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Sample records for metal halide clusters

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

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

    2013-06-17

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

  2. Photofragmentation of metal halides

    Veen, N.J.A. van.

    1980-01-01

    The author deals with photodissociation of molecules of alkali halides. It is shown that the total absorption cross section consists of two contributions arising from transitions to excited states of total electronic angular momentum Ω=0 + and Ω=1. From the inversion of the absorption continua potential energy curves of the excited states can be constructed in the Franck-Condon region. It is found that for all alkali halides the 0 + state is higher in energy than the Ω=1 state. Extensive studies are reported on three thallium halides, TlI, TlBr and TlCl at various wavelengths covering the near ultraviolet region. (Auth.)

  3. Structure and binding of molecular clusters of trivalent metal halides in an ionic model

    Akdeniz, Z.; Pastore, G.; Tosi, M.P.

    1997-10-01

    A model of ionic interactions first proposed for the molecular monomers of alkaline earth dihalides (G. Galli and M. P. Tosi, N. Ciemento D 4,413 (1984)) is used in a systematic study of the structure and binding of monomeric and dimeric units of Al, Fe ad Ga chlorides, bromides and iodides. Ionized states obtained by stripping or adding a halogen ion are considered in addition to neutral states. The main motivation for this work comes from recent studies of liquid structure in several of these systems by neutron and X-ray diffraction and Raman scattering. Main attention is consequently given in the present calculations to (i) bond lengths and bond angles in isolated clusters as precursors of local structures in melts, and (ii) stability of local structures against fluctuations into ionized states. The results are discussed in comparison with the available experimental data as well as with the results from Hartree-Fock and density functional calculations. (author)

  4. Fullerenes doped with metal halides

    Martin, T.P.; Heinebrodt, M.; Naeher, U.; Goehlich, H.; Lange, T.; Schaber, H.

    1993-01-01

    The cage-like structure of fullerenes is a challenge to every experimental to put something inside - to dope the fullerenes. In fact, the research team that first identified C 60 as a football-like molecule quickly succeeded in trapping metal atoms inside and in shrinking the cage around this atom by photofragmentation. In this paper we report the results of ''shrink-wrapping'' the fullerenes around metal halide molecules. Of special interest is the critical size (the minimum number of carbon atoms) that can still enclose the dopant. A rough model for the space available inside a carbon cage gives good agreement with the measured shrinking limits. (author). 8 refs, 6 figs

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

    Vlcek, Lukas [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Uhlik, Filip [Charles Univ., Prague (Czech Republic); Moucka, Filip [Purkinje Univ. (Czech Republic); Nezbeda, Ivo [Purkinje Univ. (Czech Republic); Academy of Sciences of the Czech Republic (ASCR), Prague (Czech Republic); Chialvo, Ariel A. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

    2015-12-16

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

  6. Structure of polyvalent metal halide melts

    Tosi, M.P.

    1990-12-01

    A short review is given of recent progress in determining and understanding the structure of molten halide salts involving polyvalent metal ions. It covers the following three main topics: (i) melting mechanisms and types of liquid structure for pure polyvalent-metal chlorides; (ii) geometry and stability of local coordination for polyvalent metal ions in molten mixtures of their halides with alkali halides; and (iii) structure breaking and electron localization on addition of metal to the melt. (author). 28 refs, 3 figs, 1 tab

  7. TRANSURANIC METAL HALIDES AND A PROCESS FOR THE PRODUCTION THEREOF

    Fried, S.

    1951-03-20

    Halides of transuranic elements are prepared by contacting with aluminum and a halogen, or with an aluminum halide, a transuranic metal oxide, oxyhalide, halide, or mixture thereof at an elevated temperature.

  8. Computational screening of mixed metal halide ammines

    Jensen, Peter Bjerre; Lysgaard, Steen; Quaade, Ulrich

    2013-01-01

    Metal halide ammines, e.g. Mg(NH3)6Cl2 and Sr(NH3)8Cl2, can reversibly store ammonia, with high volumetric hydrogen storage capacities. The storage in the halide ammines is very safe, and the salts are therefore highly relevant as a carbon-free energy carrier in future transportation infrastructure...... selection. The GA is evolving from an initial (random) population and selecting those with highest fitness, a function based on e.g. stability, release temperature and storage capacity. The search space includes all alkaline, alkaline earth, 3d and 4d metals and the four lightest halides. In total...... the search spaces consists of millions combinations, which makes a GA ideal, to reduce the number of necessary calculations. We are screening for a one step release from either a hexa or octa ammine, and we have found promising candidates, which will be further investigated ? both computationally...

  9. Alkali metal and alkali earth metal gadolinium halide scintillators

    Bourret-Courchesne, Edith; Derenzo, Stephen E.; Parms, Shameka; Porter-Chapman, Yetta D.; Wiggins, Latoria K.

    2016-08-02

    The present invention provides for a composition comprising an inorganic scintillator comprising a gadolinium halide, optionally cerium-doped, having the formula A.sub.nGdX.sub.m:Ce; wherein A is nothing, an alkali metal, such as Li or Na, or an alkali earth metal, such as Ba; X is F, Br, Cl, or I; n is an integer from 1 to 2; m is an integer from 4 to 7; and the molar percent of cerium is 0% to 100%. The gadolinium halides or alkali earth metal gadolinium halides are scintillators and produce a bright luminescence upon irradiation by a suitable radiation.

  10. Complexes in polyvalent metal - Alkali halide melts

    Akdeniz, Z.; Tosi, M.P.

    1991-03-01

    Experimental evidence is available in the literature on the local coordination of divalent and trivalent metal ions by halogens in some 140 liquid mixtures of their halides with alkali halides. After brief reference to classification criteria for main types of local coordination, we focus on statistical mechanical models that we are developing for Al-alkali halide mixtures. Specifically, we discuss theoretically the equilibrium between (AlF 6 ) 3- and (AlF 4 ) - complexes in mixtures of AlF 3 and NaF as a function of composition in the NaF-rich region, the effect of the alkali counterion on this equilibrium, the possible role of (AlF 5 ) 2- as an intermediate species in molten cryolite, and the origin of the different complexing behaviours of Al-alkali fluorides and chlorides. We also present a theoretical scenario for processes of structure breaking and electron localization in molten cryolite under addition of sodium metal. (author). 26 refs, 2 tabs

  11. Metal induced gap states at alkali halide/metal interface

    Kiguchi, Manabu; Yoshikawa, Genki; Ikeda, Susumu; Saiki, Koichiro

    2004-01-01

    The electronic state of a KCl/Cu(0 0 1) interface was investigated using the Cl K-edge near-edge X-ray absorption fine structure (NEXAFS). A pre-peak observed on the bulk edge onset of thin KCl films has a similar feature to the peak at a LiCl/Cu(0 0 1) interface, which originates from the metal induced gap state (MIGS). The present result indicates that the MIGS is formed universally at alkali halide/metal interfaces. The decay length of MIGS to an insulator differs from each other, mainly due to the difference in the band gap energy of alkali halide

  12. Definition of a high intensity metal halide discharge reference lamp

    Stoffels, W.W.; Baede, A.H.F.M.; Mullen, van der J.J.A.M.; Haverlag, M.; Zissis, G.

    2006-01-01

    The design of a ref. metal halide discharge lamp is presented. This lamp is meant as a common study object for researchers working on metal halide discharge lamps, who by using the same design will be able to compare results between research groups, diagnostic techniques and numerical models. The

  13. High temperature reactions between molybdenum and metal halides

    Boeroeczki, A.; Dobos, G.; Josepovits, V.K.; Hars, Gy.

    2006-01-01

    Good colour rendering properties, high intensity and efficacy are of vital importance for high-end lighting applications. These requirements can be achieved by high intensity discharge lamps doped with different metal halide additives (metal halide lamps). To improve their reliability, it is very important to understand the different failure processes of the lamps. In this paper, the corrosion reactions between different metal halides and the molybdenum electrical feed-through electrode are discussed. The reactions were studied in the feed-through of real lamps and on model samples too. X-ray photoelectron spectroscopy (XPS) was used to establish the chemical states. In case of the model samples we have also used atomic absorption spectroscopy (AAS) to measure the reaction product amounts. Based on the measurement results we were able to determine the most corrosive metal halide components and to understand the mechanism of the reactions

  14. Structure and energetics of trivalent metal halides

    Hutchinson, F.

    1999-01-01

    Metal trihalide (MX 3 ) systems represent a stern challenge in terms of constructing transferable potential models. Starting from a previously published set of potentials, 'extended' ionic models are developed which, at the outset, include only anion polarization. Deficiencies in these models, particularly for smaller (highly polarizing) cations, axe shown to be significant. For example, crystal structures different to those observed experimentally axe adopted. The potentials axe improved upon by reference to ab initio information available for alkali halides with the 'constraint' that the parameters transfer systematically in a physically transparent manner, for example, in terms of ion radii. The possible influence of anion compression ('breathing') and the relative abundance of anion-anion interactions are considered. Simulation techniques axe developed to allow for the effective simulation of any system symmetry and for the study of transitions between different crystals (constant stress). The developed models are fully tested for a large range of metal trichloride (MCl 3 ) systems. Particular attention is paid to the comparison with recent neutron and X-ray diffraction data on the liquid state. Polarization effects axe shown to be vital in reproducing strong experimental features. The excellent agreement between simulation and experiment allows for differences in experimental procedures to be highlighted. The transferability is further tested by modelling mixtures of the lanthanides with alkali halides with potentials unchanged from the pure systems. The complex evolution of the melt structure is highlighted as the concentration of MCl 3 increases. The effectiveness of the models is tested by reference to dynamical properties. Particular attention is paid to the comparison with Raman scattering data available for a wide range of systems and mixture concentrations. The simulated spectra are generated both by a simple molecular picture of the underlying

  15. Treatment of alcaline metals halides for developing crystals

    Spurney, R.W.

    1974-01-01

    A process is described whereby crystals of an alkaline metal halide may be dried and placed in a crucible for development by the Bridgeman-Stockbarger method. Purified alkaline halides from a suspension are dried and formed into dense cakes of transverse section slightly smaller than that of the crucible, where they are packed, melted and grown into crystals according to the Bridgeman-Stockbarger technique. This method applies to the preparation of alkaline halide crystals, particularly sodium iodide for optical elements or scintillation counters [fr

  16. 78 FR 51463 - Energy Conservation Program: Energy Conservation Standards for Metal Halide Lamp Fixtures

    2013-08-20

    ... merging the metal halide lamp fixture and the high-intensity discharge (HID) lamp rulemakings. This NOPR... Conservation Program: Energy Conservation Standards for Metal Halide Lamp Fixtures; Proposed Rule #0;#0;Federal...: Energy Conservation Standards for Metal Halide Lamp Fixtures AGENCY: Office of Energy Efficiency and...

  17. Empirical formula for the parameters of metallic monovalent halides ...

    By collating the data on melting properties and transport coefficients obtained from various experiments and theories for certain halides of monovalent metals, allinclusive linear relationship has been fashioned out. This expression holds between the change in entropy and volume on melting; it is approximately obeyed by ...

  18. Demixing in a metal halide lamp, results from modelling

    Beks, M.L.; Hartgers, A.; Mullen, van der J.J.A.M.

    2006-01-01

    Convection and diffusion in the discharge region of a metal halide lamp is studied using a computer model built with the plasma modeling package Plasimo. A model lamp contg. mercury and sodium iodide is studied. The effects of the total lamp pressure on the degree of segregation of the light

  19. Demixing in a metal halide lamp, results from modeling

    Beks, M.L.; Hartgers, A.; Mullen, van der J.J.A.M.; Veldhuizen, van E.M.

    2005-01-01

    Metal Halide (MH) lamps are high pressure discharge devices, containing a complex chemical mixture, to emit light on a broad spectrum while maintaining good efficacies. Lamps of this type were first exhibited by General Electric at the 1964 World Fair in New York [1]. They typically consist of an

  20. Alternative route to metal halide free ionic liquids

    Takao, Koichiro; Ikeda, Yasuhisa

    2008-01-01

    An alternative synthetic route to metal halide free ionic liquids using trialkyloxonium salt is proposed. Utility of this synthetic route has been demonstrated by preparing 1-ethyl-3-methylimidazolium tetrafluoroborate ionic liquid through the reaction between 1-methylimidazole and triethyloxonium tetra-fluoroborate in anhydrous ether. (author)

  1. Metal Halide Perovskite Polycrystalline Films Exhibiting Properties of Single Crystals

    Brenes, Roberto; Guo, D.; Osherov, Anna; Noel, Nakita K.; Eames, Christopher; Hutter, E.M.; Pathak, Sandeep K.; Niroui, Farnaz; Friend, Richard H.; Islam, M. Saiful; Snaith, Henry J.; Bulović, Vladimir; Savenije, T.J.; Stranks, Samuel D.

    2017-01-01

    Metal halide perovskites are generating enormous excitement for use in solar cells and light-emission applications, but devices still show substantial non-radiative losses. Here, we show that by combining light and atmospheric treatments, we can increase the internal luminescence quantum

  2. Spectroscopy on metal-halide lamps under varying gravity conditions

    Flikweert, A.J.

    2008-01-01

    Worldwide, 20% of all electricity is used for lighting. For this reason, efficient lamps are economically and ecologically important. High intensity discharge (HID) lamps are efficient lamps. The most common HID lamp these days is the metal-halide (MH) lamp. MH lamps have a good colour rendering

  3. Local coordination of polyvalent metal ions in molten halide mixtures

    Akdeniz, Z.; Tosi, M.P.

    1989-07-01

    Ample experimental evidence is available in the literature on the geometry and the stability of local coordination for polyvalent metal ions in molten mixtures of their halides with alkali halides. Recent schemes for classifying this evidence are discussed. Dissociation of tetrahedral halocomplexes in good ionic systems can be viewed as a classical Mott problem of bound-state stability in a conducting matrix. More generally, structural coordinates can be constructed from properties of the component elements, to separate out systems with long-lived fourfold or sixfold coordination and to distinguish between these. (author). 11 refs, 1 fig

  4. Synthesis of halide- and solvent free metal borohydrides

    Grinderslev, Jakob; Møller, Kasper Trans; Richter, Bo

    have challenges due to their high desorption kinetics and limited reversibility at moderate conditions.[2],[3],[4] In this work, we present a new approach to synthesize halide- and solvent free metal borohydrides starting from the respective metal hydride. The synthetic strategy ensures that no metal...... to the metal. Hence, the powdered M(BH4)3∙DMS is heated to 140 °C for 4 hours to obtain pure M(BH4)3. The rare-earth metal borohydrides have been investigated by infrared spectroscopy and thermal analysis (TGA-DSC-MS). Furthermore, the structural trends are investigated by synchrotron radiation powder X...

  5. Halides of BET-TTF: novel hydrated molecular metals

    Laukhina, E.; Ribera, E.; Vidal-Gancedo, J.; Canadell, E.; Veciana, J.; Rovira, C. [Universidad Autonoma de Barcelona, Bellaterra (Spain). Inst. de Ciencia de Materials; Khasanov, S.; Zorina, L.; Shibaeva, R. [Rossijskaya Akademiya Nauk, Chernogolovka (Russian Federation). Inst. Fiziki Tverdogo Tela; Laukhin, V. [Inst. of Problems of Chemical Physics, RAS, Chernogolovka (Russian Federation); Honold, M.; Nam, M.-S.; Singleton, J. [Clarendon Lab., Univ. of Oxford (United Kingdom)

    2000-01-07

    A hint of superconducting transition has been observed for the first time in a cation radical salt derived from bisethylenethio-tetrathiafulvalene (BET-TTF), the salt (BET-TTF){sub 2}Br.3H{sub 2}O. Here the synthesis, X-ray structure, and physical properties of two hydrated halides of BET-TTF that are isostructural and present stable metallic properties are described. (orig.)

  6. Metal-halide lamp design: atomic and molecular data needed

    Lapatovich, Walter P

    2009-01-01

    Metal-halide lamps are a subset of high intensity discharge (HID) lamps so named because of their high radiance. These lamps are low temperature (∼0.5 eV), weakly ionized plasmas sustained in refractory but light transmissive envelopes by the passage of electric current through atomic and molecular vapors. For commercial applications, the conversion of electric power to light must occur with good efficiency and with sufficient spectral content throughout the visible (380-780 nm) to permit the light so generated to render colors comparable to natural sunlight. This is achieved by adding multiple metals to a basic mercury discharge. Because the vapor pressure of most metals is very much lower than mercury itself, metal-halide salts of the desired metals, having higher vapor pressures, are used to introduce the material into the basic discharge. The metal compounds are usually polyatomic iodides, which vaporize and subsequently dissociate as they diffuse into the bulk plasma. Metals with multiple visible transitions are necessary to achieve high photometric efficiency (efficacy) and good color. Compounds of Sc, Dy, Ho, Tm, Ce, Pr, Yb and Nd are commonly used. The electrons, atoms and radicals are in local thermodynamic equilibrium (LTE), but not with the radiation field. Strong thermal (10 6 K m -1 ) and density gradients are sustained in the discharge. Atomic radiation produced in the high-temperature core transits through colder gas regions where it interacts with cold atoms and un-dissociated molecules before exiting the lamp. Power balance and spectral output of the lamp are directly affected by the strength of atomic transitions. Attempts to simulate the radiative output of functional metal-halide lamps have been successful only in very simple cases. More data (e.g. the atomic transition probabilities of Ce i) are necessary to improve lamp performance, to select appropriate radiators and in scaling the lamp geometry to various wattages for specific applications.

  7. Lamp-Ballast Compatibility Index for Efficient Ceramic Metal Halide Lamp Operation

    Sourish Chatterjee

    2013-01-01

    Development of energy efficient products and exploration of energy saving potential are major challenges for present day’s technology. Ceramic Metal Halide lamp is the latest improved version of metal halide lamp that finds its wide applications in indoor commercial lighting especially in retail shop lighting. This lamp shows better performance in terms of higher lumen per watt and colour constancy in comparison to conventional metal halide lamp. The inherent negative incremental impedance of...

  8. Sodium-metal halide and sodium-air batteries.

    Ha, Seongmin; Kim, Jae-Kwang; Choi, Aram; Kim, Youngsik; Lee, Kyu Tae

    2014-07-21

    Impressive developments have been made in the past a few years toward the establishment of Na-ion batteries as next-generation energy-storage devices and replacements for Li-ion batteries. Na-based cells have attracted increasing attention owing to low production costs due to abundant sodium resources. However, applications of Na-ion batteries are limited to large-scale energy-storage systems because of their lower energy density compared to Li-ion batteries and their potential safety problems. Recently, Na-metal cells such as Na-metal halide and Na-air batteries have been considered to be promising for use in electric vehicles owing to good safety and high energy density, although less attention is focused on Na-metal cells than on Na-ion cells. This Minireview provides an overview of the fundamentals and recent progress in the fields of Na-metal halide and Na-air batteries, with the aim of providing a better understanding of new electrochemical systems. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Status quo of ceramic material for metal halide discharge lamps

    Kappen, Theo G M M

    2005-01-01

    Polycrystalline alumina is an excellent ceramic material for use as the envelope for metal halide discharge lamps. Although this material was introduced in the mid-1960s, and is thus already known for several decades, recent years have seen considerable effort aimed at further development of these ceramic envelope materials. Developments are not only in the field of ceramic shaping technologies, but are also concentrated on the material properties of the ceramic material itself. Optical, mechanical as well as the chemical properties of the ceramic envelope are strongly controlled by the shape as well as the microstructure of the ceramics used

  10. Halide based MBE of crystalline metals and oxides

    Greenlee, Jordan D.; Calley, W. Laws; Henderson, Walter; Doolittle, W. Alan [Georgia Institute of Technology, School of Electrical and Computer Engineering, Atlanta, Georgia (United States)

    2012-02-15

    A halide based growth chemistry has been demonstrated which can deliver a range of transition metals using low to moderate effusion cell temperatures (30-700 C) even for high melting point metals. Previously, growth with transition metal species required difficult to control electron beam or impurity inducing metal organic sources. Both crystalline oxide and metal films exhibiting excellent crystal quality are grown using this halide-based growth chemistry. Films are grown using a plasma assisted Molecular Beam Epitaxy (MBE) system with metal-chloride precursors. Crystalline niobium, cobalt, iron, and nickel were grown using this chemistry but the technology can be generalized to almost any metal for which a chloride precursor is available. Additionally, the oxides LiNbO{sub 3} and LiNbO{sub 2} were grown with films exhibiting X-ray diffraction (XRD) rocking curve full-widths at half maximum of 150 and 190 arcseconds respectively. LiNbO{sub 2} films demonstrate a memristive response due to the rapid movement of lithium in the layered crystal structure. The rapid movement of lithium ions in LiNbO{sub 2} memristors is characterized using impedance spectroscopy measurements. The impedance spectroscopy measurements suggest an ionic current of.1 mA for a small drive voltage of 5 mV AC or equivalently an ionic current density of {proportional_to}87 A/cm{sup 2}. This high ionic current density coupled with low charge transfer resistance of {proportional_to}16.5 {omega} and a high relaxation frequency (6.6 MHz) makes this single crystal material appealing for battery applications in addition to memristors. (copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  11. Melting and liquid structure of polyvalent metal halides

    Tosi, M.P.

    1992-08-01

    A short review is given of recent progress in determining and understanding liquid structure types and melting mechanisms for halides of polyvalent metals. The nature of the preferred local coordination for the polyvalent metal ion in the melt can usually be ascertained from data on liquid mixtures with halogen-donating alkali halides. The stability of these local coordination states and the connectivity that arises between them in the approach to the pure melt determines the character of its short-range and possible medium-range order. A broad classification of structural and melting behaviours can be given on the basis of measured melting parameters and transport coefficients for many compounds, in combination with the available diffraction data on the liquid structure of several compounds. Correlations have been shown to exist with a simple indicator of the nature of the chemical bond and also with appropriate parameters of ionic models, wherever the latter are usefully applicable for semiquantitative calculations of liquid structure. Consequences on the mechanisms for valence electron localization in solutions of metallic elements into strongly structured molten salts are also briefly discussed. (author). 46 refs, 4 figs, 2 tabs

  12. 10 CFR 431.322 - Definitions concerning metal halide lamp ballasts and fixtures.

    2010-01-01

    ... high intensity discharge fixture, the efficiency of a lamp and ballast combination, expressed as a... lamps. Metal halide lamp means a high intensity discharge lamp in which the major portion of the light... 10 Energy 3 2010-01-01 2010-01-01 false Definitions concerning metal halide lamp ballasts and...

  13. Broadly tunable metal halide perovskites for solid-state light-emission applications

    Adjokatse, Sampson; Fang, Hong-Hua; Loi, Maria Antonietta

    2017-01-01

    The past two years have witnessed heightened interest in metal-halide perovskites as promising optoelectronic materials for solid-state light emitting applications beyond photovoltaics. Metal-halide perovskites are low-cost solution-processable materials with excellent intrinsic properties such as

  14. Metal Halide Perovskite Single Crystals: From Growth Process to Application

    Shuigen Li

    2018-05-01

    Full Text Available As a strong competitor in the field of optoelectronic applications, organic-inorganic metal hybrid perovskites have been paid much attention because of their superior characteristics, which include broad absorption from visible to near-infrared region, tunable optical and electronic properties, high charge mobility, long exciton diffusion length and carrier recombination lifetime, etc. It is noted that perovskite single crystals show remarkably low trap-state densities and long carrier diffusion lengths, which are even comparable with the best photovoltaic-quality silicon, and thus are expected to provide better optoelectronic performance. This paper reviews the recent development of crystal growth in single-, mixed-organic-cation and fully inorganic halide perovskite single crystals, in particular the solution approach. Furthermore, the application of metal hybrid perovskite single crystals and future perspectives are also highlighted.

  15. The electronic structure of the F-center in alkali-halides-The Bethe cluster - lattice

    Queiroz, S.L.A. de.

    1977-07-01

    The electronic structure of the F-center in alkali-halides with the NaCl structure has been studied using the Bethe Cluster lattice method. The central cluster has been taken as constituted by the vacancy and the nearest- and second-neighbors to it, respectively cations and anions. The optical transitions have been calculated and compared to experimental data on the location of the peak of the F-absorption band. The agreement obtained indicates that this method may be used to study properties of this defect in alkali halides. (Author) [pt

  16. A Cluster-Bethe lattice treatment for the F-center in alkali-halides

    Queiroz, S.L.A. de; Koiller, B.; Maffeo, B.; Brandi, H.S.

    1977-01-01

    The electronic structure of the F-center in alkali-halides with the NaCl structure has been studied using the Cluster-Bethe lattice method. The central cluster has been taken as constituted by the vacancy and the nearest- and second- neighbors to it, respectively, cations and anions. The optical transitions have been calculated and compared to experimental data on the location of the peak of the F-absorption band. The agreement obtained indicates that this method may be used to study properties of this defect in alkali halides [pt

  17. Thermal battery. [solid metal halide electrolytes with enhanced electrical conductance after a phase transition

    Carlsten, R.W.; Nissen, D.A.

    1973-03-06

    The patent describes an improved thermal battery whose novel design eliminates various disadvantages of previous such devices. Its major features include a halide cathode, a solid metal halide electrolyte which has a substantially greater electrical conductance after a phase transition at some temperature, and a means for heating its electrochemical cells to activation temperature.

  18. Metal halide arc discharge lamp having short arc length

    Muzeroll, Martin E. (Inventor)

    1994-01-01

    A metal halide arc discharge lamp includes a sealed light-transmissive outer jacket, a light-transmissive shroud located within the outer jacket and an arc tube assembly located within the shroud. The arc tube assembly includes an arc tube, electrodes mounted within the arc tube and a fill material for supporting an arc discharge. The electrodes have a spacing such that an electric field in a range of about 60 to 95 volts per centimeter is established between the electrodes. The diameter of the arc tube and the spacing of the electrodes are selected to provide an arc having an arc diameter to arc length ratio in a range of about 1.6 to 1.8. The fill material includes mercury, sodium iodide, scandium tri-iodide and a rare gas, and may include lithium iodide. The lamp exhibits a high color rendering index, high lumen output and high color temperature.

  19. Phase-resolved response of a metal-halide lamp

    Flikweert, A J; Beks, M L; Nimalasuriya, T; Kroesen, G M W; Van der Mullen, J J A M; Stoffels, W W

    2009-01-01

    The metal-halide (MH) lamp sometimes shows unwanted colour segregation, caused by a combination of convection and diffusion. In the past we investigated the lamp, running on a switched dc ballast of 120 Hz, using a dc approximation for the distribution of the radiating species. Here we present phase-resolved intensity measurements to verify this approximation. The MH lamp contains Hg as buffer gas and DyI 3 as salt additive; we measure the light emitted by Dy and by Hg atoms. An intensity fluctuation of ∼25% close to the electrodes is found only. The observed fluctuations are explained by the cataphoresis effect and temperature fluctuations; the time scales are in the same order. Furthermore, measurements at higher gravity in a centrifuge (up to 10g) show that the effect becomes smaller at increasing gravity levels. From these results it is concluded that a dc approximation, which is generally assumed by lamp developers, is allowed for this MH lamp.

  20. Water-Induced Dimensionality Reduction in Metal-Halide Perovskites

    Turedi, Bekir

    2018-03-30

    Metal-halide perovskite materials are highly attractive materials for optoelectronic applications. However, the instability of perovskite materials caused by moisture and heat-induced degradation impairs future prospects of using these materials. Here we employ water to directly transform films of the three-dimensional (3D) perovskite CsPbBr3 to stable two-dimensional (2D) perovskite-related CsPb2Br5. A sequential dissolution-recrystallization process governs this water induced transformation under PbBr2 rich condition. We find that these post-synthesized 2D perovskite-related material films exhibit excellent stability against humidity and high photoluminescence quantum yield. We believe that our results provide a new synthetic method to generate stable 2D perovskite-related materials that could be applicable for light emitting device applications.

  1. Non-hydrolytic metal oxide films for perovskite halide overcoating and stabilization

    Martinson, Alex B.; Kim, In Soo

    2017-09-26

    A method of protecting a perovskite halide film from moisture and temperature includes positioning the perovskite halide film in a chamber. The chamber is maintained at a temperature of less than 200 degrees Celsius. An organo-metal compound is inserted into the chamber. A non-hydrolytic oxygen source is subsequently inserted into the chamber. The inserting of the organo-metal compound and subsequent inserting of the non-hydrolytic oxygen source into the chamber is repeated for a predetermined number of cycles. The non-hydrolytic oxygen source and the organo-metal compound interact in the chamber to deposit a non-hydrolytic metal oxide film on perovskite halide film. The non-hydrolytic metal oxide film protects the perovskite halide film from relative humidity of greater than 35% and a temperature of greater than 150 degrees Celsius, respectively.

  2. Modelling current transfer to cathodes in metal halide plasmas

    Benilov, M S; Cunha, M D; Naidis, G V

    2005-01-01

    This work is concerned with investigation of the main features of current transfer to cathodes under conditions characteristic of metal halide (MH) lamps. It is found that the presence of MHs in the gas phase results in a small decrease of the cathode surface temperature and of the near-cathode voltage drop in the diffuse mode of current transfer; the range of stability of the diffuse mode expands. Effects caused by a variation of the work function of the cathode surface owing to formation of a monolayer of alkali metal atoms on the surface are studied for particular cases where the monolayer is composed of sodium or caesium. It is found that the formation of the sodium monolayer affects the diffuse mode of current transfer only moderately and in the same direction that the presence of metal atoms in the gas phase affects it. Formation of the caesium monolayer produces a dramatic effect: the cathode surface temperature decreases very strongly, the diffuse-mode current-voltage characteristic becomes N-S-shaped

  3. The Role of Surface Tension in the Crystallization of Metal Halide Perovskites

    Zhumekenov, Ayan A.; Burlakov, Victor M.; Saidaminov, Makhsud I.; Alofi, Abdulilah; Haque, Mohammed; Turedi, Bekir; Davaasuren, Bambar; Dursun, Ibrahim; Cho, Nam Chul; El-Zohry, Ahmed M.; de Bastiani, Michele; Giugni, Andrea; Torre, Bruno; Di Fabrizio, Enzo M.; Mohammed, Omar F.; Rothenberger, Alexander; Wu, Tao; Goriely, Alain; Bakr, Osman

    2017-01-01

    The exciting intrinsic properties discovered in single crystals of metal halide perovskites still await their translation into optoelectronic devices. The poor understanding and control of the crystallization process of these materials are current

  4. Trinuclear rhenium(III) halide clusters with carboxylate ligands

    Dougan, Jeffrey Steven

    Four mono(carboxylato)trirhenium complexes and three bis(carboxylato)trirhenium complexes have been synthesized and characterized, principally by mass spectrometry, with supporting evidence from X-ray diffraction. These compounds represent the first trinuclear rhenium carboxylate complexes. The reactions generally proceed readily under comparatively mild conditions. Mass spectrometry has again proved its usefulness as a technique in the field of metal cluster chemistry, having provided the initial identification of the products of the reactions studied. These compounds provide a further base to which future mass spectra of metal cluster compounds can be compared. Re-examination of a reaction reported by Taha and Wilkinson has also cast considerable doubt onto the validity of a conversion widely reported in the literature that transforms (Re3Cl9) x into [Re2(O2CCH3)4Cl 2]. We believe that the literature result is a consequence of the purity of the metal precursor, and suggest that the starting material in the earlier work may have contained ReCl4 or ReCl5. The importance of mass spectrometry in the characterization of the new compounds synthesized in this project has led to a thorough study of calculated isotopic distributions. The information gathered suggests that for isotopically simple molecules, the choice of algorithm for computing an isotopic distribution is unimportant. However, it is important to compute the mass spectrum of an isotopically complex molecule using an algorithm that can, if desired, show the underlying isotopic fine structure of a peak of interest. In the last chapter of this thesis, the results of a project in chemistry education research are presented. Predicting the success of students in general chemistry has long been of interest to the chemistry education community, and several factors have been identified as contributing factors. An off-hand comment by a student inspired an examination of whether continuity with the same instructor for

  5. Solution enthalpies of alkali metal halides in water and heavy water mixtures with dimethyl sulfoxide

    Egorov, G.I.

    1994-01-01

    Solution enthalpies of CsF, LiCl, NaI, CsI and some other halides of alkali metals and tetrabutylammonium have been measured by the method of calorimetry. Standard solution enthalpies of all alkali metals (except rubidium) halides in water and heavy water mixtures with dimethylsulfoxide at 298.15 K have been calculated. Isotopic effects in solvation enthalpy of the electrolytes mentioned in aqueous solutions of dimethylsulfoxide have been discussed. 29 refs., 2 figs., 4 tabs

  6. Influence of electrode, buffer gas and control gear on metal halide lamp performance

    Lamouri, A; Naruka, A; Sulcs, J; Varanasi, C V; Brumleve, T R

    2005-01-01

    In this paper the influence of electrode composition, buffer gas fill pressure and control gear on the performance of metal halide lamps is investigated. It is shown that pure tungsten electrodes improve lumen maintenance and reduce voltage rise over lamp life. An optimum buffer gas fill pressure condition is discovered which allows for reduced electrode erosion during lamp starting as well as under normal operating conditions. Use of electronic control gear is shown to improve the performance of metal halide lamps

  7. Broadly tunable metal halide perovskites for solid-state light-emission applications

    Adjokatse, Sampson; Fang, Hong-Hua; Loi, Maria Antonietta

    2017-01-01

    The past two years have witnessed heightened interest in metal-halide perovskites as promising optoelectronic materials for solid-state light emitting applications beyond photovoltaics. Metal-halide perovskites are low-cost solution-processable materials with excellent intrinsic properties such as broad tunability of bandgap, defect tolerance, high photoluminescence quantum efficiency and high emission color purity (narrow full-width at half maximum). In this review, the photophysical propert...

  8. Observation of vapor pressure enhancement of rare-earth metal-halide salts in the temperature range relevant to metal-halide lamps

    Curry, J. J.; Henins, A.; Hardis, J. E. [National Institute of Standards and Technology, Gaithersburg, Maryland 20899 (United States); Estupinan, E. G. [Osram Sylvania Inc., Beverly, Massachusetts 01915 (United States); Lapatovich, W. P. [Independent Consultant, 51 Pye Brook Lane, Boxford, Massachusetts 01921 (United States); Shastri, S. D. [Advanced Photon Source, Argonne National Laboratory, Argonne, Illinois 60439 (United States)

    2012-02-20

    Total vapor-phase densities of Dy in equilibrium with a DyI{sub 3}/InI condensate and Tm in equilibrium with a TmI{sub 3}/TlI condensate have been measured for temperatures between 900 K and 1400 K. The measurements show strong enhancements in rare-earth vapor densities compared to vapors in equilibrium with the pure rare-earth metal-halides. The measurements were made with x-ray induced fluorescence on the sector 1-ID beam line at the Advanced Photon Source. The temperature range and salt mixtures are relevant to the operation of metal-halide high-intensity discharge lamps.

  9. Metal halides vapor lasers with inner reactor and small active volume.

    Shiyanov, D. V.; Sukhanov, V. B.; Evtushenko, G. S.

    2018-04-01

    Investigation of the energy characteristics of copper, manganese, lead halide vapor lasers with inner reactor and small active volume 90 cm3 was made. The optimal operating pulse repetition rates, temperatures, and buffer gas pressure for gas discharge tubes with internal and external electrodes are determined. Under identical pump conditions, such systems are not inferior in their characteristics to standard metal halide vapor lasers. It is shown that the use of a zeolite halogen generator provides lifetime laser operation.

  10. Metal interactions with boron clusters

    Grimes, R.N.

    1982-01-01

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

  11. Electronic structure of metal clusters

    Wertheim, G.K.

    1989-01-01

    Photoemission spectra of valence electrons in metal clusters, together with threshold ionization potential measurements, provide a coherent picture of the development of the electronic structure from the isolated atom to the large metallic cluster. An insulator-metal transition occurs at an intermediate cluster size, which serves to define the boundary between small and large clusters. Although the outer electrons may be delocalized over the entire cluster, a small cluster remains insulating until the density of states near the Fermi level exceeds 1/kT. In large clusters, with increasing cluster size, the band structure approaches that of the bulk metal. However, the bands remain significantly narrowed even in a 1000-atom cluster, giving an indication of the importance of long-range order. The core-electron binding-energy shifts of supported metal clusters depend on changes in the band structure in the initial state, as well as on various final-state effects, including changes in core hole screening and the coulomb energy of the final-state charge. For cluster supported on amorphous carbon, this macroscopic coulomb shift is often dominant, as evidenced by the parallel shifts of the core-electron binding energy and the Fermi edge. Auger data confirm that final-state effects dominate in cluster of Sn and some other metals. Surface atom core-level shifts provide a valuable guide to the contributions of initial-state changes in band structure to cluster core-electron binding energy shifts, especially for Au and Pt. The available data indicate that the shift observed in supported, metallic clusters arise largely from the charge left on the cluster by photoemission. As the metal-insulator transition is approached from above, metallic screening is suppressed and the shift is determined by the local environment. (orig.)

  12. Designing mixed metal halide ammines for ammonia storage using density functional theory and genetic algorithms

    Jensen, Peter Bjerre; Lysgaard, Steen; Quaade, Ulrich J.

    2014-01-01

    electrolyte membrane fuel cells (PEMFC). We use genetic algorithms (GAs) to search for materials containing up to three different metals (alkaline-earth, 3d and 4d) and two different halides (Cl, Br and I) – almost 27000 combinations, and have identified novel mixtures, with significantly improved storage......Metal halide ammines have great potential as a future, high-density energy carrier in vehicles. So far known materials, e.g. Mg(NH3)6Cl2 and Sr(NH3)8Cl2, are not suitable for automotive, fuel cell applications, because the release of ammonia is a multi-step reaction, requiring too much heat...

  13. Development kinetics of silver clusters on silver halides

    Grzesiak, S.; Belloni, J.; Marignier, J.-L.

    2008-01-01

    Silver nuclei are produced by pulse radiolysis at the surface of AgCl nanocrystallites in the presence of an electron donor, the methyl viologen, which induces the growth of silver nuclei. The experimental results observed on the increase of the silver atom concentration and on the decay of the donor concentration during this process, which is similar to the photographic development by an electron donor, are compared with the kinetics obtained from numerical simulation. The model assumes that the formation of silver clusters with a supercritical nuclearity is required before the start of an electron transfer reaction from the two reduced forms of the donor methyl viologen to the silver clusters. The reaction is controlled by the access of the donor to the surface sites of the AgCl crystallite. The rate constant values of the successive steps of the mechanism are derived from the adjustment of calculated kinetics to experimental signals under various conditions, using a single set of parameters which are fairly suitable under all conditions studied

  14. The impact of alkali metal halide electron donor complexes in the photocatalytic degradation of pentachlorophenol

    Khuzwayo, Z., E-mail: zack.khuzwayo@up.ac.za; Chirwa, E.M.N

    2017-01-05

    Highlights: • Facilitation of photocatalysis using simple metal-halides as VB hole scavengers. • Recombination prevention by coupled valence and conduction band approaches. • Determination of anions critical levels beyond which process retardation occurs. • Determination of the photocatalytic process rate of reaction kinetics. - Abstract: The performance of photocatalytic oxidation of chemical pollutants is subjected to the presence of anion complexes in natural waters. This study investigated the influence of alkali metal (Na{sup +} (sodium), K{sup +} (potassium)) halides (Cl{sup −} (chloride), Br{sup −} (bromide), F{sup −} (fluoride)) as inorganic ion sources in the photocatalytic degradation of pentachlorophenol (PCP) in batch systems. It was found that the exclusive presence of halides in the absence of an electron acceptor adequately facilitated the photocatalyst process below critical levels of anion populations, where beyond the critical point the process was significantly hindered. Below the determined critical point, the performance in some cases near matches that of the facilitation of the photocatalytic process by exclusive oxygen, acting as an electron scavenger. The coupling of halide ions and oxygenation presented significantly improved photo-oxidation of PCP, this was confirmed by the inclusion of formic acid as a comparative electron donor. The Langmuir-Hinshelwood kinetic expression was used to calculate the performance rate kinetics. The probable impact of the halide anions was discussed with regards to the process of electron hole pair recombination prevention.

  15. Size selected metal clusters

    First page Back Continue Last page Overview Graphics. The Optical Absorption Spectra of Small Silver Clusters (5-11) ... Soft Landing and Fragmentation of Small Clusters Deposited in Noble-Gas Films. Harbich, W.; Fedrigo, S.; Buttet, J. Phys. Rev. B 1998, 58, 7428. CO combustion on supported gold clusters. Arenz M ...

  16. 2-D images of the metal-halide lamp obtained by experiment and model

    Flikweert, A.J.; Beks, M.L.; Nimalasuriya, T.; Kroesen, G.M.W.; Mullen, van der J.J.A.M.; Stoffels, W.W.

    2008-01-01

    The metal-halide lamp shows color segregation caused by diffusion and convection. Two-dimensional imaging of the arc discharge under varying gravity conditions aids in the understanding of the flow phenomena. In this paper, we show results obtained by experiments and by numerical simulations in

  17. A model for additive transport in metal halide lamps containing mercury and dysprosium tri-iodide

    Beks, M.L.; Haverlag, M.; Mullen, van der J.J.A.M.

    2008-01-01

    The distribution of additives in a metal halide lamp is examined through numerical modelling. A model for a lamp containing sodium iodide additives has been modified to study a discharge containing dysprosium tri-iodide salts. To study the complex chemistry the method of Gibbs minimization is used

  18. Transport phenomena in metal-halide lamps : a poly-diagnostic study

    Nimalasuriya, T.

    2007-01-01

    Worldwide about 20% of all electricity is used for lighting. It is therefore of great interest to develop a lamp that has high e±cacy, good colour rendering and long lifetime. The metal-halide lamp is a gas discharge lamp that meets all these demands. Unfortunately there are still issues with this

  19. Linkage of molecular units in the chemistry of niobium and tantalum cluster halides

    Perrin, C.; Sergent, M.

    1991-01-01

    In low valency niobium and tantalum halides, interunit linkages are observed between the (Me 6 X 12 )X 6 units. They are insulators and interesting magnetic properties are observed, due to the intrinsic potential magnetism of the Me 6 cluster and depending on the inserted cations, for instance rare earths in MM'Nb 6 Cl 18 (M = monovalent cation, M' = rare earth). Of special interest are the niobium iodides which exhibit (Me 6 X 8 )X 6 units, an exception in the niobium chemistry; interesting properties have been reported for some of these iodides

  20. Supersonic bare metal cluster beams

    Smalley, R.E.

    1991-01-01

    Progress continued this past year on two principal fronts in the study of bare metal clusters: photoelectron spectroscopy of mass selected negative ions, and surface chemisorption of cluster ions levitated in a superconducting magnet as monitored by fourier transform ion cyclotron resonance

  1. Low-Dimensional-Networked Metal Halide Perovskites: The Next Big Thing

    Saidaminov, Makhsud I.

    2017-03-03

    Low-dimensional-networked (low-DN) perovskite derivatives are bulk quantum materials in which charge carriers are localized within ordered metal halide sheets, rods, or clusters that are separated by cationic lattices. After two decades of hibernation, this class of semiconductors reemerged in the past two years, largely catalyzed by the interest in alternative, more stable absorbers to CH3NH3PbI3-type perovskites in photovoltaics. Whether low-DN perovskites will surpass other photovoltaic technologies remains to be seen, but their impressively high photo- and electroluminescence yields have already set new benchmarks in light emission applications. Here we offer our perspective on the most exciting advances in materials design of low-DN perovskites for energy- and optoelectronic-related applications. The next few years will usher in an explosive growth in this tribe of quantum materials, as only a few members have been synthesized, while the potential library of compositions and structures is believed to be much larger and is yet to be discovered.

  2. Metal cluster compounds - chemistry and importance; clusters containing isolated main group element atoms, large metal cluster compounds, cluster fluxionality

    Walther, B.

    1988-01-01

    This part of the review on metal cluster compounds deals with clusters containing isolated main group element atoms, with high nuclearity clusters and metal cluster fluxionality. It will be obvious that main group element atoms strongly influence the geometry, stability and reactivity of the clusters. High nuclearity clusters are of interest in there own due to the diversity of the structures adopted, but their intermediate position between molecules and the metallic state makes them a fascinating research object too. These both sites of the metal cluster chemistry as well as the frequently observed ligand and core fluxionality are related to the cluster metal and surface analogy. (author)

  3. Thorium valency in molten alkali halides in equilibrium with metallic thorium

    Smirnov, M.V.; Kudyakov, V.Ya.

    1983-01-01

    Metallic thorium is shown to corrode in molten alkali halides even in the absence of external oxidizing agents, alkali cations acting as oxidizing agents. Its corrosion rate grows in the series of alkali chlorides from LiCl to CsCl at constant temperature. Substituting halide anions for one another exerts a smaller influence, the rate rising slightly in going from chlorides to bromides and iodides, having the same alkali cations. Thorium valency is determined coulometrically, the metal being dissolved anodically in molten alkali halides and their mixtures. In fluoride melts it is equal to 4 but in chloride, bromide and iodide ones, as a rule, it has non-integral values between 4 and 2 which diminish as the temperature is raised, as the thorium concentration is lowered, as the radii of alkali cations decrease and those of halide anions increase. The emf of cells Th/N ThHlsub(n) + (1-N) MHl/MHl/C, Hlsub(2(g)) where Hl is Cl, Br or I, M is Li, Na, K, Cs or Na + K, and N < 0.05, is measured as a function of concentration at several temperatures. Expressions are obtained for its concentration dependence. The emf grows in the series of alkali chlorides from LiCl to CsCl, other conditions being equal. (author)

  4. Sodium-Metal-Halide Battery Energy Storage for DoD Installations

    2017-10-24

    electrical equipment for AC interface PDE Pacific Data Electric V&F Voltage and Frequency, power quality measurements VA Volt-Amp, units for apparent...Metal-Halide technology could operate at extreme ambient temperatures, but the early prototypes did struggle with managing sand ingress.  The...peak power Not tested 3. PV smoothing Measure improvement in power quality Power meter measurements Power quality improvements 15-min

  5. Development of processes for the production of solar grade silicon from halides and alkali metals

    Dickson, C. R.; Gould, R. K.

