therapy has gained considerable interest, but pure inorganic anti-cancer platforms usually suffer from degradation issues. Here, we designed metal-organic frameworks (MOFs) of Fe3O4/ZIF-8-Au25 (IZA) nanospheres through a green and economic procedure. The encapsulated Fe3O4 nanocrystals not only produce hyperthemal effects upon NIR light irradiation to effectively kill tumor cells, but also present targeting and MRI imaging capability. More importantly, the attached ultrasmall Au25(SR)18- clusters (about 2.5 nm) produce highly reactive singlet oxygen (1O2) to cause photodynamic effects through direct sensitization under NIR light irradiation. Furthermore, the Au25(SR)18- clusters also give a hand to the hyperthemal effect as photothermal fortifiers. This nanoplatform exhibits high

  13. A complete guide on the influence of metal clusters in the Diels-Alder regioselectivity of I(h)-C80 endohedral metallofullerenes.

    PubMed

    Garcia-Borràs, Marc; Osuna, Sílvia; Luis, Josep M; Swart, Marcel; Solà, Miquel

    2013-10-25

    The chemical functionalization of endohedral metallofullerenes (EMFs) has aroused considerable interest due to the possibility of synthesizing new species with potential applications in materials science and medicine. Experimental and theoretical studies on the reactivity of endohedral metallofullerenes are scarce. To improve our understanding of the endohedral metallofullerene reactivity, we have systematically studied with DFT methods the Diels-Alder cycloaddition between s-cis-1,3-butadiene and practically all X@I(h)-C80 EMFs synthesized to date: X=Sc3N, Lu3N, Y3N, La2, Y3, Sc3C2, Sc4C2, Sc3CH, Sc3NC, Sc4O2 and Sc4O3. We have studied both the thermodynamic and kinetic regioselectivity, taking into account the free rotation of the metallic cluster inside the fullerene. This systematic study has been made possible through the use of the frozen cage model (FCM), a computationally cheap approach to accurately predicting the exohedral regioselectivity of cycloaddition reactions in EMFs. Our results show that the EMFs are less reactive than the hollow I(h)-C80 cage. Except for the Y3 cluster, the additions occur predominantly at the [5,6] bond. In many cases, however, a mixture of the two possible regioisomers is predicted. In general, [6,6] addition is favored in EMFs that have a larger charge transfer from the metal cluster to the cage or a voluminous metal cluster inside. The present guide represents the first complete and exhaustive investigation of the reactivity of I(h)-C80-based EMFs.

  14. Metal- and ligand-directed one-pot syntheses, crystal structures, and properties of novel oxo-centered tetra- and hexametallic clusters.

    PubMed

    Saalfrank, Rolf W; Reimann, Uwe; Göritz, Mareike; Hampel, Frank; Scheurer, Andreas; Heinemann, Frank W; Büschel, Michael; Daub, Jörg; Schünemann, Volker; Trautwein, Alfred X

    2002-08-16

    Starting from closely related metal-ligand combinations, completely different oligomeric metal clusters are synthesized. Whereas, picoline-tetrazolylamide HL(1) (1) and zinc or nickel acetate afforded [2x2] grids [M(4)(L(1))(8)] (2), slightly different N-(2-methylthiazole-5-yl)-thiazole-2-carboxamide HL(2) (5 a) and nickel acetate yielded the monometallic complex [Ni(L(2))(2)(OH(2))(2)] (6). In contrast, reaction of 5 a with zinc acetate produced the tetrametallic zinc cluster [Zn(4)O(L(2))(4)(OAc)(2)] (7). Even more surprising, when 3-methyl-substituted HL(3) (5 b) instead of 2-methyl-substituted HL(2) (5 a) was allowed to react under identical conditions with zinc acetate, the cluster [Zn(4)O(L(3))(4)Cl(2)] (8) crystallized from dichloromethane. Clusters 7 and 8 are isostructural. As for 7, in 8 two of the edges of the tetrahedron of zinc ions are doubly bridged, two are singly bridged, and the other two are nonbridged. On the other hand, when iron(II) acetate under aerobic conditions was allowed to react with 5 a, the unprecedented complex [[Fe(3)O(L(2))(2)(OAc)(4)](2)O] (9) was isolated. Cluster 9 is composed of two trimetallic, triangular mu(3)-O(2-)-centered [Fe(3)O(L(2))(2)(OAc)(4)](+) modules, linked by an almost linear mu(2)-O(2-) bridge. The Mössbauer spectrum together with cyclic voltammetric and square-wave voltammetric measurements of 9 are reported, and 6-9 were characterized unequivocally by single-crystal X-ray structure analyses.

  15. The Hueckel Model for Small Metal Clusters. 4. Orbital Properties and Cohesive Energies for Model Clusters of Up to Several Hundred Atoms

    DTIC Science & Technology

    1989-12-01

    Cohesive Energies for Model Clusters of Up to Several Hundred Atoms by D. M. Lindsay, Youqi Wang and Thomas F. George Prepared for Publication in... Wang , Thomas F. George 13a. TYPE OF REPORT 13b. TIME COVERED 114. DATE OF REPORT (Year, Month, Day) 15. PAGE COUNT FROM TO December 1989 34 16... Wang y ........ Department of Chemistry California Institute of Technology Pasadena, California 91125 Dist Thomas F. George (hi Departments of Chemistry

  16. Directed Synthesis of the Triangular Mixed-Metal Cluster H2RhRe2Cp*(CO)9: Ligand Fluxionality and Facile Cluster Fragmentation in the Presence of CO, Halogenated Solvents, and Thiols

    SciTech Connect

    Huang, Shih-Huang Huang; Watson, William H.; Carrano, Carl J.; Wang, Xiaoping; Richmond, Michael G.

    2010-01-01

    The reaction of H2Re2(CO)8 (1) with Cp*Rh(CO)2 (2) in refluxing hexane affords the mixed-metal clusters H2RhRe2Cp*(CO)9 (4, major product), HRh2ReCp*2(CO)6 (5), and HRhRe3Cp*(CO)14 (6). 4 and 5 are electron-precise 48e- clusters and display triangular metallic cores, while 6 contains 64-valence electrons and exhibits a spiked-triangular core having a pendant Re(CO)5 moiety. Heating 1 with Cp*2Rh2(CO)2 (3) gives 4 and 5 as the principal products, in addition to H2Rh2Re2Cp*2(CO)8 (7) in low yield. Cluster 7 possesses 60e- and contains a tetrametallic core with two face-capping CO and hydride groups. Heating 4 under CO leads to cluster fragmentation and formation of Re2(CO)10 and 2 in essentially quantitative yield, as assessed by IR spectroscopy. The kinetics for the fragmentation of 4 in toluene under CO have been investigated over the temperature range 325-349 K by UV-vis spectroscopy. On the basis of the first-order rate constants and the Eyring activation parameters [ H = 25.0(8) kcal/mol; S = -2.6(3) eu], a rate-limiting step involving a polyhedral opening of 4 is supported. 4 is thermally and photochemically sensitive and reactions conducted in the presence of chlorinated solvents furnish the face-shared bioctahedral compound Cp*Rh( -Cl)3Re(CO)3 (8). Heating 4 and H2S in benzene at ca. 60 EC furnishes the 48e- triangular cluster S2Rh3Cp*(CO)4 (9), which contains two Rh(CO)2 moieties and two face-capping sulfide groups. The reaction of 4 with p-methylbenzenethiol gives the sulfido-bridged dimer Cp*Rh( -SC6H4Me-p)3Re(CO)3 (11). The dinuclear compounds Cp*Rh( -Cl)( -SC6H4Me-p)2Re(CO)3 (10) and 11 are formed when 8 is allowed to react with p-methylbenzenethiol. Treatment of 8 and 10 with excess p-methylbenzenethiol yields 11 at elevated temperature in toluene. Compounds 4-11 have been isolated and fully characterized by IR and NMR spectroscopies and by X-ray crystallography. The reactivity displayed by 4 is contrasted with the known indenyl-substituted cluster H2Re

  17. Diffusion of small clusters on metal (100) surfaces: Exact master-equation analysis for lattice-gas models

    SciTech Connect

    Sanchez, J.R.; Evans, J.W.

    1999-01-01

    Exact results are presented for the surface diffusion of small two-dimensional clusters, the constituent atoms of which are commensurate with a square lattice of adsorption sites. Cluster motion is due to the hopping of atoms along the cluster perimeter with various rates. We apply the formalism of Titulaer and Deutch [J. Chem. Phys. {bold 77}, 472 (1982)], which describes evolution in reciprocal space via a linear master equation with dimension equal to the number of cluster configurations. We focus on the regime of rapid hopping of atoms along straight close-packed edges, where certain subsets of configurations cycle rapidly between each other. Each such subset is treated as a single quasiconfiguration, thereby reducing the dimension of the evolution equation, simplifying the analysis, and elucidating limiting behavior. We also discuss the influence of concerted atom motions on the diffusion of tetramers and larger clusters. {copyright} {ital 1999} {ital The American Physical Society}

  18. Elevated levels of ferrimagnetic metals in foodchains supporting the Guam cluster of neurodegeneration: do metal nucleated crystal contaminants [corrected] evoke magnetic fields that initiate the progressive pathogenesis of neurodegeneration?