    1980-01-01

    High temperature reactions of silicon halides with alkali metals for the production of solar grade silicon in volume at low cost were studied. Experiments were performed to evaluate product separation and collection processes, measure heat release parameters for scaling purposes, determine the effects of reactants and/or products on materials of reactor construction, and make preliminary engineering and economic analyses of a scaled-up process.

  6. Fission of Polyanionic Metal Clusters

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

    2018-04-01

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

  7. Designing mixed metal halide ammines for ammonia storage using density functional theory and genetic algorithms.

    Jensen, Peter Bjerre; Lysgaard, Steen; Quaade, Ulrich J; Vegge, Tejs

    2014-09-28

    Metal halide ammines have great potential as a future, high-density energy carrier in vehicles. So far known materials, e.g. Mg(NH3)6Cl2 and Sr(NH3)8Cl2, are not suitable for automotive, fuel cell applications, because the release of ammonia is a multi-step reaction, requiring too much heat to be supplied, making the total efficiency lower. Here, we apply density functional theory (DFT) calculations to predict new mixed metal halide ammines with improved storage capacities and the ability to release the stored ammonia in one step, at temperatures suitable for system integration with polymer electrolyte membrane fuel cells (PEMFC). We use genetic algorithms (GAs) to search for materials containing up to three different metals (alkaline-earth, 3d and 4d) and two different halides (Cl, Br and I) - almost 27,000 combinations, and have identified novel mixtures, with significantly improved storage capacities. The size of the search space and the chosen fitness function make it possible to verify that the found candidates are the best possible candidates in the search space, proving that the GA implementation is ideal for this kind of computational materials design, requiring calculations on less than two percent of the candidates to identify the global optimum.

  8. Ionic behavior of organic-inorganic metal halide perovskite based metal-oxide-semiconductor capacitors.

    Wang, Yucheng; Zhang, Yuming; Pang, Tiqiang; Xu, Jie; Hu, Ziyang; Zhu, Yuejin; Tang, Xiaoyan; Luan, Suzhen; Jia, Renxu

    2017-05-24

    Organic-inorganic metal halide perovskites are promising semiconductors for optoelectronic applications. Despite the achievements in device performance, the electrical properties of perovskites have stagnated. Ion migration is speculated to be the main contributing factor for the many unusual electrical phenomena in perovskite-based devices. Here, to understand the intrinsic electrical behavior of perovskites, we constructed metal-oxide-semiconductor (MOS) capacitors based on perovskite films and performed capacitance-voltage (C-V) and current-voltage (I-V) measurements of the capacitors. The results provide direct evidence for the mixed ionic-electronic transport behavior within perovskite films. In the dark, there is electrical hysteresis in both the C-V and I-V curves because the mobile negative ions take part in charge transport despite frequency modulation. However, under illumination, the large amount of photoexcited free carriers screens the influence of the mobile ions with a low concentration, which is responsible for the normal C-V properties. Validation of ion migration for the gate-control ability of MOS capacitors is also helpful for the investigation of perovskite MOS transistors and other gate-control photovoltaic devices.

  9. Monitoring of heavy/toxic metals and halides in surface/ground water (abstract)

    Viqar-un-Nisa; Ahmed, R.; Husain, M.

    1999-01-01

    Water is essential for maintaining physical and social life. Human and animal consumption is perhaps the most evident essential use of water. Water quality and quantity have become critical issues, affecting all life. The importance of water in our lives, combined with the threats, make water resources use a global problem. Among the different pollutants toxic metals, metalloids and halides have special significance. Industrial effluents and municipal wastewater are normally drained into water streams, rivers and other reservoirs thus polluting these significantly. Quality of our water resources especially is an issue, which continues to arouse the attention of concerned scientists, legislators and the general public. Among various pollutant chemicals, the heavy metals and metalloids are present at trace levels in various compartments of the environment. Some metals become toxic even at trace levels because of the important features that distinguishes metals from other pollutants is that they are not biodegradable. The halides like Cl, Br, and I from different sources can enter easily into water systems and then they make their way directly into the human body. The intake of toxic as wells as essential elements through water and other food items like vegetables, milk wheat flour etc. is significant. The abundance or deficiency of these meals as well as halides results in abnormal metabolic functions. Due to excessive demand for trace analysis in water and other materials a variety of techniques and instrumentation has been developed. Determination of heavy metals ions is of the highest interest in environmental analysis. Among the food materials water is most important because of their large consumption by man. Also toxic metals in water may be in dissolved ionic form, which directly go into human metabolism and start their toxic action. Presence of even small amounts of toxic metals in drinking water can produce serious health hazards. (author)

  10. NMR longitudinal relaxation enhancement in metal halides by heteronuclear polarization exchange during magic-angle spinning

    Shmyreva, Anna A. [Center for Magnetic Resonance, St. Petersburg State University, St. Petersburg 198504 (Russian Federation); Safdari, Majid; Furó, István [Department of Chemistry, KTH Royal Institute of Technology, SE-10044 Stockholm (Sweden); Dvinskikh, Sergey V., E-mail: sergeid@kth.se [Department of Chemistry, KTH Royal Institute of Technology, SE-10044 Stockholm (Sweden); Laboratory of Biomolecular NMR, St. Petersburg State University, St. Petersburg 199034 (Russian Federation)

    2016-06-14

    Orders of magnitude decrease of {sup 207}Pb and {sup 199}Hg NMR longitudinal relaxation times T{sub 1} upon magic-angle-spinning (MAS) are observed and systematically investigated in solid lead and mercury halides MeX{sub 2} (Me = Pb, Hg and X = Cl, Br, I). In lead(II) halides, the most dramatic decrease of T{sub 1} relative to that in a static sample is in PbI{sub 2}, while it is smaller but still significant in PbBr{sub 2}, and not detectable in PbCl{sub 2}. The effect is magnetic-field dependent but independent of the spinning speed in the range 200–15 000 Hz. The observed relaxation enhancement is explained by laboratory-frame heteronuclear polarization exchange due to crossing between energy levels of spin-1/2 metal nuclei and adjacent quadrupolar-spin halogen nuclei. The enhancement effect is also present in lead-containing organometal halide perovskites. Our results demonstrate that in affected samples, it is the relaxation data recorded under non-spinning conditions that characterize the local properties at the metal sites. A practical advantage of fast relaxation at slow MAS is that spectral shapes with orientational chemical shift anisotropy information well retained can be acquired within a shorter experimental time.

  11. Antimicrobial properties of metal and metal-halide nanoparticles and their potential applications

    Torrey, Jason Robert

    Heavy metals, including silver and copper, have been known to possess antimicrobial properties against bacterial, fungal, and viral pathogens. Metal nanoparticles (aggregations of metal atoms 1-200 nm in size) have recently become the subject of intensive study for their increased antimicrobial properties. In the current studies, metal and metal-halide nanoparticles were evaluated for their antibacterial efficacy. Silver (Ag), silver bromide (AgBr), silver iodide (AgI), and copper iodide (CuI) nanoparticles significantly reduced bacterial numbers of the Gram-negative Pseudomonas aeruginosa and the Gram-positive Staphylococcus aureus within 24 hours and were more effective against P. aeruginosa. CuI nanoparticles were found to be highly effective, reducing both organisms by >4.43 log 10 within 15 minutes at 60 ppm Cu. CuI nanoparticles formulated with different stabilizers (sodium dodecyl sulfate, SDS; polyvinyl pyrrolidone, PVP) were further tested against representative Gram-positive and Gram-negative bacteria, Mycobacteria, a fungus (Candida albicans ), and a non-enveloped virus (poliovirus). Both nanoparticles caused significant reductions in most of the Gram-negative bacteria within five minutes (>5.09-log10). The Gram-positive bacterial species and C. albicans were more sensitive to the CuI-SDS than the CuI-PVP nanoparticles. In contrast, the acid-fast Mycobacterium smegmatis was more resistant to CuI-SDS than CuI-PVP nanoparticles. Poliovirus was more resistant than the other organisms tested except for Mycobacterium fortuitum, which displayed the greatest resistance to CuI nanoparticles. As an example of a real world antimicrobial application, polymer coatings embedded with various concentrations of CuI nanoparticles were tested for antibacterial efficacy against P. aeruginosa and S. aureus. Polyester-epoxy powder coatings were found to display superior uniformity, stability and antimicrobial properties against both organisms (>4.92 log 10 after six hours at

  12. Synthesis of Halide- and Solvent free metal borohydrides

    Grinderslev, Jakob; Møller, Kasper Trans; Jensen, Torben René

    chloride or LiBH4 is present in the sample. The synthesis pathway has been shown to work for most of the already known metal borohydrides, M = Na, Ca, Sr, Ba, Y, La, Eu, Gd, Tb, Dy, Ho, Er, Tm, and Yb, but also new borohydrides are formed, M = Pr, Nd and Lu. Besides new compounds, new polymorphs...

  13. Infrared Dielectric Screening Determines the Low Exciton Binding Energy of Metal-Halide Perovskites.

    Umari, Paolo; Mosconi, Edoardo; De Angelis, Filippo

    2018-02-01

    The performance of lead-halide perovskites in optoelectronic devices is due to a unique combination of factors, including highly efficient generation, transport, and collection of photogenerated charge carriers. The mechanism behind efficient charge generation in lead-halide perovskites is still largely unknown. Here, we investigate the factors that influence the exciton binding energy (E b ) in a series of metal-halide perovskites using accurate first-principles calculations based on solution of the Bethe-Salpeter equation, coupled to ab initio molecular dynamics simulations. We find that E b is strongly modulated by screening from low-energy phonons, which account for a factor ∼2 E b reduction, while dynamic disorder and rotational motion of the organic cations play a minor role. We calculate E b = 15 meV for MAPbI 3 , in excellent agreement with recent experimental estimates. We then explore how different material combinations (e.g., replacing Pb → Pb:Sn→ Sn; and MA → FA → Cs) may lead to different E b values and highlight the mechanisms underlying E b tuning.

  14. The Metal-Halide Lamp Under Varying Gravity Conditions Measured by Emission and Laser Absorption Spectroscopy

    Flikweert, A. J.; Nimalasuriya, T.; Kroesen, G. M. W.; Haverlag, M.; Stoffels, W. W.

    2009-11-01

    Diffusive and convective processes in the metal-halide lamp cause an unwanted axial colour segregation. Convection is induced by gravity. To understand the flow phenomena in the arc discharge lamp it has been investigated under normal laboratory conditions, micro-gravity (ISS and parabolic flights) and hyper-gravity (parabolic flights 2 g, centrifuge 1 g-10 g). The measurement techniques are webcam imaging, and emission and laser absorption spectroscopy. This paper aims to give an overview of the effect of different artificial gravity conditions on the lamp and compares the results from the three measurement techniques.

  15. Non-destructive measurement of Xe filling pressure in mercury-free metal halide lamp

    Motomura, Hideki; Enoki, Kyosuke; Jinno, Masafumi

    2010-01-01

    Mercury-free metal halide lamps (MHLs) for automotive purposes have been developing in the market. When mercury is not used, the electric and emission characteristics of the lamp strongly depend on the xenon filling pressure. Therefore a non-destructive gas pressure estimation technique is required to obtain stable performance of the lamps as commercial products. The authors have developed an estimation method by which the gas pressure is estimated from the current peak value at the initial stage of ignition under pulsed operation. It is shown that accuracy of the order of ±(0.1-0.3) atm is obtained using an empirical formula.

  16. Anionic halide···alcohol clusters in the solid state.

    Gushchin, Pavel V; Kuznetsov, Maxim L; Haukka, Matti; Kukushkin, Vadim Yu

    2014-10-09

    The cationic (1,3,5-triazapentadiene)Pt(II) complexes [1](Cl)2, [2](Cl)2, [3](Br)2, and [4](Cl)2, were crystallized from ROH-containing systems (R = Me, Et) providing alcohol solvates studied by X-ray diffraction. In the crystal structures of [1-4][(Hal)2(ROH)2] (R = Me, Et), the Hal(-) ion interacts with two or three cations [1-4](2+) by means of two or three or four contacts thus uniting stacked arrays of complexes into the layers. The solvated MeOH or EtOH molecules occupy vacant space, giving contacts with [1-4](2+), and connects to the Hal(-) ion through a hydrogen bridge via the H(1O)O(1S) H atom forming, by means of the Hal(-)···HOR (Hal = Cl, Br) contact, the halide-alcohol cluster. Properties of the Cl(-)···HO(Me) H-bond in [1][(Cl)2(MeOH)2] were analyzed using theoretical DFT methods.

  17. Comparative study of energy-efficiency and conservation systems for ceramic metal-halide discharge lamps

    Hermoso Orzáez, Manuel Jesús; Andrés Díaz, José Ramón de

    2013-01-01

    Interest in energy savings in urban lighting is gaining traction and has become a priority for municipal administrations. LED (light-emitting diode) technology appears to be the clear future lighting choice. However, this technology is still rapidly developing and has not been sufficiently tested. As an intermediate step, alternative proposals for energy-saving equipment for traditional discharge lamps are desirable so that the current technologies can coexist with the new LED counterparts for the short and medium term. This article provides a comparative study between two efficiency and energy-saving systems for discharge lamps with metal-halide and ceramic technologies, i.e., a lighting flow dimmer-stabilizer and a double-level electronic ballast. - Highlights: ► It has been demonstrated the possibility of regulating ceramic metal-halide lamps with lighting flow dimmer-stabilizer. ► Electronic ballasts can save approximately double quantity of energy than lighting flow dimmer-stabilizers. ► The use of lighting flow dimmer-stabilizer is more profitable than electronic ballasts due to costs and reliability

  18. Visualizing Carrier Transport in Metal Halide Perovskite Nanoplates via Electric Field Modulated Photoluminescence Imaging.

    Hu, Xuelu; Wang, Xiao; Fan, Peng; Li, Yunyun; Zhang, Xuehong; Liu, Qingbo; Zheng, Weihao; Xu, Gengzhao; Wang, Xiaoxia; Zhu, Xiaoli; Pan, Anlian

    2018-05-09

    Metal halide perovskite nanostructures have recently been the focus of intense research due to their exceptional optoelectronic properties and potential applications in integrated photonics devices. Charge transport in perovskite nanostructure is a crucial process that defines efficiency of optoelectronic devices but still requires a deep understanding. Herein, we report the study of the charge transport, particularly the drift of minority carrier in both all-inorganic CsPbBr 3 and organic-inorganic hybrid CH 3 NH 3 PbBr 3 perovskite nanoplates by electric field modulated photoluminescence (PL) imaging. Bias voltage dependent elongated PL emission patterns were observed due to the carrier drift at external electric fields. By fitting the drift length as a function of electric field, we obtained the carrier mobility of about 28 cm 2 V -1 S -1 in the CsPbBr 3 perovskite nanoplate. The result is consistent with the spatially resolved PL dynamics measurement, confirming the feasibility of the method. Furthermore, the electric field modulated PL imaging is successfully applied to the study of temperature-dependent carrier mobility in CsPbBr 3 nanoplates. This work not only offers insights for the mobile carrier in metal halide perovskite nanostructures, which is essential for optimizing device design and performance prediction, but also provides a novel and simple method to investigate charge transport in many other optoelectronic materials.

  19. Metal-Mediated Halogen Exchange in Aryl and Vinyl Halides: a Review

    Evano, Gwilherm; Nitelet, Antoine; Thilmany, Pierre; Dewez, Damien F.

    2018-04-01

    Halogenated arenes and alkenes are of prime importance in many areas of science, especially in the pharmaceutical, agrochemical and chemical industries. While the simplest ones are commercially available, some of them are still hardly accessible depending on their substitution patterns and the nature of the halogen atom. Reactions enabling the selective and efficient replacement of the halogen atom of an aryl or alkenyl halide by another one, lighter or heavier, are therefore of major importance since they can be used for example to turn a less reactive aryl/alkenyl chloride into the more reactive iodinated derivatives or, in a reversed sense, to block an undesired reactivity, for late-stage modifications or for the introduction of a radionuclide. If some halogen exchange reactions are possible with activated substrates, they usually require catalysis with metal complexes. Remarkably efficient processes have been developed for metal-mediated halogen exchange in aryl and vinyl halides: they are overviewed, in a comprehensive manner, in this review article.

  20. Defect formation and desorption of metal atoms from alkali halide crystals under low energy electron bombardment studied by optical absorption and mass spectroscopy

    Seifert, N.R.

    1993-04-01

    This work presents an extensive investigation of electronically induced desorption of ground-state alkali atoms from alkali halides and for the first time correlates directly the desorption with the stability and spatial distribution of the defects formed during bombardment. The electron impact results in the formation of stable F-centers and F-center clusters in the bulk of the crystals. In striking contrast a significant metallization of the surface is observed. Even at temperatures as low as 90 deg C the metallization is achieved within the time resolution of our detection system, which can only be explained by the rapid diffusion of hot holes. Superimposed to the fast and short diffusion of hot holes is the slow F-center diffusion. Measuring the distribution of defects with low energy ion sputtering techniques indicates that at least in the case of LiF the observed diffusion constant of F-centers agrees with values derived by using methods different from that applied here. At low temperatures the formation of F-center clusters and metal on the surface dominates. Colloid formation clearly requires higher temperatures (typically around 200 deg C). This is a strong evidence that efficient F-center diffusion is necessary for the formation of metallic particles (colloids) in the bulk of the crystals. Desorption of alkali atoms from alkali halides at temperatures around room temperature is due to weakly bound alkali atoms. For elevated temperatures the stability of the metallic clusters in the bulk of the crystals (i.e. colloids) are the rate limiting process. (author)

  1. Production of metal particles and clusters

    Mcmanus, S. P.

    1982-01-01

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

  2. Competition between convection and diffusion in a metal halide lamp, investigated by numerical simulations and imaging laser absorption spectroscopy

    Beks, M.L.; Flikweert, A.J.; Nimalasuriya, T.; Stoffels, W.W.; Mullen, van der J.J.A.M.

    2008-01-01

    The effect of the competition between convection and diffusion on the distribution of metal halide additives in a high pressure mercury lamp has been examined by placing COST reference lamps with mercury fillings of 5 and 10 mg in a centrifuge. By subjecting them to different accelerational

  3. Optical emission spectroscopy of metal-halide lamps: Radially resolved atomic state distribution functions of Dy and Hg

    Nimalasuriya, T.; Flikweert, A.J.; Stoffels, W.W.; Haverlag, M.; Mullen, van der J.J.A.M.; Pupat, N.B.M.

    2006-01-01

    Absolute line intensity measurements are performed on a metal-halide lamp. Several transitions of atomic and ionic Dy and atomic Hg are measured at different radial positions from which we obtain absolute atomic and ionic Dy intensity profiles. From these profiles we construct the radially resolved

  4. Analisa Teknis Pemakaian Kombinasi Lampu Metal Halide Dan Led Sebagai Pemikat Ikan Pada Kapal Pukat Cincin (Purse Seine Dan Pengaruhnya Terhadap Konsumsi Bahan Bakar Genset

    Septian Ragil Wibisono

    2017-01-01

    Full Text Available Saat ini lampu Metal Halide dipakai sebagai pemikat ikan  oleh nelayan Purse Seine. Peggunaan lampu tersebut memerlukan daya Genset yang besar karena satu lampu Metal Halide berdaya 1500 Watt. Semakin banyak lampu Metal Halide yang digunakan semakin besar pula konsumsi bahan bakar Genset. Dalam upaya penghematan energi bahan bakar maka digunakan lampu LED sebagai alternatif pemikat ikan. Lampu LED dikenal sebagai lampu yang hemat energi. Penelitian ini ditujukan untuk mengetahui dan membandingkan konsumsi bahan bakar Genset saat menggunakan kombinasi lampu Metal Halide dan LED. Penelitian ini dilakukan dengan mengambil data konsumsi bahan bakar Genset untuk menyalakan sejumlah lampu Metal Halide dan lampu LED, kemudian dilakukan analisa regresi untuk mendapatkan model persaamaan konsumsi bahan bakar Genset. Selanjutnya dilakukan ekstrapolasi untuk memprediksi konsumsi bahan bakar saat Genset dengan jumlah lampu tertentu. Hasilnya dengan besar fluks cahaya yang hampir sama, saat penggunaan 6 lampu Metal Halide konsumsi bahan bakar sebesar 13.606,03 liter, dan saat menggunakan kombinasi lampu 1 Metal Halide dan 25 lampu LED konsumsi bahan bakar sebesar 13.255,63 liter, yang artinya terjadi penghematan bahan bakar sebesar 2,58%.

  5. 40 CFR Table 3 to Subpart Ffff of... - Emission Limits for Hydrogen Halide and Halogen HAP Emissions or HAP Metals Emissions From...

    2010-07-01

    ... Halogen HAP Emissions or HAP Metals Emissions From Process Vents 3 Table 3 to Subpart FFFF of Part 63... to Subpart FFFF of Part 63—Emission Limits for Hydrogen Halide and Halogen HAP Emissions or HAP... following table that applies to your process vents that contain hydrogen halide and halogen HAP emissions or...

  6. Infrared losses from a Na/Sc metal-halide high intensity discharge arc lamp

    Smith, D J; Bonvallet, G A; Lawler, J E

    2003-01-01

    A study of the near-infrared (IR) emission from the arc of a metal-halide high intensity discharge (MH-HID) lamp with a sodium/scandium chemistry is reported. Radiometrically calibrated spectra from 0.7 to 2.5 μm were recorded as a function of position on the arc tube of a 250 W lamp. These spectra were analysed to determine the relative densities of Na and Sc atoms and the arc temperature as a function of radius. Information from these spectra, combined with absorption measurements in the companion paper (Bonvallet and Lawler 2003), were used to determine the absolute output power in the near-IR from the MH-HID lamp

  7. Double-ended metal halide arc discharge lamp with electrically isolated containment shroud

    Muzeroll, Martin M. (Inventor)

    1994-01-01

    A double-ended arc discharge lamp includes a sealed, light-transmissive outer jacket, a light-transmissive shroud mounted within the outer jacket and directly supported by the outer jacket, and an arc discharge tube mounted within the shroud. The arc tube is typically a metal halide arc discharge tube. In a preferred embodiment, the shroud includes an outwardly flared portion at each end. The outwardly flared portions space the shroud from the outer jacket and support the shroud within the outer jacket. The outwardly flared portions of the shroud can be affixed to the outer jacket by fusing. The outer jacket can be provided with inwardly extending dimples for locating the shroud with respect to the outer jacket. In another embodiment, the outer jacket includes reduced diameter portions near each end which are attached to the shroud.

  8. Radiative properties of ceramic metal-halide high intensity discharge lamps containing additives in argon plasma

    Cressault, Yann; Teulet, Philippe; Zissis, Georges

    2016-07-01

    The lighting represents a consumption of about 19% of the world electricity production. We are thus searching new effective and environment-friendlier light sources. The ceramic metal-halide high intensity lamps (C-MHL) are one of the options for illuminating very high area. The new C-MHL lamps contain additives species that reduce mercury inside and lead to a richer spectrum in specific spectral intervals, a better colour temperature or colour rendering index. This work is particularly focused on the power radiated by these lamps, estimated using the net emission coefficient, and depending on several additives (calcium, sodium, tungsten, dysprosium, and thallium or strontium iodides). The results show the strong influence of the additives on the power radiated despite of their small quantity in the mixtures and the increase of visible radiation portion in presence of dysprosium.

  9. Why does the lumen maintenance of sodium-scandium metal halide lamps improve by VHF operation?

    Van Erk, W; Luijks, G M J F; Hitchcock, W

    2011-01-01

    Lifetime experiments show that sodium-scandium metal halide lamps perform better on very high frequency (VHF) drivers than on low frequency (LF) constant wattage autotransformer (CWA) ballasts. The question why, will be addressed with focus on arc tube aspects. It is argued that at high frequency operation sodium loss is less, and that the absence of thermal fluctuations in the electrode tip causes less damage and cracking to this part of the electrode. Sudden lm W -1 drops, observed with CWA-operated lamps, most probably occur when the arc attaches on such a corroded and cracked surface. Thorium is effective as an emitter both in the CWA and the VHF operation mode, despite the absence of cataphoretic transport to the cathode in the VHF case.

  10. Why does the lumen maintenance of sodium-scandium metal halide lamps improve by VHF operation?

    Van Erk, W [Philips Lighting, Sondervick 47, 5505 NB Veldhoven (Netherlands); Luijks, G M J F [Advanced Development Lighting, Philips Lighting, PO Box 80020, 5600 JM Eindhoven (Netherlands); Hitchcock, W, E-mail: Gerard.luijks@philips.com [Philips Lighting Company, 7265 Route 54, Bath, NY 14810 (United States)

    2011-06-08

    Lifetime experiments show that sodium-scandium metal halide lamps perform better on very high frequency (VHF) drivers than on low frequency (LF) constant wattage autotransformer (CWA) ballasts. The question why, will be addressed with focus on arc tube aspects. It is argued that at high frequency operation sodium loss is less, and that the absence of thermal fluctuations in the electrode tip causes less damage and cracking to this part of the electrode. Sudden lm W{sup -1} drops, observed with CWA-operated lamps, most probably occur when the arc attaches on such a corroded and cracked surface. Thorium is effective as an emitter both in the CWA and the VHF operation mode, despite the absence of cataphoretic transport to the cathode in the VHF case.

  11. Degradation of Highly Alloyed Metal Halide Perovskite Precursor Inks: Mechanism and Storage Solutions

    Dou, Benjia [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Wheeler, Lance M [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Christians, Jeffrey A [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Moore, David [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Harvey, Steven P [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Berry, Joseph J [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Van Hest, Marinus F [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Barnes, Frank S. [University of Colorado; Shaheen, Sean E. [University of Colorado

    2018-03-02

    Whereas the promise of metal halide perovskite (MHP) photovoltaics (PV) is that they can combine high efficiency with solution-processability, the chemistry occurring in precursor inks is largely unexplored. Herein, we investigate the degradation of MHP solutions based on the most widely used solvents, dimethylformamide (DMF) and dimethyl sulfoxide (DMSO). For the MHP inks studied, which contain formamidinium (FA+), methylammonium (MA+), cesium (Cs+), lead (Pb2+), bromide (Br-), and iodide (I-), dramatic compositional changes are observed following storage of the inks in nitrogen in the dark. We show that hydrolysis of DMF in the precursor solution forms dimethylammonium formate, which subsequently incorporates into the MHP film to compromise the ability of Cs+ and MA+ to stabilize FA+-based MHP. The changes in solution chemistry lead to a modification of the perovskite film stoichiometry, band gap, and structure. The solid precursor salts are stable when ball-milled into a powder, allowing for the storage of large quantities of stoichiometric precursor materials.

  12. The Role of Surface Tension in the Crystallization of Metal Halide Perovskites

    Zhumekenov, Ayan A.

    2017-07-06

    The exciting intrinsic properties discovered in single crystals of metal halide perovskites still await their translation into optoelectronic devices. The poor understanding and control of the crystallization process of these materials are current bottlenecks retarding the shift towards single crystal-based optoelectronics. Here we theoretically and experimentally elucidate the role of surface tension in the rapid synthesis of perovskite single crystals by inverse temperature crystallization (ITC). Understanding the nucleation and growth mechanisms enabled us to exploit surface tension to direct the growth of monocrystalline films of perovskites (AMX3, where A = CH3NH3+ or MA; M = Pb2+, Sn2+; X = Br-, I-) on the solution surface. We achieve up to 1 cm2-sized monocrystalline films with thickness on the order of the charge carrier diffusion length (~5-10 µm). Our work paves the way to control the crystallization process of perovskites, including thin film deposition, which is essential to advance the performance benchmarks of perovskite optoelectronics.

  13. Highly Efficient Light-Emitting Diodes of Colloidal Metal-Halide Perovskite Nanocrystals beyond Quantum Size.

    Kim, Young-Hoon; Wolf, Christoph; Kim, Young-Tae; Cho, Himchan; Kwon, Woosung; Do, Sungan; Sadhanala, Aditya; Park, Chan Gyung; Rhee, Shi-Woo; Im, Sang Hyuk; Friend, Richard H; Lee, Tae-Woo

    2017-07-25

    Colloidal metal-halide perovskite quantum dots (QDs) with a dimension less than the exciton Bohr diameter D B (quantum size regime) emerged as promising light emitters due to their spectrally narrow light, facile color tuning, and high photoluminescence quantum efficiency (PLQE). However, their size-sensitive emission wavelength and color purity and low electroluminescence efficiency are still challenging aspects. Here, we demonstrate highly efficient light-emitting diodes (LEDs) based on the colloidal perovskite nanocrystals (NCs) in a dimension > D B (regime beyond quantum size) by using a multifunctional buffer hole injection layer (Buf-HIL). The perovskite NCs with a dimension greater than D B show a size-irrespective high color purity and PLQE by managing the recombination of excitons occurring at surface traps and inside the NCs. The Buf-HIL composed of poly(3,4-ethylenedioxythiophene)/poly(styrenesulfonate) (PEDOT:PSS) and perfluorinated ionomer induces uniform perovskite particle films with complete film coverage and prevents exciton quenching at the PEDOT:PSS/perovskite particle film interface. With these strategies, we achieved a very high PLQE (∼60.5%) in compact perovskite particle films without any complex post-treatments and multilayers and a high current efficiency of 15.5 cd/A in the LEDs of colloidal perovskite NCs, even in a simplified structure, which is the highest efficiency to date in green LEDs that use colloidal organic-inorganic metal-halide perovskite nanoparticles including perovskite QDs and NCs. These results can help to guide development of various light-emitting optoelectronic applications based on perovskite NCs.

  14. A PEG/copper(i) halide cluster as an eco-friendly catalytic system for C-N bond formation.

    Li, Cheng-An; Ji, Wei; Qu, Jian; Jing, Su; Gao, Fei; Zhu, Dun-Ru

    2018-05-22

    The catalytic activities of eight copper(i) halide clusters assembled from copper(i) halide and ferrocenyltelluroethers, 1-8, were investigated in C-N formation under various conditions. A catalytic procedure using poly(ethylene glycol) (PEG-400) as a greener alternative organic solvent has been developed. The PEG-400/5 system can achieve 99% targeted yield with a mild reaction temperature and short reaction time. After the isolation of the products by extraction with diethyl ether, this PEG-400/cluster system could be easily recycled. Spectroscopic studies elucidate a stepwise mechanism: firstly, proton-coupled electron transfer (PCET) involving the transfer of an electron from Cu+ and a proton from imidazole results in the formation of a labile penta-coordinated Cu2+ and aryl radical; the following effective electron transfer from the ferrocene unit reduces Cu2+ and forms the target product; finally, the ferrocenium unit is reduced by the I- anion. The merits of this eco-friendly synthesis are the efficient utilization of reagents and easy recyclability.

  15. Gas phase reactivity of thermal metal clusters

    Castleman, A.W. Jr.; Harms, A.C.; Leuchtner, R.E.

    1991-01-01

    Reaction kinetics of metal cluster ions under well defined thermal conditions were studied using a flow tube reactor in combination with laser vaporization. Aluminum anions and cations were reacted with oxygen, and several species which are predicted jellium shell closings, were found to have special stability. Metal alloy cluster anions comprised of Al, V and Nb were also seen to react with oxygen. Alloy clusters with an even number of electrons reacted more slowly than odd electron species, and certain clusters appeared to be exceptionally unreactive. Copper cation clusters were observed to associate with carbon monoxide with reactivities that approach bulk behavior at surprisingly small cluster size. These reactions demonstrate how the rate of reaction changes with cluster size. (orig.)

  16. Gas phase reactivity of thermal metal clusters

    Castleman, A. W., Jr.; Harms, A. C.; Leuchtner, R. E.

    1991-03-01

    Reaction kinetics of metal cluster ions under well defined thermal conditions were studied using a flow tube reactor in combination with laser vaporization. Aluminum anions and cations were reacted with oxygen, and several species which are predicted jellium shell closings, were found to have special stability. Metal alloy cluster anions comprised of Al, V and Nb were also seen to react with oxygen. Alloy clusters with an even number of electrons reacted more slowly than odd electron species, and certain clusters appeared to be exceptionally unreactive. Copper cation clusters were observed to associate with carbon monoxide with reactivities that approach bulk behavior at surprisingly small cluster size. These reactions demonstrate how the rate of reaction changes with cluster size.

  17. Special features of the formation of high-conductivity phases of halides of alkali metals at superhigh pressures

    Babushkin, A.N.; Babushkina, G.V.

    1999-01-01

    The halides of alkali metals are the simplest crystals with the ionic nature of chemical bonds and are used widely as modelling materials in high-pressure physics. As a result of previous theoretical and experimental (optical, structural, electro-physical and shock-waves) investigations it was shown that these materials may be characterised by the overlapping of the valency and conduction bands and by the formation of groups of free charge carriers at pressures of the megabaric level. However, the authors know of no data on the direct investigations of the electrophysical properties of the halides of alkali metals at such high static pressures. The end of this investigation was to examine the temperature dependences of the electrical conductivity and thermal EMF of halides of alkali metals AX (A = Na, K, Rb, Cs, X = Cl, Br, I) in a wide temperature range at pressures from 10 to 50 GPa in order to reveal the general leisure since governing the change of their electronic structures, in particular, the transition to the state with the activation-type or metallic conductivity

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

    Steinberg, Simon; Zimmermann, Sina; Brühmann, Matthias; Meyer, Eva; Rustige, Christian; Wolberg, Marike; Daub, Kathrin; Bell, Thomas; Meyer, Gerd, E-mail: gerd.meyer@uni-koeln.de

    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.

  19. Photometric metal abundances for twenty clusters

    Jennens, P.A.; Helfer, H.L.

    1975-01-01

    Metal abundances, colour excesses and distance moduli have been determined for individual giant stars, using UBViyz photometry, in NGC 188, 559, 752, 1245, 1342, 1907, 1912, 2099, 5139 (ω cen), 5316, 5617, 5822, 5823, 6067, IC 4651, 6819, 6940, 7142, 7261 and 7789. All six clusters with ages 3 to 8x10 9 yr have metal abundances agreeing with one another; their average value of [Fe/H]=-0.24+-0.05, agrees with the average found for the bright K-giants near the Sun. All six clusters are at least 140pc from the galactic plane. For the younger clusters less than approximately 10 9 yr old, one-third are metal deficient. The very young cluster, NGC 559, is probably very metal weak. (author)

  20. Collective excitations in deformed alkali metal clusters

    Lipparini, E.; Stringari, S.; Istituto Nazionale di Fisica Nucleare, Povo

    1991-01-01

    A theoretical study of collective excitations in deformed metal clusters is presented. Sum rules are used to study the splittings of the dipole surface plasma resonance originating from the cluster deformation. The vibrating potential model is developed and used to predict the occurrence of a low lying collective mode of orbital magnetic nature. (orig.)

  1. Electron scattering on metal clusters and fullerenes

    Solov'yov, A.V.

    2001-01-01

    This paper gives a survey of physical phenomena manifesting themselves in electron scattering on atomic clusters. The main emphasis is made on electron scattering on fullerenes and metal clusters, however some results are applicable to other types of clusters as well. This work is addressed to theoretical aspects of electron-cluster scattering, however some experimental results are also discussed. It is demonstrated that the electron diffraction plays important role in the formation of both elastic and inelastic electron scattering cross sections. It is elucidated the essential role of the multipole surface and volume plasmon excitations in the formation of electron energy loss spectra on clusters (differential and total, above and below ionization potential) as well as the total inelastic scattering cross sections. Particular attention is paid to the elucidation of the role of the polarization interaction in low energy electron-cluster collisions. This problem is considered for electron attachment to metallic clusters and the plasmon enhanced photon emission. Finally, mechanisms of electron excitation widths formation and relaxation of electron excitations in metal clusters and fullerenes are discussed. (authors)

  2. Metal-Halide Perovskite Transistors for Printed Electronics: Challenges and Opportunities

    Lin, Yen-Hung

    2017-10-12

    Following the unprecedented rise in photovoltaic power conversion efficiencies during the past five years, metal-halide perovskites (MHPs) have emerged as a new and highly promising class of solar-energy materials. Their extraordinary electrical and optical properties combined with the abundance of the raw materials, the simplicity of synthetic routes, and processing versatility make MHPs ideal for cost-efficient, large-volume manufacturing of a plethora of optoelectronic devices that span far beyond photovoltaics. Herein looks beyond current applications in the field of energy, to the area of large-area electronics using MHPs as the semiconductor material. A comprehensive overview of the relevant fundamental material properties of MHPs, including crystal structure, electronic states, and charge transport, is provided first. Thereafter, recent demonstrations of MHP-based thin-film transistors and their application in logic circuits, as well as bi-functional devices such as light-sensing and light-emitting transistors, are discussed. Finally, the challenges and opportunities in the area of MHPs-based electronics, with particular emphasis on manufacturing, stability, and health and environmental concerns, are highlighted.

  3. AB INITIO molecular orbital studies of some high temperature metal halide complexes

    Curtiss, L.A.

    1978-01-01

    The use of ab initio molecular orbital calculations to aid in the characterization, i.e., structures and energies, of metal halide complexes present in high temperature salt vapors has been investigated. Standard LCAO-SCF methods were used and calculations were carried out using the minimal STO-3G basis set. The complexes included in this study were Al 2 F 6 , Al 2 Cl 6 , AlF 3 NH 3 , AlCl 3 NH 3 , and AlF 3 N 2 . The Al 2 X 6 complexes are found to have D/sub 2h/ symmetry in agreement with most experimental results. A planar form was found to be considerably higher in energy. The AlX 3 NH 3 complexes are found to have C/sub 3v/ symmetry with a small barrier to rotation about the Al-N axis. The AlF 3 N 2 complex is found to be weakly bound together with a binding energy of -8.2 kcal/mole at the STO-3G level

  4. A survey of infrared continuum versus line radiation from metal halide lamps

    Kato, M; Herd, M T; Lawler, J E

    2008-01-01

    Near-infrared radiation (near-IR) losses from the arcs of six commercial metal halide high intensity discharge (MH-HID) lamps with various power levels and with both Na/Sc and rare earth doses were surveyed in this paper. A radiometrically calibrated Fourier transform infrared spectrometer was used. Lamps with rare earth doses have appreciably better color rendering indices (CRIs) than lamps with Na/Sc doses. The ratios of near-IR continuum emission over near-IR line emission from these six lamps were compared. The near-IR continuum dominates near-IR losses from lamps with rare earth doses and the continuum is significant, but not dominant, from lamps with Na/Sc doses. There was no strong dependence of this ratio on input power or color temperature (T c ). Total near-IR losses were estimated using absolutely calibrated, horizontal irradiance measurements. Estimated total near-IR losses were correlated with CRI. The lamps with rare earth doses yield the best CRIs, but have appreciably higher near-IR losses due primarily to continuum processes. One of these rare earth MH-HID lamps was used in a more detailed study of the microscopic physics of the continuum mechanism (Herd M T and Lawler E 2007 J. Phys. D: Appl. Phys. 40 3386)

  5. Improving the Stability of Metal Halide Perovskite Materials and Light-Emitting Diodes.

    Cho, Himchan; Kim, Young-Hoon; Wolf, Christoph; Lee, Hyeon-Dong; Lee, Tae-Woo

    2018-01-25

    Metal halide perovskites (MHPs) have numerous advantages as light emitters such as high photoluminescence quantum efficiency with a direct bandgap, very narrow emission linewidth, high charge-carrier mobility, low energetic disorder, solution processability, simple color tuning, and low material cost. Based on these advantages, MHPs have recently shown unprecedented radical progress (maximum current efficiency from 0.3 to 42.9 cd A -1 ) in the field of light-emitting diodes. However, perovskite light-emitting diodes (PeLEDs) suffer from intrinsic instability of MHP materials and instability arising from the operation of the PeLEDs. Recently, many researchers have devoted efforts to overcome these instabilities. Here, the origins of the instability in PeLEDs are reviewed by categorizing it into two types: instability of (i) the MHP materials and (ii) the constituent layers and interfaces in PeLED devices. Then, the strategies to improve the stability of MHP materials and PeLEDs are critically reviewed, such as A-site cation engineering, Ruddlesden-Popper phase, suppression of ion migration with additives and blocking layers, fabrication of uniform bulk polycrystalline MHP layers, and fabrication of stable MHP nanoparticles. Based on this review of recent advances, future research directions and an outlook of PeLEDs for display applications are suggested. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Metal-Halide Perovskite Transistors for Printed Electronics: Challenges and Opportunities.

    Lin, Yen-Hung; Pattanasattayavong, Pichaya; Anthopoulos, Thomas D

    2017-12-01

    Following the unprecedented rise in photovoltaic power conversion efficiencies during the past five years, metal-halide perovskites (MHPs) have emerged as a new and highly promising class of solar-energy materials. Their extraordinary electrical and optical properties combined with the abundance of the raw materials, the simplicity of synthetic routes, and processing versatility make MHPs ideal for cost-efficient, large-volume manufacturing of a plethora of optoelectronic devices that span far beyond photovoltaics. Herein looks beyond current applications in the field of energy, to the area of large-area electronics using MHPs as the semiconductor material. A comprehensive overview of the relevant fundamental material properties of MHPs, including crystal structure, electronic states, and charge transport, is provided first. Thereafter, recent demonstrations of MHP-based thin-film transistors and their application in logic circuits, as well as bi-functional devices such as light-sensing and light-emitting transistors, are discussed. Finally, the challenges and opportunities in the area of MHPs-based electronics, with particular emphasis on manufacturing, stability, and health and environmental concerns, are highlighted. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Prediction of Intrinsic Ferromagnetic Ferroelectricity in a Transition-Metal Halide Monolayer

    Huang, Chengxi; Du, Yongping; Wu, Haiping; Xiang, Hongjun; Deng, Kaiming; Kan, Erjun

    2018-04-01

    The realization of multiferroics in nanostructures, combined with a large electric dipole and ferromagnetic ordering, could lead to new applications, such as high-density multistate data storage. Although multiferroics have been broadly studied for decades, ferromagnetic ferroelectricity is rarely explored, especially in two-dimensional (2D) systems. Here we report the discovery of 2D ferromagnetic ferroelectricity in layered transition-metal halide systems. On the basis of first-principles calculations, we reveal that a charged CrBr3 monolayer exhibits in-plane multiferroicity, which is ensured by the combination of orbital and charge ordering as realized by the asymmetric Jahn-Teller distortions of octahedral Cr - Br6 units. As an example, we further show that (CrBr3)2Li is a ferromagnetic ferroelectric multiferroic. The explored phenomena and mechanism of multiferroics in this 2D system not only are useful for fundamental research in multiferroics but also enable a wide range of applications in nanodevices.

  8. Broadband enhancement of photoluminance from colloidal metal halide perovskite nanocrystals on plasmonic nanostructured surfaces.

    Zhang, Si; Liang, Yuzhang; Jing, Qiang; Lu, Zhenda; Lu, Yanqing; Xu, Ting

    2017-11-07

    Metal halide perovskite nanocrystals (NCs) as a new kind of promising optoelectronic material have attracted wide attention due to their high photoluminescence (PL) quantum yield, narrow emission linewidth and wideband color tunability. Since the PL intensity always has a direct influence on the performance of optoelectronic devices, it is of vital importance to improve the perovskite NCs' fluorescence emission efficiency. Here, we synthesize three inorganic perovskite NCs and experimentally demonstrate a broadband fluorescence enhancement of perovskite NCs by exploiting plasmonic nanostructured surface consisting of nanogrooves array. The strong near-field optical localization associated with surface plasmon polariton-coupled emission effect generated by the nanogrooves array can significantly boost the absorption of perovskite NCs and tailor the fluorescence emissions. As a result, the PL intensities of perovskite NCs are broadband enhanced with a maximum factor higher than 8-fold achieved in experimental demonstration. Moreover, the high efficiency PL of perovskite NCs embedded in the polymer matrix layer on the top of plasmonic nanostructured surface can be maintained for more than three weeks. These results imply that plasmonic nanostructured surface is a good candidate to stably broadband enhance the PL intensity of perovskite NCs and further promote their potentials in the application of visible-light-emitting devices.

  9. Extragalactic globular clusters. I. The metallicity calibration

    Brodie, J.P.; Huchra, J.P.

    1990-01-01

    The ability of absorption-line strength indices, measured from integrated globular cluster spectra, to predict mean cluster metallicity is explored. Statistical criteria, are used to identify the six best indices out of about 20 measured in a large sample of Galactic and M31 cluster spectra. Linear relations between index and metallicity have been derived along with new calibrations of infrared colors (V - K, J - K, and CO) versus Fe/H. Estimates of metallicity from the six spectroscopic index-metallicity relations have been combined in three different ways to identify the most efficient estimator and the minimum bias estimator of Fe/H - the weighted mean. This provides an estimate of Fe/H accurate to about 15 percent. 37 refs

  10. A model for additive transport in metal halide lamps containing mercury and dysprosium tri-iodide

    Beks, M L; Haverlag, M; Mullen, J J A M van der

    2008-01-01

    The distribution of additives in a metal halide lamp is examined through numerical modelling. A model for a lamp containing sodium iodide additives has been modified to study a discharge containing dysprosium tri-iodide salts. To study the complex chemistry the method of Gibbs minimization is used to decide which species have to be taken into account and to fill lookup tables with the chemical composition at different combinations of elemental abundance, lamp pressure and temperature. The results from the model with dysprosium additives were compared with earlier results from the lamp containing sodium additives and a simulation of a pure mercury lamp. It was found that radial segregation creates the conditions required for axial segregation. Radial segregation occurs due to the unequal diffusion of atoms and molecules. Under the right conditions convection currents in the lamp can cause axial demixing. These conditions depend on the ratio of axial convection and radial diffusion as expressed by the Peclet number. At a Peclet number of unity axial segregation is most pronounced. At low Peclet numbers radial segregation is at its worst, while axial segregation is not present. At large Peclet numbers the discharge becomes homogeneously mixed. The degree of axial segregation at a Peclet number of unity depends on the temperature at which the additive under consideration fully dissociates. If the molecules dissociate very close to the walls no molecules are transported by the convective currents in the lamp, and hence axial segregation is limited. If they dissociate further away from the walls in the area where the downward convective currents are strongest, more axial segregation is observed

  11. Investigation of the connection between plasma temperature and electrode temperature in metal-halide lamps

    Fromm, D.C.; Gleixner, K.H.; Lieder, G.H.

    2002-01-01

    Spatial profiles of electrode temperatures and plasma temperatures have been measured on 'real' HID lamps filled with a commercial metal-halide compound. The absolute accuracy of pyrometric determination of electrode tip temperatures was ±30 K, while the determination of plasma core temperatures, using a modified Bartels method, has an accuracy of ±100 K. We could deduce a close correlation between the plasma temperature in front of an electrode T p and its tip temperature T t due to the influence of the cataphoresis. If T p is reduced at the cathode the T t value has also lowered, whereas T p at the anode is raised together with its T t data. This correlation disappears at ballast frequencies above 100 Hz, whereas the cataphoresis influence on T p continues up to 500 Hz. Based on the latter limit, a rough estimation of the cataphoresis velocity delivers 700 cm s -1 . As a tentative interpretation, we suggest that the connection between T p and T t is caused by an increase of the ion part of the total current at the cathode due to Na accumulation before it. Thus, the cathode has to emit fewer electrons and works at a lower temperature. Further results are the temporal behaviour of T t depends on the ballast type. For vertical operation the strong influence of convection on T t has also to be taken into account. Above 100 Hz, where only convection plays a role, the upper electrode T t exceeds the T t value of the lower electrode by nearly 400 K. This discrepancy one may explain, tentatively, by convection heating of the upper electrode and convection cooling of the lower one. (author)

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

    1992-01-01

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

  13. The atomic structure of transition metal clusters

    Riley, S.J.

    1995-01-01

    Chemical reactions are used to probe the atomic (geometrical) structure of isolated clusters of transition metal atoms. The number of adsorbate molecules that saturate a cluster, and/or the binding energy of molecules to cluster surfaces, are determined as a function of cluster size. Systematics in these properties often make it possible to propose geometrical structures consistent with the experimental observations. We will describe how studies of the reactions of cobalt and nickel clusters with ammonia, water, and nitrogen provide important and otherwise unavailable structural information. Specifically, small (less than 20 atoms) clusters of cobalt and nickel atoms adopt entirely different structures, the former having packing characteristic of the bulk and the latter having pentagonal symmetry. These observations provide important input for model potentials that attempt to describe the local properties of transition metals. In particular, they point out the importance of a proper treatment of d-orbital binding in these systems, since cobalt and nickel differ so little in their d-orbital occupancy

  14. Energetics of charged metal clusters containing vacancies

    Pogosov, Valentin V.; Reva, Vitalii I.

    2018-01-01

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

  15. Parity-Forbidden Transitions and Their Impact on the Optical Absorption Properties of Lead-Free Metal Halide Perovskites and Double Perovskites.

    Meng, Weiwei; Wang, Xiaoming; Xiao, Zewen; Wang, Jianbo; Mitzi, David B; Yan, Yanfa

    2017-07-06

    Using density functional theory calculations, we analyze the optical absorption properties of lead (Pb)-free metal halide perovskites (AB 2+ X 3 ) and double perovskites (A 2 B + B 3+ X 6 ) (A = Cs or monovalent organic ion, B 2+ = non-Pb divalent metal, B + = monovalent metal, B 3+ = trivalent metal, X = halogen). We show that if B 2+ is not Sn or Ge, Pb-free metal halide perovskites exhibit poor optical absorptions because of their indirect band gap nature. Among the nine possible types of Pb-free metal halide double perovskites, six have direct band gaps. Of these six types, four show inversion symmetry-induced parity-forbidden or weak transitions between band edges, making them not ideal for thin-film solar cell applications. Only one type of Pb-free double perovskite shows optical absorption and electronic properties suitable for solar cell applications, namely, those with B + = In, Tl and B 3+ = Sb, Bi. Our results provide important insights for designing new metal halide perovskites and double perovskites for optoelectronic applications.

  16. Ultrastable Photoelectrodes for Solar Water Splitting Based on Organic Metal Halide Perovskite Fabricated by Lift-Off Process.

    Nam, SeongSik; Mai, Cuc Thi Kim; Oh, Ilwhan

    2018-05-02

    Herein, we report an integrated photoelectrolysis of water employing organic metal halide (OMH) perovskite material. As generic OMH perovskite material and device architecture are highly susceptible to degradation by aqueous electrolytes, we have developed a versatile mold-cast and lift-off process to fabricate and assemble multipurpose metal encapsulation onto perovskite devices. With the metal encapsulation effectively protecting the perovskite cell and also functioning as electrocatalyst, the high-performance perovskite photoelectrodes exhibit high photovoltage and photocurrent that are effectively inherited from the original solid-state solar cell. More importantly, thus-fabricated perovskite photoelectrode demonstrates record-long unprecedented stability even at highly oxidizing potential in strong alkaline electrolyte. We expect that this versatile lift-off process can be adapted in a wide variety of photoelectrochemical devices to protect the material surfaces from corroding electrolyte and facilitate various electrochemical reactions.

  17. Study of the stabilization energies of halide-water clusters: An application of first-principles interaction potentials based on a polarizable and flexible model

    Ayala, Regla; Martinez, Jose M.; Pappalardo, Rafael R.; Sanchez Marcos, Enrique

    2004-01-01

    The aim of this work is to compute the stabilization energy E stab (n) of [X(H 2 O) n ] - (X≡F, Br, and I for n=1-60) clusters from Monte Carlo simulations using first-principles ab initio potentials. Stabilization energy of [X(H 2 O) n ] - clusters is defined as the difference between the vertical photodeachment energy of the cluster and the electron affinity of the isolated halide. On one hand, a study about the relation between cluster structure and the E stab (n) value, as well as the dependence of the latter with temperature is performed, on the other hand, a test on the reliability of our recently developed first-principles halide ion-water interaction potentials is carried out. Two different approximations were applied: (1) the Koopmans' theorem and (2) calculation of the difference between the interaction energy of [X(H 2 O) n ] - and [X(H 2 O) n ] clusters using the same ab initio interaction potentials. The developed methodology allows for using the same interaction potentials in the case of the ionic and neutral clusters with the proviso that the charge of the halide anion was switched off in the latter. That is, no specific parametrization of the interaction potentials to fit the magnitude under study was done. The good agreement between our predicted E stab (n) and experimental data allows us to validate the first-principles interaction potentials developed elsewhere and used in this study, and supports the fact that this magnitude is mainly determined by electrostatic factors, which can be described by our interaction potentials. No relation between the value of E stab (n) and the structure of clusters has been found. The diversity of E stab (n) values found for different clusters with similar interaction energy indicates the need for statistical information to properly estimate the stabilization energy of the halide anions. The effect of temperature in the prediction of the E stab (n) is not significant as long as it was high enough to avoid

  18. A Study on Organic-Metal Halide Perovskite Film Morphology, Interfacial Layers, Tandem Applications, and Encapsulation

    Fisher, Dallas A.

    Organic-metal halide perovskites have brought about a new wave of research in the photovoltaic community due to their ideally suited optical and electronic parameters. In less than a decade, perovskite solar cell performance has skyrocketed to unprecedented efficiencies with numerous reported methodologies. Perovskites face many challenges with high-quality film morphology, interfacial layers, and long-term stability. In this work, these active areas are explored through a combination of studies. First, the importance of perovskite film precursor ratios is explored with an in-depth study of carrier lifetime and solvent-grain effects. It was found that excess lead iodide precursor greatly improves the film morphology by reducing pinholes in the solar absorber. Dimethyl sulfoxide (DMSO) solvent was found to mend grains, as well as improve carrier lifetime and device performance, possibly by passivation of grain boundary traps. Second, applications of perovskite with tandem cells is investigated, with an emphasis for silicon devices. Perovskites can easily be integrated with silicon, which already has strong market presence. Additionally, both materials' bandgaps are ideally suited for maximum tandem efficiency. The silicon/perovskite tandem device structure necessitated the optimization of inverted (p-i-n) structure devices. PEDOT:PSS, copper oxide, and nickel oxide p-type layers were explored through a combination of photoluminescent, chemical reactivity, and solar simulation results. Results were hindered due to resistive ITO and rough silicon substrates, but tandem devices displayed Voc indicative of proper monolithic performance. Third, replacement of titanium dioxide n-type layer with iron oxide (Fe 2O3, common rust) was studied. Iron oxide experiences less ultraviolet instability than that of titanium dioxide under solar illumination. It was found that current density slightly decreased due to parasitic absorption from the rust, but that open circuit voltage

  19. New projectiles: multicharged metal clusters and biopolymers

    Della-Negra, S.; Gardes, D.; Le Beyec, Y.; Waast, B.

    1991-01-01

    Metal clusters and molecules are the one mean to realize simultaneous impacts of several atoms on a reduced surface(∼100A). The interaction characteristics is the non-linearity of energy deposition; the perturbation that the cluster produces, is above than the sum of the perturbation induced by its components, taken separately. The purpose of ORION project is to accelerate these new projectiles at ORSAY Tandem. The considered mass range is from 100 Daltons to 100 000 Daltons and energy range from MeV to GeV

  20. X-ray induced fluorescence measurement of segregation in a DyI{sub 3}-Hg metal-halide lamp

    Nimalasuriya, T [Department of Applied Physics, Eindhoven University of Technology, PO Box 513, 5600 MB Eindhoven (Netherlands); Curry, J J [National Institute of Standards and Technology, 100 Bureau Drive, Stop 8422, Gaithersburg, MD 20899-8422 (United States); Sansonetti, C J [National Institute of Standards and Technology, 100 Bureau Drive, Stop 8422, Gaithersburg, MD 20899-8422 (United States); Ridderhof, E J [Department of Applied Physics, Eindhoven University of Technology, PO Box 513, 5600 MB Eindhoven (Netherlands); Shastri, S D [Advanced Photon Source, Argonne National Laboratory, Argonne, IL 60439 (United States); Flikweert, A J [Department of Applied Physics, Eindhoven University of Technology, PO Box 513, 5600 MB Eindhoven (Netherlands); Stoffels, W W [Department of Applied Physics, Eindhoven University of Technology, PO Box 513, 5600 MB Eindhoven (Netherlands); Haverlag, M [Department of Applied Physics, Eindhoven University of Technology, PO Box 513, 5600 MB Eindhoven (Netherlands); Mullen, J J A M van der [Department of Applied Physics, Eindhoven University of Technology, PO Box 513, 5600 MB Eindhoven (Netherlands)

    2007-05-07

    Segregation of elemental Dy in a DyI{sub 3}-Hg metal-halide high-intensity discharge lamp has been observed with x-ray induced fluorescence. Significant radial and axial Dy segregation are seen, with the axial segregation characterized by a Fischer parameter value of {lambda} = 0.215 {+-} 0.002 mm{sup -1}. This is within 7% of the value ({lambda} = 0.20 {+-} 0.01 mm{sup -1}) obtained by Flikweert et al (2005 J. Appl. Phys. 98 073301) based on laser absorption by neutral Dy atoms. Elemental I is seen to exhibit considerably less axial and radial segregation. Some aspects of the observed radial segregation are compatible with a simplified fluid picture describing two main transition regions in the radial coordinate. The first transition occurs in the region where DyI{sub 3} molecules are in equilibrium with neutral Dy atoms. The second transition occurs where neutral Dy atoms are in equilibrium with ionized Dy. These measurements are part of a larger study on segregation in metal-halide lamps under a variety of conditions.

  1. Origin of vertical orientation in two-dimensional metal halide perovskites and its effect on photovoltaic performance.

    Chen, Alexander Z; Shiu, Michelle; Ma, Jennifer H; Alpert, Matthew R; Zhang, Depei; Foley, Benjamin J; Smilgies, Detlef-M; Lee, Seung-Hun; Choi, Joshua J

    2018-04-06

    Thin films based on two-dimensional metal halide perovskites have achieved exceptional performance and stability in numerous optoelectronic device applications. Simple solution processing of the 2D perovskite provides opportunities for manufacturing devices at drastically lower cost compared to current commercial technologies. A key to high device performance is to align the 2D perovskite layers, during the solution processing, vertical to the electrodes to achieve efficient charge transport. However, it is yet to be understood how the counter-intuitive vertical orientations of 2D perovskite layers on substrates can be obtained. Here we report a formation mechanism of such vertically orientated 2D perovskite in which the nucleation and growth arise from the liquid-air interface. As a consequence, choice of substrates can be liberal from polymers to metal oxides depending on targeted application. We also demonstrate control over the degree of preferential orientation of the 2D perovskite layers and its drastic impact on device performance.

  2. 3D dysprosium density in the metal-halide lamp measured by emission and laser absorption spectroscopy in a centrifuge at 1-10g

    Flikweert, A.J.; Nimalasuriya, T.; Thubé, G.M.; Kroesen, G.M.W.; Stoffels, W.W.

    2007-01-01

    The metal-halide lamp is a High Intensity Discharge (HID) lamp with a high efficiency. The salt additive (DyI3) acts as prime radiator. The present lamp suffers from non-uniform light output, caused by diffusion and convection processes. To gain a better understanding of the lamp, the convection is

  3. X-ray absorption tomography of a high-pressure metal-halide lamp with a bent arc due to Lorentz-forces

    Denisova, N.; Haverlag, M.; Ridderhof, E.J.; Nimalasuriya, T.; Mullen, van der J.J.A.M.

    2007-01-01

    The arc temperature is one of the most important characteristics which cotrol the emission properties of plasma light sources. X-ray absorption technique has received some attention as a powerful method to determine the temperature in high-pressure metal-halide lamps. An important advantage of x-ray

  4. The Study of Reducing Krypton-85 Activity in Metal Halide Lamp%降低金卤灯内氪-85活度的研究

    叶碧君

    2012-01-01

    通过测试及分析不同氪-85活度填充气体的同规格金卤灯的各项性能参数,研究了在确保金卤灯各项性能的前提下,降低金卤灯中氪-85活度的可行性及金卤灯中氪-85存在的必要性,可以为今后确定金卤灯中需添加的最低氪-85活度提供参考。%By analyzing the parameters of metal halide lamps which are filled with gas with different activity of krypton-85, the paper studies the feasibility of reducing krypton-85 activity in metal halide lamp while ensuring the lamp performance, and proves the necessity of its existence of krypton-85 in metal halide lamp. it can provide us a reference to determine the minimum krypton-85 activity to he added in metal halide lamps.

  5. THE STUDY OF CLINOPTILOLITE MODIFIED WITH3d METALS HALIDES BY IR AND DIFFUSE REFLECTANCE SPECTROSCOPY

    T. L. Rakitskaya

    2015-11-01

    Full Text Available The results of investigation of natural clinoptilolite (N-CLI and that modified with 3d metal halides (MeCl2/N-CLI, where Me are Cu, Co, and Mn by IR and diffuse reflectance spectroscopy are summarized. A band at 3437 cm-1 assigned to stretching vibrations of hydroxyl groups (nOH is found in the IR spectrum of the N-CLI sample. A location of the band was practically the same as for all above MeCl2/N-CLI samples. A band of middle intensity at 1638 cm-1 in the range of deformation vibrations of zeolite water observed in the IR spectrum of N-CLI slightly displays to lower frequencies in the case of the modified samples. An intensive wide band of a complex shape in the range from 1250 to 980 cm-1 assigned to Si–O–Si and Si–O–Al vibrations appears in IR spectra of all samples. A doublet band of middle intensity at 797 and 778 cm-1 is assigned to external symmetric stretching T-O vibrations and a band at 606 cm-1-to vibrations of a double ring. A location of the above bands is the same for all listed samples but their intensity is higher for MnCl2/N-CLI and CoCl2/N-CLI samples. After the reaction with ozone, significant changes in the IR spectra are observed only for MnCl2/N-CLI. They are due to MnO2 formation on the clinoptilolite surface resulting in a high frequency displacement of some bands. Based on UV-vi spectroscopy results, it is reasonable to make conclusions about the coordination and valence state of a central atom in the MeCl2/N-CLI samples under study. A location of charge transfer bands for these samples only slightly differs from that for N-CLI however the intensity of such bands increases for the MeCl2/N-CLI samples. The UV-vis spectrum of MnCl2/N-CLI changes after the reaction with ozone: the appearance of new bands of  charge transfer at 363 and 354 nm and also the two-fold increase in intensity of a charge transfer band at 272 nm in comparison with those of N-CLI and MnCl2/N-CLI are the evidence of change in both the

  6. On halide derivatives of rare-earth metal(III) oxidomolybdates(VI) and -tungstates(VI)

    Schleid, Thomas; Hartenbach, Ingo

    2016-01-01

    Halide derivatives of rare-earth metal(III) oxidomolybdates(VI) have been investigated comprehensively over the last decade comprising the halogens fluorine, chlorine, and bromine. Iodide-containing compounds are so far unknown. The simple composition REXMoO 4 (RE=rare-earth element, X=halogen) is realized for X=F almost throughout the complete lanthanide series as well as for yttrium. While ytterbium and lutetium do not form any fluoride derivative, for lanthanum, only a fluoride-deprived compound with the formula La 3 FMo 4 O 16 is realized. Moreover, molybdenum-rich compounds with the formula REXMo 2 O 7 are also known for yttrium and the smaller lanthanoids. For X=Cl the composition REClMoO 4 is known for yttrium and the whole lanthanide series, although, four different structure types were identified. Almost the same holds for X=Br, however, only two different structure types are realized in this class of compounds. In the case of halide derivatives of rare-earth metal(III) oxidotungstates(VI) the composition REXWO 4 is found for chlorides and bromides only, so far. Due to the similar size of Mo 6+ and W 6+ cations, the structures found for the tungstates are basically the same as for the molybdates. With the larger lanthanides, the representatives for both chloride and bromide derivates exhibit similar structural motifs as seen in the molybdates, however, the crystal structure cannot be determined reliably. In case of the smaller lanthanoids, the chloride derivatives are isostructural with the respective molybdates, although the existence ranges differ slightly. The same is true for rare-earth metal(III) bromide oxidotungstates(VI).

  7. Metallicity Spreads in M31 Globular Clusters

    Bridges, Terry

    2003-07-01

    Our recent deep HST photometry of the M31 halo globular cluster {GC} Mayall II, also called G1, has revealed a red-giant branch with a clear spread that we attribute to an intrinsic metallicity dispersion of at least 0.4 dex in [Fe/H]. The only other GC exhibiting such a metallicity dispersion is Omega Centauri, the brightest and most massive Galactic GC, whose range in [Fe/H] is about 0.5 dex. These observations are obviously linked to the fact that both G1 and Omega Cen are bright and massive GC, with potential wells deep enough to keep part of their gas, which might have been recycled, producing a metallicity scatter among cluster stars. These observations dramatically challenge the notion of chemical homogeneity as a defining characteristic of GCs. It is critically important to find out how common this phenomenon is and how it can constrain scenarios/models of GC formation. The obvious targets are other bright and massive GCs, which exist in M31 but not in our Galaxy where Omega Cen is an isolated giant. We propose to acquire, with ACS/HRC, deep imaging of 3 of the brightest M31 GCs for which we have observed velocity dispersion values similar to those observed in G1 and Omega Cen. A sample of GCs with chemical abundance dispersions will provide essential information about their formation mechanism. This would represent a major step for the studies of the origin and evolution of stellar populations.

  8. Development of processes for the production of solar grade silicon from halides and alkali metals, phase 1 and phase 2

    Dickson, C. R.; Gould, R. K.; Felder, W.

    1981-01-01

    High temperature reactions of silicon halides with alkali metals for the production of solar grade silicon are described. Product separation and collection processes were evaluated, measure heat release parameters for scaling purposes and effects of reactants and/or products on materials of reactor construction were determined, and preliminary engineering and economic analysis of a scaled up process were made. The feasibility of the basic process to make and collect silicon was demonstrated. The jet impaction/separation process was demonstrated to be a purification process. The rate at which gas phase species from silicon particle precursors, the time required for silane decomposition to produce particles, and the competing rate of growth of silicon seed particles injected into a decomposing silane environment were determined. The extent of silane decomposition as a function of residence time, temperature, and pressure was measured by infrared absorption spectroscopy. A simplistic model is presented to explain the growth of silicon in a decomposing silane enviroment.

  9. Revealing the ultrafast charge carrier dynamics in organo metal halide perovskite solar cell materials using time resolved THz spectroscopy

    Ponseca, C. S., Jr.; Sundström, V.

    2016-03-01

    Ultrafast charge carrier dynamics in organo metal halide perovskite has been probed using time resolved terahertz (THz) spectroscopy (TRTS). Current literature on its early time characteristics is unanimous: sub-ps charge carrier generation, highly mobile charges and very slow recombination rationalizing the exceptionally high power conversion efficiency for a solution processed solar cell material. Electron injection from MAPbI3 to nanoparticles (NP) of TiO2 is found to be sub-ps while Al2O3 NPs do not alter charge dynamics. Charge transfer to organic electrodes, Spiro-OMeTAD and PCBM, is sub-ps and few hundreds of ps respectively, which is influenced by the alignment of energy bands. It is surmised that minimizing defects/trap states is key in optimizing charge carrier extraction from these materials.

  10. In Situ Preparation of Metal Halide Perovskite Nanocrystal Thin Films for Improved Light-Emitting Devices.

    Zhao, Lianfeng; Yeh, Yao-Wen; Tran, Nhu L; Wu, Fan; Xiao, Zhengguo; Kerner, Ross A; Lin, YunHui L; Scholes, Gregory D; Yao, Nan; Rand, Barry P

    2017-04-25

    Hybrid organic-inorganic halide perovskite semiconductors are attractive candidates for optoelectronic applications, such as photovoltaics, light-emitting diodes, and lasers. Perovskite nanocrystals are of particular interest, where electrons and holes can be confined spatially, promoting radiative recombination. However, nanocrystalline films based on traditional colloidal nanocrystal synthesis strategies suffer from the use of long insulating ligands, low colloidal nanocrystal concentration, and significant aggregation during film formation. Here, we demonstrate a facile method for preparing perovskite nanocrystal films in situ and that the electroluminescence of light-emitting devices can be enhanced up to 40-fold through this nanocrystal film formation strategy. Briefly, the method involves the use of bulky organoammonium halides as additives to confine crystal growth of perovskites during film formation, achieving CH 3 NH 3 PbI 3 and CH 3 NH 3 PbBr 3 perovskite nanocrystals with an average crystal size of 5.4 ± 0.8 nm and 6.4 ± 1.3 nm, respectively, as confirmed through transmission electron microscopy measurements. Additive-confined perovskite nanocrystals show significantly improved photoluminescence quantum yield and decay lifetime. Finally, we demonstrate highly efficient CH 3 NH 3 PbI 3 red/near-infrared LEDs and CH 3 NH 3 PbBr 3 green LEDs based on this strategy, achieving an external quantum efficiency of 7.9% and 7.0%, respectively, which represent a 40-fold and 23-fold improvement over control devices fabricated without the additives.

  11. Study of Pair and many-body interactions in rare-gas halide atom clusters using negative ion zero electron kinetic energy (ZEKE) and threshold photodetachment spectroscopy

    Yourshaw, Ivan [Univ. of California, Berkeley, CA (United States)

    1998-07-09

    The diatomic halogen atom-rare gas diatomic complexes KrBr-, XeBr-, and KrCl- are studied in this work by zero electron kinetic energy (ZEKE) spectroscopy in order to characterize the weak intermolecular diatomic potentials of these species. Also, the ZEKE and threshold photodetachment spectra of the polyatomic clusters ArnBr- (n = 2-9) and ArnI- (n = 2-19) are studied to obtain information about the non-additive effects on the interactions among the atoms. This work is part of an ongoing effort to characterize the pair and many-body potentials of the complete series of rare gas halide clusters. In these studies we obtain information about both the anionic and neutral clusters.

  12. Methods for producing single crystal mixed halide perovskites

    Zhu, Kai; Zhao, Yixin

    2017-07-11

    An aspect of the present invention is a method that includes contacting a metal halide and a first alkylammonium halide in a solvent to form a solution and maintaining the solution at a first temperature, resulting in the formation of at least one alkylammonium halide perovskite crystal, where the metal halide includes a first halogen and a metal, the first alkylammonium halide includes the first halogen, the at least one alkylammonium halide perovskite crystal includes the metal and the first halogen, and the first temperature is above about 21.degree. C.

  13. Globular cluster metallicity scale: evidence from stellar models

    Demarque, P.; King, C.R.; Diaz, A.

    1982-01-01

    Theoretical giant branches have been constructed to determine their relative positions for metallicities in the range -2.3 0 )/sub 0,g/ based on these models is presented which yields good agreement over the observed range of metallicities for galactic globular clusters and old disk clusters. The metallicity of 47 Tuc and M71 given by this calibration is about -0.8 dex. Subject headings: clusters, globular: stars: abundances: stars: interiors

  14. Heavy metal ternary halides for room-temperature x-ray and gamma-ray detection

    Liu, Zhifu; Peters, John A.; Stoumpos, Constantinos C.; Sebastian, Maria; Wessels, Bruce W.; Im, Jino; Freeman, Arthur J.; Kanatzidis, Mercouri G.

    2013-09-01

    We report our recent progress on wide bandgap ternary halide compounds CsPbBr3 and CsPbCl3 for room temperature x-ray and gamma-ray detectors. Their bandgaps are measured to be 2.24 eV and 2.86 eV, respectively. The measured mobility-lifetime products of CsPbBr3 are 1.7×10-3, 1.3×10-3 cm2/V, for electron and hole carriers, respectively, comparable to those of CdTe. We measured the room temperature spectral response of CsPbBr3 sample to Ag x-ray radiation. It has a well-resolved spectral response to the 22.4 keV Kα radiation peak and detector efficiency comparable to that of CdZnTe detector at 295 K.

  15. Deposition of metal Islands, metal clusters and metal containing single molecules on self-assembled monolayers

    Speets, Emiel Adrianus

    2005-01-01

    The central topic of this thesis is the deposition of metals on Self-Assembled Monolayers (SAMs). Metals are deposited in the form of submicron scale islands, nanometer scale clusters, and as supramolecular, organometallic coordination cages. Several SAMs on various substrates were prepared and

  16. Defect-induced local variation of crystal phase transition temperature in metal-halide perovskites.

    Dobrovolsky, Alexander; Merdasa, Aboma; Unger, Eva L; Yartsev, Arkady; Scheblykin, Ivan G

    2017-06-26

    Solution-processed organometal halide perovskites are hybrid crystalline semiconductors highly interesting for low-cost and efficient optoelectronics. Their properties are dependent on the crystal structure. Literature shows a variety of crystal phase transition temperatures and often a spread of the transition over tens of degrees Kelvin. We explain this inconsistency by demonstrating that the temperature of the tetragonal-to-orthorhombic phase transition in methylammonium lead triiodide depends on the concentration and nature of local defects. Phase transition in individual nanowires was studied by photoluminescence microspectroscopy and super-resolution imaging. We propose that upon cooling from 160 to 140 K, domains of the crystal containing fewer defects stay in the tetragonal phase longer than highly defected domains that readily transform to the high bandgap orthorhombic phase at higher temperatures. The existence of relatively pure tetragonal domains during the phase transition leads to drastic photoluminescence enhancement, which is inhomogeneously distributed across perovskite microcrystals.Understanding crystal phase transition in materials is of fundamental importance. Using luminescence spectroscopy and super-resolution imaging, Dobrovolsky et al. study the transition from the tetragonal to orthorhombic crystal phase in methylammonium lead triiodide nanowires at low temperature.

  17. Pressure-Induced Metallization of the Halide Perovskite (CH 3 NH 3 )PbI 3

    Jaffe, Adam; Lin, Yu [Photon; Mao, Wendy L. [Photon; Karunadasa, Hemamala I.

    2017-03-10

    We report the metallization of the hybrid perovskite semiconductor (MA)PbI3 (MA = CH3NH3+) with no apparent structural transition. We tracked its bandgap evolution during compression in diamond-anvil cells using absorption spectroscopy and observed strong absorption over both visible and IR wavelengths at pressures above ca. 56 GPa, suggesting the imminent closure of its optical bandgap. The metallic character of (MA)PbI3 above 60 GPa was confirmed using both IR reflectivity and variable-temperature dc conductivity measurements. The impressive semiconductor properties of halide perovskites have recently been exploited in a multitude of optoelectronic applications. Meanwhile, the study of metallic properties in oxide perovskites has revealed diverse electronic phenomena. Importantly, the mild synthetic routes to halide perovskites and the templating effects of the organic cations allow for fine structural control of the inorganic lattice. Pressure-induced closure of the 1.6 eV bandgap in (MA)PbI3 demonstrates the promise of the continued study of halide perovskites under a range of thermodynamic conditions, toward realizing wholly new electronic properties.

  18. Volume shift and charge instability of simple-metal clusters

    Brajczewska, Marta; Vieira, Armando; Fiolhais, Carlos

    1996-01-01

    Experiment indicates that small clusters show changes (mostly contractions) of the bond lengths with respect to bulk values. We use the stabilized jellium model to study the self-expansion and self-compression of spherical clusters (neutral or ionized) of simple metals. Results from Kohn — Sham density functional theory are presented for small clusters of Al and Na, including negatively-charged ones. We also examine the stability of clusters with respect to charging

  19. Volume shift and charge instability of simple-metal clusters

    Brajczewska, M.; Vieira, A.; Fiolhais, C.; Perdew, J. P.

    1996-12-01

    Experiment indicates that small clusters show changes (mostly contractions) of the bond lengths with respect to bulk values. We use the stabilized jellium model to study the self-expansion and self-compression of spherical clusters (neutral or ionized) of simple metals. Results from Kohn - Sham density functional theory are presented for small clusters of Al and Na, including negatively-charged ones. We also examine the stability of clusters with respect to charging.

  20. Impact of various lighting source (incandescent, fluorescent, metal halide and high pressure sodium) on the production performance of chicken broilers

    Guffar, A.; Rahman, K.U.; Siddique, M.; Ahmad, F.

    2009-01-01

    Light is an important aspect of an animal's environment. Avian as well as mammalian species respond to light energy in a variety of ways. Recent research has indicated that light source may affect body weight, immune response, livability and health status. Broiler behavior is strongly affected by light sources. So the present project was designed to study the effect of light sources on the production performance of broilers. For this purpose, 500 day-old broilers purchased from the local market were reared for three days (adaptation period) in one group. Then these were randomly divided into five experimental groups each comprising of 100 birds. Group A was given 25 incandescent light (INC), Group B was given fluorescent light (FC), Group C was given metal halide light (MH), Group D was given high pressure sodium light (HPS) and Group E was given no light source (control). Performance trial in terms of measurement of weekly body weight, weekly feed consumption, feed conversion ratio (FCR), daily water consumption and mortality were checked. Among various lighting sources, MH proved the best light source regarding main parameters of production performance. (author)

  1. Metal Halide Perovskite Supercrystals: Gold-Bromide Complex Triggered Assembly of CsPbBr3 Nanocubes.

    Wang, Kun-Hua; Yang, Jun-Nan; Ni, Qian-Kun; Yao, Hong-Bin; Yu, Shu-Hong

    2018-01-16

    Using nanocrystals as "artificial atoms" to construct supercrystals is an interesting process to explore the stacking style of nanoscale building blocks and corresponding collective properties. Various types of semiconducting supercrystals have been constructed via the assembly of nanocrystals driven by the entropic, electrostatic, or van der Waals interactions. We report a new type of metal halide perovskite supercrystals via the gold-bromide complex triggered assembly of newly emerged attractive CsPbBr 3 nanocubes. Through introducing gold-bromide (Au-Br) complexes into CsPbBr 3 nanocubes suspension, the self-assembly process of CsPbBr 3 nanocubes to form supercrystals was investigated with the different amount of Au-Br complexes added to the suspensions, which indicates that the driven force of the formation of CsPbBr 3 supercrystals included the van der Waals interactions among carbon chains and electrostatic interactions between Au-Br complexes and surfactants. Accordingly, the optical properties change with the assembly of CsPbBr 3 nanocubes and the variation of mesoscale structures of supercrystals with heating treatment was revealed as well, demonstrating the ionic characteristics of CsPbBr 3 nanocrystals. The fabricated CsPbBr 3 supercrystal presents a novel type of semiconducting supercrystals that will open an avenue for the assembly of ionic nanocrystals.

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

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

    2012-12-01

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

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

    Buonanno, R.; Buscema, G.; Fusi Pecci, F.; Richer, H.B.; Fahlman, G.G.

    1990-01-01

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

  4. Rotation of small clusters in sheared metallic glasses

    Delogu, Francesco

    2011-01-01

    Graphical abstract: When a Cu 50 Ti 50 metallic glass is shear-deformed, the irreversible rearrangement of local structures allows the rigid body rotation of clusters. Highlights: → A shear-deformed Cu 50 Ti 50 metallic glass was studied by molecular dynamics. → Atomic displacements occur at irreversible rearrangements of local structures. → The dynamics of such events includes the rigid body rotation of clusters. → Relatively large clusters can undergo two or more complete rotations. - Abstract: Molecular dynamics methods were used to simulate the response of a Cu 50 Ti 50 metallic glass to shear deformation. Attention was focused on the atomic displacements taking place during the irreversible rearrangement of local atomic structures. It is shown that the apparently disordered dynamics of such events hides the rigid body rotation of small clusters. Cluster rotation was investigated by evaluating rotation angle, axis and lifetimes. This permitted to point out that relatively large clusters can undergo two or more complete rotations.

  5. Ion beam induced nanosized Ag metal clusters in glass

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

    2006-01-01

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

  6. Evidence for the direct ejection of clusters from non-metallic solids during laser vaporization

    Bloomfield, L.A.; Yang, Y.A.; Xia, P.; Junkin, A.L.

    1991-01-01

    This paper reports on the formation of molecular scale particles or clusters of alkali halides and semiconductors during laser vaporization of solids. By measuring the abundances of cluster ions produced in several different source configurations, the authors have determined that clusters are ejected directly from the source sample and do not need to grow from atomic or molecular vapor. Using samples of mixed alkali halide powders, the authors have found that unalloyed clusters are easily produced in a source that prevents growth from occurring after the clusters leave the sample surface. However, melting the sample or encouraging growth after vaporization lead to the production of alloyed cluster species. The sizes of the ejected clusters are initially random, but the population spectrum quickly becomes structured as hot, unstable-sized clusters decay into smaller particles. In carbon, large clusters with odd number of atoms decay almost immediately. The hot even clusters also decay, but much more slowly. The longest lived clusters are the magic C 50 and C 60 fullerenes. The mass spectrum of large carbon clusters evolves in time from structureless, to only the even clusters, to primarily C 50 and C 60 . If cluster growth is encouraged, the odd clusters reappear and the population spectrum again becomes relatively structureless

  7. Reaction of urea thiourea and their derivatives with tertiary phosphine transition metal halides

    Adam, Eltayeb Mahala

    2000-03-01

    This thesis describes preparation characterization and some properties of a number of new compounds such as (ph 3 p)2 ML where M= cobalt (11), nickel (11), and copper (11), and L= urea, thiourea, phenylthiourea, sym diphenylurea and sym diphenylthiourea.These compounds have been prepared according according to the reaction of dichloro bis (triphenylphosphine) transition metal with urea, thiourea or some of their derivative ligands in 1:1 molar ratio.The work in this thesis is divided into three section firstly:- In the introduction chapter part one includes general definitions of coordination chemistry and related compounds and abroad definition of transition elements.Part two includes the theoretical back ground about transition metal complexes having urea, thiourea or some of their substituted derivative ligands.Part two also discusses the type of bonding between these ligands and the transition metal atom.Secondly: Chapter two describes the general techniques followed in this work such as purification of solvents recrystallization, preparation of starting materials and also gives full detailed procedures of the preparation of a number of new compounds.Thirdly: Discussion with detailed in chapter three, the results of the research are presented the preparation and characterization of a number of new compounds isolated from reaction between urea, thiourea or some of their substituted derivatives and dichloro bis (triphenyl phosphine) transition metal complex giving a general formula (ph 3 )2ML where M=cobalt, nickel, and copper, and urea, thiourea or some of their substituted derivatives ligands. The products of these experiments have been identified using infrared spectra, melting points and molar conductance. The results obtained indicated that all the compounds forming the nitrogen to metal bonds leading to the formation of a four- membered chelate ring, they are relatively thermally stable compounds, and also these compounds are non-electrolytes.(Author)

  8. METALS IN THE ICM: WITNESSES OF CLUSTER FORMATION AND EVOLUTION

    Lorenzo Lovisari

    2013-12-01

    Full Text Available The baryonic composition of galaxy clusters and groups is dominated by a hot, X-ray emitting Intra-Cluster Medium (ICM. The mean metallicity of the ICM has been found to be roughly 0.3 ÷ 0.5 times the solar value, therefore a large fraction of this gas cannot be of purely primordial origin. Indeed, the distribution and amount of metals in the ICM is a direct consequence of the past history of star formation in the cluster galaxies and of the processes responsible for the injection of enriched material into the ICM. We here shortly summarize the current views on the chemical enrichment, focusing on the observational evidence in terms of metallicity measurements in clusters, spatial metallicity distribution and evolution, and expectations from future missions.

  9. Orbital magnetism and dynamics in alkali metal clusters

    Nesterenko, V.O.; Kleinig, W.; Souza Cruz, FF. de; Marinelli, J.R.

    2000-01-01

    Two remarkable orbital magnetic resonances, M1 scissor mode and M2 twist mode, are predicted in deformed and spherical metal clusters, respectively. We show that these resonances provide a valuable information about many cluster properties (quadrupole deformation, magnetic susceptibility, single-particle spectrum, etc.)

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

    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.

  11. Oxide-supported metal clusters: models for heterogeneous catalysts

    Santra, A K; Goodman, D W

    2003-01-01

    Understanding the size-dependent electronic, structural and chemical properties of metal clusters on oxide supports is an important aspect of heterogeneous catalysis. Recently model oxide-supported metal catalysts have been prepared by vapour deposition of catalytically relevant metals onto ultra-thin oxide films grown on a refractory metal substrate. Reactivity and spectroscopic/microscopic studies have shown that these ultra-thin oxide films are excellent models for the corresponding bulk oxides, yet are sufficiently electrically conductive for use with various modern surface probes including scanning tunnelling microscopy (STM). Measurements on metal clusters have revealed a metal to nonmetal transition as well as changes in the crystal and electronic structures (including lattice parameters, band width, band splitting and core-level binding energy shifts) as a function of cluster size. Size-dependent catalytic reactivity studies have been carried out for several important reactions, and time-dependent catalytic deactivation has been shown to arise from sintering of metal particles under elevated gas pressures and/or reactor temperatures. In situ STM methodologies have been developed to follow the growth and sintering kinetics on a cluster-by-cluster basis. Although several critical issues have been addressed by several groups worldwide, much more remains to be done. This article highlights some of these accomplishments and summarizes the challenges that lie ahead. (topical review)

  12. Split and Compensated Hyperfine Fields in Magnetic Metal Clusters

    Nakamura, H.; Chudo, H.; Shiga, M.; Kohara, T.

    2004-01-01

    As prominent characteristics of magnetic metal cluster found in vanadium sulfides, we point out marked separation and compensation of the hyperfine field at the nuclear site; these are in somewhat discordance with the common sense for 3d transition-metal magnets, where the on-site isotropic field, scaling the ordered moment magnitude, is dominant.

  13. A study of the convective flow as a function of external parameters in a high-pressure metal halide discharge lamp (HgDyI3)

    Hajji, S.; HadjSalah, S.; Benhalima, A.; Charrada, K.; Zissis, G.

    2016-06-01

    This paper deals with the modelling of the convection processes in metal-halide lamp discharges (HgDyI3). For this, we realized a 3D model, a steady, direct current powered and time-depending model for the solution of conservation equations relative to mass, momentum, and energy. After validation, this model was applied to the study of the effect of some parameters that have appeared on major transport phenomena of mass and energy in studying the lamp. Indeed, the electric current, the atomic ratio (Hg/Dy), and the effect of the convective transport have been studied.

  14. Thermodynamics of Pore Filling Metal Clusters in Metal Organic Frameworks: Pd in UiO-66

    Vilhelmsen, Lasse; Sholl, David S.

    2012-01-01

    Metal organic frameworks (MOFs) have experimentally been demonstrated to be capable of supporting isolated transition-metal clusters, but the stability of these clusters with respect to aggregation is unclear. In this letter we use a genetic algorithm together with density functional theory...... calculations to predict the structure of Pd clusters in UiO-66. The cluster sizes examined are far larger than those in any previous modeling studies of metal clusters in MOFs and allow us to test the hypothesis that the physically separated cavities in UiO-66 could stabilize isolated Pd clusters. Our...... calculations show that Pd clusters in UiO-66 are, at best, metastable and will aggregate into connected pore filling structures at equilibrium....

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

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

    2016-01-01

    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 3 nm 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. - Highlights: • Field evaporation of metallic glasses is heterogeneous on a scale of up to 3 nm. • Amount of clustered evaporation depends on ion species and temperature. • Length scales of clustered evaporation and correlative evaporation are similar.

  16. Structural and Dynamical Properties of Alkaline Earth Metal Halides in Supercritical Water: Effect of Ion Size and Concentration.

    Keshri, Sonanki; Tembe, B L

    2017-11-22

    Constant temperature-constant pressure molecular dynamics simulations have been performed for aqueous alkaline earth metal chloride [M 2+ -Cl - (M = Mg, Ca, Sr, and Ba)] solutions over a wide range of concentrations (0.27-5.55 m) in supercritical (SC) and ambient conditions to investigate their structural and dynamical properties. A strong influence of the salt concentration is observed on the ion-ion pair correlation functions in both ambient and SC conditions. In SC conditions, significant clustering is observed in the 0.27 m solution, whereas the reverse situation is observed at room temperature and this is also supported by the residence times of the clusters. The concentration and ion size (cation size) seem to have opposite effects on the average number of hydrogen bonds. The simulation results show that the self-diffusion coefficients of water, cations, and the chloride ion increase with increasing temperature, whereas they decrease with increasing salt concentration. The cluster size distribution shows a strong density dependence in both ambient and SC conditions. In SC conditions, cluster sizes display a near-Gaussian distribution, whereas the distribution decays monotonically in ambient conditions.

  17. Aluminum Pitting Corrosion in Halide Media: A Quantum Model and Empirical Evidence

    Lashgari, Mohsen; Kianpour, Effat; Mohammadi, Esmaeil

    2013-12-01

    The phenomenon of localized damage of aluminum oxide surface in the presence of halide anions was scrutinized at an atomistic level, through the cluster approach and density functional theory. The phenomenon was also investigated empirically through Tafel polarization plots and scanning electron microscopy. A distinct behavior witnessed in the fluoride medium was justified through the hard-soft acid-base principle. The atomistic investigations revealed the greatest potency for chloride entrance into the metal oxide lattice and rationalized to the severity of damage. The interaction of halide anions with the oxide surface causing some displacements on the position of Al atoms provides a mechanistic insight of the phenomenon.

  18. Stable biexcitons in two-dimensional metal-halide perovskites with strong dynamic lattice disorder

    Thouin, Félix; Neutzner, Stefanie; Cortecchia, Daniele; Dragomir, Vlad Alexandru; Soci, Cesare; Salim, Teddy; Lam, Yeng Ming; Leonelli, Richard; Petrozza, Annamaria; Kandada, Ajay Ram Srimath; Silva, Carlos

    2018-03-01

    With strongly bound and stable excitons at room temperature, single-layer, two-dimensional organic-inorganic hybrid perovskites are viable semiconductors for light-emitting quantum optoelectronics applications. In such a technological context, it is imperative to comprehensively explore all the factors—chemical, electronic, and structural—that govern strong multiexciton correlations. Here, by means of two-dimensional coherent spectroscopy, we examine excitonic many-body effects in pure, single-layer (PEA) 2PbI4 (PEA = phenylethylammonium). We determine the binding energy of biexcitons—correlated two-electron, two-hole quasiparticles—to be 44 ±5 meV at room temperature. The extraordinarily high values are similar to those reported in other strongly excitonic two-dimensional materials such as transition-metal dichalcogenides. Importantly, we show that this binding energy increases by ˜25 % upon cooling to 5 K. Our work highlights the importance of multiexciton correlations in this class of technologically promising, solution-processable materials, in spite of the strong effects of lattice fluctuations and dynamic disorder.

  19. Metal nanostructures: from clusters to nanocatalysis and sensors

    Smirnov, B. M.

    2017-12-01

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

  20. Experimental studies of the chemistry of metal clusters

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

    1988-01-01

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

  1. Variable Charge and Electrical Double Layer of Mineral-Water Interfaces: Silver Halides versus Metal (Hydr)Oxides

    Hiemstra, T.

    2012-01-01

    Classically, silver (Ag) halides have been used to understand thermodynamic principles of the charging process and the corresponding development of the electrical double layer (EDL). A mechanistic approach to the processes on the molecular level has not yet been carried out using advanced surface

  2. Modeling of catalytically active metal complex species and intermediates in reactions of organic halides electroreduction.