    PubMed

    Purdey, Mark

    2004-01-01

    Elevated levels of aluminium (Al), strontium (Sr), barium (Ba), iron (Fe), manganese (Mn) cations - combined with deficiencies of magnesium (Mg)/calcium (Ca) - have been observed in the foodchains that traditionally support the Chamorro populations affected by high incidence clusters of Alzheimer (AD), Parkinson-like (PD), motor neurone diseases and multiple sclerosis on the island of Guam. Soils drawn from the cluster region demonstrated an excessive fivefold increase in 'magnetic susceptibility' readings in relation to soils from disease free adjoining regions. A multifactorial aetiological hypothesis is proposed that pivots upon the combined exposure to high levels of natural/industrial sources of ferrimagnetic/ferroelectric compounds incorporating Al, Fe, Mn, Sr, Ba (e.g., via yam/seafood consumption or exposure to world war 2 (WW2) munitions) and to low levels of Mg/Ca in all S. Pacific locations where these clusters of neurodegenerative disease have simultaneously erupted. Once gut/blood brain barrier permeability is impaired, the increased uptake of Al, Fe, Sr, Ba, or Mn into the Mg/Ca depleted brain leads to rogue metal substitutions at the Mg/Ca vacated binding domains on various enzyme/proteoglycan groups, causing a broad ranging disruption in Mg/Ca dependent systems - such as the glutamine synthetase which prevents the accumulation of neurotoxic glutamate. The rogue metals chelate sulphate, disrupting sulphated-proteoglycan mediated inhibition of crystal proliferation, as well as its regulation of the Fibroblast growth factor receptor complex which disturbs the molecular conformation of those receptors and their regulation of transphosphorylation between intracellular kinase domains; ultimately collapsing proteoglycan mediated cell-cell signalling pathways which maintain the growth and structural integrity of the neuronal networks. The depression of Mg/Ca dependent systems in conjunction with the progressive ferrimagnetisation of the CNS due to an

  19. THE EFFECT OF SECOND-GENERATION POPULATIONS ON THE INTEGRATED COLORS OF METAL-RICH GLOBULAR CLUSTERS IN EARLY-TYPE GALAXIES

    SciTech Connect

    Chung, Chul; Lee, Sang-Yoon; Yoon, Suk-Jin; Lee, Young-Wook

    2013-05-20

    The mean color of globular clusters (GCs) in early-type galaxies is in general bluer than the integrated color of halo field stars in host galaxies. Metal-rich GCs often appear more associated with field stars than metal-poor GCs, yet show bluer colors than their host galaxy light. Motivated by the discovery of multiple stellar populations in Milky Way GCs, we present a new scenario in which the presence of second-generation (SG) stars in GCs is responsible for the color discrepancy between metal-rich GCs and field stars. The model assumes that the SG populations have an enhanced helium abundance as evidenced by observations, and it gives a good explanation of the bluer optical colors of metal-rich GCs than field stars as well as strong Balmer lines and blue UV colors of metal-rich GCs. Ours may be complementary to the recent scenario suggesting the difference in stellar mass functions (MFs) as an origin for the GC-to-star color offset. A quantitative comparison is given between the SG and MF models.

  20. Double aromaticity in transition metal centered double-ring boron clusters M@B2n (M = Ti, Cr, Fe, Ni, Zn; n = 6, 7, 8)

    NASA Astrophysics Data System (ADS)

    Xu, Chang; Cheng, Longjiu; Yang, Jinlong

    2014-09-01

    It is well known that double-ring boron clusters have got the special double aromaticity with delocalized π orbitals in two directions (tangential and radial), which are potential ligands centered by a transition metal. In this article, the transition metal centered double-ring boron clusters M@B2n (M = Ti, Cr, Fe, Ni, Zn; n = 6, 7, 8) are theoretically investigated by density functional theory calculations. These endohedral compounds have also got double aromaticity in both tangential and radial directions. Interestingly, the tangential delocalized π orbitals of boron ligands following the Huckle's (4n + 2) rule do not interact with the central metal, while the radial π orbitals of boron ligands are bonded with the central mental to form spd-π endohedral bonding. The spd-π endohedral bonding follows the 18e-principle in Ni@B14 and Fe@B16. However, due to the flat shape of the compounds, 14e (Cr@B14) and 16e (Ni@B12) can also be electronically very stable where the energy levels of the spd-π orbitals delocalized in z-direction rise up. This intriguing bonding model makes sense in further study of the boron chemistry.

  1. A thorough analysis of the metal abundance gradient history in the Galactic disk by improving the statistics of well studied open clusters

    NASA Astrophysics Data System (ADS)

    Claria, Juan J.; Piatti, Andres E.; Ahumada, Andrea V.; Parisi, Maria Celeste; Palma, Tali

    2008-02-01

    Open clusters (OCs) have long been used as tracers of the evolution of the Galactic disk (GD). Although the number of studied OCs has recently increased significantly, nearly 60% of the ~ 1700 Galactic OCs known to exist are still unstudied objects. We want to examine how the abundance gradient in the GD evolved in time and along different Galactic positions by comparing the abundance gradients corresponding to various groups of open clusters (OCs) of different ages and positions. The greater the number of OCs with well determined distances, ages and metallicities, the more precise and detailed the analysis of the metal abundance gradient in the GD as well as its evolution over time. We then propose to observe some selected OCs with the Washington system C and T_1 filters mainly to determine their basic parameters for the first time, with the aim of: (1) Improving the statistics of well-studied OCs. (2) Showing how the radial abundance gradient has evolved in course of time and along different Galactic longitudes by dividing the whole sample of known OCs into age-position groups. We believe this is crucial in constraining the initial conditions and evolution of the gas and stars in the GD. (3) Shedding light on the controversial existence of an abundance gradient perpendicular to the Galactic plane and on the blurry age-metallicity relation (AMR).

  2. Stern-Gerlach experiments of one-dimensional metal-benzene sandwich clusters: Mn(C6H6)m (M = Al, Sc, Ti, and V).

    PubMed

    Miyajima, Ken; Yabushita, Satoshi; Knickelbein, Mark B; Nakajima, Atsushi

    2007-07-11

    A molecular beam of multilayer metal-benzene organometallic clusters Mn(C6H6)m (M = Al, Sc, Ti, and V) was produced by a laser vaporization synthesis method, and their magnetic deflections were measured. Multidecker sandwich clusters of transition-metal atoms and benzene Scn(C6H6)n+1 (n = 1, 2) and Vn(C6H6)n+1 (n = 1-4) possess magnetic moments that increase monotonously with n. The magnetic moments of Al(C6H6), Scn(C6H6)n+1, and Vn(C6H6)n+1 are smaller than that of their spin-only values as a result of intracluster spin relaxation, an effect that depends on the orbital angular momenta and bonding characters of the orbitals containing electron spin. While Ti(C6H6)2 was found to be nonmagnetic, Tin(C6H6)n+1 (n = 2, 3) possess nonzero magnetic moments. The mechanism of ferromagnetic spin ordering in M2(C6H6)3 (M = Sc, Ti, V) is discussed qualitatively in terms of molecular orbital analysis. These sandwich species represent a new class of one-dimensional molecular magnets in which the transition-metal atoms are formally zerovalent.

  3. A2111: A z= 0.23 Butcher-Oemler Cluster with a Non-Isothermal Atmosphere and Normal Metallicity

    NASA Technical Reports Server (NTRS)

    Wang, Q. Daniel; Henriksen, Mark

    1998-01-01

    We report results from an x-ray spectral study of the z=0.23 Abell 2111 galaxy cluster using the Advanced Satellite for Astrophysics and Cosmology and the ROSAT Position Sensitive Proportional Counter. By correcting for the energy-dependent point-spread function of the instruments, we have examined the temperature structure of the cluster. The cluster's core within 3 is found to have a temperature of 5.4 +/- 0.5 keV, significantly higher than 2.8 +/-0.7 keV in the surrounding region of r = 3-6. This radially decreasing temperature structure can be parameterized by a polytropic index of gamma less than 1.4. Furthermore, the intracluster medium appears clumpy on scales less than 1. Early studies have revealed that the x-ray centroid of the cluster shifts with spatial scale and the overall optical and x-ray morphology is strongly elongated. These results together suggest that A2111 in undergoing a merger, which is likely responsible for the high fraction of blue galaxies observed in the cluster. We have further measured the abundance of the medium as 0.25 +/- 0.14 solar. This value is similar to those of nearby clusters which do not show a large blue galaxy function, suggesting that star formation in disk galaxies and subsequent loss to the intracluster medium do not drastically alter the average abundance of a cluster since z=0.23.

  4. Structures and Stabilities of the Metal Doped Gold Nano-Clusters: M@Au10 (M = W, Mo, Ru, Co).

    PubMed

    Hossain, Delwar; Pittman, Charles U; Gwaltney, Steven R

    2014-01-01

    The structures and stabilities of a series of endohedral gold clusters containing ten gold atoms M@Au10 (M = W, Mo, Ru, Co) have been determined using density functional theory. The gradient-corrected functional BP86, the Tao-Perdew-Staroverov-Scuseria TPSS meta-GGA functional, and the hybrid density functionals B3LYP and PBE1PBE were employed to calculate the structures, binding energies, adiabatic ionization potentials, and adiabatic electron affinities for these clusters. The LanL2DZ effective core potentials and the corresponding valence basis sets were employed. The M@Au10 (M = W, Mo, Ru, Co) clusters have higher binding energies than an empty Au10 cluster. In addition, the large HOMO-LUMO gaps suggest that the M@Au10 (M = W, Mo, Ru, Co) clusters are all likely to be stable chemically. The ionization potentials and electron affinities for these clusters are very high, and the W@Au10 and Mo@Au10 clusters have electron affinities similar to the super-halogen Al13.

  5. Structures and Stabilities of the Metal Doped Gold Nano-Clusters: M@Au10 (M = W, Mo, Ru, Co)

    PubMed Central

    Hossain, Delwar; Pittman, Charles U.; Gwaltney, Steven R.