    Lytvynenko, Anton S; Kolotilov, Sergey V; Kiskin, Mikhail A; Eremenko, Igor L; Novotortsev, Vladimir M

    2015-02-28

    The results of quantum chemical modeling of organic and metal-containing intermediates that occur in electrocatalytic dehalogenation reactions of organic chlorides are presented. Modeling of processes that take place in successive steps of the electrochemical reduction of representative C1 and C2 chlorides - CHCl3 and Freon R113 (1,1,2-trifluoro-1,2,2-trichloroethane) - was carried out by density functional theory (DFT) and second-order Møller-Plesset perturbation theory (MP2). It was found that taking solvation into account using an implicit solvent model (conductor-like screening model, COSMO) or considering explicit solvent molecules gave similar results. In addition to modeling of simple non-catalytic dehalogenation, processes with a number of complexes and their reduced forms, some of which were catalytically active, were investigated by DFT. Complexes M(L1)2 (M = Fe, Co, Ni, Cu, Zn, L1H = Schiff base from 2-pyridinecarbaldehyde and the hydrazide of 4-pyridinecarboxylic acid), Ni(L2) (H2L2 is the Schiff base from salicylaldehyde and 1,2-ethylenediamine, known as salen) and Co(L3)2Cl2, representing a fragment of a redox-active coordination polymer [Co(L3)Cl2]n (L3 is the dithioamide of 1,3-benzenedicarboxylic acid), were considered. Gradual changes in electronic structure in a series of compounds M(L1)2 were observed, and correlations between [M(L1)2](0) spin-up and spin-down LUMO energies and the relative energies of the corresponding high-spin and low-spin reduced forms, as well as the shape of the orbitals, were proposed. These results can be helpful for determination of the nature of redox-processes in similar systems by DFT. No specific covalent interactions between [M(L1)2](-) and the R113 molecule (M = Fe, Co, Ni, Zn) were found, which indicates that M(L1)2 electrocatalysts act rather like electron transfer mediators via outer-shell electron transfer. A relaxed surface scan of the adducts {M(L1)2·R113}(-) (M = Ni or Co) versus the distance between the

  3. Self-assembled metal clusters on an alumina nanomesh

    Buchsbaum, A.

    2012-01-01

    Template mediated growth of metals has attracted much interest due to the remarkable magnetic and catalytic properties of clusters in the nanometer range and provides the opportunity to grow clusters with narrow size distributions. When the Ni3Al(111) surface is exposed to oxygen at elevated temperature a thin oxide film with a well-defined structure and uniform thickness grows and covers the alloy surface completely. The structure of the alumina film has been solved mainly by the help of scanning tunneling microscopy (STM) combined with density functional theory (DFT) calculations. The structure of the approx. 0.5 nm thick oxide film has sixfold symmetry and exhibits holes with a diameter of approx. 400 pm reaching down to the metal substrate at the corners of the (Sqrt(67) x Sqrt(67))R12.2° unit cell. The side length of the unit cell is 4.1 nm. The driving force for the formation of the oxide nanomesh is the reduction of the metal/oxide interface energy by the formation of energetically favorable Al-Ni bonds at the interface. Due to better wetting of metal on metal surfaces than on oxide surfaces, metal atoms prefer to bind to the substrate in the hole, not to the oxide. Therefore the oxide forms a template with a hexagonal 4.1 nm lattice for the growth of well-ordered metal clusters. Nevertheless, the growth of most metal clusters on top of the corner holes is not straightforward. Fe and Co atoms cannot jump into the corner holes due to a barrier for diffusion and nucleate at their second favorable adsorption site. However, Pd atoms trapped in these corner holes reduce the barrier for diffusion and create metallic nucleation sites where Fe as well as Co clusters can nucleate and form a well-ordered hexagonal arrangement on the oxide nanomesh. We have studied these Fe and Co clusters and applied different methods like STM and surface x-ray diffraction (SXRD) to determine the morphology and crystallography of the clusters. For Fe we found cluster growth with

  4. Structural stability, acidity, and halide selectivity of the fluoride riboswitch recognition site

    Chawla, Mohit; Credendino, Raffaele; Poater, Albert; Oliva, Romina M.; Cavallo, Luigi

    2015-01-01

    Using static and dynamics DFT methods we show that the Mg2+/F-/phosphate/water cluster at the center of the fluoride riboswitch is stable by its own and, once assembled, does not rely on any additional factor from the overall RNA fold. Further, we predict that the pKa of the water molecule bridging two Mg cations is around 8.4. We also demonstrate that the halide selectivity of the fluoride riboswitch is determined by the stronger Mg-F bond, which is capable of keeping together the cluster. Replacing F- with Cl- results in a cluster that is unstable under dynamic conditions. Similar conclusions on the structure and energetics of the cluster in the binding pocket of fluoride-inhibited pyrophosphatase suggest that the peculiarity of fluoride is in its ability to establish much stronger metal-halide bonds.

  5. Structural stability, acidity, and halide selectivity of the fluoride riboswitch recognition site

    Chawla, Mohit

    2015-01-14

    Using static and dynamics DFT methods we show that the Mg2+/F-/phosphate/water cluster at the center of the fluoride riboswitch is stable by its own and, once assembled, does not rely on any additional factor from the overall RNA fold. Further, we predict that the pKa of the water molecule bridging two Mg cations is around 8.4. We also demonstrate that the halide selectivity of the fluoride riboswitch is determined by the stronger Mg-F bond, which is capable of keeping together the cluster. Replacing F- with Cl- results in a cluster that is unstable under dynamic conditions. Similar conclusions on the structure and energetics of the cluster in the binding pocket of fluoride-inhibited pyrophosphatase suggest that the peculiarity of fluoride is in its ability to establish much stronger metal-halide bonds.

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

    Erdem-Senatalar, A.; Blackmond, D.G.; Wender, I. (Pittsburgh Univ., PA (USA). Dept. of Chemical and Petroleum Engineering); Oukaci, R. (CERHYD, Algiers (Algeria))

    1988-01-01

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

  7. Low-energy electron collisions with metal clusters: Electron capture and cluster fragmentation

    Kresin, V.V.; Scheidemann, A.; Knight, W.D.

    1993-01-01

    The authors have carried out the first measurement of absolute cross sections for the interaction between electrons and size-resolved free metal clusters. Integral inelastic scattering cross sections have been determined for electron-Na n cluster collisions in the energy range from 0.1 eV to 30 eV. At energies ≤1 eV, cross sections increase with decreasing impact energies, while at higher energies they remain essentially constant. The dominant processes are electron attachment in the low-energy range, and collision-induced fragmentation at higher energies. The magnitude of electron capture cross sections can be quantitatively explained by the effect of the strong polarization field induced in the cluster by the incident electron. The cross sections are very large, reaching values of hundreds of angstrom 2 ; this is due to the highly polarizable nature of metal clusters. The inelastic interaction range for fragmentation collisions is also found to considerably exceed the cluster radius, again reflecting the long-range character of electron-cluster interactions. The important role played by the polarization interaction represents a bridge between the study of collision processes and the extensive research on cluster response properties. Furthermore, insight into the mechanisms of electron scattering is important for understanding production and detection of cluster ions in mass spectrometry and related processes

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

    Caldwell, Nelson; Schiavon, Ricardo; Morrison, Heather; Harding, Paul; Rose, James A.

    2011-01-01

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

  9. Different Approaches for the Calculation of Electronic Excited States of Nonstoichiometric Alkali Halide Clusters: The Example of Na3F

    Durand, G.; Heitz, M. C.; Spiegelman, F.; Meier, C.; Mitrić, R.; Bonačić-Koutecký, V.; Pittner, Jiří

    2004-01-01

    Roč. 121, č. 20 (2004), s. 9898-9905 ISSN 0021-9606 R&D Projects: GA AV ČR KSK4040110 Keywords : Wigner distribution approach * optical response properties * sodium - fluoride clusters Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.105, year: 2004

  10. Mass spectrometric production of heterogeneous metal clusters using Knudsen cell

    Veljković Filip M.

    2016-01-01

    Full Text Available Knudsen effusion mass spectrometry or high-temperature method of mass spectrometry for decades gives new information about saturated vapor of hardly volatile compounds and it is an important method in the discovery of many new molecules, radicals, ions and clusters present in the gas phase. Since pioneering works until now, this method has been successfully applied to a large number of systems (ores, oxides, ceramics, glass materials, borides, carbides, sulfides, nitrates, metals, fullerenes, etc which led to the establishment of various research branches such as chemistry of clusters. This paper describes the basic principles of Knudsen cell use for both identification of chemical species created in the process of evaporation and determination of their ionization energies. Depending on detected ions intensities and the partial pressure of each gaseous component, as well as on changes in partial pressure with temperature, Knudsen cell mass spectrometry enables the determination of thermodynamic parameters of the tested system. A special attention is paid to its application in the field of small heterogeneous and homogeneous clusters of alkali metals. Furthermore, experimental results for thermodynamic parameters of some clusters, as well as capabilities of non-standard ways of using Knudsen cells in the process of synthesis of new clusters are presented herein. [Projekat Ministarstva nauke Republike Srbije, br. 172019

  11. Even-Odd Differences and Shape Deformation of Metal Clusters

    Hidetoshi, Nishioka; Yoshio, Takahashi; Department of Physics, Konan University; Faculty of General Education, Yamagata University

    1994-01-01

    The relation between even-odd difference of metal cluster and the deformation of equilibrium shape is studied in terms of two different models; (i) tri-axially deformed harmonic oscillator model, (ii) rectangular box model. Having assumed the matter density ρ kept constant for different shapes of a cluster, we can determine the equilibrium shape both for the two models. The enhancement of HOMO-LUMO gap is obtained and it is ascribed to Jahn-Teller effect. Good agreement of the calculated resu...

  12. Clusters of atoms and molecules theory, experiment, and clusters of atoms

    1994-01-01

    Clusters of Atoms and Molecules is devoted to theoretical concepts and experimental techniques important in the rapidly expanding field of cluster science. Cluster properties are dicussed for clusteres composed of alkali metals, semiconductors, transition metals, carbon, oxides and halides of alkali metals, rare gases, and neutral molecules. The book is composed of several well-integrated treatments all prepared by experts. Each contribution starts out as simple as possible and ends with the latest results so that the book can serve as a text for a course, an introduction into the field, or as a reference book for the expert.

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

    Ogut, Serdar [Univ. of Illinois, Chicago, IL (United States)

    2017-09-11

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

  14. Reactivity of halide and pseudohalide ligands

    Kukushkin, Yu.N.

    1987-01-01

    Reactivity of halide and pseudohalide (cyanide, azide, thiocyanate, cyanate) ligands tending to form bridge bonds in transition metal (Re, Mo, W) complexes is considered. Complexes where transition metal salts are ligands of other, complex-forming ion, are described. Transformation of innerspheric pseudohalide ligands is an important way of directed synthesis of these metal coordination compounds

  15. Scattering of ultrashort electromagnetic pulses on metal clusters

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

    2016-01-01

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

  16. Scattering of ultrashort electromagnetic pulses on metal clusters

    Astapenko, V. A., E-mail: astval@mail.ru; Sakhno, S. V. [Moscow Institute of Physics and Technology (State University) (Russian Federation)

    2016-12-15

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

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

    Cockcroft, Robert; Harris, William E.; Wehner, Elizabeth M. H.; Whitmore, Bradley C.; Rothberg, Barry

    2009-01-01

    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 ∼ M 0.30±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.

  18. Metal clusters on supported argon layers; Metallcluster auf dielektrischen Substraten

    Faber, Bernhard

    2011-10-21

    The deposition of small sodium clusters on supported Ar(001)-surfaces is simulated. Theoretical description is achieved by a hierarchical model consisting of time-dependent DFT and molecular dynamics. The valence electrons of the sodium atoms are considered by Kohn-Sham-Scheme with self interaction correction. The interaction of argon atoms and sodium ions is described by atom-atom potentials whereas the coupling to the QM electrons is done by local pseudo-potentials. A decisive part of the model is the dynamical polarizability of the rare-gas atoms. The optional metal support is considered by the method of image charges. The influence of the forces caused by image charges and the influence of the number of argon monolayers on structure, optical response and deposition dynamics of Na{sub 6} and Na{sub 8} is investigated. There is very little influence on cluster structure and only a small shift of the cluster perpendicular to the surface. Concerning optical response the position of the Mie plasmon peak stays robust whereas the details of spectral fragmentation react very sensitively to changes. The forces caused by image charges of the metal support play only a little role with the dynamics of deposition while the thickness of the argon surface strongly influences the dissipation. (orig.)

  19. The gas phase emitter effect of lanthanum within ceramic metal halide lamps and its dependence on the La vapor pressure and operating frequency

    Ruhrmann, C.; Hoebing, T.; Bergner, A.; Groeger, S.; Awakowicz, P.; Mentel, J. [Electrical Engineering and Plasma Technology, Ruhr University Bochum, D-44780 Bochum (Germany); Denissen, C.; Suijker, J. [Philips Lighting, Category Professional Lamps, P.O. Box 80020, NL-5600JM Eindhoven (Netherlands)

    2015-08-07

    The gas phase emitter effect increases the lamp lifetime by lowering the work function and, with it, the temperature of the tungsten electrodes of metal halide lamps especially for lamps in ceramic vessels due to their high rare earth pressures. It is generated by a monolayer on the electrode surface of electropositive atoms of certain emitter elements, which are inserted into the lamp bulb by metal iodide salts. They are vaporized, dissociated, ionized, and deposited by an emitter ion current onto the electrode surface within the cathodic phase of lamp operation with a switched-dc or ac-current. The gas phase emitter effect of La and the influence of Na on the emitter effect of La are studied by spatially and phase-resolved pyrometric measurements of the electrode tip temperature, La atom, and ion densities by optical emission spectroscopy as well as optical broadband absorption spectroscopy and arc attachment images by short time photography. An addition of Na to the lamp filling increases the La vapor pressure within the lamp considerably, resulting in an improved gas phase emitter effect of La. Furthermore, the La vapor pressure is raised by a heating of the cold spot. In this way, conditions depending on the La vapor pressure and operating frequency are identified, at which the temperature of the electrodes becomes a minimum.

  20. NMR in metal cluster compounds compared to glasses

    Staveren, M.P.J. van; Brom, H.B.; Jongh, L.J. de; Schmid, G.

    1991-01-01

    The field and temperature dependence of the 31 P nuclear spin lattice relaxation rate in the metal cluster compound Ru 55 (P(t-Bu) 3 ) 12 Cl 20 follows a power law: 1/T 1 ∝ T n B -m , with n = 1.5 ± 0.1 at 3.25 T and n = 1.3 ± 0.1 at 6.45 T; m ≅ 1.4. Such dependences have so far only been observed in inorganic glasses and been attributed to two level systems. The correspondence suggests that the relaxation rate is due to interaction of the P-nuclear moment with electronic spins of stochastically moving charge carriers, which are thought to be responsible for the electrical conductivity through hopping between neigboring cluster molecules. (orig.)

  1. Experimental observations on the competing effect of tetrahydrofuran and an electrolyte and the strength of hydrate inhibition among metal halides in mixed CO{sub 2} hydrate equilibria

    Sabil, Khalik M., E-mail: khalik_msabil@petronas.com.m [Delft University of Technology, Laboratory of Process Equipment, Mechanical, Maritime and Materials Engineering, Leeghwaterstraat 44, 2628 CA Delft (Netherlands); Universiti Teknologi PETRONAS, Chemical Engineering Programme, Bandar Seri Iskandar, 31750 Tronoh, Perak (Malaysia); Roman, Vicente R.; Witkamp, Geert-Jan [Delft University of Technology, Laboratory of Process Equipment, Mechanical, Maritime and Materials Engineering, Leeghwaterstraat 44, 2628 CA Delft (Netherlands); Peters, Cor J., E-mail: C.J.Peters@tudelft.n [Delft University of Technology, Laboratory of Process Equipment, Mechanical, Maritime and Materials Engineering, Leeghwaterstraat 44, 2628 CA Delft (Netherlands); Petroleum Institute, Chemical Engineering Program, Bu Hasa Building, Room 2207A, P.O. Box 2533, Abu Dhabi (United Arab Emirates)

    2010-03-15

    In the present work, experimental data on the equilibrium conditions of mixed CO{sub 2} and THF hydrates in aqueous electrolyte solutions are reported. Seven different electrolytes (metal halides) were used in this work namely sodium chloride (NaCl), calcium chloride (CaCl{sub 2}), magnesium chloride (MgCl{sub 2}), potassium bromide (KBr), sodium fluoride (NaF), potassium chloride (KCl), and sodium bromide (NaBr). All equilibrium data were measured by using Cailletet apparatus. Throughout this work, the overall concentration of CO{sub 2} and THF were kept constant at (0.04 and 0.05) mol fraction, respectively, while the concentration of electrolytes were varied. The experimental temperature ranged from (275 to 305) K and pressure up 7.10 MPa had been applied. From the experimental results, it is concluded that THF, which is soluble in water is able to suppress the salt inhibiting effect in the range studied. In all quaternary systems studied, a four-phase hydrate equilibrium line was observed where hydrate (H), liquid water (L{sub W}), liquid organic (L{sub V}), and vapour (V) exist simultaneously at specific pressure and temperature. The formation of this four-phase equilibrium line is mainly due to a liquid-liquid phase split of (water + THF) mixture when pressurized with CO{sub 2} and the split is enhanced by the salting-out effect of the electrolytes in the quaternary system. The strength of hydrate inhibition effect among the electrolytes was compared. The results shows the hydrate inhibiting effect of the metal halides is increasing in the order NaF < KBr < NaCl < NaBr < CaCl{sub 2} < MgCl{sub 2}. Among the cations studied, the strength of hydrate inhibition increases in the following order: K{sup +} < Na{sup +} < Ca{sup 2+} < Mg{sup 2+}. Meanwhile, the strength of hydrate inhibition among the halogen anion studied decreases in the following order: Br{sup -} > Cl{sup -} > F{sup -}. Based on the results, it is suggested that the probability of formation and

  2. Experimental observations on the competing effect of tetrahydrofuran and an electrolyte and the strength of hydrate inhibition among metal halides in mixed CO2 hydrate equilibria

    Sabil, Khalik M.; Roman, Vicente R.; Witkamp, Geert-Jan; Peters, Cor J.

    2010-01-01

    In the present work, experimental data on the equilibrium conditions of mixed CO 2 and THF hydrates in aqueous electrolyte solutions are reported. Seven different electrolytes (metal halides) were used in this work namely sodium chloride (NaCl), calcium chloride (CaCl 2 ), magnesium chloride (MgCl 2 ), potassium bromide (KBr), sodium fluoride (NaF), potassium chloride (KCl), and sodium bromide (NaBr). All equilibrium data were measured by using Cailletet apparatus. Throughout this work, the overall concentration of CO 2 and THF were kept constant at (0.04 and 0.05) mol fraction, respectively, while the concentration of electrolytes were varied. The experimental temperature ranged from (275 to 305) K and pressure up 7.10 MPa had been applied. From the experimental results, it is concluded that THF, which is soluble in water is able to suppress the salt inhibiting effect in the range studied. In all quaternary systems studied, a four-phase hydrate equilibrium line was observed where hydrate (H), liquid water (L W ), liquid organic (L V ), and vapour (V) exist simultaneously at specific pressure and temperature. The formation of this four-phase equilibrium line is mainly due to a liquid-liquid phase split of (water + THF) mixture when pressurized with CO 2 and the split is enhanced by the salting-out effect of the electrolytes in the quaternary system. The strength of hydrate inhibition effect among the electrolytes was compared. The results shows the hydrate inhibiting effect of the metal halides is increasing in the order NaF 2 2 . Among the cations studied, the strength of hydrate inhibition increases in the following order: K + + 2+ 2+ . Meanwhile, the strength of hydrate inhibition among the halogen anion studied decreases in the following order: Br - > Cl - > F - . Based on the results, it is suggested that the probability of formation and the strength of ionic-hydrogen bond between an ion and water molecule and the effects of this bond on the ambient water

  3. Electronic structure of vacancies and vacancy clusters in simple metals

    Manninen, M.; Nieminen, R.M.

    1978-05-01

    The self-consistent density functional approach has been applied in a study of electronic properties of vacancies and vacancy clusters in simple metals. The electron density profiles and potentials have been obtained for spherical voids of varying size. The formation energies and residual resistivities have been calculated for vacancies using both perturbational and variational inclusion of discrete lattice effects. The relation of the void properties to the plane surface ones is studied, and the inadequacy of the jellium-based methods to high-index faces is demonstrated. (author)

  4. Damage clustering in metals: Importance, advances and challenges

    Nordlund, K.; Sand, A.E.; Granberg, F.; Levo, E.; Djurabekova, F.

    2016-01-01

    The damage produced in metals has traditionally been primarily characterized in terms of the total damage production, which typically is first estimated with the dpa number. As discussed in previous meetings of this CRP, the dpa is not actually very well suited for typical dense metals, since the number it gives is typically about 3 times larger than the number of actual defects produced, and 30 times smaller than the actual number of defects produced. Hence we developed the improved arc-dpa and rpa standards, that give in a simple analytical form a defect number that does correspond well to MD and experimental data. Section 2 summarizes the development of the arc-dpa and rpa standards. In sections 3 and 4 we discuss the role of damage clustering in damage production

  5. Spectra of matrix isolated metal atoms and clusters

    Meyer, B.

    1977-01-01

    The matrix isolation spectra of all of the 40 presently known atomic metal species show strong matrix effects. The transition energies are increased, and the bands are broad and exhibit splitting of sublevels which are degenerate in the gas phase. Several models have been proposed for splitting of levels, but basic effects are not yet understood, and spectra cannot be predicted, yet it is possible to correlate gas phase and matrix in many of the systems. Selective production of diatomics and clusters via thermal and optical annealing of atomic species can be monitored by optical spectra, but yields spectroscopically complex systems which, however, especially in the case of transition metals, can be used as precursors in novel chemical reactions. A combination of absorption, emission, ir, Raman, ESR, and other methods is now quickly yielding data which will help correlate the increasing wealth of existing data. 55 references, 6 figures

  6. Tuning aromaticity in trigonal alkaline earth metal clusters and their alkali metal salts.

    Jiménez-Halla, J Oscar C; Matito, Eduard; Blancafort, Lluís; Robles, Juvencio; Solà, Miquel

    2009-12-01

    In this work, we analyze the geometry and electronic structure of the [X(n)M(3)](n-2) species (M = Be, Mg, and Ca; X = Li, Na, and K; n = 0, 1, and 2), with special emphasis on the electron delocalization properties and aromaticity of the cyclo-[M(3)](2-) unit. The cyclo-[M(3)](2-) ring is held together through a three-center two-electron bond of sigma-character. Interestingly, the interaction of these small clusters with alkali metals stabilizes the cyclo-[M(3)](2-) ring and leads to a change from sigma-aromaticity in the bound state of the cyclo-[M(3)](2-) to pi-aromaticity in the XM(3) (-) and X(2)M(3) metallic clusters. Our results also show that the aromaticity of the cyclo-[M(3)](2-) unit in the X(2)M(3) metallic clusters depends on the nature of X and M. Moreover, we explored the possibility for tuning the aromaticity by simply moving X perpendicularly to the center of the M(3) ring. The Na(2)Mg(3), Li(2)Mg(3), and X(2)Ca(3) clusters undergo drastic aromaticity alterations when changing the distance from X to the center of the M(3) ring, whereas X(2)Be(3) and K(2)Mg(3) keep its aromaticity relatively constant along this process. (c) 2009 Wiley Periodicals, Inc.

  7. Order and chaos in nuclear and metal cluster deformation

    Radu, S.

    1995-08-01

    The vast amount of nuclear and metal cluster data indicates that shell structure and deformation are two simultaneous properties. A conflicting situation is therefore encountered as the shell structure, a firm expression of order, is apparently not compatible with the non-integrable nature of the models incorporating deformation. The main issue covered in this thesis is the intricate connection between deformation and chaotic behaviour in deformation models pertinent to nuclear structure and metal cluster physics. It is shown that, at least in some cases, it is possible to reconcile the occurrence of shell structure with non-integrability. The coupling of an axially deformed harmonic oscillator to an axially symmetric octupole term renders the problem non-integrable. The chaotic character of the motion is strongly dependent on the type of deformation, in that a prolate shape shows virtually no chaos, while in an oblate case the motion exhibits fully developed chaos when the octupole term is switched on. Whereas the problem is non-integrable, the quantum mechanical spectrum nevertheless shows some shell structure in the prolate case for particular, yet fairly large octupole strengths; for spherical or oblate deformation the shell structure disappears. This result is explained in terms of classical periodic orbits which are found by employing the 'removal of resonances method'. Particular emphasis is put on the effect of the hexadecapole deformation which is important in fission processes. The combined effect of octupole and hexadecapole deformation leads to important conclusions for the experimental work as a high degree of ambiguity is signaled for the interpretation of data. The ambiguity results from the discovery of a mutual cancellation of the octupole and hexadecapole deformation in prolate superdeformed systems. The phenomenological Nilsson model is treated in a similar way. It is argued that while in nuclei it produces good results for the low-lying levels

  8. Sulphur in the metal poor globular cluster NGC 6397

    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.

  9. Structure and Mobility of Metal Clusters in MOFs: Au, Pd, and AuPd Clusters in MOF-74

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

    2012-01-01

    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......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 Au8, Pd8, and Au4Pd4 we find that the organic part of the MOF...

  10. APPARATUS FOR THE PRODUCTION OF LITHIUM METAL

    Baker, P.S.; Duncan, F.R.; Greene, H.B.

    1961-08-22

    Methods and apparatus for the production of high-purity lithium from lithium halides are described. The apparatus is provided for continuously contacting a molten lithium halide with molten barium, thereby forming lithium metal and a barium halide, establishing separate layers of these reaction products and unreacted barium and lithium halide, and continuously withdrawing lithium and barium halide from the reaction zone. (AEC)

  11. CHARGE-TRANSFER SATELLITES AND MULTIPLET SPLITTING IN X-RAY PHOTOEMISSION SPECTRA OF LATE TRANSITION-METAL HALIDES

    OKADA, K; KOTANI, A; THOLE, BT

    1992-01-01

    Core-level X-ray photoemission spectra (XPS) are calculated for Ni and Co dihalides with an MX6 cluster model (M = Ni, Co; X = F, Cl, Br), where intra-atomic multiplet coupling as well as covalency mixing is taken into account. The effects of the intra-atomic configuration interaction between

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

    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.

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

    Belloni, J

    1998-11-01

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

  14. Organic-inorganic perovskites containing trivalent metal halide layers: the templating influence of the organic cation layer.

    Mitzi, D B

    2000-12-25

    Thin sheetlike crystals of the metal-deficient perovskites (H2AEQT)M2/3I4 [M = Bi or Sb; AEQT = 5,5"'-bis-(aminoethyl)-2,2':5',2'':5'',2'''-quaterthiophene] were formed from slowly cooled ethylene glycol/2-butanol solutions containing the bismuth(III) or antimony(III) iodide and AEQT.2HI salts. Each structure was refined in a monoclinic (C2/m) subcell, with the lattice parameters a = 39.712(13) A, b = 5.976(2) A, c = 6.043(2) A, beta = 92.238(5) degrees, and Z = 2 for M = Bi and a = 39.439(7) A, b = 5.952(1) A, c = 6.031(1) A, beta = 92.245(3) degrees, and Z = 2 for M = Sb. The trivalent metal cations locally adopt a distorted octahedral coordination, with M-I bond lengths ranging from 3.046(1) to 3.218(3) A (3.114 A average) for M = Bi and 3.012(1) to 3.153(2) A (3.073 A average) for M = Sb. The new organic-inorganic hybrids are the first members of a metal-deficient perovskite family consisting of (Mn+)2/nV(n-2)/nX4(2-) sheets, where V represents a vacancy (generally left out of the formula) and the metal cation valence, n, is greater than 2. The organic layers in the AEQT-based organic-inorganic hybrids feature edge-to-face aromatic interactions among the rigid, rodlike quaterthiophene moieties, which may help to stabilize the unusual metal-deficient layered structures.

  15. Electroless deposition of metal nanoparticle clusters: Effect of pattern distance

    Gentile, Francesco

    2014-04-03

    Electroless plating is a deposition technique in which metal ions are reduced as atoms on specific patterned sites of a silicon surface to form metal nanoparticles (NPs) aggregates with the desired characteristics. Those NPs, in turn, can be used as constituents of surface enhanced Raman spectroscopy substrates, which are devices where the electromagnetic field and effects thereof are giantly amplified. Here, the electroless formation of nanostructures was studied as a function of the geometry of the substrate. High resolution, electron beam lithography techniques were used to obtain nonperiodic arrays of circular patterns, in which the spacing of patterns was varied over a significant range. In depositing silver atoms in those circuits, the authors found that the characteristics of the aggregates vary with the pattern distance. When the patterns are in close proximity, the interference of different groups of adjacent aggregates cannot be disregarded and the overall growth is reduced. Differently from this, when the patterns are sufficiently distant, the formation of metal clusters of NPs is independent on the spacing of the patterns. For the particular subset of parameters used here, this critical correlation distance is about three times the pattern diameter. These findings were explained within the framework of a diffusion limited aggregation model, which is a simulation method that can decipher the formation of nanoaggregates at an atomic level. In the discussion, the authors showed how this concept can be used to fabricate ordered arrays of silver nanospheres, where the size of those spheres may be regulated on varying the pattern distance, for applications in biosensing and single molecule detection.

  16. Electroless deposition of metal nanoparticle clusters: Effect of pattern distance

    Gentile, Francesco; Laura Coluccio, Maria; Candeloro, Patrizio; Barberio, Marianna; Perozziello, Gerardo; Francardi, Marco; Di Fabrizio, Enzo M.

    2014-01-01

    Electroless plating is a deposition technique in which metal ions are reduced as atoms on specific patterned sites of a silicon surface to form metal nanoparticles (NPs) aggregates with the desired characteristics. Those NPs, in turn, can be used as constituents of surface enhanced Raman spectroscopy substrates, which are devices where the electromagnetic field and effects thereof are giantly amplified. Here, the electroless formation of nanostructures was studied as a function of the geometry of the substrate. High resolution, electron beam lithography techniques were used to obtain nonperiodic arrays of circular patterns, in which the spacing of patterns was varied over a significant range. In depositing silver atoms in those circuits, the authors found that the characteristics of the aggregates vary with the pattern distance. When the patterns are in close proximity, the interference of different groups of adjacent aggregates cannot be disregarded and the overall growth is reduced. Differently from this, when the patterns are sufficiently distant, the formation of metal clusters of NPs is independent on the spacing of the patterns. For the particular subset of parameters used here, this critical correlation distance is about three times the pattern diameter. These findings were explained within the framework of a diffusion limited aggregation model, which is a simulation method that can decipher the formation of nanoaggregates at an atomic level. In the discussion, the authors showed how this concept can be used to fabricate ordered arrays of silver nanospheres, where the size of those spheres may be regulated on varying the pattern distance, for applications in biosensing and single molecule detection.

  17. Lasagna-type arrays with halide-nitromethane cluster filling. The first recognition of the Hal(-)···HCH2NO2 (Hal = Cl, Br, I) hydrogen bonding.

    Gushchin, Pavel V; Kuznetsov, Maxim L; Wang, Qian; Karasik, Andrey A; Haukka, Matti; Starova, Galina L; Kukushkin, Vadim Yu

    2012-06-21

    The previously predicted ability of the methyl group of nitromethane to form hydrogen bonding with halides is now confirmed experimentally based on X-ray data of novel nitromethane solvates followed by theoretical ab initio calculations at the MP2 level of theory. The cationic (1,3,5-triazapentadiene)Pt(II) complexes [Pt{HN=C(NC(5)H(10))N(Ph)C(NH(2))=NPh}(2)](Cl)(2), [1](Hal)(2) (Hal = Cl, Br, I), and [Pt{HN=C(NC(4)H(8)O)N(Ph)C(NH(2))=NPh}(2)](Cl)(2), [2](Cl)(2), were crystallized from MeNO(2)-containing systems providing nitromethane solvates studied by X-ray diffraction. In the crystal structure of [1][(Hal)(2)(MeNO(2))(2)] (Hal = Cl, Br, I) and [2][(Cl)(2)(MeNO(2))(2)], the solvated MeNO(2) molecules occupy vacant spaces between lasagna-type layers and connect to the Hal(-) ion through a weak hydrogen bridge via the H atom of the methyl thus forming, by means of the Hal(-)···HCH(2)NO(2) contact, the halide-nitromethane cluster "filling". The quantum-chemical calculations demonstrated that the short distance between the Hal(-) anion and the hydrogen atom of nitromethane in clusters [1][(Hal)(2)(MeNO(2))(2)] and [2][(Cl)(2)(MeNO(2))(2)] is not just a consequence of the packing effect but a result of the moderately strong hydrogen bonding.

  18. Dislocation unpinning model of acoustic emission from alkali halide ...

    The present paper reports the dislocation unpinning model of acoustic emis- sion (AE) from ... Acoustic emission; dislocation; alkali halide crystals; plastic deformation. ..... [5] T Nishimura, A Tahara and T Kolama, Jpn. Metal Inst. 64, 339 (2000).

  19. Entrapment of metal clusters in metal-organic framework channels by extended hooks anchored at open metal sites.

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

    2013-07-17

    Reported here are the new concept of utilizing open metal sites (OMSs) for architectural pore design and its practical implementation. Specifically, it is shown here that OMSs can be used to run extended hooks (isonicotinates in this work) from the framework walls to the channel centers to effect the capture of single metal ions or clusters, with the concurrent partitioning of the large channel spaces into multiple domains, alteration of the host-guest charge relationship and associated guest-exchange properties, and transfer of OMSs from the walls to the channel centers. The concept of the extended hook, demonstrated here in the multicomponent dual-metal and dual-ligand system, should be generally applicable to a range of framework types.

  20. Magnetic properties of free alkali and transition metal clusters

    Heer, W. de; Milani, P.; Chatelain, A.

    1991-01-01

    The Stern-Gerlach deflections of small alkali clusters (N<6) and iron clusters (10< N<500) show that the paramagnetic alkali clusters always have a nondeflecting component, while the iron clusters always deflect in the high field direction. Both of these effects appear to be related to spin relaxation however in the case of alkali clusters it is shown that they are in fact caused by avoided level crossing in the Zeeman diagram. For alkali clusters the relatively weak couplings cause reduced magnetic moments where levels cross. For iron clusters however the total spin is strongly coupled to the molecular framework. Consequently this coupling is responsible for avoided level crossing which ultimately cause the total energy of the cluster to decrease with increasing magnetic field so that the iron clusters will deflect in one direction when introduced in an inhomogeneous magnetic field. Experiment and theory are discussed for both cases. (orig.)

  1. Plasmon resonances in large noble-metal clusters

    Soennichsen, C; Franzl, T; Wilk, T; Plessen, G von; Feldmann, J

    2002-01-01

    We investigate the optical properties of spherical gold and silver clusters with diameters of 20 nm and larger. The light scattering spectra of individual clusters are measured using dark-field microscopy, thus avoiding inhomogeneous broadening effects. The dipolar plasmon resonances of the clusters are found to have nearly Lorentzian line shapes. With increasing size we observe polaritonic red-shifts of the plasmon line and increased radiation damping for both gold and silver clusters. Apart from some cluster-to-cluster variations of the plasmon lines, agreement with Mie theory is reasonably good for the gold clusters. However, it is less satisfactory for the silver clusters, possibly due to cluster faceting or chemical effects

  2. Shell structures and chaos in nuclei and large metallic clusters

    Heiss, W.D.; University of the Witwatersrand, Johannesburg; Nazmitdinov, R.G.; Radu, S.; University of the Witwatersrand, Johannesburg

    1995-01-01

    A reflection-asymmetric deformed oscillator potential is analyzed from the classical and quantum mechanical point of view. The connection between occurrence of shell structures and classical periodic orbits is studied using the ''removal of resonances method'' in a classical analysis. In this approximation, the effective single particle potential becomes separable and the frequencies of the classical trajectories are easily determined. It turns out that the winding numbers calculated in this way are in good agreement with the ones found from the corresponding quantum mechanical spectrum using the particle number dependence of the fluctuating part of the total energy. When the octupole term is switched on it is found that prolate shapes are stable against chaos and can exhibit shells where spherical and oblate cases become chaotic. An attempt is made to explain this difference in the quantum mechanical context by looking at the distribution of exceptional points which results from the matrix structure of the respective Hamiltonians. In a similar way we analyze the modified Nilsson model and discuss its consequences for metallic clusters. (orig.)

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

    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.

  4. Entropy in halide perovskites

    Katan, Claudine; Mohite, Aditya D.; Even, Jacky

    2018-05-01

    Claudine Katan, Aditya D. Mohite and Jacky Even discuss the possible impact of various entropy contributions (stochastic structural fluctuations, anharmonicity and lattice softness) on the optoelectronic properties of halide perovskite materials and devices.

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

    Vlček, L.; Uhlík, F.; Moučka, F.; Nezbeda, Ivo; Chialvo, L.

    2015-01-01

    Roč. 119, č. 3 (2015), s. 488-500 ISSN 1089-5639 Institutional support: RVO:67985858 Keywords : monte-carlo simulations * molecular-dynamic simulations * classical drude oscillators Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.883, year: 2015

  6. Magnetic behavior of clusters of ferromagnetic transition metals

    Khanna, S. N.; Linderoth, Søren

    1991-01-01

    The effective magnetic moments of small iron and cobalt clusters have been calculated by assuming that the clusters undergo superparamagnetic relaxation. The effective moments per atom are found to be much below the bulk values, even at low temperatures (100 K). They increase with particle size a...... moments in small clusters compared to bulk as being due to melting of surface spins....

  7. Chemisorption on size-selected metal clusters: activation barriers and chemical reactions for deuterium and aluminum cluster ions

    Jarrold, M.F.; Bower, J.E.

    1988-01-01

    The authors describe a new approach to investigating chemisorption on size-selected metal clusters. This approach involves investigating the collision-energy dependence of chemisorption using low-energy ion beam techniques. The method provides a direct measure of the activation barrier for chemisorption and in some cases an estimate of the desorption energy as well. They describe the application of this technique to chemisorption of deuterium on size-selected aluminum clusters. The activation barriers increase with cluster size (from a little over 1 eV for Al 10 + to around 2 eV for Al 27 + ) and show significant odd-even oscillations. The activation barriers for the clusters with an odd number of atoms are larger than those for the even-numbered clusters. In addition to chemisorption of deuterium onto the clusters, chemical reactions were observed, often resulting in cluster fragmentation. The main products observed were Al/sub n-1/D + , Al/sub n-2/ + , and Al + for clusters with n + and Al/sub n-1/D + for the larger clusters

  8. Investigating the gas phase emitter effect of caesium and cerium in ceramic metal halide lamps in dependence on the operating frequency

    Ruhrmann, C; Westermeier, M; Bergner, A; Awakowicz, P; Mentel, J [Ruhr University Bochum, Electrical Engineering and Plasma Technology, D-44780 Bochum (Germany); Luijks, G M J F, E-mail: juergen.mentel@ruhr-uni-bochum.de [Philips Lighting, GBU HID, PO box 80020, 5600JM Eindhoven (Netherlands)

    2011-09-07

    The work function and with it the temperature of tungsten electrodes in HID lamps can be lowered and the lifetime of lamps increased by the gas phase emitter effect. A determination of the emitter effect of Cs and Ce is performed by phase resolved measurements of the electrode tip temperature T{sub tip}({psi}), plasma temperature T{sub pl}({psi}) and particle densities N({psi}) by means of pyrometric, optical emission and broadband absorption spectroscopy in dependence on the operating frequency. The investigated HID lamps are ceramic metal halide lamps with transparent discharge vessels made of YAG, filled with a buffer gas consisting of Ar, Kr and predominantly Hg and seeded with CsI or CeI{sub 3}. In the YAG lamp seeded with CsI and CeI{sub 3} as well as in a YAG lamp seeded with DyI{sub 3} (corresponding results can be found in a preceding paper) a gas phase emitter effect is observed in the cathodic phase due to a Cs, Ce or Dy ion current. In the YAG lamp seeded with CsI the phase averaged coverage of the electrode surface with emitter atoms decreases and the electrode temperature rises with increasing frequency, whereas the emitter effect of Ce and Dy is extended to the anodic phase, which leads to a decreased average temperature T{sub tip}({psi}) with increasing frequency. This different behaviour of the averaged values of T{sub tip}({psi}) for increasing frequency is caused by the differing adsorption energies E{sub a} of the respective emitter materials. In spite of the influence of E{sub a} on the coverage of the electrode with emitter atoms, the cathodic gas phase emitter effect produces in the YAG lamps seeded with CsI, CeI{sub 3} and DyI{sub 3} a general reduction in the electrode tip temperature T{sub tip}({psi}) in comparison with a YAG lamp with Hg filling only.

  9. Photodynamic therapy using a novel irradiation source, LED lamp, is similarly effective to photodynamic therapy using diode laser or metal-halide lamp on DMBA- and TPA-induced mouse skin papillomas.

    Takahashi, Hidetoshi; Nakajima, Susumu; Ogasawara, Koji; Asano, Ryuji; Nakae, Yoshinori; Sakata, Isao; Iizuka, Hajime

    2014-08-01

    Photodynamic therapy (PDT) is useful for superficial skin tumors such as actinic keratosis and Bowen disease. Although PDT is non-surgical and easily-performed treatment modality, irradiation apparatus is large and expensive. Using 7, 12-dimethylbenz[a]anthracene (DMBA) and 12-ο-tetradecanoylphorbol-13-acetate (TPA)-induced mouse skin papilloma model, we compared the efficacy of TONS501- and ALA-PDT with a LED lamp, a diode laser lamp or a metal-halide lamp on the skin tumor regression. TONS501-PDT using 660 nm LED lamp showed anti-tumor effect at 1 day following the irradiation and the maximal anti-tumor effect was observed at 3 days following the irradiation. There was no significant difference in the anti-tumor effects among TONS501-PDT using LED, TONS501-PDT using diode laser, and 5-aminolevulinic acid hydrochloride (ALA)-PDT using metal-halide lamp. Potent anti-tumor effect on DMBA- and TPA-induced mouse skin papilloma was observed by TONS501-PDT using 660 nm LED, which might be more useful for clinical applications. © 2014 Japanese Dermatological Association.

  10. Living Colloidal Metal Particles from Solvated Metal Atoms. Clustering of Metal Atoms in Organic Media 15.

    1986-09-23

    attributed to these solutions, especially toward heart disease. And in 1618 Antoni published Panacea Aurea : Auro Potabile 4 which centered on the...probably a slow process (discussed next under the electrophoresis section ). Electrophoresis: Electrophoresis, the movement of charged particles in...electrical properties. Experimental Section Preparation of a Typical Au-Acetone Colloid The metal atom reactor has been described previo sly. 3 9 ’ 5 9 ’ 6 0

  11. Size dependent magnetism of mass selected deposited transition metal clusters

    Lau, T.

    2002-05-01

    The size dependent magnetic properties of small iron clusters deposited on ultrathin Ni/Cu(100) films have been studied with circularly polarised synchrotron radiation. For X-ray magnetic circular dichroism studies, the magnetic moments of size selected clusters were aligned perpendicular to the sample surface. Exchange coupling of the clusters to the ultrathin Ni/Cu(100) film determines the orientation of their magnetic moments. All clusters are coupled ferromagnetically to the underlayer. With the use of sum rules, orbital and spin magnetic moments as well as their ratios have been extracted from X-ray magnetic circular dichroism spectra. The ratio of orbital to spin magnetic moments varies considerably as a function of cluster size, reflecting the dependence of magnetic properties on cluster size and geometry. These variations can be explained in terms of a strongly size dependent orbital moment. Both orbital and spin magnetic moments are significantly enhanced in small clusters as compared to bulk iron, although this effect is more pronounced for the spin moment. Magnetic properties of deposited clusters are governed by the interplay of cluster specific properties on the one hand and cluster-substrate interactions on the other hand. Size dependent variations of magnetic moments are modified upon contact with the substrate. (orig.)

  12. Comparison between XAS, AWAXS and DAFS applied to nanometer scale supported metallic clusters. Pt.1; monometallic clusters

    Bazin, D.C.; Sayers, D.A.

    1993-01-01

    The structural information found using three techniques related to synchrotron radiation are compared. XAS (X-ray Absorption Spectroscopy), AWAXS (Anomalous Wide Angle X-ray Scattering) and DAFS (Diffraction Anomalous Fine Structure) are applied to nanometer scale metallic clusters. (author)

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

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

    2018-02-01

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

  14. The influence of nanoscale morphology on the resistivity of cluster-assembled nanostructured metallic thin films

    Barborini, E; Bertolini, G; Repetto, P; Leccardi, M; Vinati, S; Corbelli, G; Milani, P

    2010-01-01

    We have studied in situ the evolution of the electrical resistivity of Fe, Pd, Nb, W and Mo cluster-assembled films during their growth by supersonic cluster beam deposition. We observed resistivity of cluster-assembled films several orders of magnitude larger than the bulk, as well as an increase in resistivity by increasing the film thickness in contrast to what was observed for atom-assembled metallic films. This suggests that the nanoscale morphological features typical of ballistic films growth, such as the minimal cluster-cluster interconnection and the evolution of surface roughness with thickness, are responsible for the observed behaviour.

  15. Mass spectrometric probes of metal cluster distributions and metastable ion decay

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

    1988-01-01

    The study of metal clusters has provided both an opportunity and a challenge to the application of mass spectrometry. These days the most often-used technique for cluster generation - laser vaporization - leads to extensive distributions of cluster sizes, from one to perhaps thousands of atoms, and most studies reported to date use excimer laser ionization and time-of-flight mass spectrometry for cluster detection. Our apparatus is a simple one-stage TOF design employing Wiley-McLauren spatial focusing and a one-meter drift tube. In a second apparatus employing a pulsed valve in the cluster source, we see asymmetric broadening of niobium cluster mass peaks under multiphoton ionization conditions, indicating metastable decay of parent cluster ions. Other studies of niobium clusters have shown no such asymmetric peaks. 2 figs

  16. Energy Characteristics of Small Metal Clusters Containing Vacancies

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

    2018-02-01

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

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

    NONE

    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.

  18. Properties and origin of the old, metal rich, star cluster, NGC 6791

    Carraro, Giovanni

    2013-01-01

    In this contribution I summarize the unique properties of the old, metal rich, star cluster NGC 6791, with particular emphasis on its population of extreme blue horizontal branch stars. I then conclude providing my personal view on the origin of this fascinating star cluster.

  19. Structure Determination of Anionic Metal Clusters via Infrared Resonance Enhanced Multiple Photon Electron Detachment Spectroscopy

    Haertelt, M.; Lapoutre, V. J. F.; Bakker, J. M.; Redlich, B.; Harding, D. J.; Fielicke, A.; Meijer, G.

    2011-01-01

    We report vibrational spectra of anionic metal clusters, measured via electron detachment following resonant absorption of multiple infrared photons. To facilitate the sequential absorption of the required large number of photons, the cluster beam interacts with the infrared radiation inside the

  20. Van der Waals coefficients for alkali metal clusters and their size

    In this paper we employ the hydrodynamic formulation of time-dependent density functional theory to obtain the van der Waals coefficients 6 and 8 of alkali metal clusters of various sizes including very large clusters. Such calculations become computationally very demanding in the orbital-based Kohn-Sham formalism, ...

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

    Chakraborty, Debdutta; Chattaraj, Pratim Kumar

    2017-10-01

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

  2. Hydrolysis in the organic phase during the extraction of alkali metal halides and water by copper bis(2-ethylhexyl)phosphate

    Golovanov, V.I.; Kuznetsov, S.M.

    2001-01-01

    Experimental data on extraction of halides, among which are LiCl and CsCl, and water by copper di-(2-ethylhexyl)phosphate solutions in respect to hydrolysis mechanism of reaction are generalized. Copper di-(2-ethylhexyl)phosphate manifests properties of ionogen colloidal surfactant in water. Extraction of halides by copper di-(2-ethylhexyl)phosphate was shown to be visualized by the process of capsule formation in MHal molecules, as well as in hydrolyzed MOH and HHal forms of electrolyte by Cu 4 (D2EHF) 8 · hH 2 O clathrate-like micellar associates. The model of hydrolysis mechanism is not different from proposed earlier model of electrolyte extraction with their partial dissociation in organic phase [ru

  3. Systemic analysis of thermodynamic properties of lanthanide halides

    Mirsaidov, U.; Badalov, A.; Marufi, V.K.

    1992-01-01

    System analysis of thermodynamic characteristics of lanthanide halides was carried out. A method making allowances for the influence of spin and orbital moments of momentum of the main states of lanthanide trivalent ions in their natural series was employed. Unknown in literature thermodynamic values were calculated and corrected for certain compounds. The character of lanthanide halide thermodynamic parameter change depending on ordinal number of the metals was ascertained. Pronouncement of tetrad-effect in series of compounds considered was pointed out

  4. Metallicity Variations in the Type II Globular Cluster NGC 6934

    Marino, A. F.; Yong, D.; Milone, A. P.; Piotto, G.; Lundquist, M.; Bedin, L. R.; Chené, A.-N.; Da Costa, G.; Asplund, M.; Jerjen, H.

    2018-06-01

    The Hubble Space Telescope photometric survey of Galactic globular clusters (GCs) has revealed a peculiar “chromosome map” for NGC 6934. In addition to a typical sequence, similar to that observed in Type I GCs, NGC 6934 displays additional stars on the red side, analogous to the anomalous Type II GCs, as defined in our previous work. We present a chemical abundance analysis of four red giants in this GC. Two stars are located on the chromosome map sequence common to all GCs, and another two lie on the additional sequence. We find (i) star-to-star Fe variations, with the two anomalous stars being enriched by ∼0.2 dex. Because of our small-size sample, this difference is at the ∼2.5σ level. (ii) There is no evidence for variations in the slow neutron-capture abundances over Fe, at odds with what is often observed in anomalous Type II GCs, e.g., M 22 and ω Centauri (iii) no large variations in light elements C, O, and Na, compatible with locations of the targets on the lower part of the chromosome map where such variations are not expected. Since the analyzed stars are homogeneous in light elements, the only way to reproduce the photometric splits on the sub-giant (SGB) and the red giant (RGB) branches is to assume that red RGB/faint SGB stars are enhanced in [Fe/H] by ∼0.2. This fact corroborates the spectroscopic evidence of a metallicity variation in NGC 6934. The observed chemical pattern resembles only partially the other Type II GCs, suggesting that NGC 6934 might belong either to a third class of GCs, or be a link between normal Type I and anomalous Type II GCs. Based on observations with the NASA/ESA Hubble Space Telescope, obtained at the Space Telescope Science Institute, which is operated by AURA, Inc., under NASA contract NAS 5-26555. This paper includes data gathered with the 6.5 m Magellan Telescopes located at Las Campanas Observatory, Chile, and Gemini Telescope at Canada–France–Hawaii Telescope.

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

    Luther, George W.; Rickard, David T.

    2005-01-01

    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

  6. Formation of metal clusters in halloysite clay nanotubes

    Vinokurov, Vladimir A.; Stavitskaya, Anna V.; Chudakov, Yaroslav A.; Ivanov, Evgenii V.; Shrestha, Lok Kumar; Ariga, Katsuhiko; Darrat, Yusuf A.; Lvov, Yuri M.

    2017-12-01

    We developed ceramic core-shell materials based on abundant halloysite clay nanotubes with enhanced heavy metal ions loading through Schiff base binding. These clay tubes are formed by rolling alumosilicate sheets and have diameter of c.50 nm, a lumen of 15 nm and length 1 μm. This allowed for synthesis of metal nanoparticles at the selected position: (1) on the outer surface seeding 3-5 nm metal particles on the tubes; (2) inside the tube's central lumen resulting in 10-12 nm diameter metal cores shelled with ceramic wall; and (3) smaller metal nanoparticles intercalated in the tube's wall allowing up to 9 wt% of Ru, and Ag loading. These composite materials have high surface area providing a good support for catalytic nanoparticles, and can also be used for sorption of metal ions from aqueous solutions.

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

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

    2018-01-01

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

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

    Arslan, Ilke [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Dixon, David A. [Univ. of Alabama, Tuscaloosa, AL (United States); Gates, Bruce C. [Univ. of California, Davis, CA (United States); Katz, Alexander [Univ. of California, Berkeley, CA (United States)

    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

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

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

    2014-01-01

    Theoretical studies on the structure, stability, and magnetic properties of icosahedral TM 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 13 clusters, Co 13 is absorbed relatively more strongly on pristine and defective graphene as compared to Fe 13 and Ni 13 clusters. The adsorbed clusters show reduced magnetic moment compared to the free clusters

  10. A study of the convective flow as a function of external parameters in a high-pressure metal halide discharge lamp (HgDyI{sub 3})

    Hajji, S.; HadjSalah, S.; Benhalima, A.; Charrada, K. [Unité d' Etude des Milieux Ionisés et Réactifs, IPEIM, 5019 route de Kairouan Monastir, Université de Monastir (Tunisia); Zissis, G. [Laboratoire Plasma et Conversion d' Énergie, 118 rte Narbonne, Bât3R2, 31062 Toulouse (France)

    2016-06-15

    This paper deals with the modelling of the convection processes in metal–halide lamp discharges (HgDyI{sub 3}). For this, we realized a 3D model, a steady, direct current powered and time-depending model for the solution of conservation equations relative to mass, momentum, and energy. After validation, this model was applied to the study of the effect of some parameters that have appeared on major transport phenomena of mass and energy in studying the lamp. Indeed, the electric current, the atomic ratio (Hg/Dy), and the effect of the convective transport have been studied.

  11. Associated equilibria with participatian of single and mixed silver, lead and cadmium halide complexes in mixtures of molten alkali and alkaline earth metal nitrates

    Gouk, Kh.S.; Gupta, R.K.; Vekma, K.V.

    1983-01-01

    Associated equilibria in the systems, which contain single and mixed silver, cadmium and lead halide complexes in the KNO 3 -Ba(N0 3 ) 2 (87.6:12.4 and 89:11 mol.%) and NaNO 3 -Ba(NO 3 ) 2 (94.2-5.8 mol%) melts in the temperature range from 568.2 up to 698.2 K are investigated. Applicability of equations derivated on the base of quasi-lattice model to description of temperature coefficients of association constants is analized

  12. Catalytic effect of halide additives ball milled with magnesium hydride

    Malka, I.E.; Bystrzycki, J. [Department of Advanced Materials and Technologies, Military University of Technology, Kaliskiego 2, 00-908 Warsaw (Poland); Czujko, T. [Department of Advanced Materials and Technologies, Military University of Technology, Kaliskiego 2, 00-908 Warsaw (Poland); CanmetENERGY, Hydrogen Fuel Cells and Transportation Energy, Natural Resources (Canada)

    2010-02-15

    The influence of various halide additives milled with magnesium hydride (MgH{sub 2}) on its decomposition temperature was studied. The optimum amount of halide additive and milling conditions were evaluated. The MgH{sub 2} decomposition temperature and energy of activation reduction were measured by temperature programmed desorption (TPD) and differential scanning calorimetry (DSC). The difference in catalytic efficiency between chlorides and fluorides of the various metals studied is presented. The effects of oxidation state, valence and position in the periodic table for selected halides on MgH{sub 2} decomposition temperature were also studied. The best catalysts, from the halides studied, for magnesium hydride decomposition were ZrF{sub 4}, TaF{sub 5}, NbF{sub 5}, VCl{sub 3} and TiCl{sub 3}. (author)

  13. Computer simulations of small semiconductor and metal clusters

    Andreoni, W.

    1991-01-01

    A brief survey is presented of recent simulations of small clusters, made with both ab-initio and classical approaches, with particular emphasis on the application of the Car-Parrinello method. The discussion mainly focusses on the structural properties of a variety of materials and on the effects of temperature. (orig.)

  14. Metal cluster fission: jellium model and Molecular dynamics simulations

    Lyalin, Andrey G.; Obolensky, Oleg I.; Solov'yov, Ilia

    2004-01-01

    Fission of doubly charged sodium clusters is studied using the open-shell two-center deformed jellium model approximation and it ab initio molecular dynamic approach accounting for all electrons in the system. Results of calculations of fission reactions Na_10^2+ --> Na_7^+ + Na_3^+ and Na_18...

  15. Relation between the electroforming voltage in alkali halide-polymer diodes and the bandgap of the alkali halide

    Bory, Benjamin F.; Wang, Jingxin; Janssen, René A. J.; Meskers, Stefan C. J.; Gomes, Henrique L.; De Leeuw, Dago M.

    2014-01-01

    Electroforming of indium-tin-oxide/alkali halide/poly(spirofluorene)/Ba/Al diodes has been investigated by bias dependent reflectivity measurements. The threshold voltages for electrocoloration and electroforming are independent of layer thickness and correlate with the bandgap of the alkali halide. We argue that the origin is voltage induced defect formation. Frenkel defect pairs are formed by electron–hole recombination in the alkali halide. This self-accelerating process mitigates injection barriers. The dynamic junction formation is compared to that of a light emitting electrochemical cell. A critical defect density for electroforming is 10 25 /m 3 . The electroformed alkali halide layer can be considered as a highly doped semiconductor with metallic transport characteristics

  16. Measuring age differences among globular clusters having similar metallicities - A new method and first results

    Vandenberg, D.A.; Bolte, M.; Stetson, P.B.

    1990-01-01

    A color-difference technique for estimating the relative ages of globular clusters with similar chemical compositions on the basis of their CM diagrams is described and demonstrated. The theoretical basis and implementation of the procedure are explained, and results for groups of globular clusters with m/H = about -2, -1.6, and -1.3, and for two special cases (Palomar 12 and NGC 5139) are presented in extensive tables and graphs and discussed in detail. It is found that the more metal-deficient globular clusters are nearly coeval (differences less than 0.5 Gyr), whereas the most metal-rich globular clusters exhibit significant age differences (about 2 Gyr). This result is shown to contradict Galactic evolution models postulating halo collapse in less than a few times 100 Myr. 77 refs

  17. POLYMER COMPOSITE FILMS WITH SIZE-SELECTED METAL NANOPARTICLES FABRICATED BY CLUSTER BEAM TECHNIQUE

    Ceynowa, F. A.; Chirumamilla, Manohar; Popok, Vladimir

    2017-01-01

    Formation of polymer films with size-selected silver and copper nanoparticles (NPs) is studied. Polymers are prepared by spin coating while NPs are fabricated and deposited utilizing a magnetron sputtering cluster apparatus. The particle embedding into the films is provided by thermal annealing...... after the deposition. The degree of immersion can be controlled by the annealing temperature and time. Together with control of cluster coverage the described approach represents an efficient method for the synthesis of thin polymer composite layers with either partially or fully embedded metal NPs....... Combining electron beam lithography, cluster beam deposition and thermal annealing allows to form ordered arrays of metal NPs on polymer films. Plasticity and flexibility of polymer host and specific properties added by coinage metal NPs open a way for different applications of such composite materials...

  18. Metallicity in galactic clusters from high signal-to-noise spectroscopy

    Boesgaard, A.M.

    1989-01-01

    High-quality spectroscopic data on selected F dwarfs in six Galactic clusters are used to determine global (Fe/H) values for the clusters. For the two youngest clusters, Pleiades and Alpha Per, the (Fe/H) values are solar: 0.017 + or - 0.055. The Hyades and Praesepe are slightly metal-enhanced at (Fe/H) = + 0.125 + or - 0.032, even though they are an order of magnitude older than the Pleiades. Coma and the UMa Group at the age of the Hyades are slightly metal-deficient with (Fe/H) = - 0.082 + or - 0.039. The lack of an age-metallicity relationship indicates that the enrichment and mixing in the Galactic disk have not been uniform on time scales less than a billion years. 39 references

  19. Nonequilibrium electron energy-loss kinetics in metal clusters

    Guillon, C; Fatti, N D; Vallee, F

    2003-01-01

    Ultrafast energy exchanges of a non-Fermi electron gas with the lattice are investigated in silver clusters with sizes ranging from 4 to 26 nm using a femtosecond pump-probe technique. The results yield evidence for a cluster-size-dependent slowing down of the short-time energy losses of the electron gas when it is strongly athermal. A constant rate is eventually reached after a few hundred femtoseconds, consistent with the electron gas internal thermalization kinetics, this behaviour reflecting evolution from an individual to a collective electron-lattice type of coupling. The timescale of this transient regime is reduced in small nanoparticles, in agreement with speeding up of the electron-electron interactions with size reduction. The experimental results are in quantitative agreement with numerical simulations of the electron kinetics.

  20. Electronic properties of large metal clusters in Jellium and pseudo-jellium models

    Catara, F.; Van Giai, N.; Chomaz, P.

    1994-08-01

    The energy-density functional approach and jellium-like models are used to examine two important electronic properties of metal (Li, Na, K) clusters: their shell and supershell structures, and the behaviour of plasmon energies with increasing cluster sizes. A comparative study is made between predictions of the usual jellium model and those of the pseudo-jellium model where pseudo-Hamiltonians are used. (authors) 10 figs., 5 tabs., 16 refs

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

    Valentino, F.; Daddi, E.; Strazzullo, V.; Gobat, R.; Bournaud, F.; Juneau, S.; Zanella, A. [Laboratoire AIM-Paris-Saclay, CEA/DSM-CNRS-Université Paris Diderot, Irfu/Service d’Astrophysique, CEA Saclay, Orme des Merisiers, F-91191 Gif sur Yvette (France); Onodera, M.; Carollo, M. [Institute for Astronomy, ETH Zürich Wolfgang-Pauli-strasse 27, 8093 Zürich (Switzerland); Renzini, A. [INAF-Osservatorio Astronomico di Padova Vicolo dell’Osservatorio 5, I-35122 Padova (Italy); Arimoto, N., E-mail: francesco.valentino@cea.fr [Subaru Telescope, National Astronomical Observatory of Japan 650 North A’ohoku Place, Hilo, HI 96720 (United States)

    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.

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

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

    1990-01-01

    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

  3. Metal oxide/polyaniline nanocomposites: Cluster size and ...

    Wintec

    Metal oxide/polyaniline nanocomposites; structural properties; magnetic properties. 1. Introduction ... The powder obtained was ground in a motor and pestle, sonicated in ... Figure 1. XRD of (a) iron oxide nanoparticles and (b) iron oxide/PANI (1 : 0⋅4) composite. .... shape of the particles and the anisotropy energy, as also.

  4. Chemical probes of metal cluster structure--Fe, Co, Ni, and Cu

    Parks, E.K.; Zhu, L.; Ho, J.; Riley, S.J.

    1992-01-01

    Chemical reactivity is one of the few methods currently available for investigating the geometrical structure of isolated transition metal clusters. In this paper we summarize what is currently known about the structures of clusters of four transition metals, Fe, Co, Ni, and Cu, in the size range from 13 to 180 atoms. Chemical probes used to determine structural information include reactions with H 2 (D 2 ), H 2 0, NH 3 and N 2 . Measurements at both low coverage and at saturation are discussed

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

    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 star as a function of redshift, and on the observed galaxy stellar mass function up to redshift z ∼ 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 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 ∼ 2, and the metal-poor subpopulation is composed of clusters accreted from satellites, and formed at redshifts z ∼ 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 ∼0.5 at redshift z ∼ 4 to a value of ∼0.1 at

  6. Proofs of cluster formation and transitions in liquid metals and alloys

    Filippov, E.S.

    1985-01-01

    Calculational and experimental proofs are presented indicating to existence of clusters in liquid metals and alloys. Systems of liquid alloys both on the base of ferrous metals and non-ferrous metals (Fe-C, Ni-C, Co-C, Fe-Ni, Ni-Mo, Co-Cr, Co-V as well as In-Sn, Bi-Sn, Si-Ge and others) are studied experimentally. It is shown that the general feature of the systems studied is sensitivity of a volume to change in structure, to replacement fcc structure on bcc or to initiation-dissociation of intermetallic compounds AxBy. It is shown that both in pure liquid metals and in their.alloys there are clusters as ordered aggregate of atoms

  7. Atomic structures and covalent-to-metallic transition of lead clusters Pbn (n=2-22)

    Wang Baolin; Zhao Jijun; Chen Xiaoshuang; Shi Daning; Wang Guanghou

    2005-01-01

    The lowest-energy structures and electronic properties of the lead clusters are studied by density-functional-theory calculations with Becke-Lee-Yang-Parr gradient correction. The lowest-energy structures of Pb n (n=2-22) clusters are determined from a number of structural isomers, which are generated from empirical genetic algorithm simulations. The competition between atom-centered compact structures and layered stacking structures leads to the alternative appearance of the two types of structures as global minimum. The size evolution of geometric and electronic properties from covalent bonding towards bulk metallic behavior in Pb clusters is discussed

  8. Structure of s - p bonded metal clusters with 8, 20 and 40 valence electrons

    Kumar, V.

    1992-10-01

    From studies on some clusters of metals and semiconductors, there appear some similarities in the structure of clusters with a given number of atoms and having the number of valence electrons corresponding to a shell closing. Here we present results of the atomic and electronic structure of a few other clusters with 20 and 40 valence electrons, namely Sb 4 , Sn 5 and Sb 8 using the density functional molecular dynamics method. We suggest that the similarities in the structure and deviation from them may help to understand bonding characteristics in clusters and its evolution to bulk behaviour. Our results on Sb 8 cluster are preliminary but indicate that above room temperature its structure is two weakly interacting tetrahedra which is in general agreement with the observation of predominently antimony tetramers at T > 300 K. (author). 16 refs, 2 figs

  9. On the role of resonances in photoionization of metal clusters

    Wopperer, P; Dinh, P M; Suraud, E; Reinhard, P G

    2013-01-01

    We analyze electron emission from irradiated clusters by means of time-dependent density-functional theory (TDDFT) in real time. We focus on photo-electron spectra (PES) which deliver an invaluable tool to explore static and dynamical properties of irradiated species. We discuss, in particular, the role of resonances in the PES once the laser frequency is below the emission threshold which implies multiphoton processes. We show that the resonances in the electronic spectrum lead to the occurrence of several peaks in the PES and also strongly affect the standard scaling relations between ionization and the number of required photons for electronic emission.

  10. Impurity cluster interaction in fcc metals studied by PAC

    Deicher, M.; Echt, O.; Recknagel, E.; Wichert, T.

    1981-01-01

    A defect configuration of high thermal stability has been observed by PAC in Au, showing the same properties as previously published configuration in Cu and Ni. We prove that these configurations cannot consist of any small defect complex with well-defined size; especially the observed influence of the damaging conditions on the thermal stability of the defects in Au and Cu would contradict such an assumption. It is shown that probe atoms trapped at large clusters of variable size can nevertheless experience a unique electric field gradient, and that in our case intrinsic stacking faults, formed by vacancies, can account for all the measured properties. (orig.)

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

    Chen, Renyu; Trzynadlowski, Bart; Dunham, Scott T. [Department of Electrical Engineering, University of Washington, Seattle, Washington 98195 (United States)

    2014-02-07

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

  12. Nonlinear Color–Metallicity Relations of Globular Clusters. VII. Nonlinear Absorption-line Index versus Metallicity Relations and Bimodal Index Distributions of NGC 5128 Globular Clusters

    Kim, Sooyoung; Yoon, Suk-Jin, E-mail: sjyoon0691@yonsei.ac.kr [Department of Astronomy and Center for Galaxy Evolution Research, Yonsei University, Seoul 120-749 (Korea, Republic of)

    2017-07-01

    Spectroscopy on the globular cluster (GC) system of NGC 5128 revealed bimodality in absorption-line index distributions of its old GCs. GC division is a widely observed and studied phenomenon whose interpretation has depicted host galaxy formation and evolution such that it harbors two distinct metallicity groups. Such a conventional view of GC bimodality has mainly been based on photometry. The recent GC photometric data, however, presented an alternative perspective in which the nonlinear metallicity-to-color transformation is responsible for color bimodality of GC systems. Here we apply the same line of analysis to the spectral indices and examine the absorption-line index versus metallicity relations for the NGC 5128 GC system. NGC 5128 GCs display nonlinearity in the metallicity-index planes, most prominently for the Balmer lines and by a non-negligible degree for the metallicity-sensitive magnesium line. We demonstrate that the observed spectroscopic division of NGC 5128 GCs can be caused by the nonlinear nature of the metallicity-to-index conversions and thus one does not need to resort to two separate GC subgroups. Our analysis incorporating this nonlinearity provides a new perspective on the structure of NGC 5128's GC system, and a further piece to the global picture of the formation of GC systems and their host galaxies.

  13. Pulse laser-induced generation of cluster codes from metal nanoparticles for immunoassay applications

    Chia-Yin Chang

    2017-05-01

    Full Text Available In this work, we have developed an assay for the detection of proteins by functionalized nanomaterials coupled with laser-induced desorption/ionization mass spectrometry (LDI-MS by monitoring the generation of metal cluster ions. We achieved selective detection of three proteins [thrombin, vascular endothelial growth factor-A165 (VEGF-A165, and platelet-derived growth factor-BB (PDGF-BB] by modifying nanoparticles (NPs of three different metals (Au, Ag, and Pt with the corresponding aptamer or antibody in one assay. The Au, Ag, and Pt acted as metal bio-codes for the analysis of thrombin, VEGF-A165, and PDGF-BB, respectively, and a microporous cellulose acetate membrane (CAM served as a medium for an in situ separation of target protein-bound and -unbound NPs. The functionalized metal nanoparticles bound to their specific proteins were subjected to LDI-MS on the CAM. The functional nanoparticles/CAM system can function as a signal transducer and amplifier by transforming the protein concentration into an intense metal cluster ion signal during LDI-MS analysis. This system can selectively detect proteins at picomolar concentrations. Most importantly, the system has great potential for the detection of multiple proteins without any pre-concentration, separation, or purification process because LDI-MS coupled with CAM effectively removes all signals except for those from the metal cluster ions.

  14. Bipolarons in metal-metal halide solutions

    Fois, E.S.; Selloni, A.; Parrinello, M.; Car, R.

    1988-06-02

    A novel molecular dynamics method is used to follow the adiabatic dynamics of two electrons solvated in molten KCl. The electrons are treated quantum mechanically within the local spin density approximation. A coupled set of Newtonian and time-dependent Schroedinger-like equations is used to describe the evolution of the ions and of the Kohn-Sham orbitals. The authors find that parallel spin electrons repel each other and form separate F-center-like states. Antiparallel spin electrons, instead, attract each other and coalesce into a single bipolaronic complex. The electrons sit mostly in an ionic cavity which is surrounded by cations. The diffusion of the bipolaron, while bound, occurs on an ionic time scale. However, dissociation processes occur during which the electrons can acquire a high mobility leading on average to a large electronic diffusion.

  15. The evoluation of the galactic globular clusters; I Metal abundance calibrations

    Lee, S.W.; Park, N.K.

    1984-01-01

    Five different calibrations of metal abundances of globular clusters are examined and these are compared with metallicity ranking parameters such as (Sp)sub(c), , Q39 and IR-indices. Except for the calibration *(Fe/H*)sub(H) by the high dispersion echelle analysis, the other calibration scales are correlated with the morphological parameters of red giant branch. In the *(Fe/H*)sub(Hsup(-))scale, the clusters later than approx.F8 have nearly a constant metal abundance, *(Fe/H*)sub(H)approx.-1.05, regardless of morphological characteristics of horizontal branch and red giant branch. By the two fundamental calibration scales of *(Fe/H*)sub(L) (derived by the low dispersion analysis), and *(Fe/H*)sub(delta S) (derived by the spectral analysis of RR Lyrae stars), the globular clusters are divided into the halo clusters with *(Fe/H*)<-1.0 and the disk clusters confined within the galactocentric distance rsub(G)=10 kpc and galactic plane distance absolute z=3 kpc. In this case the abundance gradient is given by d*(Fe/H*)/drsub(G)approx.-0.05kpcsup(-1) and d*(Fe/H*)/d absolute z approx. -0.08 kpcsup(-1) within rsub(G)=20 kpc and absolute z=10 kpc, respectively. According to these characteristics of the spatial distribution of globular clusters, the chemical evolution of the galactic globular clusters can be accounted for by the two-zone (disk-halo) slow collapse model when the *(Fe/H*)sub(Lsup(-)) or *(Fe/H*)sub(DELTA Ssup(-))scale is applied. In the case of *(Fe/H*)sub(Hsup(-))scale, the one-zone fast collapse model is preferred for the evolution of globular clusters. (Author)

  16. NEAR-IR PHOTOMETRIC PROPERTIES OF HB, MSTO, AND SGB FOR METAL POOR GALACTIC GLOBULAR CLUSTERS

    J.-W. Kim

    2007-03-01

    Full Text Available We report photometric features of the HB, MSTO, and SGB for a set of metal-poor Galactic globular clusters on the near-IR CMDs. The magnitude and color of the MSTO and SGB are measured on the fiducial normal points of the CMDs by applying a polynomial fit. The near-IR luminosity functions of horizontal branch stars in the classical second parameter pair M3 and M13 indicate that HB stars in M13 are dominated by hot stars that are rotatively faint in the infrared, whereas HB stars in M3 are brighter than those in M13. The luminosity functions of HB stars in the observed bulge clusters, except for NGC 6717, show a trend that the fainter hot HB stars are dominated in the relatively metal-poor clusters while the relatively metal-rich clusters contain the brighter HB stars. It is suggestive that NGC 6717 would be an extreme example of the second-parameter phenomenon for the bulge globular clusters.

  17. Optical trapping of metal-dielectric nanoparticle clusters near photonic crystal microcavities.

    Mejia, Camilo A; Huang, Ningfeng; Povinelli, Michelle L

    2012-09-01

    We predict the formation of optically trapped, metal-dielectric nanoparticle clusters above photonic crystal microcavities. We determine the conditions on particle size and position for a gold particle to be trapped above the microcavity. We then show that strong field redistribution and enhancement near the trapped gold nanoparticle results in secondary trapping sites for a pair of dielectric nanoparticles.

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

    Smirnov, B. M., E-mail: bmsmirnov@gmail.com [Russian Academy of Sciences, Joint Institute for High Temperatures (Russian Federation)

    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.

  19. Nonlocality and particle-clustering effects on the optical response of composite materials with metallic nanoparticles

    Chen, C. W.; Chung, H. Y.; Chiang, H.-P.; Lu, J. Y.; Chang, R.; Tsai, D. P.; Leung, P. T.

    2010-10-01

    The optical properties of composites with metallic nanoparticles are studied, taking into account the effects due to the nonlocal dielectric response of the metal and the coalescing of the particles to form clusters. An approach based on various effective medium theories is followed, and the modeling results are compared with those from the cases with local response and particles randomly distributed through the host medium. Possible observations of our modeling results are illustrated via a calculation of the transmission of light through a thin film made of these materials. It is found that the nonlocal effects are particularly significant when the particles coalesce, leading to blue-shifted resonances and slightly lower values in the dielectric functions. The dependence of these effects on the volume fraction and fractal dimension of the metal clusters is studied in detail.

  20. Medium-induced change of the optical response of metal clusters in rare-gas matrices

    Xuan, Fengyuan; Guet, Claude

    2017-10-01

    Interaction with the surrounding medium modifies the optical response of embedded metal clusters. For clusters from about ten to a few hundreds of silver atoms, embedded in rare-gas matrices, we study the environment effect within the matrix random phase approximation with exact exchange (RPAE) quantum approach, which has proved successful for free silver clusters. The polarizable surrounding medium screens the residual two-body RPAE interaction, adds a polarization term to the one-body potential, and shifts the vacuum energy of the active delocalized valence electrons. Within this model, we calculate the dipole oscillator strength distribution for Ag clusters embedded in helium droplets, neon, argon, krypton, and xenon matrices. The main contribution to the dipole surface plasmon red shift originates from the rare-gas polarization screening of the two-body interaction. The large size limit of the dipole surface plasmon agrees well with the classical prediction.

  1. Electrochemistry of plutonium in molten halides

    McCurry, L.E.; Moy, G.M.M.; Bowersox, D.F.

    1987-01-01

    The electrochemistry of plutonium in molten halides is of technological importance as a method of purification of plutonium. Previous authors have reported that plutonium can be purified by electrorefining impure plutonium in various molten haldies. Work to eluciate the mechanism of the plutonium reduction in molten halides has been limited to a chronopotentiometric study in LiCl-KCl. Potentiometric studies have been carried out to determine the standard reduction potential for the plutonium (III) couple in various molten alkali metal halides. Initial cyclic voltammetric experiments were performed in molten KCL at 1100 K. A silver/silver chloride (10 mole %) in equimolar NaCl-KCl was used as a reference electrode. Working and counter electrodes were tungsten. The cell components and melt were contained in a quartz crucible. Background cyclic voltammograms of the KCl melt at the tungsten electrode showed no evidence of electroactive impurities in the melt. Plutonium was added to the melt as PuCl/sub 3/, which was prepared by chlorination of the oxide. At low concentrations of PuCl/sub 3/ in the melt (0.01-0.03 molar), no reduction wave due to the reduction of Pu(III) was observed in the voltammograms up to the potassium reduction limit of the melt. However on scan reversal after scanning into the potassium reduction limit a new oxidation wave was observed

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

    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.

  3. Resonant halide perovskite nanoparticles

    Tiguntseva, Ekaterina Y.; Ishteev, Arthur R.; Komissarenko, Filipp E.; Zuev, Dmitry A.; Ushakova, Elena V.; Milichko, Valentin A.; Nesterov-Mueller, Alexander; Makarov, Sergey V.; Zakhidov, Anvar A.

    2017-09-01

    The hybrid halide perovskites is a prospective material for fabrication of cost-effective optical devices. Unique perovskites properties are used for solar cells and different photonic applications. Recently, perovskite-based nanophotonics has emerged. Here, we consider perovskite like a high-refractive index dielectric material, which can be considered to be a basis for nanoparticles fabrication with Mie resonances. As a result, we fabricate and study resonant perovskite nanoparticles with different sizes. We reveal, that spherical nanoparticles show enhanced photoluminescence signal. The achieved results lay a cornerstone in the field of novel types of organic-inorganic nanophotonics devices with optical properties improved by Mie resonances.

  4. Metals on graphene and carbon nanotube surfaces: From mobile atoms to atomtronics to bulk metals to clusters and catalysts

    Sarkar, Santanu C.

    2014-01-14

    In this Perspective, we present an overview of recent fundamental studies on the nature of the interaction between individual metal atoms and metal clusters and the conjugated surfaces of graphene and carbon nanotube with a particular focus on the electronic structure and chemical bonding at the metal-graphene interface. We discuss the relevance of organometallic complexes of graphitic materials to the development of a fundamental understanding of these interactions and their application in atomtronics as atomic interconnects, high mobility organometallic transistor devices, high-frequency electronic devices, organometallic catalysis (hydrogen fuel generation by photocatalytic water splitting, fuel cells, hydrogenation), spintronics, memory devices, and the next generation energy devices. We touch on chemical vapor deposition (CVD) graphene grown on metals, the reactivity of its surface, and its use as a template for asymmetric graphene functionalization chemistry (ultrathin Janus discs). We highlight some of the latest advances in understanding the nature of interactions between metals and graphene surfaces from the standpoint of metal overlayers deposited on graphene and SWNT thin films. Finally, we comment on the major challenges facing the field and the opportunities for technological applications. © 2013 American Chemical Society.

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

    Petropoulou, V.; Vilchez, J.; Iglesias-Paramo, J. [Instituto de Astrofisica de Andalucia-C.S.I.C., Glorieta de la Astronomia, 18008 Granada (Spain)

    2012-04-20

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

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

    Petropoulou, V.; Vílchez, J.; Iglesias-Páramo, J.

    2012-01-01

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

  7. Nanocomposite metal/plasma polymer films prepared by means of gas aggregation cluster source

    Polonskyi, O.; Solar, P.; Kylian, O.; Drabik, M.; Artemenko, A.; Kousal, J.; Hanus, J.; Pesicka, J.; Matolinova, I. [Charles University in Prague, Faculty of Mathematics and Physics, V Holesovickach 2, 18000 Prague 8 (Czech Republic); Kolibalova, E. [Tescan, Libusina trida 21, 632 00 Brno (Czech Republic); Slavinska, D. [Charles University in Prague, Faculty of Mathematics and Physics, V Holesovickach 2, 18000 Prague 8 (Czech Republic); Biederman, H., E-mail: bieder@kmf.troja.mff.cuni.cz [Charles University in Prague, Faculty of Mathematics and Physics, V Holesovickach 2, 18000 Prague 8 (Czech Republic)

    2012-04-02

    Nanocomposite metal/plasma polymer films have been prepared by simultaneous plasma polymerization using a mixture of Ar/n-hexane and metal cluster beams. A simple compact cluster gas aggregation source is described and characterized with emphasis on the determination of the amount of charged clusters and their size distribution. It is shown that the fraction of neutral, positively and negatively charged nanoclusters leaving the gas aggregation source is largely influenced by used operational conditions. In addition, it is demonstrated that a large portion of Ag clusters is positively charged, especially when higher currents are used for their production. Deposition of nanocomposite Ag/C:H plasma polymer films is described in detail by means of cluster gas aggregation source. Basic characterization of the films is performed using transmission electron microscopy, ultraviolet-visible and Fourier-transform infrared spectroscopies. It is shown that the morphology, structure and optical properties of such prepared nanocomposites differ significantly from the ones fabricated by means of magnetron sputtering of Ag target in Ar/n-hexane mixture.

  8. Crystal growth, structure and phase studies on gold halides

    Janssen, Eugenius Maria Wilhelmus Janssen

    1977-01-01

    Only very corrosive substances attack gold, the most noble metal. In this study the reactivity and the phase diagrams of gold with the halogens chlorine, bromine and iodine have been investigated. owing to the noble behaviour of gold, its halides are sensitive to heat; on heating they decompose into

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

    Kamiguchi, Satoshi, E-mail: kamigu@riken.jp [Advanced Catalysis Research Group, RIKEN Center for Sustainable Resource Science, 2-1 Hirosawa, Wako City, Saitama 351-0198 (Japan); Organometallic Chemistry Laboratory, RIKEN, 2-1 Hirosawa, Wako City, Saitama 351-0198 (Japan); Okumura, Kazu [School of Advanced Engineering, Kogakuin University, Nakano-machi, Hachioji City, Tokyo 192-0015 (Japan); Nagashima, Sayoko; Chihara, Teiji [Graduate School of Science and Engineering, Saitama University, Shimo-Okubo, Sakura-ku, Saitama City, Saitama 338-8570 (Japan)

    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.

  10. Cluster-based bulk metallic glass formation in Fe-Si-B-Nb alloy systems

    Zhu, C L; Wang, Q; Li, F W; Li, Y H; Wang, Y M; Dong, C [State Key Laboratory of Materials Modification, Dalian University of Technology (DUT), Dalian 116024 (China); Zhang, W; Inoue, A, E-mail: dong@dlut.edu.c [Institute for Materials Research (IMR), Tohoku University, Katahira 2-1-1, Aoba-Ku, Sendai 980-8577 (Japan)

    2009-01-01

    Bulk metallic glass formations have been explored in Fe-B-Si-Nb alloy system using the so-called atomic cluster line approach in combination with minor alloying guideline. The atomic cluster line refers to a straight line linking binary cluster to the third element in a ternary system. The basic ternary compositions in Fe-B-Si system are determined by the inetersection points of two cluster lines, namely Fe-B cluster to Si and Fe-Si cluster to B, and then further alloyed with 3-5 at. % Nb for enhancing glass forming abilities. BMG rods with a diameter of 3 mm are formed under the case of minor Nb alloying the basic intersecting compositions of Fe{sub 8}B{sub 3}-Si with Fe{sub 12}Si-B and Fe{sub 8}B{sub 2}-Si with Fe{sub 9}Si-B. The BMGs also exhibit high Vickers hardness (H{sub v}) of 1130-1164 and high Young's modulous (E) of 170-180 GPa

  11. Cluster perturbation theory for calculation of electronic properties of ensembles of metal nanoclusters

    Zhumagulov, Yaroslav V.; Krasavin, Andrey V.; Kashurnikov, Vladimir A.

    2018-05-01

    The method is developed for calculation of electronic properties of an ensemble of metal nanoclusters with the use of cluster perturbation theory. This method is applied to the system of gold nanoclusters. The Greens function of single nanocluster is obtained by ab initio calculations within the framework of the density functional theory, and then is used in Dyson equation to group nanoclusters together and to compute the Greens function as well as the electron density of states of the whole ensemble. The transition from insulator state of a single nanocluster to metallic state of bulk gold is observed.

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

    Sreedhar, Yuvraj Harsha; Rakos, Karl D.; Hensler, Gerhard; Zeilinger, Werner W. [University of Vienna, Institute of Astronomy, Tuerkenschanzstrasse 17, A-1180 Vienna (Austria); Odell, Andrew P. [Department of Physics and Astronomy, Northern Arizona University, Flagstaff, AZ (United States)

    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

  13. Linear and nonlinear surface spectroscopy of supported size selected metal clusters and organic adsorbates

    Thaemer, Martin Georg

    2012-03-08

    The spectroscopic investigation of supported size selected metal clusters over a wide wavelength range plays an important role for understanding their outstanding catalytic properties. The challenge which must be overcome to perform such measurements is the difficult detection of the weak spectroscopic signals from these samples. As a consequence, highly sensitive spectroscopic methods are applied, such as surface Cavity Ringdown Spectroscopy and surface Second Harmonic Generation Spectroscopy. The spectroscopic apparatus developed is shown to have a sensitivity which is high enough to detect sub-monolayer coverages of adsorbates on surfaces. In the measured spectra of small supported silver clusters of the sizes Ag{sub 4}2, Ag{sub 2}1, Ag{sub 9}, and Ag atoms a stepwise transition from particles with purely metallic character to particles with molecule-like properties can be observed within this size range.

  14. Electronic relaxation dynamics of a metal atom deposited on argon cluster

    Awali, Slim

    2014-01-01

    This thesis is a study on the interaction between electronically excited atomic states and a non-reactive environment. We have theoretically and experimentally studied situations where a metal atom (Ba or K) is placed in a finite size environment (argon cluster). The presence of the medium affects the electronic levels of the atom. On the other side, the excitation of the atom induces a relaxation dynamics of the electronic energy through the deformation of the cluster. The experimental part of this work focuses on two aspects: the spectroscopy and the dynamics. In both cases a first laser electronically excites the metal atom and the second ionizes the excited system. The observable is the photoelectron spectrum recorded after photoionization and possibly information on the photoion which are also produced. This pump/probe technique, with also two lasers, provide the ultrafast dynamic when the lasers pulses used are of ultrashort (60 fs). The use of nanosecond lasers leads to resonance spectroscopic measurement, unresolved temporally, which give information on the position of the energy levels of the studied system. From a theoretical point-of-view, the excited states of M-Ar n were calculated at the ab initio level, using large core pseudo-potential to limit the active electrons of the metal to valence electrons. The study of alkali metals (potassium) is especially well adapted to this method since only one electron is active. The ab-initio calculation and a Monte-Carlo simulation where coupled to optimize the geometry of the KAr n (n = 1-10) cluster when K is in the ground state of the neutral and the ion, or excited in the 4p or 5s state. Calculations were also conducted in collaboration with B. Gervais (CIMAP, Caen) on KAr n clusters having several tens of argon atoms. Absorption spectra were also calculated. From an experimental point-of-view, we were able to characterize the excited states of potassium and barium perturbed by the clusters. In both cases a

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

    Lentz, Nicholas B. [Iowa State Univ., Ames, IA (United States)

    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

  16. Magnetron sputtering cluster apparatus for formation and deposition of size-selected metal nanoparticles

    Hanif, Muhammad; Popok, Vladimir

    2015-01-01

    selection is achieved using an electrostatic quadrupole mass selector. The deposited silver clusters are studied using atomic force microscopy. The height distributions show typical relative standard size deviation of 9-13% for given sizes in the range between 5-23 nm. Thus, the apparatus demonstrates good...... capability in formation of supported size-selected metal nanoparticles with controllable coverage for various practical applications....

  17. Giant metal sputtering yields induced by 20-5000 keV/atom gold clusters

    Andersen, H.H.; Brunelle, A.; Della-Negra, S.; Depauw, J.; Jacquet, D.; Le Beyec, Y.

    1997-01-01

    Very large non-linear effects have been found in cluster-induced metal sputtering over a broad projectile energy interval for the first time. Recently available cluster beams from tandem accelerators have allowed sputtering yield measurements to be made with Au 1 to Au 5 from 20 keV/atom to 5 MeV/atom. The cluster-sputtering yield maxima were found at the same total energy but not at the same energy/atom as expected. For Au 5 a yield as high as 3000 was reached at 150 keV/atom while the Au 1 yield was only 55 at the same velocity. The Sigmund-Claussen thermal spike theory, which fits published data at low energy, cannot reproduce our extended new data set. (author)

  18. Stability and mobility of defect clusters and dislocation loops in metals

    Osetsky, Y.N.; Bacon, D.J.; Serra, A.

    2000-01-01

    has been observed in the computer simulation of small vacancy loops in alpha-Fe. In the present paper we summarise results obtained by molecular dynamics simulations of defect clusters and small dislocation loops in alpha-Fe(bcc) and Cu(fcc). The structure and stability of vacancy and interstitial......According to the production bias model, glissile defect clusters and small dislocation loops play an important role in the microstructural evolution during irradiation under cascade damage conditions. The atomic scale computer simulations carried out in recent years have clarified many questions...... loops are reviewed, and the dynamics of glissile clusters assessed. The relevance and importance of these results in establishing a better understanding of the observed differences in the damage accumulation behaviour between bcc and fee metals irradiated under cascade damage conditions are pointed out...

  19. The Next Generation Virgo Cluster Survey (NGVS). XXVI. The Issues of Photometric Age and Metallicity Estimates for Globular Clusters

    Powalka, Mathieu; Lançon, Ariane; Duc, Pierre-Alain [Observatoire Astronomique de Strasbourg, Université de Strasbourg, CNRS, UMR 7550, 11 rue de l’Université, F-67000 Strasbourg (France); Puzia, Thomas H.; Muñoz, Roberto P.; Zhang, Hongxin [Institute of Astrophysics, Pontificia Universidad Católica de Chile, 7820436 Macul, Santiago (Chile); Peng, Eric W. [Department of Astronomy, Peking University, Beijing 100871 (China); Liu, Chengze [Center for Astronomy and Astrophysics, Department of Physics and Astronomy, Shanghai Jiao Tong University, Shanghai 200240 (China); Blakeslee, John P.; Côté, Patrick; Ferrarese, Laura; Roediger, Joel; Gwyn, S. D. J. [National Research Council of Canada, Herzberg Astronomy and Astrophysics Program, Victoria, BC V9E 2E7 (Canada); Sánchez-Janssen, Rúben [UK Astronomy Technology Centre, Royal Observatory Edinburgh, Blackford Hill, Edinburgh EH9 3HJ (United Kingdom); Durrell, Patrick R. [Department of Physics and Astronomy, Youngstown State University, Youngstown, OH (United States); Cuillandre, Jean-Charles [AIM Paris Saclay, CNRS/INSU, CEA/Irfu,Université Paris Diderot, Orme des Merisiers, F-91191 Gif sur Yvette cedex (France); Guhathakurta, Puragra [UCO/Lick Observatory, University of California, Santa Cruz, 1156 High Street, Santa Cruz, CA 95064 (United States); Hudelot, Patrick, E-mail: mathieu.powalka@astro.unistra.fr [Institut d’Astrophysique de Paris, UMR 7095 CNRS and UPMC, 98bis Bd Arago, F-75014 Paris (France); and others

    2017-08-01

    Large samples of globular clusters (GC) with precise multi-wavelength photometry are becoming increasingly available and can be used to constrain the formation history of galaxies. We present the results of an analysis of Milky Way (MW) and Virgo core GCs based on 5 optical-near-infrared colors and 10 synthetic stellar population models. For the MW GCs, the models tend to agree on photometric ages and metallicities, with values similar to those obtained with previous studies. When used with Virgo core GCs, for which photometry is provided by the Next Generation Virgo cluster Survey (NGVS), the same models generically return younger ages. This is a consequence of the systematic differences observed between the locus occupied by Virgo core GCs and models in panchromatic color space. Only extreme fine-tuning of the adjustable parameters available to us can make the majority of the best-fit ages old. Although we cannot exclude that the formation history of the Virgo core may lead to more conspicuous populations of relatively young GCs than in other environments, we emphasize that the intrinsic properties of the Virgo GCs are likely to differ systematically from those assumed in the models. Thus, the large wavelength coverage and photometric quality of modern GC samples, such as those used here, is not by itself sufficient to better constrain the GC formation histories. Models matching the environment-dependent characteristics of GCs in multi-dimensional color space are needed to improve the situation.