    2014-01-01

    The structures and stabilities of a series of endohedral gold clusters containing ten gold atoms M@Au10 (M = W, Mo, Ru, Co) have been determined using density functional theory. The gradient-corrected functional BP86, the Tao-Perdew-Staroverov-Scuseria TPSS meta-GGA functional, and the hybrid density functionals B3LYP and PBE1PBE were employed to calculate the structures, binding energies, adiabatic ionization potentials, and adiabatic electron affinities for these clusters. The LanL2DZ effective core potentials and the corresponding valence basis sets were employed. The M@Au10 (M = W, Mo, Ru, Co) clusters have higher binding energies than an empty Au10 cluster. In addition, the large HOMO–LUMO gaps suggest that the M@Au10 (M = W, Mo, Ru, Co) clusters are all likely to be stable chemically. The ionization potentials and electron affinities for these clusters are very high, and the W@Au10 and Mo@Au10 clusters have electron affinities similar to the super-halogen Al13. PMID:24611036

  6. The Ages, Metallicities, and Alpha Element Enhancements of Globular Clusters in the Elliptical NGC 5128: A Homogeneous Spectroscopic Study with Gemini/Gemini Multi-Object Spectrograph

    NASA Astrophysics Data System (ADS)

    Woodley, Kristin A.; Harris, William E.; Puzia, Thomas H.; Gómez, Matías; Harris, Gretchen L. H.; Geisler, Doug

    2010-01-01

    We present new integrated light spectroscopy of globular clusters (GCs) in NGC 5128, a nearby giant elliptical galaxy less than 4 Mpc away, in order to measure radial velocities and derive ages, metallicities, and alpha-element abundance ratios. Using the Gemini South 8 meter telescope with the instrument Gemini Multi-Object Spectrograph, we obtained spectroscopy in the range of ~3400-5700 Å for 72 GCs with a signal-to-noise ratio greater than 30 Å-1 and we have also discovered 35 new GCs within NGC 5128 from our radial velocity measurements. We measured and compared the Lick indices from Hδ A through Fe5406 with the single stellar population models of Thomas et al. in order to derive age, metallicity, and [α/Fe] values. We also measure Lick indices for 41 Milky Way GCs from Puzia et al. and Schiavon et al. with the same methodology for direct comparison. Our results show that 68% of the NGC 5128 GCs have old ages (>8 Gyr), 14% have intermediate ages (5-8 Gyr), and 18% have young ages (<5 Gyr). However, when we look at the metallicity of the GCs as a function of age, we find 92% of metal-poor GCs and 56% of metal-rich GCs in NGC 5128 have ages >8 Gyr, indicating that the majority of both metallicity subpopulations of GCs formed earlier, with a significant population of young and metal-rich GCs forming later. Our metallicity distribution function generated directly from spectroscopic Lick indices is clearly bimodal, as is the color distribution of the same set of GCs. Thus, the metallicity bimodality is real and not an artifact of the color to metallicity conversion. However, the metallicity distribution function obtained from comparison with the single stellar population models is consistent with a unimodal, bimodal, or multimodal shape. The [α/Fe] values are supersolar with a mean value of 0.14 ± 0.04, indicating a fast formation timescale. However, the GCs in NGC 5128 are not as [α/Fe] enhanced as the Milky Way GCs also examined in this study. Our measured

  7. Tracking Rh Atoms in Zeolite HY: First Steps of Metal Cluster Formation and Influence of Metal Nuclearity on Catalysis of Ethylene Hydrogenation and Ethylene Dimerization

    SciTech Connect

    Yang, Dong; Xu, Pinghong; Browning, Nigel D.; Gates, Bruce C.

    2016-07-07

    The initial steps of rhodium cluster formation from zeolite-supported mononuclear Rh(C2H4)2 complexes in H2 at 373 K and 1 bar were investigated by infrared and extended X-ray absorption fine structure spectroscopies and scanning transmission electron microscopy (STEM). The data show that ethylene ligands on the rhodium react with H2 to give supported rhodium hydrides and trigger the formation of rhodium clusters. STEM provided the first images of the smallest rhodium clusters (Rh2) and their further conversion into larger clusters. The samples were investigated in a plug-flow reactor as catalysts for the conversion of ethylene + H2 in a molar ratio of 4:1 at 1 bar and 298 K, with the results showing how the changes in catalyst structure affect the activity and selectivity; the rhodium clusters are more active for hydrogenation of ethylene than the single-site complexes, which are more selective for dimerization of ethylene to give butenes

  8. Cluster expansion reactions of group 6 and 8 metallaboranes using transition metal carbonyl compounds of groups 7-9.

    PubMed

    Geetharani, K; Bose, Shubhankar Kumar; Sahoo, Satyanarayan; Varghese, Babu; Mobin, Shaikh M; Ghosh, Sundargopal

    2011-06-20

    The reinvestigation of an early synthesis of heterometallic cubane-type clusters has led to the isolation of a number of new clusters which have been characterized by spectroscopic and crystallographic techniques. The thermolysis of [(Cp*Mo)(2)B(4)H(4)E(2)] (1: E = S; 2: E = Se; Cp* = η(5)-C(5)Me(5)) in presence of [Fe(2)(CO)(9)] yielded cubane-type clusters [(Cp*Mo)(2)(μ(3)-E)(2)B(2)H(μ-H){Fe(CO)(2)}(2)Fe(CO)(3)], 4 and 5 (4: E = S; 5: E = Se) together with fused clusters [(Cp*Mo)(2)B(4)H(4)E(2)Fe(CO)(2)Fe(CO)(3)] (8: E = S; 9: E = Se). In a similar fashion, reaction of [(Cp*RuCO)(2)B(2)H(6)], 3, with [Fe(2)(CO)(9)] yielded [(Cp*Ru)(2)(μ(3)-CO)(2)B(2)H(μ-H){Fe(CO)(2)}(2)Fe(CO)(3)], 6, and an incomplete cubane cluster [(μ(3)-BH)(3)(Cp*Ru)(2){Fe(CO)(3)}(2)], 7. Clusters 4-6 can be described as heterometallic cubane clusters containing a Fe(CO)(3) moiety exo-bonded to the cubane, while 7 has an incomplete cubane [Ru(2)Fe(2)B(3)] core. The geometry of both compounds 8 and 9 consist of a bicapped octahedron [Mo(2)Fe(2)B(3)E] and a trigonal bipyramidal [Mo(2)B(2)E] core, fused through a common three vertex [Mo(2)B] triangular face. In addition, thermolysis of 3 with [Mn(2)(CO)(10)] permits the isolation of arachno-[(Cp*RuCO)(2)B(3)H(7)], 10. Cluster 10 constitutes a diruthenaborane analogue of 8-sep pentaborane(11) and has a structural isomeric relationship to 1,2-[{Cp*Ru}(2)(CO)(2)B(3)H(7)].

  9. Hydride mobility in trinuclear sulfido clusters with the core [Rh3(μ-H)(μ3-S)2]: molecular models for hydrogen migration on metal sulfide hydrotreating catalysts.

    PubMed

    Jiménez, M Victoria; Lahoz, Fernando J; Lukešová, Lenka; Miranda, José R; Modrego, Francisco J; Nguyen, Duc H; Oro, Luis A; Pérez-Torrente, Jesús J

    2011-07-11

    The treatment of [{Rh(μ-SH){P(OPh)(3)}(2)}(2)] with [{M(μ-Cl)(diolef)}(2)] (diolef=diolefin) in the presence of NEt(3) affords the hydrido-sulfido clusters [Rh(3)(μ-H)(μ(3)-S)(2)(diolef){P(OPh)(3)}(4)] (diolef=1,5-cyclooctadiene (cod) for 1, 2,5-norbornadiene (nbd) for 2, and tetrafluorobenzo[5,6]bicyclo[2.2.2]octa-2,5,7-triene (tfb) for 3) and [Rh(2)Ir(μ-H)(μ(3)-S)(2)(cod){P(OPh)(3)}(4)] (4). Cluster 1 can be also obtained by treating [{Rh(μ-SH){P(OPh)(3)}(2)}(2)] with [{Rh(μ-OMe)(cod)}(2)], although the main product of the reaction with [{Ir(μ-OMe)(cod)}(2)] was [RhIr(2)(μ-H)(μ(3)-S)(2)(cod)(2){P(OPh)(3)}(2)] (5). The molecular structures of clusters 1 and 4 have been determined by X-ray diffraction methods. The deprotonation of a hydrosulfido ligand in [{Rh(μ-SH)(CO)(PPh(3))}(2)] by [M(acac)(diolef)] (acac=acetylacetonate) results in the formation of hydrido-sulfido clusters [Rh(3)(μ-H)(μ(3)-S)(2)(CO)(2) (diolef)(PPh(3))(2)] (diolef=cod for 6, nbd for 7) and [Rh(2)Ir(μ-H)(μ(3)-S)(2)(CO)(2)(cod)(PPh(3))(2)] (8). Clusters 1-3 and 5 exist in solution as two interconverting isomers with the bridging hydride ligand at different edges. Cluster 8 exists as three isomers that arise from the disposition of the PPh(3) ligands in the cluster (cis and trans) and the location of the hydride ligand. The dynamic behaviour of clusters with bulky triphenylphosphite ligands, which involves hydrogen migration from rhodium to sulfur with a switch from hydride to proton character, is significant to understand hydrogen diffusion on the surface of metal sulfide hydrotreating catalysts.

  10. Encapsulation of [(SO₄)₄(H₂O)1₁₂]⁸⁻ clusters in a metal organic framework of pyridyl functionalized cyanuric acid based tris-urea.

    PubMed

    Dutta, Ranjan; Akhuli, Bidyut; Ghosh, Pradyut

    2015-09-14

    Encapsulation of hydrated sulfate in a bowl-shaped metal organic coordination polymer formed by Zn(2+) assisted self-assembly of a 3-pyridyl terminated cyanuric acid platform based urea receptor is reported in aqueous medium. Trapping of an unusual [(SO4)4(H2O)12](8-) cluster in a [Zn(H2O)6](2+) capped self-assembled structure is characterized by single crystal X-ray crystallography. Furthermore, selective binding of SO4(2-) is established from the (1)H-NMR titration study.

  11. Metallicities and Alpha-to-Iron Ratios in Globular Cluster Stars on a Homogeneous Scale: Search for Multiple Populations

    NASA Astrophysics Data System (ADS)

    Dias, B.; Saviane, I.; Barbuy, B.; Held, E.; Da Costa, G.; Ortolani, S.; Vasquez, S.

    2015-05-01

    We are carrying out a survey of 51 poorly studied Milky Way globular clusters by means of spectroscopy of ˜20 red giant stars per cluster. Optical spectra (4600-5800 Å) were obtained with FORS2@VLT/ESO, at a resolution Δλ ˜ 2.5 Å. We used the ETOILE code to derive radial velocities, Teff, log g, [Fe/H], and [Mg/Fe] for each star by identifying the best fitted spectrum among a grid of stellar spectra. The stellar library can be a collection of observed or synthetic spectra. The main contributions of this work are to provide a homogeneous scale of [Fe/H], [Mg/Fe], and radial velocities for 51 clusters (in particular for the 29 distant and/or highly reddened ones), to provide a catalogue of confirmed member stars for each cluster, and to identify interesting clusters for follow-up with high resolution data (e.g., the massive clusters M 22 and NGC 5824, for which a spread in [Fe/H] was found).