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

    Brodie, Jean P.; Conroy, Charlie; Arnold, Jacob A.; Romanowsky, Aaron J. [University of California Observatories and Department of Astronomy and Astrophysics, University of California, Santa Cruz, CA 95064 (United States); Usher, Christopher; Forbes, Duncan A. [Centre for Astrophysics and Supercomputing, Swinburne University, Hawthorn, VIC 3122 (Australia); Strader, Jay, E-mail: brodie@ucolick.org [Department of Physics and Astronomy, Michigan State University, East Lansing, MI 48824 (United States)

    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.

  1. Interaction of Model Inhibitor Compounds with Minimalist Cluster Representations of Hydroxyl Terminated Metal Oxide Surfaces

    Christopher D. Taylor

    2018-01-01

    Full Text Available The computational modeling of corrosion inhibitors at the level of molecular interactions has been pursued for decades, and recent developments are allowing increasingly realistic models to be developed for inhibitor–inhibitor, inhibitor–solvent and inhibitor–metal interactions. At the same time, there remains a need for simplistic models to be used for the purpose of screening molecules for proposed inhibitor performance. Herein, we apply a reductionist model for metal surfaces consisting of a metal cation with hydroxide ligands and use quantum chemical modeling to approximate the free energy of adsorption for several imidazoline class candidate corrosion inhibitors. The approximation is made using the binding energy and the partition coefficient. As in some previous work, we consider different methods for incorporating solvent and reference systems for the partition coefficient. We compare the findings from this short study with some previous theoretical work on similar systems. The binding energies for the inhibitors to the metal hydroxide clusters are found to be intermediate to the binding energies calculated in other work for bare metal vs. metal oxide surfaces. The method is applied to copper, iron, aluminum and nickel metal systems.

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

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

    2012-01-01

    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.

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

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

    2011-01-01

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

  4. Two-Dimensional Halide Perovskites for Emerging New- Generation Photodetectors

    Tang, Yingying; Cao, Xianyi; Chi, Qijin

    2018-01-01

    Compared to their conventional three-dimensional (3D) counterparts, two-dimensional (2D) halide perovskites have attracted more interests recently in a variety of areas related to optoelectronics because of their unique structural characteristics and enhanced performances. In general, there are two...... distinct types of 2D halide perovskites. One represents those perovskites with an intrinsic layered crystal structure (i.e. MX6 layers, M = metal and X = Cl, Br, I), the other defines the perovskites with a 2D nanostructured morphology such as nanoplatelets and nanosheets. Recent studies have shown that 2D...... halide perovskites hold promising potential for the development of new-generation photodetectors, mainly arising from their highly efficient photoluminescence and absorbance, color tunability in the visible-light range and relatively high stability. In this chapter, we present the summary and highlights...

  5. Lattice and Valence Electronic Structures of Crystalline Octahedral Molybdenum Halide Clusters-Based Compounds, Cs2[Mo6X14] (X = Cl, Br, I), Studied by Density Functional Theory Calculations.

    Saito, Norio; Cordier, Stéphane; Lemoine, Pierric; Ohsawa, Takeo; Wada, Yoshiki; Grasset, Fabien; Cross, Jeffrey S; Ohashi, Naoki

    2017-06-05

    The electronic and crystal structures of Cs 2 [Mo 6 X 14 ] (X = Cl, Br, I) cluster-based compounds were investigated by density functional theory (DFT) simulations and experimental methods such as powder X-ray diffraction, ultraviolet-visible spectroscopy, and X-ray photoemission spectroscopy (XPS). The experimentally determined lattice parameters were in good agreement with theoretically optimized ones, indicating the usefulness of DFT calculations for the structural investigation of these clusters. The calculated band gaps of these compounds reproduced those experimentally determined by UV-vis reflectance within an error of a few tenths of an eV. Core-level XPS and effective charge analyses indicated bonding states of the halogens changed according to their sites. The XPS valence spectra were fairly well reproduced by simulations based on the projected electron density of states weighted with cross sections of Al K α , suggesting that DFT calculations can predict the electronic properties of metal-cluster-based crystals with good accuracy.

  6. GLOBULAR CLUSTER ABUNDANCES FROM HIGH-RESOLUTION, INTEGRATED-LIGHT SPECTROSCOPY. II. EXPANDING THE METALLICITY RANGE FOR OLD CLUSTERS AND UPDATED ANALYSIS TECHNIQUES

    Colucci, Janet E.; Bernstein, Rebecca A.; McWilliam, Andrew [The Observatories of the Carnegie Institution for Science, 813 Santa Barbara St., Pasadena, CA 91101 (United States)

    2017-01-10

    We present abundances of globular clusters (GCs) in the Milky Way and Fornax from integrated-light (IL) spectra. Our goal is to evaluate the consistency of the IL analysis relative to standard abundance analysis for individual stars in those same clusters. This sample includes an updated analysis of seven clusters from our previous publications and results for five new clusters that expand the metallicity range over which our technique has been tested. We find that the [Fe/H] measured from IL spectra agrees to ∼0.1 dex for GCs with metallicities as high as [Fe/H] = −0.3, but the abundances measured for more metal-rich 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.

  7. A High-precision Trigonometric Parallax to an Ancient Metal-poor Globular Cluster

    Brown, T. M.; Casertano, S.; Strader, J.; Riess, A.; VandenBerg, D. A.; Soderblom, D. R.; Kalirai, J.; Salinas, R.

    2018-03-01

    Using the Wide Field Camera 3 (WFC3) on the Hubble Space Telescope (HST), we have obtained a direct trigonometric parallax for the nearest metal-poor globular cluster, NGC 6397. Although trigonometric parallaxes have been previously measured for many nearby open clusters, this is the first parallax for an ancient metal-poor population—one that is used as a fundamental template in many stellar population studies. This high-precision measurement was enabled by the HST/WFC3 spatial-scanning mode, providing hundreds of astrometric measurements for dozens of stars in the cluster and also for Galactic field stars along the same sightline. We find a parallax of 0.418 ± 0.013 ± 0.018 mas (statistical, systematic), corresponding to a true distance modulus of 11.89 ± 0.07 ± 0.09 mag (2.39 ± 0.07 ± 0.10 kpc). The V luminosity at the stellar main-sequence turnoff implies an absolute cluster age of 13.4 ± 0.7 ± 1.2 Gyr. Based on observations made with the NASA/ESA Hubble Space Telescope, obtained at the Space Telescope Science Institute, which is operated by the Association of Universities for Research in Astronomy, Inc., under NASA contract NAS 5-26555. These observations are associated with programs GO-13817, GO-14336, and GO-14773.

  8. Quantum kinetic theory of metal clusters in an intense electromagnetic field

    M.Bonitz

    2004-01-01

    Full Text Available A quantum kinetic theory for weakly inhomogeneous charged particle systems is derived within the framework of nonequilibrium Green's functions. The results are of relevance for valence electrons of metal clusters as well as for confined Coulomb systems, such as electrons in quantum dots or ultracold ions in traps and similar systems. To be specific, here we concentrate on the application to metal clusters, but the results are straightforwardly generalized. Therefore, we first give an introduction to the physics of correlated valence electrons of metal clusters in strong electromagnetic fields. After a brief overview on the jellium model and the standard density functional approach to the ground state properties, we focus on the extension of the theory to nonequilibrium. To this end a general gauge-invariant kinetic theory is developed. The results include the equations of motion of the two-time correlation functions, the equation for the Wigner function and an analysis of the spectral function. Here, the concept of an effective quantum potential is introduced which retains the convenient local form of the propagators. This allows us to derive explicit results for the spectral function of electrons in a combined strong electromagnetic field and a weakly inhomogeneous confinement potential.

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

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

    2014-01-01

    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

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

    Malavolta, Luca; Piotto, Giampaolo; Nascimbeni, Valerio [Dipartimento di Fisica e Astronomia, Vicolo dell' Osservatorio 3, I-35122 Padova (Italy); Sneden, Christopher [Department of Astronomy and McDonald Observatory, The University of Texas, Austin, TX 78712 (United States); Milone, Antonino P. [Research School of Astronomy and Astrophysics, The Australian National University, Cotter Road, Weston, ACT 2611 (Australia); Bedin, Luigi R., E-mail: luca.malavolta@unipd.it, E-mail: giampaolo.piotto@unipd.it, E-mail: valerio.nascimbeni@unipd.it, E-mail: luigi.bedin@oapd.inaf.it, E-mail: chris@verdi.as.utexas.edu, E-mail: milone@mso.anu.edu.au [INAF-Osservatorio Astronomico di Padova, Vicolo dell' Osservatorio 5, I-35122 Padova (Italy)

    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.

  11. Magneto-structural properties and magnetic anisotropy of small transition-metal clusters: a first-principles study

    Blonski, Piotr; Hafner, Juergen

    2011-01-01

    Ab initio density-functional calculations including spin-orbit coupling (SOC) have been performed for Ni and Pd clusters with three to six atoms and for 13-atom clusters of Ni, Pd, and Pt, extending earlier calculations for Pt clusters with up to six atoms (2011 J. Chem. Phys. 134 034107). The geometric and magnetic structures have been optimized for different orientations of the magnetization with respect to the crystallographic axes of the cluster. The magnetic anisotropy energies (MAE) and the anisotropies of spin and orbital moments have been determined. Particular attention has been paid to the correlation between the geometric and magnetic structures. The magnetic point group symmetry of the clusters varies with the direction of the magnetization. Even for a 3d metal such as Ni, the change in the magnetic symmetry leads to small geometric distortions of the cluster structure, which are even more pronounced for the 4d metal Pd. For a 5d metal the SOC is strong enough to change the energetic ordering of the structural isomers. SOC leads to a mixing of the spin states corresponding to the low-energy spin isomers identified in the scalar-relativistic calculations. Spin moments are isotropic only for Ni clusters, but anisotropic for Pd and Pt clusters, orbital moments are anisotropic for the clusters of all three elements. The magnetic anisotropy energies have been calculated. The comparison between MAE and orbital anisotropy invalidates a perturbation analysis of magnetic anisotropy for these small clusters.

  12. Electronic and magnetic properties of 3d transition metal-doped strontium clusters: Prospective magnetic superatoms

    Chauhan, Vikas; Sen, Prasenjit

    2013-01-01

    Highlights: • Structural, electronic and magnetic properties of TM-Sr clusters are studied using DFT methods. • CrSr 9 and MnSr 10 have enhanced stability in the CrSr n and MnSrn series. • These two clusters behave as magnetic superatoms. • A qualitative understanding of the magnetic coupling between two superatom units is offered. • Reactivity of these superatoms to molecular oxygen also studied. - Abstract: Structural, electronic and magnetic properties of 3d transition metal doped strontium clusters are studied using first-principles electronic structure methods based on density functional theory. Clusters with enhanced kinetic and thermodynamic stability are identified by studying their hardness, second order energy difference and adiabatic spin excitation energy. CrSr 9 and MnSr 10 are found to have enhanced stability. They retain their structural identities in assemblies, and are classified as magnetic superatoms. A qualitative understanding of the magnetic coupling between two cluster units is arrived at. Reactivity of these superatoms with O 2 molecule is also studied. Prospects for using these magnetic superatoms in applications are discussed

  13. A numerical study of spin-dependent organization of alkali-metal atomic clusters using density-functional method

    Liu Xuan; Ito, Haruhiko; Torikai, Eiko

    2012-01-01

    We calculate the different geometric isomers of spin clusters composed of a small number of alkali-metal atoms using the UB3LYP density-functional method. The electron density distribution of clusters changes according to the value of total spin. Steric structures as well as planar structures arise when the number of atoms increases. The lowest spin state is the most stable and Li n , Na n , K n , Rb n , and Cs n with n = 2–8 can be formed in higher spin states. In the highest spin state, the preparation of clusters depends on the kind and the number of constituent atoms. The interaction energy between alkali-metal atoms and rare-gas atoms is smaller than the binding energy of spin clusters. Consequently, it is possible to self-organize the alkali-metal-atom clusters on a non-wetting substrate coated with rare-gas atoms.

  14. Metal-Organic Framework of Lanthanoid Dinuclear Clusters Undergoes Slow Magnetic Relaxation

    Hikaru Iwami

    2017-01-01

    Full Text Available Lanthanoid metal-organic frameworks (Ln-MOFs can adopt a variety of new structures due to the large coordination numbers of Ln metal ions, and Ln-MOFs are expected to show new luminescence and magnetic properties due to the localized f electrons. In particular, some Ln metal ions, such as Dy(III and Tb(III ions, work as isolated quantum magnets when they have magnetic anisotropy. In this work, using 4,4′,4″-s-triazine-2,4,6-triyl-tribenzoic acid (H3TATB as a ligand, two new Ln-MOFs, [Dy(TATB(DMF2] (1 and [Tb(TATB(DMF2] (2, were obtained. The Ln-MOFs contain Ln dinuclear clusters as secondary building units, and 1 underwent slow magnetic relaxation similar to single-molecule magnets.

  15. Three exciting areas of experimental physical sciences : high temperature superconductors, metal clusters and super molecules of carbon

    Rao, C.N.

    1992-01-01

    The author has narrated his experience in carrying out research in three exciting areas of physical sciences. These areas are : high temperature superconductors, metal clusters and super molecules of carbon. (M.G.B.)

  16. Spectra of globular clusters in the Sombrero galaxy: evidence for spectroscopic metallicity bimodality

    Alves-Brito, Alan; Hau, George K. T.; Forbes, Duncan A.; Spitler, Lee R.; Strader, Jay; Brodie, Jean P.; Rhode, Katherine L.

    2011-11-01

    We present a large sample of over 200 integrated-light spectra of confirmed globular clusters (GCs) associated with the Sombrero (M104) galaxy taken with the Deep Imaging Multi-Object Spectrograph (DEIMOS) instrument on the Keck telescope. A significant fraction of the spectra have signal-to-noise ratio levels high enough to allow measurements of GC metallicities using the method of Brodie & Huchra. We find a distribution of spectroscopic metallicities in the range -2.2 < [Fe/H] < +0.1 that is bimodal, with peaks at [Fe/H]˜-1.4 and -0.6. Thus, the GC system of the Sombrero galaxy, like a few other galaxies now studied in detail, reveals a bimodal spectroscopic metallicity distribution supporting the long-held belief that colour bimodality reflects two metallicity subpopulations. This further suggests that the transformation from optical colour to metallicity for old stellar populations, such as GCs, is not strongly non-linear. We also explore the radial and magnitude distribution with metallicity for GC subpopulations but small number statistics prevent any clear trends in these distributions. Based on observations obtained at the W. M. Keck Observatory, which is operated as a scientific partnership among the California Institute of Technology, the University of California and the National Aeronautics and Space Administration.

  17. Clustered atom-replaced structure in single-crystal-like metal oxide

    Araki, Takeshi; Hayashi, Mariko; Ishii, Hirotaka; Yokoe, Daisaku; Yoshida, Ryuji; Kato, Takeharu; Nishijima, Gen; Matsumoto, Akiyoshi

    2018-06-01

    By means of metal organic deposition using trifluoroacetates (TFA-MOD), we replaced and localized two or more atoms in a single-crystalline structure having almost perfect orientation. Thus, we created a new functional structure, namely, clustered atom-replaced structure (CARS), having single-crystal-like metal oxide. We replaced metals in the oxide with Sm and Lu and localized them. Energy dispersive x-ray spectroscopy results, where the Sm signal increases with the Lu signal in the single-crystalline structure, confirm evidence of CARS. We also form other CARS with three additional metals, including Pr. The valence number of Pr might change from 3+ to approximately 4+, thereby reducing the Pr–Ba distance. We directly observed the structure by a high-angle annular dark-field image, which provided further evidence of CARS. The key to establishing CARS is an equilibrium chemical reaction and a combination of additional larger and smaller unit cells to matrix cells. We made a new functional metal oxide with CARS and expect to realize CARS in other metal oxide structures in the future by using the above-mentioned process.

  18. Making and Breaking of Lead Halide Perovskites

    Manser, Joseph S.

    2016-02-16

    A new front-runner has emerged in the field of next-generation photovoltaics. A unique class of materials, known as organic metal halide perovskites, bridges the gap between low-cost fabrication and exceptional device performance. These compounds can be processed at low temperature (typically in the range 80–150 °C) and readily self-assemble from the solution phase into high-quality semiconductor thin films. The low energetic barrier for crystal formation has mixed consequences. On one hand, it enables inexpensive processing and both optical and electronic tunability. The caveat, however, is that many as-formed lead halide perovskite thin films lack chemical and structural stability, undergoing rapid degradation in the presence of moisture or heat. To date, improvements in perovskite solar cell efficiency have resulted primarily from better control over thin film morphology, manipulation of the stoichiometry and chemistry of lead halide and alkylammonium halide precursors, and the choice of solvent treatment. Proper characterization and tuning of processing parameters can aid in rational optimization of perovskite devices. Likewise, gaining a comprehensive understanding of the degradation mechanism and identifying components of the perovskite structure that may be particularly susceptible to attack by moisture are vital to mitigate device degradation under operating conditions. This Account provides insight into the lifecycle of organic–inorganic lead halide perovskites, including (i) the nature of the precursor solution, (ii) formation of solid-state perovskite thin films and single crystals, and (iii) transformation of perovskites into hydrated phases upon exposure to moisture. In particular, spectroscopic and structural characterization techniques shed light on the thermally driven evolution of the perovskite structure. By tuning precursor stoichiometry and chemistry, and thus the lead halide charge-transfer complexes present in solution, crystallization

  19. Influence of a transition metal atom on the geometry and electronic structure of Mg and Mg-H clusters

    Siretskiy, M.Yu.; Shelyapina, M.G.; Fruchart, D.; Miraglia, S.; Skryabina, N.E.

    2009-01-01

    We report on the study of (MgH 2 ) n + M complexes (M = Ti or Ni) carried out within the framework of the cluster density functional theory (DFT) method. The influence of such transition metal atoms on the cluster geometry and electronic structure is discussed considering the stability of MgH 2 hydride.

  20. Major signal suppression from metal ion clusters in SFC/ESI-MS - Cause and effects.

    Haglind, Alfred; Hedeland, Mikael; Arvidsson, Torbjörn; Pettersson, Curt E

    2018-05-01

    The widening application area of SFC-MS with polar analytes and water-containing samples facilitates the use of quick and simple sample preparation techniques such as "dilute and shoot" and protein precipitation. This has also introduced new polar interfering components such as alkali metal ions naturally abundant in e.g. blood plasma and urine, which have shown to be retained using screening conditions in SFC/ESI-TOF-MS and causing areas of major ion suppression. Analytes co-eluting with these clusters will have a decreased signal intensity, which might have a major effect on both quantification and identification. When investigating the composition of the alkali metal clusters using accurate mass and isotopic pattern, it could be concluded that they were previously not described in the literature. Using NaCl and KCl standards and different chromatographic conditions, varying e.g. column and modifier, the clusters proved to be formed from the alkali metal ions in combination with the alcohol modifier and make-up solvent. Their compositions were [(XOCH 3 ) n  + X] + , [(XOH) n  + X] + , [(X 2 CO 3 ) n  + X] + and [(XOOCOCH 3 ) n  + X] + for X = Na + or K + in ESI+. In ESI-, the clusters depended more on modifier, with [(XCl) n  + Cl] - and [(XOCH 3 ) n  + OCH 3 ] - mainly formed in pure methanol and [(XOOCH) n  + OOCH] - when 20 mM NH 4 Fa was added. To prevent the formation of the clusters by avoiding methanol as modifier might be difficult, as this is a widely used modifier providing good solubility when analyzing polar compounds in SFC. A sample preparation with e.g. LLE would remove the alkali ions, however also introducing a time consuming and discriminating step into the method. Since the alkali metal ions were retained and affected by chromatographic adjustments as e.g. mobile phase modifications, a way to avoid them could therefore be chromatographic tuning, when analyzing samples containing them. Copyright © 2018 Elsevier

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

    Leaman, Ryan

    2012-01-01

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

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

    Fernandez, Ricardo; Bryan, Greg L.

    2018-05-01

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

  3. SOLAR-LIKE OSCILLATIONS IN A METAL-POOR GLOBULAR CLUSTER WITH THE HUBBLE SPACE TELESCOPE

    Stello, Dennis; Gilliland, Ronald L.

    2009-01-01

    We present analyses of variability in the red giant stars in the metal-poor globular cluster NGC 6397, based on data obtained with the Hubble Space Telescope. We use a nonstandard data reduction approach to turn a 23 day observing run originally aimed at imaging the white dwarf population, into time-series photometry of the cluster's highly saturated red giant stars. With this technique we obtain noise levels in the final power spectra down to 50 parts per million, which allows us to search for low-amplitude solar-like oscillations. We compare the observed excess power seen in the power spectra with estimates of the typical frequency range, frequency spacing, and amplitude from scaling the solar oscillations. We see evidence that the detected variability is consistent with solar-like oscillations in at least one and perhaps up to four stars. With metallicities 2 orders of magnitude lower than those of the Sun, these stars present so far the best evidence of solar-like oscillations in such a low-metallicity environment.

  4. 40 CFR 63.2465 - What requirements must I meet for process vents that emit hydrogen halide and halogen HAP or HAP...

    2010-07-01

    ... process vents that emit hydrogen halide and halogen HAP or HAP metals? 63.2465 Section 63.2465 Protection... and halogen HAP or HAP metals? (a) You must meet each emission limit in Table 3 to this subpart that... section. (b) If any process vents within a process emit hydrogen halide and halogen HAP, you must...

  5. Development of halide copper vapor laser (the characteristics of using Cul)

    Oouti, Kazumi; Wada, Yukio; Sasao, Nobuyuki

    1990-01-01

    We are developing halide copper vapor laser that is high efficiency and high reputation rate visible laser. Halide copper vapor laser uses halide copper of copper vapor source. It melts low temperature in comporison with metal copper, because laser tube structure is very simple and it can operate easy. This time, we experiment to use Cul for copper vapor source. We resulted maximum output energy 17.8 (W) and maximum efficiency 0.78 (%) when operate condition was reputation rate 30 (kHz), gas pressure 90 (Torr), charging voltage 13 (kV). (author)

  6. Chemical study of the metal-rich globular cluster NGC 5927

    Mura-Guzmán, A.; Villanova, S.; Muñoz, C.; Tang, B.

    2018-03-01

    Globular clusters (GCs) are natural laboratories where stellar and chemical evolution can be studied in detail. In addition, their chemical patterns and kinematics can tell us to which Galactic structure (disc, bulge, halo or extragalactic) the cluster belongs to. NGC 5927 is one of most metal-rich GCs in the Galaxy and its kinematics links it to the thick disc. We present abundance analysis based on high-resolution spectra of seven giant stars. The data were obtained using Fibre Large Array Multi Element Spectrograph/Ultraviolet Echelle Spectrograph (UVES) spectrograph mounted on UT2 telescope of the European Southern Observatory. The principal objective of this work is to perform a wide and detailed chemical abundance analysis of the cluster and look for possible Multiple Populations (MPs). We determined stellar parameters and measured 22 elements corresponding to light (Na, Al), alpha (O, Mg, Si, Ca, Ti), iron-peak (Sc, V, Cr, Mn, Fe, Co, Ni, Cu, Zn), and heavy elements (Y, Zr, Ba, Ce, Nd, Eu). We found a mean iron content of [Fe/H] = -0.47 ± 0.02 (error on the mean). We confirm the existence of MPs in this GC with an O-Na anti-correlation, and moderate spread in Al abundances. We estimate a mean [α/Fe] = 0.25 ± 0.08. Iron-peak elements show no significant spread. The [Ba/Eu] ratios indicate a predominant contribution from SNeII for the formation of the cluster.

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

    Keil, Th; Bauer, D

    2014-01-01

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

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

    Alcaino, G.; Liller, W.

    1980-01-01

    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 (Δm=3/sup m/.60), the CTIO 4-m telescope (Δm=6/sup m/.83), and the ESO 3.6-m telescope (Δm=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) 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 9 yr. The large uncertainty in this value emphasizes the dire need for more work on cluster evolution

  9. Tuning the magnetic properties of deposited transition metal clusters by decoration

    Minar, Jan; Bornemann, S.; Ebert, H. [Dept. Chemie, LMU, Butenandtstr. 5-13, 81377 Muenchen (Germany); Staunton, J.B. [Department of Physics, University of Warwick (United Kingdom); Rusponi, S.; Brunne, H. [EPF Lausanne (Switzerland)

    2008-07-01

    Using the fully relativistic version of the KKR-method for electronic structure calculations within local spin density functional theory (LSDA) the magnetic properties of Fe, Co and Ni clusters deposited on the Pt(111) surface have been investigated. Of central interest are the role of spin-orbit coupling as it influences the spontaneous formation and orientation of magnetic moments and gives rise amongst others to the occurrence of orbital magnetic moments, the magnetic anisotropy energy (MAE) and magnetic circular dichroism in X-ray absorption (XMCD). Our systematic investigations of different clusters and nanostructures aim to reveal the mutual relationship among their spin-orbit induced properties. In addition they show how their various magnetic properties depend on the structural properties and chemical composition of the studied system. For large two-dimensional clusters we focussed especially on the dependency of the MAE on decoration with another transition metal. Our results are in qualitative agreement with recent experimental findings. We resolved the MAE contributions for inequivalent cluster atoms and will discuss the effect of the induced MAE within the Pt substrate.

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

    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

  11. Synthesis and characterization of αzirconium (IV) hydrogenphosphate containing metallic copper clusters

    Souza, Alexilda Oliveira de; Rangel, Maria do Carmo; Alves, Oswaldo Luiz

    2005-01-01

    The α-zirconium (IV) hydrogenphosphate (α-ZrP) has received great attention in the last years due to its properties like ion exchange, intercalation, ionic conductivity and catalytic activity. This work reports a method to produce metallic copper clusters on α-ZrP to be used as catalysts in petrochemical processes. It was found that the solids were non-crystalline regardless of the uptake of copper and the reduction. The specific surface area increased as a consequence of the increase of the interlayer distance to accept the copper ions between the layers. During the reduction, big clusters of copper (0,5-11μ) with different sizes and shapes were produced. (author)

  12. Making and Breaking of Lead Halide Perovskites

    Manser, Joseph S.; Saidaminov, Makhsud I.; Christians, Jeffrey A.; Bakr, Osman; Kamat, Prashant V.

    2016-01-01

    To date, improvements in perovskite solar cell efficiency have resulted primarily from better control over thin film morphology, manipulation of the stoichiometry and chemistry of lead halide and alkylammonium halide precursors, and the choice

  13. Cation-Dependent Light-Induced Halide Demixing in Hybrid Organic-Inorganic Perovskites.

    Sutter-Fella, Carolin M; Ngo, Quynh P; Cefarin, Nicola; Gardner, Kira L; Tamura, Nobumichi; Stan, Camelia V; Drisdell, Walter S; Javey, Ali; Toma, Francesca M; Sharp, Ian D

    2018-06-13

    Mixed cation metal halide perovskites with increased power conversion efficiency, negligible hysteresis, and improved long-term stability under illumination, moisture, and thermal stressing have emerged as promising compounds for photovoltaic and optoelectronic applications. Here, we shed light on photoinduced halide demixing using in situ photoluminescence spectroscopy and in situ synchrotron X-ray diffraction (XRD) to directly compare the evolution of composition and phase changes in CH(NH 2 ) 2 CsPb-halide (FACsPb-) and CH 3 NH 3 Pb-halide (MAPb-) perovskites upon illumination, thereby providing insights into why FACs-perovskites are less prone to halide demixing than MA-perovskites. We find that halide demixing occurs in both materials. However, the I-rich domains formed during demixing accumulate strain in FACsPb-perovskites but readily relax in MA-perovskites. The accumulated strain energy is expected to act as a stabilizing force against halide demixing and may explain the higher Br composition threshold for demixing to occur in FACsPb-halides. In addition, we find that while halide demixing leads to a quenching of the high-energy photoluminescence emission from MA-perovskites, the emission is enhanced from FACs-perovskites. This behavior points to a reduction of nonradiative recombination centers in FACs-perovskites arising from the demixing process and buildup of strain. FACsPb-halide perovskites exhibit excellent intrinsic material properties with photoluminescence quantum yields that are comparable to MA-perovskites. Because improved stability is achieved without sacrificing electronic properties, these compositions are better candidates for photovoltaic applications, especially as wide bandgap absorbers in tandem cells.

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

    Boberg, Owen M.; Friel, Eileen D.; Vesperini, Enrico [Astronomy Department, Indiana University, Bloomington, IN 47405 (United States)

    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.

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

    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.

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

    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 lang[Fe/H]rang = -1.16 (σ = 0.09) after fixing the microturbulent velocity. These values are consistent with previous studies that have performed detailed analyses of brighter RGB stars at higher spectroscopic resolution and wavelength coverage. It is not clear if the small mean metallicity difference between brighter and fainter M4 members is real or is the result of the low signal-to-noise characteristics of the fainter stars. The strength of our approach is shown by recovering a metallicity close to a single value for more than 2000 stars, using a data set that is non-optimal for atmospheric analyses. This technique is particularly suitable for noisy data taken in difficult observing conditions.

  17. Room-Temperature Synthesis of Transition Metal Clusters and Main Group Polycations from Ionic Liquids

    Ahmed, Ejaz

    2011-01-01

    Main group polycations and transition metal clusters had traditionally been synthesized via high-temperature routes by performing reactions in melts or by CTR, at room-temperature or lower temperature by using so-called superacid solvents, and at room-temperature in benzene–GaX3 media. Considering the major problems associated with higher temperature routes (e.g. long annealing time, risk of product decomposition, and low yield) and taking into account the toxicity of benzene and liquid SO2 i...

  18. Cation-Dependent Light-Induced Halide Demixing in Hybrid Organic-Inorganic Perovskites

    Sutter-Fella, CM; Ngo, QP; Cefarin, N; Gardener, K; Tamura, N; Stan, CV; Drisdell, WS; Javey, A; Toma, FM; Sharp, ID

    2018-01-01

    © 2018 American Chemical Society. Mixed cation metal halide perovskites with increased power conversion efficiency, negligible hysteresis, and improved long term stability under illumination, moisture, and thermal stressing have emerged as promising compounds for photovoltaic and optoelectronic applications. Here, we shed light on photo-induced halide demixing using in-situ photoluminescence spectroscopy and in-situ synchrotron X-ray diffraction (XRD) to directly compare the evolution of comp...

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

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

    2014-01-01

    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.

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

    Saha, Arjun; Raghavachari, Krishnan [Department of Chemistry, Indiana University, Bloomington, Indiana 47405 (United States)

    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 −})

  1. Maximizing and stabilizing luminescence from halide perovskites with potassium passivation

    Abdi-Jalebi, Mojtaba; Andaji-Garmaroudi, Zahra; Cacovich, Stefania; Stavrakas, Camille; Philippe, Bertrand; Richter, Johannes M.; Alsari, Mejd; Booker, Edward P.; Hutter, Eline M.; Pearson, Andrew J.; Lilliu, Samuele; Savenije, Tom J.; Rensmo, Håkan; Divitini, Giorgio; Ducati, Caterina; Friend, Richard H.; Stranks, Samuel D.

    2018-03-01

    Metal halide perovskites are of great interest for various high-performance optoelectronic applications. The ability to tune the perovskite bandgap continuously by modifying the chemical composition opens up applications for perovskites as coloured emitters, in building-integrated photovoltaics, and as components of tandem photovoltaics to increase the power conversion efficiency. Nevertheless, performance is limited by non-radiative losses, with luminescence yields in state-of-the-art perovskite solar cells still far from 100 per cent under standard solar illumination conditions. Furthermore, in mixed halide perovskite systems designed for continuous bandgap tunability (bandgaps of approximately 1.7 to 1.9 electronvolts), photoinduced ion segregation leads to bandgap instabilities. Here we demonstrate substantial mitigation of both non-radiative losses and photoinduced ion migration in perovskite films and interfaces by decorating the surfaces and grain boundaries with passivating potassium halide layers. We demonstrate external photoluminescence quantum yields of 66 per cent, which translate to internal yields that exceed 95 per cent. The high luminescence yields are achieved while maintaining high mobilities of more than 40 square centimetres per volt per second, providing the elusive combination of both high luminescence and excellent charge transport. When interfaced with electrodes in a solar cell device stack, the external luminescence yield—a quantity that must be maximized to obtain high efficiency—remains as high as 15 per cent, indicating very clean interfaces. We also demonstrate the inhibition of transient photoinduced ion-migration processes across a wide range of mixed halide perovskite bandgaps in materials that exhibit bandgap instabilities when unpassivated. We validate these results in fully operating solar cells. Our work represents an important advance in the construction of tunable metal halide perovskite films and interfaces that can

  2. Relaxation processes in optically excites metal clusters; Relaxationsprozesse in optisch angeregten Metallclustern

    Stanzel, J.

    2007-08-10

    The present work is concerned with the dynamics of optically excited metal clusters in the gas phase. Small mass-selected gold and tungsten cluster anions (Au{sup -}{sub n}, n=5-8, 14, 20 and W{sup -}{sub n}, n=3-14) are studied using femtosecond time-resolved photoelectron spectroscopy. Depending on the electronic structure in the valence region as well as on the optical excitation energy fundamentally different relaxation processes are observed. In small gold cluster anions excited with 1.56 eV an isolated electronically excited state is populated. The time-dependent measurements are strongly sizedependent and open insights into photoinduced geometry changes of the nuclear framework. Oscillatory vibrational wavepacket motion in Au{sup -}{sub 5}, an extremely longlived ({tau} >90 ns) electronically excited state in Au{sup -}{sub 6} as well as photoinduced melting in Au{sup -}{sub 7} and Au{sup -}{sub 8} is monitored in real time. By increasing the OPTICAL excitation energy to 3.12 eV a completely different scenario is observed. A multitude of electronically excited states can be reached upon optical excitation and as a consequence electronic relaxation processes that take place on a time scale of 1 ps are dominating. This is shown for Au{sup -}{sub 7}, Au{sup -}{sub 14} and Au{sup -}{sub 20}. Compared to gold clusters, tungsten clusters are characterized by a significantly higher electronic density of states in the valence region. Therefore electronic relaxation processes are much more likely and take place on a significantly faster time scale. The fast electronic relaxation processes are distinguished from pure vibrational relaxation. It is shown that already in the four atomic tungsten cluster W{sup -}{sub 4} electronic relaxation processes take place on a time scale of 30 fs. In all investigated tungsten cluster anions (W{sup -}{sub n}, n=3-14) an equilibrium between electronic and vibrational system is reached within around 1 ps after optical excitation which

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

    Mucciarelli, A.; Lovisi, L.; Lanzoni, B.; Ferraro, F. R. [Dipartimento di Fisica and Astronomia, Università degli Studi di Bologna, Viale Berti Pichat 6/2, I-40127 Bologna (Italy)

    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.

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

    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.

  5. Hot stars in young massive clusters: Mapping the current Galactic metallicity

    de la Fuente, Diego; Najarro, Francisco; Davies, Ben; Trombley, Christine; Figer, Donald F.; Herrero, Artemio

    2013-06-01

    Young Massive Clusters (YMCs) with ages guarantee that these objects present the same chemical composition than the surrounding environment where they are recently born. Finally, the YMCs host very massive stars whose extreme luminosities allow to accomplish detailed spectroscopic analyses even in the most distant regions of the Milky Way. Our group has carried out ISAAC/VLT spectroscopic observations of hot massive stars belonging to several YMCs in different locations around the Galactic disk. As a result, high signal-to-noise, near-infrared spectra of dozens of blue massive stars (including many OB supergiants, Wolf-Rayet stars and a B hypergiant) have been obtained. These data are fully reduced, and NLTE spherical atmosphere modeling is in process. Several line diagnostics will be combined in order to calculate metal abundances accurately for each cluster. The diverse locations of the clusters will allow us to draw a two-dimensional chemical map of the Galactic disk for the first time. The study of the radial and azimuthal variations of elemental abundances will be crucial for understanding the chemical evolution of the Milky Way. Particularly, the ratio between Fe-peak and alpha elements will constitute a powerful tool to investigate the past stellar populations that originated the current Galactic chemistry.

  6. Theoretical study of electronic and dynamic properties of simple metal clusters in jellium model

    El-Amine Madjet, M.

    1994-01-01

    We have studied the electronic properties of alkali-metal clusters in various theoretical approximations and in the framework of the spherical jellium model. We have investigated the ground state properties of alkali clusters both in the LDA (local density approximation) and in HF (Hartree-Fock) theory. We have compared the LDA predictions of the ground state properties to predictions obtained within the HF theory. Such a comparison permitted us to check the validity of the local density functional theory in describing the ground state of a finite fermion system. For the study of collective dipolar excitations in clusters, we have considered an electromagnetic excitation. We have investigated the collective modes in the following approximations: random phase approximation (RPA), time-dependent local-density approximation (TDLDA) and the sum-rules approach. An assessment of the approximation for the continuum state within the RPA is made by comparing with TDLDA calculations for the static and dynamic electronic properties. The comparative study that we have done on the exchange-correlation effects on the electronic and optical properties have shown that the discrepancies with measured data are due mostly to the jellium approximation for the ionic background. (author). 69 refs., 30 figs., 18 tabs

  7. Density-functional theory study of ionic inhomogeneity in metal clusters using SC-ISJM

    Payami, Mahmoud; Mahmoodi, Tahereh

    2017-12-01

    In this work we have applied the recently formulated self-compressed inhomogeneous stabilized jellium model [51] to describe the equilibrium electronic and geometric properties of atomic-closed-shell simple metal clusters of AlN (N = 13, 19, 43, 55, 79, 87, 135, 141), NaN, and CsN (N = 9, 15, 27, 51, 59, 65, 89, 113). To validate the results, we have also performed first-principles pseudo-potential calculations and used them as our reference. In the model, we have considered two regions consisting of ;surface; and ;inner; ones, the border separating them being sharp. This generalization makes possible to decouple the relaxations of different parts of the system. The results show that the present model correctly predicts the size reductions seen in most of the clusters. It also predicts increase in size of some clusters, as observed from first-principles results. Moreover, the changes in inter-layer distances, being as contractions or expansions, are in good agreement with the atomic simulation results. For a more realistic description of the properties, it is possible to improve the method of choosing the surface thicknesses or generalize the model to include more regions than just two.

  8. Homochiral coordination polymers with helixes and metal clusters based on lactate derivatives

    Xu, Zhong-Xuan, E-mail: xuzhongxuan4201@163.com [Department of Chemistry, Zunyi Normal College, Zunyi, Guizhou 563002 (China); Ma, Yu-Lu [School of Chemical Science and Technology, Yunnan University, Kunming 650091 (China); Lv, Guo-ling [Department of Chemistry, Zunyi Normal College, Zunyi, Guizhou 563002 (China)

    2017-05-15

    Utilizing the lactic acid derivatives (R)-4-(1-carboxyethoxy)benzoic acid (denoted: (R)-H{sub 2}CBA) and (S)-4-(1-carboxyethoxy)benzoic acid (denoted: (S)-H{sub 2}CBA)as chiral linkers to self-assemble with 4, 4′-bipyridine (denoted: BIP) and Cd(II) ions, a couple of three-dimensional homochiral coordination polymers, namely [Cd{sub 3}((R)-CBA){sub 3} (BIP){sub 2}(H{sub 2}O)]·xGuest (1-D) and [Cd{sub 3}((S)-CBA){sub 3}(BIP){sub 2}(H{sub 2}O)]·xGuest (1-L), have been synthesized under solvothermal reaction condition. Single crystal X-ray diffraction analysis reveals the two complexes contain single helical chains based on enantiopure ligands and cadmium clusters. Moreover, some physical characteristics such as PXRD, thermal stability, solid-state circular dichroism (CD) and luminescent were also investigated. - Graphical abstract: Utilizing enantiomeric lactic acid derivatives (R)-H{sub 2}CBA and (S)-H{sub 2}CBA to assemble with Cd{sup 2+} ions and ancillary BIP ligands, a couple of 3D homochiral coordination polymers with metal clusters and helical chains have been prepared by hydrothermal reaction. - Highlights: • Chiral lactic acid derivative. • Enantiomeric coordination polymer. • Helical chain. • Trinuclear cadmium cluster.

  9. PROCESSING OF URANIUM-METAL-CONTAINING FUEL ELEMENTS

    Moore, R.H.

    1962-10-01

    A process is given for recovering uranium from neutronbombarded uranium- aluminum alloys. The alloy is dissolved in an aluminum halide--alkali metal halide mixture in which the halide is a mixture of chloride and bromide, the aluminum halide is present in about stoichiometric quantity as to uranium and fission products and the alkali metal halide in a predominant quantity; the uranium- and electropositive fission-products-containing salt phase is separated from the electronegative-containing metal phase; more aluminum halide is added to the salt phase to obtain equimolarity as to the alkali metal halide; adding an excess of aluminum metal whereby uranium metal is formed and alloyed with the excess aluminum; and separating the uranium-aluminum alloy from the fission- productscontaining salt phase. (AEC)

  10. clusters

    2017-09-27

    Sep 27, 2017 ... Author for correspondence (zh4403701@126.com). MS received 15 ... lic clusters using density functional theory (DFT)-GGA of the DMOL3 package. ... In the process of geometric optimization, con- vergence thresholds ..... and Postgraduate Research & Practice Innovation Program of. Jiangsu Province ...

  11. clusters

    environmental as well as technical problems during fuel gas utilization. ... adsorption on some alloys of Pd, namely PdAu, PdAg ... ried out on small neutral and charged Au24,26,27, Cu,28 ... study of Zanti et al.29 on Pdn (n = 1–9) clusters.

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

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

    2017-06-01

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

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

    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

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

    Anokhina, Ekaterina V.

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

  15. Luminescent decay and spectra of impurity-activated alkali halides under high pressure

    Klick, D.I.

    1977-01-01

    The effect of high pressure on the luminescence of alkali halides doped with the transition-metal ions Cu + and Ag + and the heavy-metal ions In + and Tl + was investigated to 140 kbar. Measurement of spectra allowed the prediction of kinetic properties, and the predictions agree with lifetime data

  16. Metal halide-phosphorus halide-alkyl halide complexes: reaction with niobium and tantalum pentachlorides

    Puri, D.M.; Saini, M.S.

    1978-01-01

    The reactions of niobium and tantalum pentachlorides with trichlorophosphine and phenyldichlorophosphine have been studied in presence of alkylating agents such as sec-butyl chloride, iso-butyl chloride, tert-butyl chloride, tert-anylchloride, cyclohexyl chloride and triphenylmethyl chloride. Solid products have been isolated and characterised by vibrational spectroscopy as ionic complexes of alkyl- and/or aryl-phosphonium cations with hexachloroniobate and hexachlorotantalate anions. (author)

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

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

    2008-01-01

    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

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

    Zhou Shengqiang; Potzger, K; Talut, G; Reuther, H; Kuepper, K; Grenzer, J; Xu Qingyu; Muecklich, A; Helm, M; Fassbender, J; Arenholz, E

    2008-01-01

    We investigated ZnO(0 0 0 1) 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

  19. Formation of transition metal cluster adducts on the surface of single-walled carbon nanotubes: HRTEM studies

    Kalinina, Irina V.

    2014-01-01

    We report the formation of chromium clusters on the outer walls of single-walled carbon nanotubes (SWNTs). The clusters were obtained by reacting purified SWNTs with chromium hexacarbonyl in dibutyl ether at 100°C. The functionalized SWNTs were characterized by thermogravimetic analysis, XPS, and high-resolution TEM. The curvature of the SWNTs and the high mobility of the chromium moieties on graphitic surfaces allow the growth of the metal clusters and we propose a mechanism for their formation. © 2014 Taylor and Francis Group, LLC.

  20. Low Metallicities and Old Ages for Three Ultra-diffuse Galaxies in the Coma Cluster

    Gu, Meng; Conroy, Charlie; Law, David; van Dokkum, Pieter; Yan, Renbin; Wake, David; Bundy, Kevin; Merritt, Allison; Abraham, Roberto; Zhang, Jielai; Bershady, Matthew; Bizyaev, Dmitry; Brinkmann, Jonathan; Drory, Niv; Grabowski, Kathleen; Masters, Karen; Pan, Kaike; Parejko, John; Weijmans, Anne-Marie; Zhang, Kai

    2018-05-01

    A large population of ultra-diffuse galaxies (UDGs) was recently discovered in the Coma cluster. Here we present optical spectra of three such UDGs, DF 7, DF 44, and DF 17, which have central surface brightnesses of μ g ≈ 24.4–25.1 mag arcsec‑2. The spectra were acquired as part of an ancillary program within the SDSS-IV MaNGA Survey. We stacked 19 fibers in the central regions from larger integral field units (IFUs) per source. With over 13.5 hr of on-source integration, we achieved a mean signal-to-noise ratio in the optical of 9.5 Å‑1, 7.9 Å‑1, and 5.0 Å‑1, respectively, for DF 7, DF 44, and DF 17. Stellar population models applied to these spectra enable measurements of recession velocities, ages, and metallicities. The recession velocities of DF 7, DF 44, and DF 17 are {6599}-25+40 km s‑1, {6402}-39+41 km s‑1, and {8315}-43+43 km s‑1, spectroscopically confirming that all of them reside in the Coma cluster. The stellar populations of these three galaxies are old and metal-poor, with ages of {7.9}-2.5+3.6 Gyr, {8.9}-3.3+4.3 Gyr, and {9.1}-5.5+3.9 Gyr, and iron abundances of [Fe/H] -{1.0}-0.4+0.3, -{1.3}-0.4+0.4, and -{0.8}-0.5+0.5, respectively. Their stellar masses are (3–6) × 108 M ⊙. The UDGs in our sample are as old or older than galaxies at similar stellar mass or velocity dispersion (only DF 44 has an independently measured dispersion). They all follow the well-established stellar mass–stellar metallicity relation, while DF 44 lies below the velocity dispersion-metallicity relation. These results, combined with the fact that UDGs are unusually large for their stellar masses, suggest that stellar mass plays a more important role in setting stellar population properties for these galaxies than either size or surface brightness.

  1. Liquid-liquid phase separation and cluster formation at deposition of metals under inhomogeneous magnetic field

    Gorobets, O. Yu; Gorobets, Yu I.; Rospotniuk, V. P.; Grebinaha, V. I.; Kyba, A. A.

    2017-10-01

    The formation and dynamic of expansion and deformation of the liquid-liquid interface of an electrolyte at deposition of metals at the surface of the magnetized steel ball is considered in this paper. The electrochemical processes were investigated in an external magnetic field directed at an arbitrary angle to the force of gravity. These processes are accompanied by the formation of effectively paramagnetic clusters of electrochemical products - magnions. Tyndall effect was used for detection of the presence of magnions near the magnetized steel electrode in a solution. The shape of the interface separating the regions with different concentration of magnions, i.e. different magnetic susceptibilities, was described theoretically based on the equation of hydrostatic equilibrium which takes into account magnetic, hydrostatic and osmotic pressures.

  2. Assessment of Heavy Metal Pollution in Macrophytes, Water and Sediment of a Tropical Wetland System Using Hierarchical Cluster Analysis Technique

    , N. Kumar J.I.; , M. Das; , R. Mukherji; , R.N. Kumar

    2011-01-01

    Heavy metal pollution in aquatic ecosystems is becoming a global phenomenon because these metals are indestructible and most of them have toxic effects on living organisms. Most of the fresh water bodies all over the world are getting contaminated thus declining their suitability. Therefore, monitoring and assessment of such freshwater systems has become an environmental concern. This study aims to elucidate the useful role of the cluster analysis to assess the relationship and interdependenc...

  3. Development of Halide and Oxy-Halides for Isotopic Separations

    Martin, Leigh R. [Idaho National Lab. (INL), Idaho Falls, ID (United States); Johnson, Aaron T. [Idaho National Lab. (INL), Idaho Falls, ID (United States); Pfeiffer, Jana [Idaho National Lab. (INL), Idaho Falls, ID (United States); Finck, Martha R. [Idaho National Lab. (INL), Idaho Falls, ID (United States)

    2014-10-01

    The goal of this project was to synthesize a volatile form of Np for introduction into mass spectrometers at INL. Volatile solids of the 5f elements are typically those of the halides (e.g. UF6), however fluorine is highly corrosive to the sensitive internal components of the mass separator, and the other volatile halides exist as several different stable isotopes in nature. However, iodide is both mono-isotopic and volatile, and as such presents an avenue for creation of a form of Np suitable for introduction into the mass separator. To accomplish this goal, the technical work in the project sought to establish a novel synthetic route for the conversion NpO2+ (dissolved in nitric acid) to NpI3 and NpI4.

  4. LIGHT-ELEMENT ABUNDANCE VARIATIONS AT LOW METALLICITY: THE GLOBULAR CLUSTER NGC 5466

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

    2010-01-01

    We present low-resolution (R ≅850) spectra for 67 asymptotic giant branch (AGB), horizontal branch, and red giant branch (RGB) stars in the low-metallicity globular cluster NGC 5466, taken with the VIRUS-P integral-field spectrograph at the 2.7 m Harlan J. Smith telescope at McDonald Observatory. Sixty-six stars are confirmed, and one rejected, as cluster members based on radial velocity, which we measure to an accuracy of 16 km s -1 via template-matching techniques. CN and CH band strengths have been measured for 29 RGB and AGB stars in NGC 5466, and the band-strength indices measured from VIRUS-P data show close agreement with those measured from Keck/LRIS spectra previously taken for five of our target stars. We also determine carbon abundances from comparisons with synthetic spectra. The RGB stars in our data set cover a range in absolute V magnitude from +2 to -3, which permits us to study the rate of carbon depletion on the giant branch as well as the point of its onset. The data show a clear decline in carbon abundance with rising luminosity above the luminosity function 'bump' on the giant branch, and also a subdued range in CN band strength, suggesting ongoing internal mixing in individual stars but minor or no primordial star-to-star variation in light-element abundances.

  5. Electron detachment energies in high-symmetry alkali halide solvated-electron anions

    Anusiewicz, Iwona; Berdys, Joanna; Simons, Jack; Skurski, Piotr

    2003-07-01

    We decompose the vertical electron detachment energies (VDEs) in solvated-electron clusters of alkali halides in terms of (i) an electrostatic contribution that correlates with the dipole moment (μ) of the individual alkali halide molecule and (ii) a relaxation component that is related to the polarizability (α) of the alkali halide molecule. Detailed numerical ab initio results for twelve species (MX)n- (M=Li,Na; X=F,Cl,Br; n=2,3) are used to construct an interpolation model that relates the clusters' VDEs to their μ and α values as well as a cluster size parameter r that we show is closely related to the alkali cation's ionic radius. The interpolation formula is then tested by applying it to predict the VDEs of four systems [i.e., (KF)2-, (KF)3-, (KCl)2-, and (KCl)3-] that were not used in determining the parameters of the model. The average difference between the model's predicted VDEs and the ab initio calculated electron binding energies is less than 4% (for the twelve species studied). It is concluded that one can easily estimate the VDE of a given high-symmetry solvated electron system by employing the model put forth here if the α, μ and cation ionic radii are known. Alternatively, if VDEs are measured for an alkali halide cluster and the α and μ values are known, one can estimate the r parameter, which, in turn, determines the "size" of the cluster anion.

  6. A numerical study of spin-dependent organization of alkali-metal atomic clusters using density-functional method

    Liu Xuan, E-mail: liu.x.ad@m.titech.ac.jp; Ito, Haruhiko [Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology (Japan); Torikai, Eiko [Interdisciplinary Graduate School of Medicine and Engineering, University of Yamanashi (Japan)

    2012-08-15

    We calculate the different geometric isomers of spin clusters composed of a small number of alkali-metal atoms using the UB3LYP density-functional method. The electron density distribution of clusters changes according to the value of total spin. Steric structures as well as planar structures arise when the number of atoms increases. The lowest spin state is the most stable and Li{sub n}, Na{sub n}, K{sub n}, Rb{sub n}, and Cs{sub n} with n = 2-8 can be formed in higher spin states. In the highest spin state, the preparation of clusters depends on the kind and the number of constituent atoms. The interaction energy between alkali-metal atoms and rare-gas atoms is smaller than the binding energy of spin clusters. Consequently, it is possible to self-organize the alkali-metal-atom clusters on a non-wetting substrate coated with rare-gas atoms.

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

    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. Independent control of metal cluster and ceramic particle characteristics during one-step synthesis of Pt/TiO2

    Schulz, H.; Madler, L.; Strobel, R.

    2005-01-01

    Rapid quenching during flame spray synthesis of Pt/TiO2 (0-10 Wt% Pt) is demonstrated as a versatile method for independent control of support (TiO2) and noble metal (Pt)cluster characteristics. Titania grain size, morphology, crystal phase structure, and crystal size were analyzed by nitrogen ad...

  9. Investigating the synthesis of ligated metal clusters in solution using a flow reactor and electrospray ionization mass spectrometry.

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

    2014-09-18

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

  10. Heterofacial alkylation of alkylenediamines by higher alkyl halides

    Semenov, V.A.; Kryshko, G.M.; Sokal'skaya, L.I.; Zhukova, N.G.

    1985-01-01

    A study of the physiochemical properties of alkylenediamines substituted by lower alkyls, showed that they possess increased complex-forming ability with respect to salts of different metals as titanium, niobium, zirconium, molybdenum, and zinc. To create a simpler method of synthesis of higher tetraaklyalkylalklyenediamines, based on the use of the accessible domestic raw material, the authors investigated the reaction of alkylenediamines with various alkyl halides. It was established that the best reagents can be obtained using alkyl bromides. It is concluded that the procedure of alkylation of alkylenediamines by higher alkyl halides in the presence of water developed permits the production of terraalkylalkylenediamines in one step with good yield and with purity acceptable for use as extraction reagents

  11. Correlations between entropy and volume of melting in halide salts

    Akdeniz, Z.; Tosi, M.P.

    1991-09-01

    Melting parameters and transport coefficients in the melt are collated for halides of monovalent, divalent and trivalent metals. A number of systems show a deficit of entropy of melting relative to the linear relationships between entropy change and relative volume change on melting that are found to be approximately obeyed by a majority of halides. These behaviours are discussed on the basis of structural and transport data. The deviating systems are classified into three main classes, namely (i) fast-ion conductors in the high-temperature crystal phase such as AgI, (ii) strongly structured network-like systems such as ZnCl 2 , and (iii) molecular systems melting into associated molecular liquids such as SbCl 3 . (author). 35 refs, 1 fig., 3 tabs

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

    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.

  13. Generalized vibrating potential model for collective excitations in spherical, deformed and superdeformed systems: (1) atomic nuclei, (2) metal clusters

    Nesterenko, V.O.; Kleinig, W.

    1995-01-01

    The self-consistent vibrating potential model (VPM) is extended for description of Eλ collective excitations in atomic nuclei and metal clusters with practically any kind of static deformation. The model is convenient for a qualitative analysis and provides the RPA accuracy of numerical calculations. The VPM is applied to study Eλ giant resonances in spherical metal clusters and deformed and superdeformed nuclei. It is shown that the deformation splitting of superdeformed nuclei results in a very complicated (''jungle-like'') structure of the resonances, which makes the experimental observation of E2 and E3 giant resonances in superdeformed nuclei quite problematic. Calculations of E1 giant resonance in spherical sodium clusters Na 8 , Na 20 and Na 40 are presented, as a test of the VPM in this field. The results are in qualitative agreement with the experimental data. (orig.)

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

    Çakır, D; Gülseren, O

    2012-01-01

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

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

    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. Computational Screening of Mixed Metal Halide Ammines

    Jensen, Peter Bjerre; Lysgaard, Steen; Quaade, Ulrich

    selected by a Genetic Algorithm (GA), relying on biological principles of natural selection. The GA is evolving from an initial (random) population and selecting those with highest fitness, e.g. stability, release temperature and storage capacity. The search space includes all alkaline, alkaline earth, 3d...

  17. Charge carrier localised in zero-dimensional (CH3NH3)3Bi2I9 clusters.

    Ni, Chengsheng; Hedley, Gordon; Payne, Julia; Svrcek, Vladimir; McDonald, Calum; Jagadamma, Lethy Krishnan; Edwards, Paul; Martin, Robert; Jain, Gunisha; Carolan, Darragh; Mariotti, Davide; Maguire, Paul; Samuel, Ifor; Irvine, John

    2017-08-01

    A metal-organic hybrid perovskite (CH 3 NH 3 PbI 3 ) with three-dimensional framework of metal-halide octahedra has been reported as a low-cost, solution-processable absorber for a thin-film solar cell with a power-conversion efficiency over 20%. Low-dimensional layered perovskites with metal halide slabs separated by the insulating organic layers are reported to show higher stability, but the efficiencies of the solar cells are limited by the confinement of excitons. In order to explore the confinement and transport of excitons in zero-dimensional metal-organic hybrid materials, a highly orientated film of (CH 3 NH 3 ) 3 Bi 2 I 9 with nanometre-sized core clusters of Bi 2 I 9 3- surrounded by insulating CH 3 NH 3 + was prepared via solution processing. The (CH 3 NH 3 ) 3 Bi 2 I 9 film shows highly anisotropic photoluminescence emission and excitation due to the large proportion of localised excitons coupled with delocalised excitons from intercluster energy transfer. The abrupt increase in photoluminescence quantum yield at excitation energy above twice band gap could indicate a quantum cutting due to the low dimensionality.Understanding the confinement and transport of excitons in low dimensional systems will aid the development of next generation photovoltaics. Via photophysical studies Ni et al. observe 'quantum cutting' in 0D metal-organic hybrid materials based on methylammonium bismuth halide (CH 3 NH 3 )3Bi 2 I 9 .

  18. Super-solar Metallicity Stars in the Galactic Center Nuclear Star Cluster: Unusual Sc, V, and Y Abundances

    Do, Tuan; Kerzendorf, Wolfgang; Konopacky, Quinn; Marcinik, Joseph M.; Ghez, Andrea; Lu, Jessica R.; Morris, Mark R.

    2018-03-01

    We present adaptive-optics assisted near-infrared high-spectral-resolution observations of late-type giants in the nuclear star cluster of the Milky Way. The metallicity and elemental abundance measurements of these stars offer us an opportunity to understand the formation and evolution of the nuclear star cluster. In addition, their proximity to the supermassive black hole (∼0.5 pc) offers a unique probe of the star formation and chemical enrichment in this extreme environment. We observed two stars identified by medium spectral-resolution observations as potentially having very high metallicities. We use spectral-template fitting with the PHOENIX grid and Bayesian inference to simultaneously constrain the overall metallicity, [M/H], alpha-element abundance [α/Fe], effective temperature, and surface gravity of these stars. We find that one of the stars has very high metallicity ([M/H] > 0.6) and the other is slightly above solar metallicity. Both Galactic center stars have lines from scandium (Sc), vanadium (V), and yttrium (Y) that are much stronger than allowed by the PHOENIX grid. We find, using the spectral synthesis code Spectroscopy Made Easy, that [Sc/Fe] may be an order of magnitude above solar. For comparison, we also observed an empirical calibrator in NGC 6791, the highest metallicity cluster known ([M/H] ∼ 0.4). Most lines are well matched between the calibrator and the Galactic center stars, except for Sc, V, and Y, which confirms that their abundances must be anomalously high in these stars. These unusual abundances, which may be a unique signature of nuclear star clusters, offer an opportunity to test models of chemical enrichment in this region.

  19. Comparison between XAS, AWAXS and DAFS applied to nanometer scale supported metallic clusters. Pt.2; bimetallic clusters

    Bazin, D.; Sayers, D.

    1993-01-01

    The structural information obtained using three techniques related to synchrotron radiation are compared. XAS (X-ray Absorption Spectroscopy), AWAXS (Anomalous Wide Angle X-ray Scattering) and DAFS (Diffraction Anomalous Fine Structure) are applied to the study of nanometer scale bimetallic clusters. (author)

  20. Metal nitride cluster as a template to tune the electronic and magnetic properties of rare-earth metal containing endohedral fullerenes

    Zhang, Yang

    2013-10-16

    Rare-earth metal containing endohedral fullerenes have attracted much attention due to the feasibility of encaging metal atom, atoms or cluster inside of carbon cages. By switching the metal atom or cluster entrapped inside of the carbon cage the physical and chemical properties of the fullerene compounds can be tuned. The understanding of magnetic and electrochemical properties of endohedral fullerenes plays an essential role in fundamental scientific researches and potential applications in materials science. In this thesis, synthesizing novel rare-earth metal containing endohedral fullerene structures, studying the properties of these isolated endohedral fullerenes and the strategies of tuning the electronic and magnetic properties of endohedral fullerenes were introduced. The DC-arc discharging synthesis of different lanthanide metal-based (Ho, Ce and Pr) mixed metal nitride clusterfullerenes was achieved. Those rare-earth metal containing endohedral fullerenes were isolated by multi-step HPLC. The isolated samples were characterized by spectroscopic techniques included UV-vis-NIR, FTIR, Raman, LDI-TOF mass spectrometry, NMR and electrochemistry. The Ho-based mixed metal nitride clusterfullerenes Ho{sub x}M{sub 3-x}N rate at C{sub 80} (M= Sc, Lu, Y; x=1, 2) were synthesized by ''reactive gas atmosphere'' method or ''selective organic solid'' route. The isolated samples were characterized by LDI-TOF mass spectrometry, UV-vis-NIR, FTIR, Raman and NMR spectroscopy. The {sup 13}C NMR spectroscopic studies demonstrated exceptional NMR behaviors that resulted from switching the second metal inside of the mixed metal nitride cluster Ho{sub x}M{sub 3-x}N from Sc to Lu and further to Y. The LnSc{sub 2}N rate at C{sub 80} (Ln= Ce, Pr, Nd, Tb, Dy, Ho, Lu) MMNCFs were characterized by {sup 13}C and {sup 45}Sc NMR study respectively. According to Bleaney's theory and Reilley method, the separation of δ{sup PC} and δ{sup con

  1. Metal nitride cluster as a template to tune the electronic and magnetic properties of rare-earth metal containing endohedral fullerenes

    Zhang, Yang

    2013-01-01

    Rare-earth metal containing endohedral fullerenes have attracted much attention due to the feasibility of encaging metal atom, atoms or cluster inside of carbon cages. By switching the metal atom or cluster entrapped inside of the carbon cage the physical and chemical properties of the fullerene compounds can be tuned. The understanding of magnetic and electrochemical properties of endohedral fullerenes plays an essential role in fundamental scientific researches and potential applications in materials science. In this thesis, synthesizing novel rare-earth metal containing endohedral fullerene structures, studying the properties of these isolated endohedral fullerenes and the strategies of tuning the electronic and magnetic properties of endohedral fullerenes were introduced. The DC-arc discharging synthesis of different lanthanide metal-based (Ho, Ce and Pr) mixed metal nitride clusterfullerenes was achieved. Those rare-earth metal containing endohedral fullerenes were isolated by multi-step HPLC. The isolated samples were characterized by spectroscopic techniques included UV-vis-NIR, FTIR, Raman, LDI-TOF mass spectrometry, NMR and electrochemistry. The Ho-based mixed metal nitride clusterfullerenes Ho x M 3-x N rate at C 80 (M= Sc, Lu, Y; x=1, 2) were synthesized by ''reactive gas atmosphere'' method or ''selective organic solid'' route. The isolated samples were characterized by LDI-TOF mass spectrometry, UV-vis-NIR, FTIR, Raman and NMR spectroscopy. The 13 C NMR spectroscopic studies demonstrated exceptional NMR behaviors that resulted from switching the second metal inside of the mixed metal nitride cluster Ho x M 3-x N from Sc to Lu and further to Y. The LnSc 2 N rate at C 80 (Ln= Ce, Pr, Nd, Tb, Dy, Ho, Lu) MMNCFs were characterized by 13 C and 45 Sc NMR study respectively. According to Bleaney's theory and Reilley method, the separation of δ PC and δ con from δ para was achieved by the primary 13 C and 45 Sc NMR analysis of LnSc 2 N rate at C 80 (I). The

  2. The role of halide ions on the electrochemical behaviour of iron in alkali solutions

    Begum, S. Nathira; Muralidharan, V. S.; Basha, C. Ahmed

    2008-02-01

    Active dissolution and passivation of transition metals in alkali solutions is of technological importance in batteries. The performance of alkaline batteries is decided by the presence of halides as they influence passivation. Cyclic voltammetric studies were carried out on iron in different sodium hydroxide solutions in presence of halides. In alkali solutions iron formed hydroxo complexes and their polymers in the interfacial diffusion layer. With progress of time they formed a cation selective layer. The diffusion layer turned into bipolar ion selective layer consisted of halides, a selective inner sublayer to the metal side and cation selective outer layer to the solution side. At very high anodic potentials, dehydration and deprotonation led to the conversion of salt layer into an oxide.

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

    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

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

    Balasubramanian, Krishnan

    2009-01-01

    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 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 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 2 back to Au and H 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 3 , Nb 2 + etc., have been confirmed experimentally by Prof. Lombardi and coworkers using resonance Raman spectroscopy. We have also been studying larger complexes critical to the environmental management of high

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

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

    2010-01-01

    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.

  6. Radiation clusters formation and evolution in FCC metals at low-temperature neutron irradiation up to small damage fluences

    Kozlov, A.V.; Shcherbakov, E.N.; Asiptsov, O.I.; Skryabin, L.A.; Portnykh, I.A.

    2006-01-01

    Methods of transmission electron microscopy and precision size measurements are used to study the formation of radiation-induced clusters in FCC metals (Ni, Pt, austenitic steels EhI-844, ChS-68) irradiated with fast neutron (E>0.1 MeV) fluences from 7 x 10 21 up to 3.5 x 10 22 m -2 at a temperature of 310 K. Using statistical thermodynamic methods the process of radiation clusters formation and evolution is described quantitatively. The change in the concentration of point defects under irradiation as well as size variations of irradiated specimens on annealing are calculated [ru

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

    Abbas, Mohamad A. [Astronomisches Rechen-Institut, Zentrum für Astronomie der Universität Heidelberg, Mönchhofstr. 12-14, D-69120 Heidelberg (Germany); Layden, Andrew C.; Guldenschuh, Katherine A. [Physics and Astronomy Department, Bowling Green State University, Bowling Green, OH 43403 (United States); Reichart, D. E.; Ivarsen, K. M.; Haislip, J. B.; Nysewander, M. C.; LaCluyze, A. P. [Department of Physics and Astronomy, University of North Carolina, Chapel Hill, NC 27599 (United States); Welch, Douglas L., E-mail: mabbas@ari.uni-heidelberg.de, E-mail: laydena@bgsu.edu [Department of Physics and Astronomy, McMaster University, Hamilton, Ontario, L8 S 4M1 (Canada)

    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.

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

    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.

  9. Stellar Population Properties of Ultracompact Dwarfs in M87: A Mass–Metallicity Correlation Connecting Low-metallicity Globular Clusters and Compact Ellipticals

    Zhang, Hong-Xin; Puzia, Thomas H.; Peng, Eric W.; Liu, Chengze; Côté, Patrick; Ferrarese, Laura; Duc, Pierre-Alain; Eigenthaler, Paul; Lim, Sungsoon; Lançon, Ariane; Muñoz, Roberto P.; Roediger, Joel; Sánchez-Janssen, Ruben; Taylor, Matthew A.; Yu, Jincheng

    2018-05-01

    We derive stellar population parameters for a representative sample of ultracompact dwarfs (UCDs) and a large sample of massive globular clusters (GCs) with stellar masses ≳ 106 M ⊙ in the central galaxy M87 of the Virgo galaxy cluster, based on model fitting to the Lick-index measurements from both the literature and new observations. After necessary spectral stacking of the relatively faint objects in our initial sample of 40 UCDs and 118 GCs, we obtain 30 sets of Lick-index measurements for UCDs and 80 for GCs. The M87 UCDs have ages ≳ 8 Gyr and [α/Fe] ≃ 0.4 dex, in agreement with previous studies based on smaller samples. The literature UCDs, located in lower-density environments than M87, extend to younger ages and smaller [α/Fe] (at given metallicities) than M87 UCDs, resembling the environmental dependence of the stellar nuclei of dwarf elliptical galaxies (dEs) in the Virgo cluster. The UCDs exhibit a positive mass–metallicity relation (MZR), which flattens and connects compact ellipticals at stellar masses ≳ 108 M ⊙. The Virgo dE nuclei largely follow the average MZR of UCDs, whereas most of the M87 GCs are offset toward higher metallicities for given stellar masses. The difference between the mass–metallicity distributions of UCDs and GCs may be qualitatively understood as a result of their different physical sizes at birth in a self-enrichment scenario or of galactic nuclear cluster star formation efficiency being relatively low in a tidal stripping scenario for UCD formation. The existing observations provide the necessary but not sufficient evidence for tidally stripped dE nuclei being the dominant contributors to the M87 UCDs.

  10. [Ti8Zr2O12(COO)16] Cluster: An Ideal Inorganic Building Unit for Photoactive Metal-Organic Frameworks.

    Yuan, Shuai; Qin, Jun-Sheng; Xu, Hai-Qun; Su, Jie; Rossi, Daniel; Chen, Yuanping; Zhang, Liangliang; Lollar, Christina; Wang, Qi; Jiang, Hai-Long; Son, Dong Hee; Xu, Hongyi; Huang, Zhehao; Zou, Xiaodong; Zhou, Hong-Cai

    2018-01-24

    Metal-organic frameworks (MOFs) based on Ti-oxo clusters (Ti-MOFs) represent a naturally self-assembled superlattice of TiO 2 nanoparticles separated by designable organic linkers as antenna chromophores, epitomizing a promising platform for solar energy conversion. However, despite the vast, diverse, and well-developed Ti-cluster chemistry, only a scarce number of Ti-MOFs have been documented. The synthetic conditions of most Ti-based clusters are incompatible with those required for MOF crystallization, which has severely limited the development of Ti-MOFs. This challenge has been met herein by the discovery of the [Ti 8 Zr 2 O 12 (COO) 16 ] cluster as a nearly ideal building unit for photoactive MOFs. A family of isoreticular photoactive MOFs were assembled, and their orbital alignments were fine-tuned by rational functionalization of organic linkers under computational guidance. These MOFs demonstrate high porosity, excellent chemical stability, tunable photoresponse, and good activity toward photocatalytic hydrogen evolution reactions. The discovery of the [Ti 8 Zr 2 O 12 (COO) 16 ] cluster and the facile construction of photoactive MOFs from this cluster shall pave the way for the development of future Ti-MOF-based photocatalysts.

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

    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, St?phane; 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 ...

  12. On the Chemical Abundances of Miras in Clusters: V1 in the Metal-rich Globular NGC 5927

    D’Orazi, V.; Magurno, D.; Bono, G.; Matsunaga, N.; Braga, V. F.; Elgueta, S. S.; Fukue, K.; Hamano, S.; Inno, L.; Kobayashi, N.; Kondo, S.; Monelli, M.; Nonino, M.; Przybilla, N.; Sameshima, H.; Saviane, I.; Taniguchi, D.; Thevenin, F.; Urbaneja-Perez, M.; Watase, A.; Arai, A.; Bergemann, M.; Buonanno, R.; Dall’Ora, M.; Da Silva, R.; Fabrizio, M.; Ferraro, I.; Fiorentino, G.; Francois, P.; Gilmozzi, R.; Iannicola, G.; Ikeda, Y.; Jian, M.; Kawakita, H.; Kudritzki, R. P.; Lemasle, B.; Marengo, M.; Marinoni, S.; Martínez-Vázquez, C. E.; Minniti, D.; Neeley, J.; Otsubo, S.; Prieto, J. L.; Proxauf, B.; Romaniello, M.; Sanna, N.; Sneden, C.; Takenaka, K.; Tsujimoto, T.; Valenti, E.; Yasui, C.; Yoshikawa, T.; Zoccali, M.

    2018-03-01

    We present the first spectroscopic abundance determination of iron, α-elements (Si, Ca, and Ti), and sodium for the Mira variable V1 in the metal-rich globular cluster NGC 5927. We use high-resolution (R ∼ 28,000), high signal-to-noise ratio (∼200) spectra collected with WINERED, a near-infrared (NIR) spectrograph covering simultaneously the wavelength range 0.91–1.35 μm. The effective temperature and the surface gravity at the pulsation phase of the spectroscopic observation were estimated using both optical (V) and NIR time-series photometric data. We found that the Mira is metal-rich ([Fe/H] = ‑0.55 ± 0.15) and moderately α-enhanced ([α/Fe] = 0.15 ± 0.01, σ = 0.2). These values agree quite well with the mean cluster abundances based on high-resolution optical spectra of several cluster red giants available in the literature ([Fe/H] = ‑ 0.47 ± 0.06, [α/Fe] = + 0.24 ± 0.05). We also found a Na abundance of +0.35 ± 0.20 that is higher than the mean cluster abundance based on optical spectra (+0.18 ± 0.13). However, the lack of similar spectra for cluster red giants and that of corrections for departures from local thermodynamical equilibrium prevents us from establishing whether the difference is intrinsic or connected with multiple populations. These findings indicate a strong similarity between optical and NIR metallicity scales in spite of the difference in the experimental equipment, data analysis, and in the adopted spectroscopic diagnostics. Based on spectra collected with the WINERED spectrograph available as a visitor instrument at the ESO New Technology Telescope (NTT), La Silla, Chile (ESO Proposal: 098.D-0878(A), PI: G. Bono).

  13. Effect of clustering on the mechanical properties of SiC particulate-reinforced aluminum alloy 2024 metal matrix composites

    Hong, Soon-Jik; Kim, Hong-Moule; Huh, Dae; Suryanarayana, C.; Chun, Byong Sun

    2003-01-01

    Al 2024-SiC metal matrix composite (MMC) powders produced by centrifugal atomization were hot extruded to investigate the effect of clustering on their mechanical properties. Fracture toughness and tension tests were conducted on specimens reinforced with different volume fractions of SiC. A model was proposed to suggest that the strength of the MMCs could be estimated from the load transfer model approach that takes into consideration the extent of clustering. This model has been successful in predicting the experimentally observed strength and fracture toughness values of the Al 2024-SiC MMCs. On the basis of experimental observations, it is suggested that the strength of particulate-reinforced MMCs may be calculated from the relation: σ y =σ m V m +σ r (V r -V c )-σ r V c , where σ and V represent the yield strength and volume fraction, respectively, and the subscripts m, r, and c represent the matrix, reinforcement, and clusters, respectively

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

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

    2010-01-01

    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.

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

    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.

  16. A study of new rare-earth metal group-13 chalcohalides. Structures, chemistry, and optical properties

    Dorhout, P.K.; Van Calcar, P.M.

    1998-01-01

    Full text: Several new quaternary compounds from the rare-earth metal group-13 chalcohalide family have been prepared from alkaline earth halide flux reactions of binary and elemental starting materials. One compound, for example, Ca 2 La 6G a 2 S 1 4 , crystallizes as needles in an hexagonal cell while another, more disordered structure, La 11 Ga 19 Cl 6 S 42 , crystallizes as monoclinic plates. The former is a condensed structure with channels that contain the alkaline earth element while the latter forms a layered structure containing rare-earth halide clusters within interlayer galleries. These compounds are new members of a family of rare-earth metal main-group chalcogenides which show promise as electroluminescent materials. Structural and spectroscopic studies of these and related compounds will be discussed

  17. Mass-spectrometric study of ion clustering in alkali-metal hydroxide vapor: cluster-ion energy and structural characteristics

    Kudin, L.S.; Butman, M.F.; Krasnov, K.S.

    1986-01-01

    Various positive and negative ions have been recorded in the equilibrium vapors from alkali-metal hydroxides: M/sup +/-/, OH - , O - , MO - , MOH - , and X/sup +/-/ (MOH)/sub n/, where X = M/sup +/-/, OH - , n = 1-6. The equilibrium constants have been measured for X/sup +/-/(MOH)/sub n/ = x/sup +/-/ + nMOH(k), n = 1-3, and the enthalpies of reaction have been determined, from which the enthalpies of formation and dissociation energies of X/sup +/-/ (MOH)/sub n/ have been calculated. The relative stabilities of the ions in the series from Na to Cs are examined

  18. Plasmonic characterization of photo-induced silver nanoparticles extracted from silver halide based TEM film

    Sudheer,, E-mail: sudheer@rrcat.gov.in; Tiwari, P.; Rai, V. N.; Srivastava, A. K. [Indus Synchrotrons Utilization Division, Raja Ramanna Centre for Advanced Technology Indore, Madhya Pradesh 452013 (India); Varshney, G. K. [Laser Bio-medical Applications & Instrumentation Division, Raja Ramanna Centre for Advanced Technology Indore, Madhya Pradesh 452013 (India)

    2016-05-23

    The plasmonic responses of silver nanoparticles extracted from silver halide based electron microscope film are investigated. Photo-reduction process is carried out to convert the silver halide grains into the metallic silver. The centrifuge technique is used for separating the silver nanoparticles from the residual solution. Morphological study performed by field emission scanning electron microscope (FESEM) shows that all the nanoparticles have an average diameter of ~120 nm with a high degree of mono dispersion in size. The localized surface plasmon resonance (LSPR) absorption peak at ~537 nm confirms the presence of large size silver nanoparticles.

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

    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

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

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

    2016-01-01

    The structural, electronic, and magnetic properties of monolayer BN doped with 3D metal trioxide and tetraoxide superhalogen clusters are investigated using first-principle calculations. TMO_3_(_4_)-doped monolayer BN exhibits a low negative formation energy, whereas TM atoms embedded in monolayer BN show a high positive formation energy. TMO_3_(_4_) clusters are embedded more easily in monolayer BN than TM atoms. Compared with TMO_3-doped structures, TMO_4-doped structures have a higher structural stability because of their higher binding energies. Given their low negative formation energies, TMO_4-doped structures are more favored for specific applications than TMO_3-doped structures and TM atom-doped structures. Large magnetic moments per supercell and significant ferromagnetic couplings between a TM atom and neighboring B and N atoms on the BN layer were observed in all TMO_4-doped structures, except for TiO_4-doped structures. - Highlights: • TMO_3_(_4_) superhalogen clusters incorporated into monolayer BN were investigated. • TMO_3_(_4_) clusters are embedded more easily in monolayer BN than TM atoms. • TMO_4-doped structures are more favored for specific applications. • Large magnetic moments were observed in TMO_4-doped structures. • The band gap was sensitively dependent on the doped clusters.

  1. Voltage-dependent cluster expansion for electrified solid-liquid interfaces: Application to the electrochemical deposition of transition metals

    Weitzner, Stephen E.; Dabo, Ismaila

    2017-11-01

    The detailed atomistic modeling of electrochemically deposited metal monolayers is challenging due to the complex structure of the metal-solution interface and the critical effects of surface electrification during electrode polarization. Accurate models of interfacial electrochemical equilibria are further challenged by the need to include entropic effects to obtain accurate surface chemical potentials. We present an embedded quantum-continuum model of the interfacial environment that addresses each of these challenges and study the underpotential deposition of silver on the gold (100) surface. We leverage these results to parametrize a cluster expansion of the electrified interface and show through grand canonical Monte Carlo calculations the crucial need to account for variations in the interfacial dipole when modeling electrodeposited metals under finite-temperature electrochemical conditions.

  2. Metals on graphene and carbon nanotube surfaces: From mobile atoms to atomtronics to bulk metals to clusters and catalysts

    Sarkar, Santanu C.; Moser, Matthew L.; Tian, Xiaojuan; Zhang, Xixiang; Al-Hadeethi, Yas Fadel; Haddon, Robert C.

    2014-01-01

    , and the next generation energy devices. We touch on chemical vapor deposition (CVD) graphene grown on metals, the reactivity of its surface, and its use as a template for asymmetric graphene functionalization chemistry (ultrathin Janus discs). We highlight some

  3. Analogy of the Coordination Chemistry of Alkaline Earth Metal and Lanthanide Ln²⁺ Ions: The Isostructural Zoo of Mixed Metal Cages [IM(OtBu)₄{Li(thf)}₄(OH)] (M=Ca, Sr, Ba, Eu), [MM′₆(OPh)₈(thf)₆] (M=Ca, Sr, Ba, Sm, Eu, M′=Li, Na), and their Derivatives with 1,2-Dimethoxyethane

    Maudez, William; Meuwly, Markus; Fromm, Katharina M.

    2008-01-01

    As previously shown, alkali and alkaline earth metal iodides in nonaqueous, aprotic solvents behave like transition metal halides, forming cis- and trans-dihalides with various neutral O-donor ligands. These compounds can be used as precursors for the synthesis of new mixed alkali/alkaline earth metal aggregates. We show here that Ln²⁺ ions form isostructural cluster compounds. Thus, with LiOtBu, 50 % of the initial iodide can be replaced in MI₂, M=Ca, Sr, Ba, Eu, to generate the mixed-metal ...

  4. Condensation and dissociation rates for gas phase metal clusters from molecular dynamics trajectory calculations

    Yang, Huan; Goudeli, Eirini; Hogan, Christopher J.

    2018-04-01

    In gas phase synthesis systems, clusters form and grow via condensation, in which a monomer binds to an existing cluster. While a hard-sphere equation is frequently used to predict the condensation rate coefficient, this equation neglects the influences of potential interactions and cluster internal energy on the condensation process. Here, we present a collision rate theory-molecular dynamics simulation approach to calculate condensation probabilities and condensation rate coefficients. We use this approach to examine atomic condensation onto 6-56-atom Au and Mg clusters. The probability of condensation depends upon the initial relative velocity (v) between atom and cluster and the initial impact parameter (b). In all cases, there is a well-defined region of b-v space where condensation is highly probable, and outside of which the condensation probability drops to zero. For Au clusters with more than 10 atoms, we find that at gas temperatures in the 300-1200 K range, the condensation rate coefficient exceeds the hard-sphere rate coefficient by a factor of 1.5-2.0. Conversely, for Au clusters with 10 or fewer atoms and for 14- and 28-atom Mg clusters, as cluster equilibration temperature increases, the condensation rate coefficient drops to values below the hard-sphere rate coefficient. Calculations also yield the self-dissociation rate coefficient, which is found to vary considerably with gas temperature. Finally, calculations results reveal that grazing (high b) atom-cluster collisions at elevated velocity (>1000 m s-1) can result in the colliding atom rebounding (bounce) from the cluster surface or binding while another atom dissociates (replacement). The presented method can be applied in developing rate equations to predict material formation and growth rates in vapor phase systems.

  5. Highly Efficient Broadband Yellow Phosphor Based on Zero-Dimensional Tin Mixed-Halide Perovskite.

    Zhou, Chenkun; Tian, Yu; Yuan, Zhao; Lin, Haoran; Chen, Banghao; Clark, Ronald; Dilbeck, Tristan; Zhou, Yan; Hurley, Joseph; Neu, Jennifer; Besara, Tiglet; Siegrist, Theo; Djurovich, Peter; Ma, Biwu

    2017-12-27

    Organic-inorganic hybrid metal halide perovskites have emerged as a highly promising class of light emitters, which can be used as phosphors for optically pumped white light-emitting diodes (WLEDs). By controlling the structural dimensionality, metal halide perovskites can exhibit tunable narrow and broadband emissions from the free-exciton and self-trapped excited states, respectively. Here, we report a highly efficient broadband yellow light emitter based on zero-dimensional tin mixed-halide perovskite (C 4 N 2 H 14 Br) 4 SnBr x I 6-x (x = 3). This rare-earth-free ionically bonded crystalline material possesses a perfect host-dopant structure, in which the light-emitting metal halide species (SnBr x I 6-x 4- , x = 3) are completely isolated from each other and embedded in the wide band gap organic matrix composed of C 4 N 2 H 14 Br - . The strongly Stokes-shifted broadband yellow emission that peaked at 582 nm from this phosphor, which is a result of excited state structural reorganization, has an extremely large full width at half-maximum of 126 nm and a high photoluminescence quantum efficiency of ∼85% at room temperature. UV-pumped WLEDs fabricated using this yellow emitter together with a commercial europium-doped barium magnesium aluminate blue phosphor (BaMgAl 10 O 17 :Eu 2+ ) can exhibit high color rendering indexes of up to 85.

  6. [Electronic and structural properties of individual nanometer-size supported metallic clusters

    Reifenberger, R.

    1993-01-01

    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

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

    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.

  8. Structure investigation of metal ions clustering in dehydrated gel using x-ray anomalous dispersion effect

    Soejima, Y; Sugiyama, M; Annaka, M; Nakamura, A; Hiramatsu, N; Hara, K

    2003-01-01

    The structure of copper ion clusters in dehydrated N-isopropylacrylamide/sodium acrylate (NIPA/SA) gel has been studied by means of small angle X-ray scattering (SAXS) method. In order to distinguish the intensity scattered by Cu ions, the X-ray anomalous dispersion effect around the Cu K absorption edge has been coupled with SAXS. It is found that the dispersion effect dependent on the incident X-ray energy is remarkable only at the momentum transfer q = 0.031 A sup - sup 1 , where a SAXS peak is observed. The results indicate that copper ions form clusters in the dehydrated gel, and that the mean size of clusters is the same as that of SA clusters produced by microphase separation. It is therefore naturally presumed that copper ions are adsorbed into the SA molecules. On the basis of the presumption, a mechanism is proposed for microphase-separation and clustering of Cu ions.

  9. Insights into magnetic interactions in a monodisperse Gd{sub 12}Fe{sub 14} metal cluster

    Zheng, Xiu-Ying; Zhang, Hui; Liu, Pengxin; Du, Ming-Hao; Han, Ying-Zi; Wei, Rong-Jia; Kong, Xiang-Jian; Long, La-Sheng; Zheng, Lan-Sun [Collaborative Innovation Center of Chemistry for Energy Materials, State Key Lab. of Physical Chemistry of Solid Surface and Dept. of Chemistry, College of Chemistry and Chemical Engineering, Xiamen Univ. (China); Wang, Zhenxing; Ouyang, Zhong-Wen [Wuhan National High Magnetic Field Center and School of Physics, Huazhong University of Science and Technology, Wuhan (China); Zhuang, Gui-Lin [College of Chemcal Engineering, Zhejiang University of Technology, Hangzhou (China)

    2017-09-11

    The largest Ln-Fe metal cluster [Gd{sub 12}Fe{sub 14}(μ{sub 3}-OH){sub 12}(μ{sub 4}-OH){sub 6}(μ{sub 4}-O){sub 12}(TEOA){sub 6}(CH{sub 3}COO){sub 16}(H{sub 2} O){sub 8}].(CH{sub 3}COO){sub 2}(CH{sub 3}CN){sub 2}.(H{sub 2}O){sub 20} (1) and the core-shell monodisperse metal cluster of 1 a rate at SiO{sub 2} (1 a=[Gd{sub 12}Fe{sub 14}(μ{sub 3}-OH){sub 12}(μ{sub 4}-OH){sub 6}(μ{sub 4}-O){sub 12}(TEOA){sub 6}(CH{sub 3}COO){sub 16} (H{sub 2}O){sub 8}]{sup 2+}) were prepared. Experimental and theoretical studies on the magnetic properties of 1 and 1 a rate at SiO{sub 2} reveal that encapsulation of one cluster into one silica nanosphere not only effectively decreases intermolecular magnetic interactions but also significantly increases the zero-field splitting effect of the outer layer Fe{sup 3+} ions. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  10. Irradiation characteristics of metal-cluster-complex ions containing diverse multi-elements with large mass differences

    Fujiwara, Yukio; Kondou, Kouji; Teranishi, Yoshikazu; Nonaka, Hidehiko; Saito, Naoaki; Fujimoto, Toshiyuki; Kurokawa, Akira; Ichimura, Shingo; Tomita, Mitsuhiro

    2007-01-01

    Tetrairidium dodecacarbonyl, Ir 4 (CO) 12 , is a metal cluster complex which has a molecular weight of 1104.9. Using a metal-cluster-complex ion source, the interaction between Ir 4 (CO) n + ions (n=0-12) and silicon substrates was studied at a beam energy ranging from 2keV to 10keV at normal incidence. By adjusting Wien-filter voltage, the influence of CO ligands was investigated. Experimental results showed that sputtering yield of silicon bombarded with Ir 4 (CO) n + ions at 10keV decreased with the number of CO ligands. In the case of 2keV, deposition tended to be suppressed by removing CO ligands from the impinging cluster ions. The influence of CO ligands was explained by considering changes in surface properties caused by the irradiation of Ir 4 (CO) n + ions. It was also found that the bombardment with Ir 4 (CO) 7 + ions at 2.5keV caused deposition on silicon target

  11. Metal Substitution in Keggin-Type Tridecameric Aluminum-Oxo-Hydroxy Clusters.

    Parker, Wallace O'Neil; Millini, Roberto; Kiricsi, Imre

    1997-02-12

    The species resulting from a typical preparation for metal-substituted hybrids of the Keggin tridecamer, Al 13 or [AlO 4 Al 12 (OH) 24 (OH 2 ) 12 ] 7+ , were examined by performing 27 Al NMR on the solutions during aging and by studying the precipitated sulfate salts via solid state 27 Al NMR and powder X-ray diffraction (XRD). Aqueous mixtures (0.25 mol L -1 ) of AlCl 3 and another metal ion (M), in a 12:1 mole ratio (Al:M), where M = Fe 3+ , Zn 2+ , Ga 3+ , In 3+ , Sn 2+ , La 3+ , and Bi 3+ , were subjected to forced hydrolysis by addition of NaOH (1.0 mol L -1 ) until OH/(Al + M) = 2.25, and the kinetics of Al 13 formation and disappearance with aging at 80 °C was monitored by 27 Al NMR spectroscopy. Al 13 units polymerize on aging with an apparent rate constant (k) of 4.8(8) × 10 -2 h -1 to form a species referred to as AlP 2 . Only the solutions containing Ga 3+ and Sn 2+ exhibited faster Al 13 conversion rates. GaAl 12 forms quickly at 80 °C (k = 0.54 h -1 ) and is more stable than AlP 2 . Sn 2+ apparently promotes AlP 2 formation (k = 0.38 h -1 ). XRD and solid state NMR reveal that only the Ga hybrid can be prepared by this method. No hybrid formation was evidenced using M = Mg 2+ , Fe 3+ , Co 2+ , Ni 2+ , Cu 2+ , Zn 2+ , In 3+ , La 3+ , or Ce 3+ at 25 °C or M = Co 2+ or La 3+ under reflux conditions. Isostructural (cubic symmetry) single crystals were obtained for the sulfate salts of Al 13 and GaAl 12 . Single-crystal XRD analysis of these two polyoxocations provides the first rigorous comparison between them and shows they have very similar structures. The main crystallographic data for Al 13 and GaAl 12 are as follows:  Na[AlO 4 Al 12 (OH) 24 (H 2 O) 12 ](SO 4 ) 4 ·10H 2 O, cubic, F4̄3m, a = 17.856(2) Å, Z = 4; Na[GaO 4 Al 12 (OH) 24 (H 2 O) 12 ](SO 4 ) 4 ·10H 2 O, cubic, F4̄3m, a = 17.869(3) Å, Z = 4. Thus, the greater thermal stability of GaAl 12 cannot be rationalized in terms of the overall geometric considerations, as suggested by

  12. Quantum molecular dynamics: Numerical methods and physical study of the structure, thermodynamics, stability and fragmentation of sodium metallic clusters

    Blaise, Philippe

    1998-01-01

    The aim of this thesis is to study metallic sodium clusters by numerical simulation. We have developed two ab initio molecular dynamics programs within the formalism of density functional theory. The first is based on the semi-classical extended Thomas-Fermi approach. We use a real-space grid and a Car-Parrinello-like scheme. The computational cost is O(N), and we have built a pseudopotential that speeds up the calculations. By neglecting quantum shell effects, we are able to study a very large set of clusters. We show that sodium cluster energies fit well a liquid drop formula, by adjusting a few parameters. We have investigated breathing modes, surface oscillations and the net charge density. We have shown that the surface energy varies strongly with temperature, and that clusters have a lower melting point than bulk material. We have calculated fission barriers by a constraint method. The second program is based on the quantum Kohn-Sham approach. We use a real-space grid, and combine a generalized Broyden scheme for assuring self-consistency with an iterative Davidson-Lanczos algorithm for solving the Eigen-problem. The cost of the method is much higher. First of all, we have calculated some stable structures for small clusters and their energetics. We obtained very good agreement with previous works. Then, we have investigated highly charged cluster dynamics. We have identified a chaotic fission process. For high fissility systems, we observe a multi-fragmentation dynamics and we find preferential emission of monomers on a characteristic time scale less than a pico-second. This has been simulated for the first time, with the help of our adaptive grid method which follows each fragment as they move apart during the fragmentation. (author)

  13. Clustering of nucleosides in the presence of alkali metals: Biologically relevant quartets of guanosine, deoxyguanosine and uridine observed by ESI-MS/MS.