  12. Mixed-metal chloro sulfido cluster complex of molybdenum and platinum, (Mo sub 3 Pt sub 2 S sub 4 Cl sub 4 (PEt sub 3 ) sub 6 )

    SciTech Connect

    Saito, Taro; Tsuboi, Toshio; Kajitani, Yoshimichi; Yamagata, Tsuneaki; Imoto, Hideo )

    1991-09-04

    In the authors recent publication, syntheses of mixed-metal chloro sulfido and chloro selenido complexes of molybdenum and nickel were reported. They were prepared by the reaction of (Mo{sub 3}X{sub 4}Cl{sub 4}(PEt{sub 3}){sub 3}(MeOH){sub 2}) (X = S, Se){sup 2} with Ni(cod){sub 2} (cod = 1,5-cyclooctadiene). In the present study, another excellent building block compound, Pt(cot){sub 2}, was reacted with the same trinuclear molybdenum complex, and the mixed-metal cluster complex (Mo{sub 3}Pt{sub 2}S{sub 4}Cl{sub 4}(PEt{sub 3}){sub 6}) (1) with an unexpected structure was obtained.

  13. Fermi-level depinning and contact resistance reduction in metal/n-Ge junctions by insertion of W-encapsulating Si cluster films

    SciTech Connect

    Okada, Naoya; Uchida, Noriyuki; Kanayama, Toshihiko

    2014-02-10

    We demonstrate Fermi-level depinning in metal/Ge junctions and a significant reduction of specific contact resistivity of n-Ge by inserting an ultra-thin semiconducting Si-rich W silicide film (WSi{sub n}, n = 12–14) composed of W-encapsulating Si clusters. Dependence of the specific contact resistivity on the electron Schottky barrier height followed the ideal exponential relation for various contact metal species. This result indicates that the insertion of the WSi{sub n} film provides a negligible contribution to contact resistivity because its tunneling resistance is very low owing to the low offset of the conduction band edge of Ge.

  14. THE OLD, SUPER-METAL-RICH OPEN CLUSTER, NGC 6791—ELEMENTAL ABUNDANCES IN TURN-OFF STARS FROM KECK/HIRES SPECTRA

    SciTech Connect

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

    2015-02-01

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

  15. The Old, Super-metal-rich Open Cluster, NGC 6791—Elemental Abundances in Turn-off Stars from Keck/HIRES Spectra

    NASA Astrophysics Data System (ADS)

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

    2015-02-01

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

  16. Multi-color photometry of the Galactic globular cluster M 75 = NGC 6864. A new sensitive metallicity indicator and the position of the horizontal branch in UV

    NASA Astrophysics Data System (ADS)

    Kravtsov, V.; Alcaíno, G.; Marconi, G.; Alvarado, F.

    2007-07-01

    Aims:We carry out and analyze new multi-color photometry of the Galactic globular cluster (GC) M 75 in UBVI and focus on the brighter sequences of the color-magnitude diagram (CMD), with particular emphasis on their location in U-based CMD. Specifically, we study the level both of the horizontal (HB) and red giant branches (RGB) relative to the main-sequence turnoff (TO) in the U magnitude. Methods: Along with the presented photometry of M 75, we use our collection of photometric data on GCs belonging to the metal-poor range, [Fe/H]{ZW}<-1.1 dex, obtained from observations with different equipment, but calibrated by standard stars situated in the observed cluster fields. Results: We confirm our earlier finding, and extend it to a larger magnitude range. We demonstrate that Δ U_TO^BHB expressing the difference in U magnitude between the TO point and the level of the blue HB, near its red boundary, of the metal-poor GCs observed with the EMMI camera of the NTT/ESO telescope is about 0.4-0.5 mag smaller as compared to GCs observed with the 100 arcsec telescope and 1.3 m Warsaw telescope of the Las Campanas Observatory. At the same time, Δ U_TO^RGB, the difference in U magnitude between the TO and RGB inflection (brightest) points, does not show such an apparent dependence on the characteristics of U filters used, but it depends on cluster metallicity. We have shown, for the first time, the dependence of the parameter Δ U_TO^RGB on [Fe/H] and have estimated its analytical expression, by assuming a linear relation between the parameter and metallicity. Its slope, Δ U_TO^RGB/Δ[Fe/H] 1.2 mag/dex, is approximately a factor of two steeper than that of the dependence of the RGB bump position in the V magnitude on metallicity. The asymptotic giant branch (AGB) clump and features of the RGB luminosity function (LF) of M 75 are also discussed. Based on observations with the 1.3 m Warsaw telescope at Las Campanas Observatory. Individual photometry measurements are only

  17. Analysis of heterogeneous water vapor uptake by metal iodide cluster ions via differential mobility analysis-mass spectrometry.

    PubMed

    Oberreit, Derek; Rawat, Vivek K; Larriba-Andaluz, Carlos; Ouyang, Hui; McMurry, Peter H; Hogan, Christopher J

    2015-09-14

    The sorption of vapor molecules onto pre-existing nanometer sized clusters is of importance in understanding particle formation and growth in gas phase environments and devising gas phase separation schemes. Here, we apply a differential mobility analyzer-mass spectrometer based approach to observe directly the sorption of vapor molecules onto iodide cluster ions of the form (MI)xM(+) (x = 1-13, M = Na, K, Rb, or Cs) in air at 300 K and with water saturation ratios in the 0.01-0.64 range. The extent of vapor sorption is quantified in measurements by the shift in collision cross section (CCS) for each ion. We find that CCS measurements are sensitive enough to detect the transient binding of several vapor molecules to clusters, which shift CCSs by only several percent. At the same time, for the highest saturation ratios examined, we observed CCS shifts of up to 45%. For x < 4, cesium, rubidium, and potassium iodide cluster ions are found to uptake water to a similar extent, while sodium iodide clusters uptake less water. For x ≥ 4, sodium iodide cluster ions uptake proportionally more water vapor than rubidium and potassium iodide cluster ions, while cesium iodide ions exhibit less uptake. Measured CCS shifts are compared to predictions based upon a Kelvin-Thomson-Raoult (KTR) model as well as a Langmuir adsorption model. We find that the Langmuir adsorption model can be fit well to measurements. Meanwhile, KTR predictions deviate from measurements, which suggests that the earliest stages of vapor uptake by nanometer scale species are not well described by the KTR model.

  18. Analysis of heterogeneous water vapor uptake by metal iodide cluster ions via differential mobility analysis-mass spectrometry

    NASA Astrophysics Data System (ADS)

    Oberreit, Derek; Rawat, Vivek K.; Larriba-Andaluz, Carlos; Ouyang, Hui; McMurry, Peter H.; Hogan, Christopher J.

    2015-09-01

    The sorption of vapor molecules onto pre-existing nanometer sized clusters is of importance in understanding particle formation and growth in gas phase environments and devising gas phase separation schemes. Here, we apply a differential mobility analyzer-mass spectrometer based approach to observe directly the sorption of vapor molecules onto iodide cluster ions of the form (MI)xM+ (x = 1-13, M = Na, K, Rb, or Cs) in air at 300 K and with water saturation ratios in the 0.01-0.64 range. The extent of vapor sorption is quantified in measurements by the shift in collision cross section (CCS) for each ion. We find that CCS measurements are sensitive enough to detect the transient binding of several vapor molecules to clusters, which shift CCSs by only several percent. At the same time, for the highest saturation ratios examined, we observed CCS shifts of up to 45%. For x < 4, cesium, rubidium, and potassium iodide cluster ions are found to uptake water to a similar extent, while sodium iodide clusters uptake less water. For x ≥ 4, sodium iodide cluster ions uptake proportionally more water vapor than rubidium and potassium iodide cluster ions, while cesium iodide ions exhibit less uptake. Measured CCS shifts are compared to predictions based upon a Kelvin-Thomson-Raoult (KTR) model as well as a Langmuir adsorption model. We find that the Langmuir adsorption model can be fit well to measurements. Meanwhile, KTR predictions deviate from measurements, which suggests that the earliest stages of vapor uptake by nanometer scale species are not well described by the KTR model.

  19. Analysis of heterogeneous water vapor uptake by metal iodide cluster ions via differential mobility analysis-mass spectrometry

    SciTech Connect

    Oberreit, Derek; Rawat, Vivek K.; Larriba-Andaluz, Carlos; Ouyang, Hui; McMurry, Peter H.; Hogan, Christopher J.

    2015-09-14

    The sorption of vapor molecules onto pre-existing nanometer sized clusters is of importance in understanding particle formation and growth in gas phase environments and devising gas phase separation schemes. Here, we apply a differential mobility analyzer-mass spectrometer based approach to observe directly the sorption of vapor molecules onto iodide cluster ions of the form (MI){sub x}M{sup +} (x = 1-13, M = Na, K, Rb, or Cs) in air at 300 K and with water saturation ratios in the 0.01-0.64 range. The extent of vapor sorption is quantified in measurements by the shift in collision cross section (CCS) for each ion. We find that CCS measurements are sensitive enough to detect the transient binding of several vapor molecules to clusters, which shift CCSs by only several percent. At the same time, for the highest saturation ratios examined, we observed CCS shifts of up to 45%. For x < 4, cesium, rubidium, and potassium iodide cluster ions are found to uptake water to a similar extent, while sodium iodide clusters uptake less water. For x ≥ 4, sodium iodide cluster ions uptake proportionally more water vapor than rubidium and potassium iodide cluster ions, while cesium iodide ions exhibit less uptake. Measured CCS shifts are compared to predictions based upon a Kelvin-Thomson-Raoult (KTR) model as well as a Langmuir adsorption model. We find that the Langmuir adsorption model can be fit well to measurements. Meanwhile, KTR predictions deviate from measurements, which suggests that the earliest stages of vapor uptake by nanometer scale species are not well described by the KTR model.

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

    SciTech Connect

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

    2013-01-10

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

  1. Reactivity of metal oxide clusters with hydrogen peroxide and water--a DFT study evaluating the performance of different exchange-correlation functionals.

    PubMed

    Lousada, Cláudio M; Johansson, Adam Johannes; Brinck, Tore; Jonsson, Mats

    2013-04-21

    We have performed a density functional theory (DFT) investigation of the interactions of H2O2, H2O and HO radicals with clusters of ZrO2, TiO2 and Y2O3. Different modes of H2O adsorption onto the clusters were studied. In almost all the cases the dissociative adsorption is more exothermic than molecular adsorption. At the surfaces where H2O has undergone dissociative adsorption, the adsorption of H2O2 and the transition state for its decomposition are mediated by hydrogen bonding with the surface HO groups. Using the functionals B3LYP, B3LYP-D and M06 with clusters of 26 and 8 units of ZrO2, the M06 functional performed better than B3LYP in describing the reaction of decomposition of H2O2 and the adsorption of H2O. Additionally, we investigated clusters of the type (ZrO2)2, (TiO2)2 and (Y2O3) and the performance of the functionals B3LYP, B3LYP-D, B3LYP*, M06, M06-L, PBE0, PBE and PWPW91 in describing H2O2, H2O and HO˙ adsorption and the energy barrier for decomposition of H2O2. The trends obtained for HO˙ adsorption onto the clusters are discussed in terms of the ionization energy of the metal cation present in the oxide. In order to correctly account for the existence of an energy barrier for the decomposition of H2O2, the functional used must include Hartree-Fock exchange. Using minimal cluster models, the best performance in describing the energy barrier for H2O2 decomposition was obtained with the M06 and PBE0 functionals - the average absolute deviations from experiments are 6 kJ mol(-1) and 5 kJ mol(-1) respectively. With the M06 functional and a larger monoclinic (ZrO2)8 cluster model, the performance is in excellent agreement with experimental data. For the different oxides, PBE0 was found to be the most effective functional in terms of performance and computational time cost.

  2. Strömgren and near-infrared photometry of metal-rich bulge globular clusters. I. NGC 6528 and its surrounding field

    NASA Astrophysics Data System (ADS)

    Calamida, A.; Bono, G.; Lagioia, E. P.; Milone, A. P.; Fabrizio, M.; Saviane, I.; Moni Bidin, C.; Mauro, F.; Buonanno, R.; Ferraro, I.; Iannicola, G.; Zoccali, M.

    2014-05-01

    We present Strömgren and near-infrared (NIR) photometry of the bulge cluster NGC 6528 and its surrounding field in Baade's Window. uvby images were collected with EFOSC2 on the New Technology Telescope (NTT, La Silla, ESO). The NIR catalogs are based on J,K-band VIRCAM at VISTA (Paranal, ESO) and SOFI at NTT photometry. We matched the aforementioned data sets with Hubble Space Telescope photometry to obtain proper-motion-cleaned samples of NGC 6528 and bulge stars. Furthermore, we were able to correct the Strömgren-NIR photometry for differential reddening. The huge color sensitivity of the Strömgren-NIR color-magnitude-diagrams (CMDs) helped us in separating age and metallicity effects. The red giant branch (RGB) of NGC 6528 is well reproduced in all the CMDs by adopting scaled solar isochrones with solar abundance, that is Z = 0.0198, or α-enhanced isochrones with the same iron content, that is Z = 0.04, and an age range of t = 10-12 Gyr. The same isochrones well reproduce most of the color spread of Baade's Window RGB. These findings support the literature age estimates for NGC 6528. We also performed a new theoretical visual-NIR metallicity calibration based on the Strömgren index m1 and on visual-NIR colors for red giant (RG) stars. Scaled solar and α-enhanced models were adopted and we validated the new metallicity-index-color (MIC) relations by applying them to estimate the photometric metal abundance of a sample of field RGs and of a metal-poor (M 92, [Fe/H] ~-2.3) and a metal-rich (NGC 6624, [Fe/H] ~ -0.7) globular cluster. We applied the calibration to estimate the mean metal abundance of NGC 6528, finding [Fe/H] = [M/H] = -0.04 ± 0.02, with a mean intrinsic dispersion of σ = 0.27 dex, by averaging the metallicities obtained with the scaled solar [m], y - J and [m], y - K MIC relations, and of -0.11 ± 0.01, with σ = 0.27 dex, by using the m1, y - J and m1, y - K relations. These findings support results based on high-resolution spectroscopy

  3. a Chirped Pulse Fourier Transform Microwave Cp-Ftmw Spectrometer with Laser Ablation Source to Search for Actinide-Containing Molecules and Noble Metal Clusters

    NASA Astrophysics Data System (ADS)

    Marshall, Frank E.; Gillcrist, David Joseph; Persinger, Thomas D.; Moon, Nicole; Grubbs, G. S., II

    2016-06-01

    Microwave spectroscopic techniques have traditionally been part of the foundation of molecular structure and this conference. Instrumental developments by Brooks Pate and sourcing developments by Steve Cooke on these instruments have allowed for the dawning of a new era in modern microwave spectroscopic techniques. With these advances and the growth of powerful computational approaches, microwave spectroscopists can now search for molecules and/or cluster systems of actinide and noble metal-containing species with increasing certainty in molecular assignment even with the difficulties presented with spin-orbit coupling and relativistic effects. Spectrometer and ablation design will be presented along with any preliminary results on actinide-containing molecules or noble metal clusters or interactions. G. G. Brown, B. C. Dian, K. O. Douglass, S. M. Geyer, S. T. Shipman, B. H. Pate, Rev. Sci. Instrum. 79 (2008) 053103-1 - 053103-13 G. S. Grubbs II, C. T. Dewberry, K. C. Etchison, K. E. Kerr, S. A. Cooke, Rev. Sci. Instrum. 78 (2007) 096106-1 - 096106-3

  4. Atomic collisions in suprafluid helium-nanodroplets: timescales for metal-cluster formation derived from He-density functional theory.

    PubMed

    Hauser, Andreas W; Volk, Alexander; Thaler, Philipp; Ernst, Wolfgang E

    2015-04-28

    Collision times for the coinage metal atoms Cu, Ag and Au in He-droplets are derived from helium density functional theory and molecular dynamics simulations. The strength of the attractive interaction between the metal atoms turns out to be less important than the mass of the propagating metal atoms. Even for small droplets consisting of a few thousand helium atoms, the collision times are shortest for Cu, followed by Ag and Au, despite the higher binding energy of Au2 compared to Cu2.

  5. Atomic collisions in suprafluid helium-nanodroplets: timescales for metal-cluster formation derived from He-density functional theory

    PubMed Central

    Volk, Alexander; Thaler, Philipp

    2015-01-01

    Collision times for the coinage metal atoms Cu, Ag and Au in He-droplets are derived from helium density functional theory and molecular dynamics simulations. The strength of the attractive interaction between the metal atoms turns out to be less important than the mass of the propagating metal atoms. Even for small droplets consisting of a few thousand helium atoms, the collision times are shortest for Cu, followed by Ag and Au, despite the higher binding energy of Au2 compared to Cu2. PMID:25812719

  6. Large O2 Cluster Ions as Sputter Beam for ToF-SIMS Depth Profiling of Alkali Metals in Thin SiO2 Films.

    PubMed

    Holzer, Sabine; Krivec, Stefan; Kayser, Sven; Zakel, Julia; Hutter, Herbert

    2017-02-21

    A sputter beam, consisting of large O2 clusters, was used to record depth profiles of alkali metal ions (Me(+)) within thin SiO2 layers. The O2 gas cluster ion beam (O2-GCIB) exhibits an erosion rate comparable to the frequently used O2(+) projectiles. However, because of its high sputter yield the necessary beam current is considerably lower (factor 50), resulting in a decreased amount of excess charges at the SiO2 surface. Hence, a reduced electric field is obtained within the remaining dielectric layer. This drastically mitigates the Me(+) migration artifact, commonly observed in depth profiles of various dielectric materials, if analyzed by time-of-flight secondary ion mass spectrometry (ToF-SIMS) in dual beam mode. It is shown, that the application of O2-GCIB results in a negligible residual ion migration for Na(+) and K(+). This enables artifact-free depth profiling with high sensitivity and low operational effort. Furthermore, insight into the migration behavior of Me(+) during O2(+) sputtering is given by switching the sputter beam from O2(+) to O2 clusters and vice versa. K(+) is found to be transported through the SiO2 layer only within the proceeding sputter front. For Na(+) a steadily increasing fraction is observed, which migrates through the unaffected SiO2 layer toward the adjacent Si/SiO2 interface.

  7. Theoretical study of structural and optical properties of noble metal cluster-dipeptide hybrids at defect centers of MgO.

    PubMed

    Kulesza, Alexander; Mitrić, Roland; Bonačić-Koutecký, Vlasta

    2012-07-14

    We present the theoretical investigation of structural and optical properties of silver and gold cluster-dipeptide hybrids bound to the F(S) defect of the MgO (100) surface. We use DFT and its TDDFT variant combined with the polarizable embedded cluster model for the description of the extended MgO environment. As model peptide we have chosen CysTrp since the cysteine residue interacts strongly with metal particles through the sulfur atom and tryptophan is the most important chromophoric amino acid. Our results show that in the case of CysTrp bound to the supported Ag(4) cluster an intense optical signal arises at 400 nm. In contrast, in the case of gold no strongly localized absorption is present since the optical response of supported gold-peptide hybrids is dominated by a large number of low intensity d-electron excitations spread over a broad energy range. Such a localized optical signal which is present in supported silver hybrids can be exploited for the optical detection of peptides and thus can serve as basis for the development of biosensing materials.

  8. Modeling the Break-up of Nano-particle Clusters in Aluminum- and Magnesium-Based Metal Matrix Nano-composites

    NASA Astrophysics Data System (ADS)

    Manoylov, Anton; Bojarevics, Valdis; Pericleous, Koulis

    2015-07-01

    Aluminum- and magnesium-based metal matrix nano-composites with ceramic nano-reinforcements promise low weight with high durability and superior strength, desirable properties in aerospace, automobile, and other applications. However, nano-particle agglomerations lead to adverse effects on final properties: large-size clusters no longer act as dislocation anchors, but instead become defects; the resulting particle distribution will be uneven, leading to inconsistent properties. To prevent agglomeration and to break-up clusters, ultrasonic processing is used via an immersed sonotrode, or alternatively via electromagnetic vibration. A study of the interaction forces holding the nano-particles together shows that the choice of adhesion model significantly affects estimates of break-up force and that simple Stokes drag due to stirring is insufficient to break-up the clusters. The complex interaction of flow and co-joint particles under a high frequency external field (ultrasonic, electromagnetic) is addressed in detail using a discrete-element method code to demonstrate the effect of these fields on de-agglomeration.

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

    PubMed

    Müller, Achim; Gouzerh, Pierre

    2012-11-21

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

  10. Calculations of One- and Two-Photon Absorption Spectra for Molecular Metal Chalcogenide Clusters with Electron-Acceptor Ligands.

    PubMed

    Nguyen, Kiet A; Pachter, Ruth; Day, Paul N

    2017-03-02

    We present calculated one- and two-photon absorption (OPA, TPA) spectra for molecular neutral, cation, and anion cadmium chalcogenide nonstoichiometric clusters [CdnE'm'(ER)m, E = S and Se, R = hydrogen, methyl, phenyl, para-nitrophenyl, para-cyanophenyl], ranging from less than 1 nm to more than 2 nm in size with well-defined structures. A systematic treatment of the clusters is carried out to assess the effects of size and ligand on their linear and nonlinear optical properties. Ligands and cluster size were found to have a large influence on the color and intensity of the electronic absorption spectra. TPA cross sections were found to increase linearly with cluster size. Electron-accepting ligands were also found to induce linear enhancement in TPA cross sections. Blue shifts of TPA maxima were observed for the first band with reduced molecular size. The effects of phenyl, para-nitrophenyl, and para-cyanophenyl substitutions, as well as changes in the chalcogenide atom, have been analyzed in detail.

  11. On the Critical Effect of the Metal (Mo vs. W) on the [3+2] Cycloaddition Reaction of M3 S4 Clusters with Alkynes: Insights from Experiment and Theory.

    PubMed

    Bustelo, Emilio; Gushchin, Artem L; Fernández-Trujillo, M Jesús; Basallote, Manuel G; Algarra, Andrés G

    2015-10-12

    Whereas the cluster [Mo3 S4 (acac)3 (py)3 ](+) ([1](+) , acac=acetylacetonate, py=pyridine) reacts with a variety of alkynes, the cluster [W3 S4 (acac)3 (py)3 ](+) ([2](+) ) remains unaffected under the same conditions. The reactions of cluster [1](+) show polyphasic kinetics, and in all cases clusters bearing a bridging dithiolene moiety are formed in the first step through the concerted [3+2] cycloaddition between the C≡C atoms of the alkyne and a Mo(μ-S)2 moiety of the cluster. A computational study has been conducted to analyze the effect of the metal on these concerted [3+2] cycloaddition reactions. The calculations suggest that the reactions of cluster [2](+) with alkynes feature ΔG(≠) values only slightly larger than its molybdenum analogue, however, the differences in the reaction free energies between both metal clusters and the same alkyne reach up to approximately 10 kcal mol(-1) , therefore indicating that the differences in the reactivity are essentially thermodynamic. The activation strain model (ASM) has been used to get more insights into the critical effect of the metal center in these cycloadditions, and the results reveal that the change in reactivity is entirely explained on the basis of the differences in the interaction energies Eint between the cluster and the alkyne. Further decomposition of the Eint values through the localized molecular orbital-energy decomposition analysis (LMO-EDA) indicates that substitution of the Mo atoms in cluster [1](+) by W induces changes in the electronic structure of the cluster that result in weaker intra- and inter-fragment orbital interactions.

  12. Spitzer Clusters

    NASA Astrophysics Data System (ADS)

    Krick, Kessica

    examine the effect that evolutions of cluster redshift and dynamical state have on SFG and AGN in groups and clusters. In addition to environment, we will study the timescales of chemical enrichment of the ICM, using the SFG and AGN as tracers of processes that can transport metals outside of galaxies. Cosmological parameters can be measured based on observing galaxy clusters as signposts of the growth of structure in the universe. The best way to select a redshift independent sample is to use the SZ effect with mm observations to detect a shift in the cosmic microwave background spectrum as those photons scatter off hot gas in clusters. However, such mm observations are contaminated by the emission of SFG and AGN. We intend to characterize the magnitude of this effect on SZ surveys by understanding the frequency, radial distribution, and redshift distribution of these galaxies in clusters. Lastly, a compiled cluster catalog of all Spitzer observed clusters would be useful to the broader astronomical community. We plan to incorporate ancillary multi-wavelength data, where available, and to both publish our catalog in journals, and work with NED to make the catalog easily accessible in an efficient manner by the community.

  13. THE SUPERNOVA DELAY TIME DISTRIBUTION IN GALAXY CLUSTERS AND IMPLICATIONS FOR TYPE-Ia PROGENITORS AND METAL ENRICHMENT

    SciTech Connect

    Maoz, Dan; Sharon, Keren; Avishay Gal-Yam

    2010-10-20

    Knowledge of the supernova (SN) delay time distribution (DTD)-the SN rate versus time that would follow a hypothetical brief burst of star formation-can shed light on SN progenitors and physics, as well as on the timescales of chemical enrichment in different environments. We compile recent measurements of the Type-Ia SN (SN Ia) rate in galaxy clusters at redshifts from z = 0 out to z = 1.45, just 2 Gyr after cluster star formation at z {approx} 3. We review the plausible range for the observed total iron-to-stellar mass ratio in clusters, based on the latest data and analyses, and use it to constrain the time-integrated number of SN Ia events in clusters. With these data, we recover the DTD of SNe Ia in cluster environments. The DTD is sharply peaked at the shortest time-delay interval we probe, 0Gyr < t < 2.2 Gyr, with a low tail out to delays of {approx}10 Gyr, and is remarkably consistent with several recent DTD reconstructions based on different methods, applied to different environments. We test DTD models from the literature, requiring that they simultaneously reproduce the observed cluster SN rates and the observed iron-to-stellar mass ratios. A parameterized power-law DTD of the form t {sup -1.2{+-}0.3} from t = 400 Myr to a Hubble time can satisfy both constraints. Shallower power laws such as t {sup -1/2} cannot, assuming a single DTD, and a single star formation burst (either brief or extended) at high z. This implies that 50%-85% of SNe Ia explode within 1 Gyr of star formation. DTDs from double-degenerate (DD) models, which generically have {approx}t {sup -1} shapes over a wide range of timescales, match the data, but only if their predictions are scaled up by factors of 5-10. Single-degenerate (SD) DTDs always give poor fits to the data, due to a lack of delayed SNe and overall low numbers of SNe. The observations can also be reproduced with a combination of two SN Ia populations-a prompt SD population of SNe Ia that explodes within a few Gyr of star

  14. Density functional investigation of mercury and arsenic adsorption on nitrogen doped graphene decorated with palladium clusters: A promising heavy metal sensing material in farmland

    NASA Astrophysics Data System (ADS)

    Zhao, Chunjiang; Wu, Huarui

    2017-03-01

    Density functional theory calculations are carried out to study the adsorption of mercury and arsenic on Pdn (n = 1-6) supported on pyridine-like nitrogen doped graphene (PNG). Owing to the promising sensitivity in trace amounts of atoms or molecules, PNG can be acted as micro-sensor for sensing heavy metals in agriculture soils. Through the analyses of structural and electronic properties of pristine PNG and Pd atom decorated PNG, we find that the most favorable adsorption site for Pd atom is the vacancy site. The analyses of structural and electronic properties reveal that the Pd atom or clusters can enhance the reactivity for Hg and AsH3 adsorption on PNG. The adsorption ability of Hg on Pdn decorated PNG is found to be related to the d-band center (εd) of the Pdn, in which the closer εd of Pdn to the Fermi level, the higher adsorption strength for Hg on Pdn decorated PNG. Moreover, the charge transfer between Pdn and arsenic may constitute arsenic adsorption on Pdn decorated PNG. Further design of highly efficient carbon based sorbents for heavy metals removal should be focused on tailoring εd of adsorbed metals.

  15. Independent metal-thiolate cluster formation in C-terminal Cys-rich region of a rice type 1 metallothionein isoform.

    PubMed

    Malekzadeh, Rahim; Shahpiri, Azar

    2017-03-01

    In this study we examined the independent self assembly of metal-binding in C-terminal Cys- rich region of a type 1 metallothionein (MT) isoform from rice (OsMTI-1b). To this end the N-terminal of OsMTI-1b (C-OsMTI-1b) was heterologously expressed in Escherichia coli as fusion protein with glutathione-S-transferase (GST). As compared with control (The E. coli cells containing pET41a without gene), transgenic E. coli cells expressing GST-C-OsMTI-1b accumulated more Ni(2+), Cd(2+), and Zn(2+) from culture medium and showed increased tolerance against these metals. The recombinant GST-C-OsMTI-1b was purified using affinity chromatography. According to in vitro assays the protein GST-C-OsMTI-1b was able to form complexes with Ni(2+), Cd(2+) and Zn(2+). These results demonstrate the formation of independent metal-thiolate cluster at C-terminal Cys-rich region of OsMTI-1b without participation of N-terminal Cys-rich region.

  16. Characterizing the intrinsic stability of gas-phase clusters of transition metal complex dianions with alkali metal counterions: counterion perturbation of multiply charged anions.

    PubMed

    Burke, Ruth M; Boxford, William E; Dessent, Caroline E H

    2007-02-14

    The authors report the gas-phase generation and characterization of a series of cation-dianion clusters, e.g., M(+).PtCl(6) (2-), M(+).PtCl(4) (2-), M(+).Pt(CN)(6) (2-), and M(+).Pd(CN)(4) (2-), where M(+)=Na(+),K(+),Rb(+), as model systems for investigating gas-phase contact ionpairs. Low-energy collisional excitation of these systems isolated within a quadrupole ion trap reveals that the fragmentation products are determined by the dianion and are independent of the counterion. This indicates that cation-dianion clusters represent gaseous ion-pair complexes, in line with recent findings for K(+).Pt(CN)(n) (2-), n=4,6 [Burke et al., J. Chem. Phys. 125, 021105 (2006)]. The relative fragmentation energies of several cation-dianion systems are obtained as a function of the counterion to explore the nature of ion-pair binding. For most of the systems studied, e.g., M(+).PtCl(6) (2-), the fragmentation energy increases as the cation size decreases, in line with a simple electrostatic description of the cation-dianion binding. However, the M(+).Pt(CN)(4) (2-) clusters displayed the reverse trend with the fragmentation energy increasing as the cation size increases. Density functional theory calculations of the cation-dianion fragmentation potential energy surfaces reveal the existence of a novel double-minima surface, separated by a repulsive Coulomb barrierlike feature at short range. The experimentally observed trends in the fragmentation energies can be fully understood with reference to the computed surfaces, hence providing strong support for the existence of the double-minima surface.

  17. Investigation of Metal and Metal Oxide Clusters Small Enough to Constitute the Critical Size for Gas Phase Nucleation in Combustion Processes.

    DTIC Science & Technology

    1980-11-01

    contract a variety of techniques have been employed to study the properties of small atomic and molecular clusters formed in the gas phase via...an inert carrier gas (e.g. helium), or as a mixing process using a hot condensable (e.g. lead, s-ilver, copper, indium or bismuth) and a cold carrier... gas (e.g. argon, j DD 0" 1473 EDITION OF I NOV81 IS OBSOLETE NS/N 0102-014736601 I SECURITY CLASSIFICATION OF THIS PAGE (U~h.. De Sneered) S’",A

  18. 40 CFR 716.25 - Adequate file search.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Adequate file search. 716.25 Section 716.25 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT HEALTH AND SAFETY DATA REPORTING General Provisions § 716.25 Adequate file search. The scope of...

  19. 40 CFR 716.25 - Adequate file search.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Adequate file search. 716.25 Section 716.25 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT HEALTH AND SAFETY DATA REPORTING General Provisions § 716.25 Adequate file search. The scope of...

  20. "Something Adequate"? In Memoriam Seamus Heaney, Sister Quinlan, Nirbhaya

    ERIC Educational Resources Information Center

    Parker, Jan

    2014-01-01

    Seamus Heaney talked of poetry's responsibility to represent the "bloody miracle", the "terrible beauty" of atrocity; to create "something adequate". This article asks, what is adequate to the burning and eating of a nun and the murderous gang rape and evisceration of a medical student? It considers Njabulo Ndebele's…

  1. 40 CFR 716.25 - Adequate file search.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Adequate file search. 716.25 Section... ACT HEALTH AND SAFETY DATA REPORTING General Provisions § 716.25 Adequate file search. The scope of a person's responsibility to search records is limited to records in the location(s) where the...

  2. 40 CFR 51.354 - Adequate tools and resources.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 2 2013-07-01 2013-07-01 false Adequate tools and resources. 51.354... Requirements § 51.354 Adequate tools and resources. (a) Administrative resources. The program shall maintain the administrative resources necessary to perform all of the program functions including...

  3. 40 CFR 51.354 - Adequate tools and resources.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 2 2014-07-01 2014-07-01 false Adequate tools and resources. 51.354... Requirements § 51.354 Adequate tools and resources. (a) Administrative resources. The program shall maintain the administrative resources necessary to perform all of the program functions including...

  4. 40 CFR 51.354 - Adequate tools and resources.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 2 2010-07-01 2010-07-01 false Adequate tools and resources. 51.354... Requirements § 51.354 Adequate tools and resources. (a) Administrative resources. The program shall maintain the administrative resources necessary to perform all of the program functions including...

  5. 40 CFR 51.354 - Adequate tools and resources.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 2 2011-07-01 2011-07-01 false Adequate tools and resources. 51.354... Requirements § 51.354 Adequate tools and resources. (a) Administrative resources. The program shall maintain the administrative resources necessary to perform all of the program functions including...

  6. 40 CFR 51.354 - Adequate tools and resources.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 2 2012-07-01 2012-07-01 false Adequate tools and resources. 51.354... Requirements § 51.354 Adequate tools and resources. (a) Administrative resources. The program shall maintain the administrative resources necessary to perform all of the program functions including...

  7. 9 CFR 305.3 - Sanitation and adequate facilities.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... 9 Animals and Animal Products 2 2012-01-01 2012-01-01 false Sanitation and adequate facilities. 305.3 Section 305.3 Animals and Animal Products FOOD SAFETY AND INSPECTION SERVICE, DEPARTMENT OF... OF VIOLATION § 305.3 Sanitation and adequate facilities. Inspection shall not be inaugurated if...

  8. 9 CFR 305.3 - Sanitation and adequate facilities.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... 9 Animals and Animal Products 2 2011-01-01 2011-01-01 false Sanitation and adequate facilities. 305.3 Section 305.3 Animals and Animal Products FOOD SAFETY AND INSPECTION SERVICE, DEPARTMENT OF... OF VIOLATION § 305.3 Sanitation and adequate facilities. Inspection shall not be inaugurated if...

  9. 9 CFR 305.3 - Sanitation and adequate facilities.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... 9 Animals and Animal Products 2 2014-01-01 2014-01-01 false Sanitation and adequate facilities. 305.3 Section 305.3 Animals and Animal Products FOOD SAFETY AND INSPECTION SERVICE, DEPARTMENT OF... OF VIOLATION § 305.3 Sanitation and adequate facilities. Inspection shall not be inaugurated if...

  10. 9 CFR 305.3 - Sanitation and adequate facilities.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 9 Animals and Animal Products 2 2010-01-01 2010-01-01 false Sanitation and adequate facilities. 305.3 Section 305.3 Animals and Animal Products FOOD SAFETY AND INSPECTION SERVICE, DEPARTMENT OF... OF VIOLATION § 305.3 Sanitation and adequate facilities. Inspection shall not be inaugurated if...

  11. 9 CFR 305.3 - Sanitation and adequate facilities.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... 9 Animals and Animal Products 2 2013-01-01 2013-01-01 false Sanitation and adequate facilities. 305.3 Section 305.3 Animals and Animal Products FOOD SAFETY AND INSPECTION SERVICE, DEPARTMENT OF... OF VIOLATION § 305.3 Sanitation and adequate facilities. Inspection shall not be inaugurated if...

  12. 21 CFR 201.5 - Drugs; adequate directions for use.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 4 2011-04-01 2011-04-01 false Drugs; adequate directions for use. 201.5 Section 201.5 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) DRUGS: GENERAL LABELING General Labeling Provisions § 201.5 Drugs; adequate directions for use....

  13. Controllable Encapsulation of “Clean” Metal Clusters within MOFs through Kinetic Modulation: Towards Advanced Heterogeneous Nanocatalysts

    PubMed Central

    Liu, Hongli; Chang, Lina; Bai, Cuihua; Chen, Liyu

    2016-01-01

    Abstract Surfactant‐free tiny Pt clusters were successfully encapsulated within MOFs with controllable size and spatial distribution by a novel kinetically modulated one‐step strategy. Our synthesis relies on the rational manipulation of the reduction rate of Pt ions and/or the growth rate of MOFs by using H2 as assistant reducing agent and/or acetic acid as MOF‐formation modulator. The as‐prepared Pt@MOF core–shell composites exhibited exceedingly high activity and excellent selectivity in the oxidation of alcohols as a result of the ultrafine “clean” Pt clusters, as well as interesting molecular‐sieving effects derived from the outer platinum‐free MOF shell. PMID:26970412

  14. Copper Sensing Function of Drosophila Metal-Responsive Transcription Factor-1 Is Mediated By a Tetranuclear Cu(I) Cluster

    SciTech Connect

    Chen, X.; Hua, H.; Balamurugan, K.; Kong, X.; Zhang, L.; George, G.N.; Georgiev, O.; Schaffner, W.; Giedroc, D.P.

    2009-05-12

    Drosophila melanogaster MTF-1 (dMTF-1) is a copper-responsive transcriptional activator that mediates resistance to Cu, as well as Zn and Cd. Here, we characterize a novel cysteine-rich domain which is crucial for sensing excess intracellular copper by dMTF-1. Transgenic flies expressing mutant dMTF-1 containing alanine substitutions of two, four or six cysteine residues within the sequence {sup 547}CNCTNCKCDQTKSCHGGDC{sup 565} are significantly or completely impaired in their ability to protect flies from copper toxicity and fail to up-regulate MtnA (metallothionein) expression in response to excess Cu. In contrast, these flies exhibit wild-type survival in response to copper deprivation thus revealing that the cysteine cluster domain is required only for sensing Cu load by dMTF-1. Parallel studies show that the isolated cysteine cluster domain is required to protect a copper-sensitive S. cerevisiae ace1 strain from copper toxicity. Cu(I) ligation by a Cys-rich domain peptide fragment drives the cooperative assembly of a polydentate [Cu{sub 4}-S{sub 6}] cage structure, characterized by a core of trigonally S{sub 3} coordinated Cu(I) ions bound by bridging thiolate ligands. While reminiscent of Cu{sub 4}-L{sub 6} (L = ligand) tetranuclear clusters in copper regulatory transcription factors of yeast, the absence of significant sequence homology is consistent with convergent evolution of a sensing strategy particularly well suited for Cu(I).

  15. New mechanistic insight into stepwise metal-center exchange in a metal-organic framework based on asymmetric Zn(4) clusters.

    PubMed

    Meng, Wei; Li, Huijun; Xu, Zhouqing; Du, Shanshan; Li, Yunxia; Zhu, Yanyan; Han, Yi; Hou, Hongwei; Fan, Yaoting; Tang, Mingsheng

    2014-03-03

    Herein, a mechanism of stepwise metal-center exchange for a specific metal-organic framework, namely, [Zn4 (dcpp)2 (DMF)3 (H2 O)2 ]n (H4 dcpp=4,5-bis(4'-carboxylphenyl)phthalic acid), is disclosed for the first time. The coordination stabilities between the central metal atoms and the ligands as well as the coordination geometry are considered to be dominant factors in this stepwise exchange mechanism. A new magnetic analytical method and a theoretical model confirmed that the exchange mechanism is reasonable. When the metathesis reaction occurs between Cu(II) ions and framework Zn(II) ions, the magnetic exchange interaction of each pair of Cu(II) centers gradually strengthens with increasing amount of framework Cu(II) ions. By analyzing the changes of coupling constants in the Cu-exchanged products, it was deduced that Zn4 and Zn3 are initially replaced, and then Zn1 and Zn2 are replaced later. The theoretical calculation further verified that Zn4 is replaced first, Zn3 next, then Zn1 and Zn2 last, and the coordination stability dominates the Cu/Zn exchange process. For the Ni/Zn and Co/Zn exchange processes, besides the coordination stability, the preferred coordination geometry was also considered in the stepwise-exchange behavior. As Ni(II) and Co(II) ions especially favor octahedral coordination geometry in oxygen-ligand fields, Ni(II) ions and Co(II) ions could only selectively exchange with the octahedral Zn(II) ions, as was also confirmed by the experimental results. The stepwise metal-exchange process occurs in a single crystal-to-single crystal fashion.

  16. Planar Mn4O cluster homochiral metal-organic framework for HPLC separation of pharmaceutically important (±)-ibuprofen racemate.

    PubMed

    Hailili, Reshalaiti; Wang, Li; Qv, Junzhang; Yao, Ruxin; Zhang, Xian-Ming; Liu, Huwei

    2015-04-20

    A planar tetracoordinated oxygen containing a homochiral metal-organic framework (MOF) has been synthesized and characterized that can be used as a new chiral stationary phase in high-performance liquid chromatography to efficiently separate racemates such as pharmaceutically important (±)-ibuprofen and (±)-1-phenyl-1,2-ethanediol.

  17. Mechanisms of formation of nonlinear optical light guide structures in metal cluster composites produced by ion beam implantation

    SciTech Connect

    Sarkisov, S.S.; Williams, E.K.; Curley, M.; Smith, C.C.; Ila, D.; Venkateswarlu, P.; Poker, D.B.; Hensley, D.K.

    1997-11-01

    Ion implantation has been shown to produce a high density of metal colloids in glasses and crystalline materials. The high-precipitate volume fraction and small size of metal nanoclusters formed leads to values for the third-order susceptibility much greater than those for metal doped solids. This has stimulated interest in use of ion implantation to make nonlinear optical materials. On the other side, LiNbO{sub 3} has proved to be a good material for optical waveguides produced by MeV ion implantation. Light confinement in these waveguides is produced by refractive index step difference between the implanted region and the bulk material. Implantation of LiNbO{sub 3} with MeV metal ions can therefore result into nonlinear optical waveguide structures with great potential in a variety of device applications. The authors describe linear and nonlinear optical properties of a waveguide structure in LiNbO{sub 3}-based composite material produced by silver ion implantation in connection with mechanisms of its formation.

  18. Metallic behavior and negative differential resistance properties of (InAs){sub n} (n = 2 − 4) molecule cluster junctions via a combined non–equilibrium Green's function and density functional theory study

    SciTech Connect

    Wang, Qi; Li, Rong; Xu, Yuanlan; Zhang, Jianbing; Miao, Xiangshui; Zhang, Daoli

    2014-06-21

    In this present work, the geometric structures and electronic transport properties of (InAs){sub n} (n = 2, 3, 4) molecule cluster junctions are comparatively investigated using NEGF combined with DFT. Results indicate that all (InAs){sub n} molecule cluster junctions present metallic behavior at the low applied biases ([−2V, 2V]), while NDR appears at a certain high bias range. Our calculation shows that the current of (InAs){sub 4} molecule cluster–based junction is almost the largest at any bias. The mechanisms of the current–voltage characteristics of all the three molecule cluster junctions are proposed.

  19. A hybrid Jacobi-Davidson method for interior cluster eigenvalues with large null-space in three dimensional lossless Drude dispersive metallic photonic crystals

    NASA Astrophysics Data System (ADS)

    Huang, Tsung-Ming; Lin, Wen-Wei; Wang, Weichung

    2016-10-01

    We study how to efficiently solve the eigenvalue problems in computing band structure of three-dimensional dispersive metallic photonic crystals with face-centered cubic lattices based on the lossless Drude model. The discretized Maxwell equations result in large-scale standard eigenvalue problems whose spectrum contains many zero and cluster eigenvalues, both prevent existed eigenvalue solver from being efficient. To tackle this computational difficulties, we propose a hybrid Jacobi-Davidson method (hHybrid) that integrates harmonic Rayleigh-Ritz extraction, a new and hybrid way to compute the correction vectors, and a FFT-based preconditioner. Intensive numerical experiments show that the hHybrid outperforms existed eigenvalue solvers in terms of timing and convergence behaviors.

  20. Microchip in situ electrosynthesis of silver metallic oxide clusters for ultra-FAST detection of galactose in galactosemic newborns' urine samples.

    PubMed

    García-Carmona, Laura; Rojas, Daniel; González, María Cristina; Escarpa, Alberto

    2016-10-17

    This work describes for the first time the coupling of microfluidic chips (MC) to electrosynthetized silver metallic oxide clusters (AgMOCs). As an early demonstration of this novel approach, the ultrafast detection of galactose in galactosemic newborns' urine samples is proposed. AgMOCs were in situ electrosynthetized on integrated microchip platinum electrodes using a double pulse technique and characterized in full using scanning electronic microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), X-ray photoelectron spectroscopy (XPS) and electrochemical techniques revealing the presence of silver oxides and electrocatalysis towards galactose as a galactosemia biomarker. Galactose detection in galactosemic newborns' urine samples proceeded in less than 30 s, differentiating between ill and healthy urine samples and requiring negligible urine sample consumption. The significance of the newborns' urine samples confirmed the analytical potency of the MC-AgMOCs approach for future implementation of screening for rare disease diagnosis such as galactosemia.

  1. A description of how metal pollution occurs in the Tinto-Odiel rias (Huelva-Spain) through the application of cluster analysis.

    PubMed

    Grande, J A; Borrego, J; Morales, J A; de la Torre, M L

    2003-04-01

    In the last few decades, the study of space-time distribution and variations of heavy metals in estuaries has been extensively studied as an environmental indicator. In the case described here, the combination of acid water from mines, industrial effluents and sea water plays a determining role in the evolutionary process of the chemical makeup of the water in the estuary of the Tinto and Odiel Rivers, located in the southwest of the Iberian Peninsula. Based on the statistical treatment of the data from the analysis of the water samples from this system, which has been affected by processes of industrial and mining pollution, the 16 variables analyzed can be grouped into two large families. Each family presents high, positive Pearson r values that suggest common origins (fluvial or sea) for the pollutants present in the water analyzed and allow their subsequent contrast through cluster analysis.

  2. Precipitation, pH and metal load in AMD river basins: an application of fuzzy clustering algorithms to the process characterization.

    PubMed

    Grande, J A; Andújar, J M; Aroba, J; de la Torre, M L; Beltrán, R

    2005-04-01

    In the present work, Acid Mine Drainage (AMD) processes in the Chorrito Stream, which flows into the Cobica River (Iberian Pyrite Belt, Southwest Spain) are characterized by means of clustering techniques based on fuzzy logic. Also, pH behavior in contrast to precipitation is clearly explained, proving that the influence of rainfall inputs on the acidity and, as a result, on the metal load of a riverbed undergoing AMD processes highly depends on the moment when it occurs. In general, the riverbed dynamic behavior is the response to the sum of instant stimuli produced by isolated rainfall, the seasonal memory depending on the moment of the target hydrological year and, finally, the own inertia of the river basin, as a result of an accumulation process caused by age-long mining activity.

  3. Vacancy defects and defect clusters in alkali metal ion-doped MgO nanocrystallites studied by positron annihilation and photoluminescence spectroscopy

    NASA Astrophysics Data System (ADS)

    Sellaiyan, S.; Uedono, A.; Sivaji, K.; Janet Priscilla, S.; Sivasankari, J.; Selvalakshmi, T.

    2016-10-01

    Pure and alkali metal ion (Li, Na, and K)-doped MgO nanocrystallites synthesized by solution combustion technique have been studied by positron lifetime and Doppler broadening spectroscopy methods. Positron lifetime analysis exhibits four characteristic lifetime components for all the samples. Doping reduces the Mg vacancy after annealing to 800 °C. It was observed that Li ion migrates to the vacancy site to recover Mg vacancy-type defects, reducing cluster vacancies and micropores. For Na- and K-doped MgO, the aforementioned defects are reduced and immobile at 800 °C. Coincidence Doppler broadening studies show the positron trapping sites as vacancy clusters. The decrease in the S parameter is due to the particle growth and reduction in the defect concentration at 800 °C. Photoluminescence study shows an emission peak at 445 nm and 498 nm, associated with F2 2+ and recombination of higher-order vacancy complexes. Further, annealing process is likely to dissociate F2 2+ to F+ and this F+ is converted into F centers at 416 nm.

  4. Longitudinal cutting of pure and doped carbon nanotubes to form graphitic nanoribbons using metal clusters as nanoscalpels.

    PubMed

    Elías, Ana Laura; Botello-Méndez, Andrés R; Meneses-Rodríguez, David; Jehová González, Viviana; Ramírez-González, Daniel; Ci, Lijie; Muñoz-Sandoval, Emilio; Ajayan, Pulickel M; Terrones, Humberto; Terrones, Mauricio

    2010-02-10

    We report the use of transition metal nanoparticles (Ni or Co) to longitudinally cut open multiwalled carbon nanotubes in order to create graphitic nanoribbons. The process consists of catalytic hydrogenation of carbon, in which the metal particles cut sp(2) hybridized carbon atoms along nanotubes that results in the liberation of hydrocarbon species. Observations reveal the presence of unzipped nanotubes that were cut by the nanoparticles. We also report the presence of partially open carbon nanotubes, which have been predicted to have novel magnetoresistance properties.(1) The nanoribbons produced are typically 15-40 nm wide and 100-500 nm long. This method offers an alternative approach for making graphene nanoribbons, compared to the chemical methods reported recently in the literature.

  5. The age-mass-metallicity-activity relation for solar-type stars: comparisons with asteroseismology and the NGC 188 open cluster

    NASA Astrophysics Data System (ADS)

    Lorenzo-Oliveira, D.; Porto de Mello, G. F.; Schiavon, R. P.

    2016-10-01

    Context. The Mount Wilson Ca ii index log(R'_HK) is the accepted standard metric of calibration for the chromospheric activity versus age relation for FGK sta