    Aggerholm, Tenna; Nanita, Sergio C; Koch, Kim J; Cooks, R Graham

    2003-01-01

    Electrospray ionization (ESI) mass spectra of nucleosides, recorded in the presence of alkali metals, display alkali metal ion-bound quartets and other clusters that may have implications for understanding non-covalent interactions in DNA and RNA. The tetramers of guanosine and deoxyguanosine and also their metaclusters (clusters of clusters), cationized by alkali metals, were observed as unusually abundant magic number clusters. The observation of these species in the gas phase parallels previous condensed-phase studies, which show that guanine derivatives can form quartets and metaclusters of quartets in solution in the presence of metal cations. This parallel behavior and also internal evidence suggest that bonding in the guanosine tetramers involves the bases rather than the sugar units. The nucleobases thymine and uracil are known to form magic number pentameric adducts with K+, Cs+ and NH4+ in the gas phase. In sharp contrast, we now show that the nucleosides uridine and deoxythymidine do not form the pentameric clusters characteristic of the corresponding bases. More subtle effects of the sugars are evident in the fact that adenosine and cytidine form numerous higher order clusters with alkali metals, whereas deoxyadenosine and deoxycytidine show no clustering. It is suggested that hydrogen bonding between the bases in the tetramers of dG and rG are the dominant interactions in the clusters, hence changing the ribose group to deoxyribose (and vice versa) generally has little effect. However, the additional hydroxyl group of RNA nucleosides enhances the non-selective formation of higher-order aggregates for adenosine and cytidine and results in the lack of highly stable magic number clusters. Some clusters are the result of aggregation in the course of ionization (ESI) whereas others appear to be intrinsic to the solution being examined. Copyright 2003 John Wiley & Sons, Ltd.

  14. The Metal-poor non-Sagittarius (?) Globular Cluster NGC 5053: Orbit and Mg, Al, and Si Abundances

    Tang, Baitian; Fernández-Trincado, J. G.; Geisler, Doug; Zamora, Olga; Mészáros, Szabolcs; Masseron, Thomas; Cohen, Roger E.; García-Hernández, D. A.; Dell’Agli, Flavia; Beers, Timothy C.; Schiavon, Ricardo P.; Sohn, Sangmo Tony; Hasselquist, Sten; Robin, Annie C.; Shetrone, Matthew; Majewski, Steven R.; Villanova, Sandro; Schiappacasse Ulloa, Jose; Lane, Richard R.; Minnti, Dante; Roman-Lopes, Alexandre; Almeida, Andres; Moreno, E.

    2018-03-01

    Metal-poor globular clusters (GCs) exhibit intriguing Al–Mg anti-correlations and possible Si–Al correlations, which are important clues to decipher the multiple-population phenomenon. NGC 5053 is one of the most metal-poor GCs in the nearby universe and has been suggested to be associated with the Sagittarius (Sgr) dwarf galaxy, due to its similarity in location and radial velocity with one of the Sgr arms. In this work, we simulate the orbit of NGC 5053, and argue against a physical connection between Sgr and NGC 5053. On the other hand, the Mg, Al, and Si spectral lines, which are difficult to detect in the optical spectra of NGC 5053 stars, have been detected in the near-infrared APOGEE spectra. We use three different sets of stellar parameters and codes to derive the Mg, Al, and Si abundances. Regardless of which method is adopted, we see a large Al variation, and a substantial Si spread. Along with NGC 5053, metal-poor GCs exhibit different Mg, Al, and Si variations. Moreover, NGC 5053 has the lowest cluster mass among the GCs that have been identified to exhibit an observable Si spread until now.

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

    Hirai, Kenji; Isobe, Shigehito; Sada, Kazuki

    2015-12-18

    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.

  16. Self-trapped holes in alkali silver halide crystals

    Awano, T.; Ikezawa, M.; Matsuyama, T.

    1995-01-01

    γ-Ray irradiation at 77 K induces defects in M 2 AgX 3 (M=Rb, K and NH 4 ; X=Br and I) crystals. The irradiation induces self-trapped holes of the form of I 0 in the case of alkali silver iodides, and (halogen) 2 - and (halogen) 0 in the case of ammonium silver halides. The (halogen) 0 is weakly coupled with the nearest alkali metal ion or ammonium ion. It is able to be denoted as RbI + , KI + , NH 4 I + or NH 4 Br + . The directions of hole distribution of (halogen) 2 - and (halogen) 0 were different in each case of the alkali silver iodides, ammonium silver halides and mixed crystal of them. The (halogen) 0 decayed at 160 K in annealing process. The (halogen) 2 - was converted into another form of (halogen) 2 - at 250 K and this decayed at 310 K. A formation of metallic layers was observed on the crystal surface parallel with the c-plane of (NH 4 ) 2 AgI 3 irradiated at room temperature. (author)

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

    Holmlid, Leif, E-mail: holmlid@chem.gu.se [Atmospheric Science, Department of Chemistry, University of Gothenburg, SE-412 96 Göteborg (Sweden); Kotzias, Bernhard [Airbus DS, Department Mechanical Engineering, D28199 Bremen (Germany)

    2016-04-15

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

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

    Holmlid, Leif; Kotzias, Bernhard

    2016-01-01

    Ultra-dense hydrogen H(0) with its typical H-H bond distance of 2.3 pm is superfluid at room temperature as expected for quantum fluids. It also shows a Meissner effect at room temperature, which indicates that a transition point to a non-superfluid state should exist above room temperature. This transition point is given by a disappearance of the superfluid long-chain clusters H_2_N(0). This transition point is now measured for several metal carrier surfaces at 405 - 725 K, using both ultra-dense protium p(0) and deuterium D(0). Clusters of ordinary Rydberg matter H(l) as well as small symmetric clusters H_4(0) and H_3(0) (which do not give a superfluid or superconductive phase) all still exist on the surface at high temperature. This shows directly that desorption or diffusion processes do not remove the long superfluid H_2_N(0) clusters. The two ultra-dense forms p(0) and D(0) have different transition temperatures under otherwise identical conditions. The transition point for p(0) is higher in temperature, which is unexpected.

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

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

    2015-01-01

    Free electron laser light sources delivering high intensity pulses of short wavelength radiation are opening novel possibilities for the investigation of matter at the nanoscale and for the discovery and understanding of new physical processes occurring at the exotic transient states they make accessible. Strong ionization of atomic constituents of a nano-sized sample is a representative example of such processes and the understanding of ionization dynamics is crucial for a realistic description of the experiments. We report here on multiple ionization experiments on free clusters of titanium, a high cohesive energy metal. The time of flight ion spectra reveal a saturation of the cluster ionization at ∼10 16 photons per pulse per cm 2 . Our results also show a clear lack of any explosion process, opposite to what is observed for a rare-gas cluster under similar conditions. A simple and generalized multi-step ionization model including Coulomb frustration of the photoemission process effectively reproduces with a good agreement the main features of the experimental observation and points to an interpretation of the data involving a substantial energy deposition into the cluster through electronic system heating upon scattering events within photoemission. (paper)

  20. Quantum size correction to the work function and the centroid of excess charge in positively ionized simple metal clusters

    M. Payami

    2003-12-01

    Full Text Available  In this work, we have shown the important role of the finite-size correction to the work function in predicting the correct position of the centroid of excess charge in positively charged simple metal clusters with different values . For this purpose, firstly we have calculated the self-consistent Kohn-Sham energies of neutral and singly-ionized clusters with sizes in the framework of local spin-density approximation and stabilized jellium model (SJM as well as simple jellium model (JM with rigid jellium. Secondly, we have fitted our results to the asymptotic ionization formulas both with and without the size correction to the work function. The results of fittings show that the formula containing the size correction predict a correct position of the centroid inside the jellium while the other predicts a false position, outside the jellium sphere.

  1. Quantum size correction to the work function and centroid of excess charge in positively ionized simple metal clusters

    Payami, M.

    2004-01-01

    In this work, we have shown the important role of the finite-size correction to the work function in predicting the correct position of the centroid of excess charge in positively charged simple metal clusters with different r s values (2≤ r s ≥ 7). For this purpose, firstly we have calculated the self-consistent Kohn-Sham energies of neutral and singly-ionized clusters with sizes 2≤ N ≥100 in the framework of local spin-density approximation and stabilized jellium model as well as simple jellium model with rigid jellium. Secondly, we have fitted our results to the asymptotic ionization formulas both with and without the size correction to the work function. The results of fittings show that the formula containing the size correction predict a correct position of the centroid inside the jellium while the other predicts a false position, outside the jellium sphere

  2. Arrays of Size-Selected Metal Nanoparticles Formed by Cluster Ion Beam Technique

    Ceynowa, F. A.; Chirumamilla, Manohar; Zenin, Volodymyr

    2018-01-01

    Deposition of size-selected copper and silver nanoparticles (NPs) on polymers using cluster beam technique is studied. It is shown that ratio of particle embedment in the film can be controlled by simple thermal annealing. Combining electron beam lithography, cluster beam deposition, and heat...... with required configurations which can be applied for wave-guiding, resonators, in sensor technologies, and surface enhanced Raman scattering....

  3. Simulation of resonance hyper-Rayleigh scattering of molecules and metal clusters using a time-dependent density functional theory approach.

    Hu, Zhongwei; Autschbach, Jochen; Jensen, Lasse

    2014-09-28

    Resonance hyper-Rayleigh scattering (HRS) of molecules and metal clusters have been simulated based on a time-dependent density functional theory approach. The resonance first-order hyperpolarizability (β) is obtained by implementing damped quadratic response theory using the (2n + 1) rule. To test this implementation, the prototypical dipolar molecule para-nitroaniline (p-NA) and the octupolar molecule crystal violet are used as benchmark systems. Moreover, small silver clusters Ag 8 and Ag 20 are tested with a focus on determining the two-photon resonant enhancement arising from the strong metal transition. Our results show that, on a per atom basis, the small silver clusters possess two-photon enhanced HRS comparable to that of larger nanoparticles. This finding indicates the potential interest of using small metal clusters for designing new nonlinear optical materials.

  4. Advancement on Lead-Free Organic-Inorganic Halide Perovskite Solar Cells: A Review.

    Sani, Faruk; Shafie, Suhaidi; Lim, Hong Ngee; Musa, Abubakar Ohinoyi

    2018-06-14

    Remarkable attention has been committed to the recently discovered cost effective and solution processable lead-free organic-inorganic halide perovskite solar cells. Recent studies have reported that, within five years, the reported efficiency has reached 9.0%, which makes them an extremely promising and fast developing candidate to compete with conventional lead-based perovskite solar cells. The major challenge associated with the conventional perovskite solar cells is the toxic nature of lead (Pb) used in the active layer of perovskite material. If lead continues to be used in fabricating solar cells, negative health impacts will result in the environment due to the toxicity of lead. Alternatively, lead free perovskite solar cells could give a safe way by substituting low-cost, abundant and non toxic material. This review focuses on formability of lead-free organic-inorganic halide perovskite, alternative metal cations candidates to replace lead (Pb), and possible substitutions of organic cations, as well as halide anions in the lead-free organic-inorganic halide perovskite architecture. Furthermore, the review gives highlights on the impact of organic cations, metal cations and inorganic anions on stability and the overall performance of lead free perovskite solar cells.

  5. Combining in situ transmission electron microscopy irradiation experiments with cluster dynamics modeling to study nanoscale defect agglomeration in structural metals

    Xu Donghua; Wirth, Brian D.; Li Meimei; Kirk, Marquis A.

    2012-01-01

    We present a combinatorial approach that integrates state-of-the-art transmission electron microscopy (TEM) in situ irradiation experiments and high-performance computing techniques to study irradiation defect dynamics in metals. Here, we have studied the evolution of visible defect clusters in nanometer-thick molybdenum foils under 1 MeV krypton ion irradiation at 80 °C through both cluster dynamics modeling and in situ TEM experiments. The experimental details are reported elsewhere; we focus here on the details of model construction and comparing the model with the experiments. The model incorporates continuous production of point defects and/or small clusters, and the accompanying interactions, which include clustering, recombination and loss to the surfaces that result from the diffusion of the mobile defects. To account for the strong surface effect in thin TEM foils, the model includes one-dimensional spatial dependence along the foil depth, and explicitly treats the surfaces as black sinks. The rich amount of data (cluster number density and size distribution at a variety of foil thickness, irradiation dose and dose rate) offered by the advanced in situ experiments has allowed close comparisons with computer modeling and permitted significant validation and optimization of the model in terms of both physical model construct (damage production mode, identities of mobile defects) and parameterization (diffusivities of mobile defects). The optimized model exhibits good qualitative and quantitative agreement with the in situ TEM experiments. The combinatorial approach is expected to bring a unique opportunity for the study of radiation damage in structural materials.

  6. Electronic and magnetic properties of 3d-metal trioxides superhalogen cluster-doped monolayer MoS2: A first-principles study

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

    2014-01-01

    Utilizing first-principle calculations, the structural, electronic, and magnetic properties of monolayer MoS 2 doped with 3d transition-metal (TM) atoms and 3d-metal trioxides (TMO 3 ) superhalogen clusters are investigated. 3d-metal TMO 3 superhalogen cluster-doped monolayers MoS 2 almost have negative formation energies except CoO 3 and NiO 3 doped monolayer MoS 2 , which are much lower than those of 3d TM-doped structures. 3d-metal TMO 3 superhalogen clusters are more easily embedded in monolayer MoS 2 than 3d-metal atoms. MnO 3 , FeO 3 , CoO 3 , and NiO 3 incorporated into monolayer MoS 2 are magnetic, and the total magnetic moments are approximately 1.0, 2.0, 3.0, and 4.0 μB per supercell, respectively. MnO 3 and FeO 3 incorporated into monolayer MoS 2 become semiconductors, whereas CoO 3 and NiO 3 incorporated into monolayer MoS 2 become half-metallic. Our studies demonstrate that the half-metallic ferromagnetic nature of 3d-metal TMO 3 superhalogen clusters-doped monolayer MoS 2 has a great potential for MoS 2 -based spintronic device applications. -- Highlights: •TMO 3 superhalogen clusters incorporated into monolayer MoS 2 were investigated. •TMO 3 doped structures have much lower formation energies than TM doped structures. •TMO 3 cluster-doped MoS 2 are thermodynamically favored. •Significant charge transfers between O atoms and Mo atoms in TMO 3 doped structures. •MnO 3 , FeO 3 , CoO 3 , and NiO 3 incorporated into monolayer MoS 2 are magnetic.

  7. 2D halide perovskite-based van der Waals heterostructures: contact evaluation and performance modulation

    Guo, Yaguang; Saidi, Wissam A.; Wang, Qian

    2017-09-01

    Halide perovskites and van der Waals (vdW) heterostructures are both of current interest owing to their novel properties and potential applications in nano-devices. Here, we show the great potential of 2D halide perovskite sheets (C4H9NH3)2PbX4 (X  =  Cl, Br and I) that were synthesized recently (Dou et al 2015 Science 349 1518-21) as the channel materials contacting with graphene and other 2D metallic sheets to form van der Waals heterostructures for field effect transistor (FET). Based on state-of-the-art theoretical simulations, we show that the intrinsic properties of the 2D halide perovskites are preserved in the heterojunction, which is different from the conventional contact with metal surfaces. The 2D halide perovskites form a p-type Schottky barrier (Φh) contact with graphene, where tunneling barrier exists, and a negative band bending occurs at the lateral interface. We demonstrate that the Schottky barrier can be turned from p-type to n-type by doping graphene with nitrogen atoms, and a low-Φh or an Ohmic contact can be realized by doping graphene with boron atoms or replacing graphene with other high-work-function 2D metallic sheets such as ZT-MoS2, ZT-MoSe2 and H-NbS2. This study not only predicts a 2D halide perovskite-based FETs, but also enhances the understanding of tuning Schottky barrier height in device applications.

  8. Scattering of neutral metal clusters: Long-range interactions and response properties

    Kresin, V.V.; Scheidemann, A.

    1993-01-01

    The absolute integral cross sections for low-energy collisions of neutral sodium clusters Na n (n=2--40) with atoms and molecules (Ar, N 2 , O 2 , and halogens) have been measured. The cross sections are found to be exceptionally large (up to thousands of square angstroms), showing the dominant role of long-range intermolecular interactions. Elastic scattering proceeding under the influence of the van der Waals force, and a reaction channel involving electron transfer can successfully describe the measurements. The strength of the van der Waals potential is defined by such cluster response properties as the electric polarizability and the frequency of the giant dipole resonance. The reactive electron-jump channel, in turn, is described by the ''harpooning'' mechanism which is sensitive to the cluster ionization potential. Employing parameters taken from spectroscopic studies of alkali clusters, we obtain good agreement with the observed cross sections. This provides a direct connection between beam scattering experiments and studies of cluster electromagnetic response properties

  9. Thermochromic halide perovskite solar cells

    Lin, Jia; Lai, Minliang; Dou, Letian; Kley, Christopher S.; Chen, Hong; Peng, Fei; Sun, Junliang; Lu, Dylan; Hawks, Steven A.; Xie, Chenlu; Cui, Fan; Alivisatos, A. Paul; Limmer, David T.; Yang, Peidong

    2018-03-01

    Smart photovoltaic windows represent a promising green technology featuring tunable transparency and electrical power generation under external stimuli to control the light transmission and manage the solar energy. Here, we demonstrate a thermochromic solar cell for smart photovoltaic window applications utilizing the structural phase transitions in inorganic halide perovskite caesium lead iodide/bromide. The solar cells undergo thermally-driven, moisture-mediated reversible transitions between a transparent non-perovskite phase (81.7% visible transparency) with low power output and a deeply coloured perovskite phase (35.4% visible transparency) with high power output. The inorganic perovskites exhibit tunable colours and transparencies, a peak device efficiency above 7%, and a phase transition temperature as low as 105 °C. We demonstrate excellent device stability over repeated phase transition cycles without colour fade or performance degradation. The photovoltaic windows showing both photoactivity and thermochromic features represent key stepping-stones for integration with buildings, automobiles, information displays, and potentially many other technologies.

  10. Thermochromic halide perovskite solar cells.

    Lin, Jia; Lai, Minliang; Dou, Letian; Kley, Christopher S; Chen, Hong; Peng, Fei; Sun, Junliang; Lu, Dylan; Hawks, Steven A; Xie, Chenlu; Cui, Fan; Alivisatos, A Paul; Limmer, David T; Yang, Peidong

    2018-03-01

    Smart photovoltaic windows represent a promising green technology featuring tunable transparency and electrical power generation under external stimuli to control the light transmission and manage the solar energy. Here, we demonstrate a thermochromic solar cell for smart photovoltaic window applications utilizing the structural phase transitions in inorganic halide perovskite caesium lead iodide/bromide. The solar cells undergo thermally-driven, moisture-mediated reversible transitions between a transparent non-perovskite phase (81.7% visible transparency) with low power output and a deeply coloured perovskite phase (35.4% visible transparency) with high power output. The inorganic perovskites exhibit tunable colours and transparencies, a peak device efficiency above 7%, and a phase transition temperature as low as 105 °C. We demonstrate excellent device stability over repeated phase transition cycles without colour fade or performance degradation. The photovoltaic windows showing both photoactivity and thermochromic features represent key stepping-stones for integration with buildings, automobiles, information displays, and potentially many other technologies.

  11. Electron pairing in dilute liquid metal-metal halide solutions

    Selloni, A.; Car, R.; Parrinello, M.; Carnevali, P.

    1987-09-10

    Spin density functional theory is used to describe the interaction between solvated electrons in KCl in the high dilution limit. In agreement with recent calculations based on the path integral method our results for antiparallel spin predict a strong tendency to form localized bielectronic complexes. At variance with numerical path integral, our method can efficiently treat the case of parallel spins. For this case we find that electrons repel each other and localize into separate F-center-like states.

  12. On the applicability of deformed jellium model to the description of metal clusters

    Lyalin, Andrey G.; Matveentsev, Anton; Solov'yov, Ilia

    2003-01-01

    -density approximation deformed jellium model we have calculated the binding energies per atom, ionization potentials, deformation parameters and the optimized values of the Wigner-Seitz radii for neutral and singly charged sodium clusters with the number of atoms $N0$. These characteristics are compared...... shape deformations in the formation cluster properties and the quite reasonable level of applicability of the deformed jellium model.......This work is devoted to the elucidation the applicability of jellium model to the description of alkali cluster properties on the basis of comparison the jellium model results with those derived from experiment and within ab initio theoretical framework. On the basis of the Hartree-Fock and local...

  13. Metal cluster cation reactions: Carbon monoxide association to Cu + n ions

    Leuchtner, R. E.; Harms, A. C.; Castleman, A. W., Jr.

    1990-06-01

    Copper cluster cations (Cu+n,n=1-14) were produced in a laser vaporization/flow tube apparatus and equilibrated to room temperature. The association rate constants of carbon monoxide onto these ions were measured; low-pressure, termolecular behavior was observed for the smaller species while for clusters greater than Cu+7, the longer lifetimes due to the increased number of degrees of freedom leads to pressure independence (>0.3 Torr) of the effective bimolecular rates. Unimolecular decay theory (RRKM) is used to explain the overall trend and when intrinsic surface site reactivity is taken into account, excellent agreement with measured reactivity is obtained.

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

    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

    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.

  15. Density functional study of structural and catalytic properties of free and supported metal nano cluster; Dichtefunktionalstudie der strukturellen und katalytischen Eigenschaften freier und getraegerter Metallnanocluster

    Huber, B.

    2007-04-11

    The structural and catalytic properties of metal clusters were determined in the framework of density functional theory. The first part of this work investigates the electronic and geometrical structure of sodium clusters with up to 309 atoms. The ground-state structures of the clusters are determined and the corresponding electronic density of states is compared to experimental photoelectron spectras. The excellent agreement to the experimental results indicates that the correct growth motive of the sodium clusters was found. Small clusters from Na{sup -}{sub 20} to Na{sup -}{sub 42} prefer pentagonal and icosahedral structures with anti-Mackay overlayers, while clusters larger than Na{sup -}{sub 50} prefer icosahedral structures with Mackay overlayers. Clusters between the closed-shell Mackay Clusters often exhibit a twist deformation with respect to the regular Mackay positions. The second part of this work investigates the catalytic properties of free and supported palladium clusters. For both cases the oxidation of small Pd{sub N} clusters (N {<=} 9) was studied. It turned out that MgO supported Pd-clusters dissociate oxygen with a significant lower reaction energy than free clusters or supported systems with particles consisting of several thousands of atoms. The reaction with oxygen transforms the non-crystalline Pd-clusters into crystalline Pd{sub x}O{sub y} nano-oxide clusters that are in epitaxy with the underlying support. Simulations of the CO oxidation on the Pd{sub x}O{sub y} cluster predict a low-temperature reaction mechanism. By calculating the electronic density of states and CO stretch frequencies, different ways of verifying the results experimentally are discussed. (orig.)

  16. Oxygen abundances in halo giants. I - Giants in the very metal-poor globular clusters M92 and M15 and the metal-poor halo field

    Sneden, Christopher; Kraft, Robert P.; Prosser, Charles F.; Langer, G. E.

    1991-12-01

    Oxygen, iron, vanadium, and scandium abundances are derived for very metal-poor giants in the globular clusters M92 and M15, and giants of comparable metallicity in the local halo field. The forbidden O I line dublet (6300, 6363) and nearby metallic lines in spectra are analyzed using line analysis and spectral synthesis codes. The Fe/H abundance for M92 is estimated at -2.25 +/-0.02 based on nine giants with a range of 500 K in effective temperature. No evidence for star-to-star variations in the Fe/H abundance was found. O-rich and O-poor stars appear intermixed in the H-R diagram. O - N nuclear synthesis and mixing to the surface are proposed as the best explanation for the low-oxygen giants. The nitrogen abundances obtained earlier for nine of the ten halo field giants in this sample are incompatible with the very large nitrogen abundances expected of the O/Fe abundance of about + 1.2 in halo field subdwarfs, as found by Abia and Rebolo (1989), and not more than 0.6 in halo giants, as found in this and other studies.

  17. Methane Oxidation to Methanol Catalyzed by Cu-Oxo Clusters Stabilized in NU-1000 Metal-Organic Framework.

    Ikuno, Takaaki; Zheng, Jian; Vjunov, Aleksei; Sanchez-Sanchez, Maricruz; Ortuño, Manuel A; Pahls, Dale R; Fulton, John L; Camaioni, Donald M; Li, Zhanyong; Ray, Debmalya; Mehdi, B Layla; Browning, Nigel D; Farha, Omar K; Hupp, Joseph T; Cramer, Christopher J; Gagliardi, Laura; Lercher, Johannes A

    2017-08-02

    Copper oxide clusters synthesized via atomic layer deposition on the nodes of the metal-organic framework (MOF) NU-1000 are active for oxidation of methane to methanol under mild reaction conditions. Analysis of chemical reactivity, in situ X-ray absorption spectroscopy, and density functional theory calculations are used to determine structure/activity relations in the Cu-NU-1000 catalytic system. The Cu-loaded MOF contained Cu-oxo clusters of a few Cu atoms. The Cu was present under ambient conditions as a mixture of ∼15% Cu + and ∼85% Cu 2+ . The oxidation of methane on Cu-NU-1000 was accompanied by the reduction of 9% of the Cu in the catalyst from Cu 2+ to Cu + . The products, methanol, dimethyl ether, and CO 2 , were desorbed with the passage of 10% water/He at 135 °C, giving a carbon selectivity for methane to methanol of 45-60%. Cu oxo clusters stabilized in NU-1000 provide an active, first generation MOF-based, selective methane oxidation catalyst.

  18. New insights into the origin and evolution of the old, metal-rich open cluster NGC 6791

    Martinez-Medina, Luis A.; Gieles, Mark; Pichardo, Barbara; Peimbert, Antonio

    2018-02-01

    NGC 6791 is one of the most studied open clusters, it is massive (˜5000 M⊙), located at the solar circle, old (˜8 Gyr) and yet the most metal-rich cluster ([Fe/H] ≃ 0.4) known in the Milky Way. By performing an orbital analysis within a Galactic model including spiral arms and a bar, we found that it is plausible that NGC 6791 formed in the inner thin disc or in the bulge, and later displaced by radial migration to its current orbit. We apply different tools to simulate NGC 6791, including direct N-body summation in time-varying potentials, to test its survivability when going through different Galactic environments. In order to survive the 8-Gyr journey moving on a migrating orbit, NGC 6791 must have been more massive, M0 ≥ 5 × 104 M⊙, when formed. We find independent confirmation of this initial mass in the stellar mass function, which is observed to be flat; this can only be explained if the average tidal field strength experienced by the cluster is stronger than what it is at its current orbit. Therefore, the birth place and journeys of NGC 6791 are imprinted in its chemical composition, in its mass-loss and in its flat stellar mass function, supporting its origin in the inner thin disc or in the bulge.

  19. Communication: IR spectroscopy of neutral transition metal clusters through thermionic emission

    Lapoutre, V. J. F.; Haertelt, M.; Meijer, G.; Fielicke, A.; Bakker, J. M.

    2013-01-01

    The resonant multiple photon excitation of neutral niobium clusters using tunable infrared (IR) radiation leads to thermionic emission. By measuring the mass-resolved ionization yield as a function of IR wavenumber species selective IR spectra are obtained for Nb-n (n = 5-20) over the 200-350 cm(-1)

  20. Chemical Bonding of Transition-Metal Co13 Clusters with Graphene.

    Alonso-Lanza, Tomás; Ayuela, Andrés; Aguilera-Granja, Faustino

    2015-12-01

    We carried out density functional calculations to study the adsorption of Co13 clusters on graphene. Several free isomers were deposited at different positions with respect to the hexagonal lattice nodes, allowing us to study even the hcp 2d isomer, which was recently obtained as the most stable one. Surprisingly, the Co13 clusters attached to graphene prefer icosahedron-like structures in which the low-lying isomer is much distorted; in such structures, they are linked with more bonds than those reported in previous works. For any isomer, the most stable position binds to graphene by the Co atoms that can lose electrons. We find that the charge transfer between graphene and the clusters is small enough to conclude that the Co-graphene binding is not ionic-like but chemical. Besides, the same order of stability among the different isomers on doped graphene is kept. These findings could also be of interest for magnetic clusters on graphenic nanostructures such as ribbons and nanotubes. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Non-Linear Optically Active Metal Clusters in Nanoscaled Systems Including Self-Assembled Organic Films

    Balzer, Frank; Jett, S. D.; Rubahn, Horst-Günter

    2000-01-01

    are initially monitored in ultrahigh vacuum by comparison of calculated with measured polarization-dependent extinction spectra. We find that at low surface temperatures (150 K) the cluster growth is very similar to growth directly on insulating substrates. With increasing surface temperature the size...

  2. Halide-Dependent Electronic Structure of Organolead Perovskite Materials

    Buin, Andrei; Comin, Riccardo; Xu, Jixian; Ip, Alexander H.; Sargent, Edward H.

    2015-01-01

    -based perovskites, in line with recent experimental data. As a result, the optimal growth conditions are also different for the distinct halide perovskites: growth should be halide-rich for Br and Cl, and halide-poor for I-based perovskites. We discuss stability

  3. Cluster-cluster clustering

    Barnes, J.; Dekel, A.; Efstathiou, G.; Frenk, C.S.; Yale Univ., New Haven, CT; California Univ., Santa Barbara; Cambridge Univ., England; Sussex Univ., Brighton, England)

    1985-01-01

    The cluster correlation function xi sub c(r) is compared with the particle correlation function, xi(r) in cosmological N-body simulations with a wide range of initial conditions. The experiments include scale-free initial conditions, pancake models with a coherence length in the initial density field, and hybrid models. Three N-body techniques and two cluster-finding algorithms are used. In scale-free models with white noise initial conditions, xi sub c and xi are essentially identical. In scale-free models with more power on large scales, it is found that the amplitude of xi sub c increases with cluster richness; in this case the clusters give a biased estimate of the particle correlations. In the pancake and hybrid models (with n = 0 or 1), xi sub c is steeper than xi, but the cluster correlation length exceeds that of the points by less than a factor of 2, independent of cluster richness. Thus the high amplitude of xi sub c found in studies of rich clusters of galaxies is inconsistent with white noise and pancake models and may indicate a primordial fluctuation spectrum with substantial power on large scales. 30 references

  4. Muonium centers in the alkali halides

    Baumeler, H.; Kiefl, R.F.; Keller, H.; Kuendig, W.; Odermatt, W.; Patterson, B.D.; Schneider, J.W.; Savic, I.M.

    1986-01-01

    Muonium centers (Mu) in single crystals and powdered alkali halides have been studied using the high-timing-resolution transverse field μSR technique. Mu has been observed and its hyperfine parameter (HF) determined in every alkali halide. For the rocksalt alkali halides, the HF parameter A μ shows a systematic dependence on the host lattice constant. A comparison of the Mu HF parameter with hydrogen ESR data suggests that the Mu center is the muonic analogue of the interstitial hydrogen H i 0 -center. The rate of Mu diffusion can be deduced from the motional narrowing of the nuclear hyperfine interaction. KBr shows two different Mu states, a low-temperature Mu I -state and a high-temperature Mu II -state. (orig.)

  5. 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

    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

  6. Collision induced fragmentation dynamics of small metallic clusters; Dynamique de fragmentation induite par collision de petits agregats metalliques

    Picard, Y

    1999-04-15

    The goal of this work is the complete analysis of the fragmentation of alkali clusters (Na{sub n}{sup +} (n < 10), NaK{sup +} and K{sub 2}{sup +}) induced by collision with light atomic (He) or molecular (H{sub 2}) targets. The main point is to study how the energy is transmitted to the cluster during the collision and how this energy is shared among the various degrees of freedom of the system and leads to its fragmentation. Two types of interactions govern the collision induced dissociation processes: on one hand, the electronic mechanisms where the target perturbs the electronic cloud and brings the molecule into a dissociative state, and on the other hand, the impulsive mechanisms where the momentum transferred to the atomic cores leads to the rotational-vibrational dissociation of the molecule. The experimental procedure is based on the measurement of the velocity vectors of the outgoing fragments detected in coincidence. This allows to reconstruct the full kinematics of the fragmentation and to separate and characterize for the first time the two types of interactions. The two basic mechanisms of collision induced dissociation are then clearly resolved for the diatomic molecule Na{sub 2}{sup +}. For the heteronuclear molecular ion NaK{sup +}, it is shown that the dissociation process is due to a combination of electronic and impulsive mechanisms in some of the dissociation pathways. The extension to the study of metallic clusters Na{sub n}{sup +} (n < 10) fragmentation shows the role and the relative importance of the electronic and impulsive mechanisms and their evolution with the cluster size. The complete analysis of Na{sub 3}{sup +} multi-fragmentation is also presented. (author)

  7. The Effect of Radiation "Memory" in Alkali-Halide Crystals

    Korovkin, M. V.; Sal'nikov, V. N.

    2017-01-01

    The exposure of the alkali-halide crystals to ionizing radiation leads to the destruction of their structure, the emergence of radiation defects, and the formation of the electron and hole color centers. Destruction of the color centers upon heating is accompanied by the crystal bleaching, luminescence, and radio-frequency electromagnetic emission (REME). After complete thermal bleaching of the crystal, radiation defects are not completely annealed, as the electrons and holes released from the color centers by heating leave charged and locally uncompensated defects. Clusters of these "pre centers" lead to electric microheterogeneity of the crystal, the formation of a quasi-electret state, and the emergence of micro-discharges accompanied by radio emission. The generation of REME associated with residual defectiveness, is a manifestation of the effect of radiation "memory" in dielectrics.

  8. M-center growth in alkali halides: computer simulation

    Aguilar, M.; Jaque, F.; Agullo-Lopez, F.

    1983-01-01

    The heterogeneous interstitial nucleation model previously proposed to explain F-center growth curves in irradiated alkali halides has been extended to account for M-center kinetics. The interstitials produced during the primary irradiation event are assumed to be trapped at impurities and interstitial clusters or recombine with F and M centers. For M-center formation two cases have been considered: (a) diffusion and aggregation of F centers, and (b) statistical generation and pairing of F centers. Process (b) is the only one consistent with the quadratic relationship between M and F center concentrations. However, to account for the F/M ratios experimentally observed as well as for the role of dose-rate, a modified statistical model involving random creation and association of F + -F pairs has been shown to be adequate. (author)

  9. Validity of the classical monte carlo method to model the magnetic properties of a large transition-metal cluster: Mn19.

    Lima, Nicola; Caneschi, Andrea; Gatteschi, Dante; Kritikos, Mikael; Westin, L Gunnar

    2006-03-20

    The susceptibility of the large transition-metal cluster [Mn19O12(MOE)14(MOEH)10].MOEH (MOE = OC2H2O-CH3) has been fitted through classical Monte Carlo simulation, and an estimation of the exchange coupling constants has been done. With these results, it has been possible to perform a full-matrix diagonalization of the cluster core, which was used to provide information on the nature of the low-lying levels.

  10. Metal borohydrides and derivatives

    Paskevicius, Mark; Haarh Jepsen, Lars; Schouwink, Pascal

    2017-01-01

    major classes of metal borohydride derivatives have also been discovered: anion-substituted compounds where the complex borohydride anion, BH4 -, is replaced by another anion, i.e. a halide or amide ion; and metal borohydrides modified with neutral molecules, such as NH3, NH3BH3, N2H4, etc. Here, we...

  11. Energetics and dynamics in organic–inorganic halide perovskite photovoltaics and light emitters

    Sum, Tze Chien; Chen, Shi; Xing, Guichuan; Liu, Xinfeng; Wu, Bo

    2015-01-01

    The rapid transcendence of organic–inorganic metal halide perovskite solar cells to above the 20% efficiency mark has captivated the broad photovoltaic community. As the efficiency race continues unabated, it is essential that fundamental studies keep pace with these developments. Further gains in device efficiencies are expected to be increasingly arduous and harder to come by. The key to driving the perovskite solar cell efficiencies towards their Shockley–Queisser limit is through a clear understanding of the interfacial energetics and dynamics between perovskites and other functional materials in nanostructured- and heterojunction-type devices. In this review, we focus on the current progress in basic characterization studies to elucidate the interfacial energetics (energy-level alignment and band bending) and dynamical processes (from the ultrafast to the ultraslow) in organic–inorganic metal halide perovskite photovoltaics and light emitters. Major findings from these studies will be distilled. Open questions and scientific challenges will also be highlighted. (topical review)

  12. Superconducting nitride halides MNX (M = Ti, Zr, Hf; X = Cl, Br, I)

    Schurz, Christian M.; Shlyk, Larysa; Schleid, Thomas; Niewa, Rainer [Stuttgart Univ. (Germany). Inst. fuer Anorganische Chemie

    2011-07-01

    Two different polymorphs of the metal nitride halides MNX (M = Ti, Zr, Hf; X = Cl, Br, I) are known to crystallize in layered structures. The two crystal structures differ in the way {sub {infinity}}{sup 2}{l_brace}X[M{sub 2}N{sub 2}]X{r_brace} slabs are stacked along the c-axes. Metal atoms and/or organic molecules can be intercalated into the van-der-Waals gap between these layers. After such an electron-doping via intercalation the prototypic band insulators change into superconductors with moderate high critical temperatures T{sub c} up to 25.5 K. This review gathers information on synthesis routes, structural characteristics and properties of the prototypic nitride halides and the derivatives after electron-doping with a focus on superconductivity. (orig.)

  13. Binuclear trivalent and tetravalent uranium halides and cyanides supported by cyclooctatetraene ligands

    Wang, Cong-Zhi; Wu, Qun-Yan; Lan, Jian-Hui; Shi, Wei-Qun; Gibson, John K.

    2017-01-01

    Although the first organoactinide chloride Cp_3UCl (Cp = η"5-C_5H_5) was synthesized more than 50 years ago, binuclear uranium halides remain very rare in organoactinide chemistry. Herein, a series of binuclear trivalent and tetravalent uranium halides and cyanides with cyclooctatetraene ligands, (COT)_2U_2X_n (COT = η"8-C_8H_8; X=F, Cl, CN; n=2, 4), have been systematically studied using scalar-relativistic density functional theory (DFT). The structures with bridging halide or cyanide ligands were predicted to be the most stable complexes of (COT)_2U_2X_n, and all the complexes show weak antiferromagnetic interactions between the uranium centers. However, for each species, there is no significant uranium-uranium bonding interaction. The bonding between the metal and the ligands shows some degree of covalent character, especially between the metal and terminal halide or cyanide ligands. The U-5f and 6d orbitals are predominantly involved in the metal-ligand bonding. All the (COT)_2U_2X_n species were predicted to be more stable compared to the mononuclear half-sandwich complexes at room temperature in the gas phase such that (COT)_2U_2X_4 might be accessible through the known (COT)_2U complex. The tetravalent derivatives (COT)_2U_2X_4 are more energetically favorable than the trivalent (COT)_2U_2X_2 analogs, which may be attributed to the greater number of strong metal-ligand bonds in the former complexes.

  14. Binuclear trivalent and tetravalent uranium halides and cyanides supported by cyclooctatetraene ligands

    Wang, Cong-Zhi; Wu, Qun-Yan; Lan, Jian-Hui; Shi, Wei-Qun [Chinese Academy of Sciences, Beijing (China). Laboratory of Nuclear Energy Chemistry and Key Laboratory for Biomedical Effects of Nanomaterials and Nanosafety; Chai, Zhi-Fang [Chinese Academy of Sciences, Beijing (China). Laboratory of Nuclear Energy Chemistry and Key Laboratory for Biomedical Effects of Nanomaterials and Nanosafety; Soochow Univ., Suzhou (China). School of Radiological and Interdisciplinary Sciences (RAD-X); Gibson, John K. [Lawrence Berkeley National Laboratory, CA (United States). Chemical Sciences Division

    2017-03-01

    Although the first organoactinide chloride Cp{sub 3}UCl (Cp = η{sup 5}-C{sub 5}H{sub 5}) was synthesized more than 50 years ago, binuclear uranium halides remain very rare in organoactinide chemistry. Herein, a series of binuclear trivalent and tetravalent uranium halides and cyanides with cyclooctatetraene ligands, (COT){sub 2}U{sub 2}X{sub n} (COT = η{sup 8}-C{sub 8}H{sub 8}; X=F, Cl, CN; n=2, 4), have been systematically studied using scalar-relativistic density functional theory (DFT). The structures with bridging halide or cyanide ligands were predicted to be the most stable complexes of (COT){sub 2}U{sub 2}X{sub n}, and all the complexes show weak antiferromagnetic interactions between the uranium centers. However, for each species, there is no significant uranium-uranium bonding interaction. The bonding between the metal and the ligands shows some degree of covalent character, especially between the metal and terminal halide or cyanide ligands. The U-5f and 6d orbitals are predominantly involved in the metal-ligand bonding. All the (COT){sub 2}U{sub 2}X{sub n} species were predicted to be more stable compared to the mononuclear half-sandwich complexes at room temperature in the gas phase such that (COT){sub 2}U{sub 2}X{sub 4} might be accessible through the known (COT){sub 2}U complex. The tetravalent derivatives (COT){sub 2}U{sub 2}X{sub 4} are more energetically favorable than the trivalent (COT){sub 2}U{sub 2}X{sub 2} analogs, which may be attributed to the greater number of strong metal-ligand bonds in the former complexes.

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

    Rafique, Muhammad [School of Energy Science and Engineering, Harbin Institute of Technology, 92 West Dazhi Street, Harbin 150001 (China); M.U.E.T, S.Z.A.B, Campus Khairpur Mir' s, Sindh (Pakistan); Shuai, Yong, E-mail: shuaiyong1978@gmail.com [School of Energy Science and Engineering, Harbin Institute of Technology, 92 West Dazhi Street, Harbin 150001 (China); Tan, He-Ping; Hassan, Muhammad [School of Energy Science and Engineering, Harbin Institute of Technology, 92 West Dazhi Street, Harbin 150001 (China)

    2017-03-31

    Highlights: • First-principles calculations are performed for TMO{sub 3} cluster-doped and TM atoms adsorbed at three O atoms-doped graphene. • Significant magnetic coupling behavior is observed between TM atoms and neighboring C and O atoms for both cases. • The direction of charge transfer is always from monolayer graphene to TMO{sub 3} clusters incorporated into graphene. • TiO{sub 3} and VO{sub 3} doped structures display dilute magnetic semiconductor behavior. • Five different orbitals (d{sub xy}, d{sub yz}, d{sub z}{sup 2}, d{sub xz} and d{sub x}{sup 2}{sub -y}{sup 2}) of 3d TM atoms give rise to magnetic moments for both cases. - Abstract: 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 TMO{sub 3} halogen clusters. In this paper we used two approaches for 3d metal trioxide clusters (i) TMO{sub 3} 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 TMO{sub 3} doped graphene layer, the bond length between C−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 TiO{sub 3} and VO{sub 3} substitution, system exhibits semiconductor properties. Interestingly, TiO{sub 3}-substituted system shows dilute magnetic semiconductor behavior with 2.00 μ{sub B} magnetic moment. On the other hand, the substitution of CoO{sub 3}, CrO{sub 3}, FeO{sub 3} and MnO{sub 3} induced 1.015 μ{sub B}, 2

  16. Photography: enhancing sensitivity by silver-halide crystal doping

    Belloni, Jacqueline

    2003-01-01

    The physical chemistry of the silver photography processes, exposure, development and fixing, is briefly summarized. The mechanism of the autocatalytic development by the developer of the clusters produced in silver bromide crystals during the exposure which is controlled by the critical nuclearity of these clusters was understood from pulse radiolysis studies. The effective quantum yield PHI eff of photoinduced silver cluster formation in silver halide microcrystals is usually much lower than the photoionization theoretical limit PHI theor =1 electron-hole pair per photon absorbed, owing to a subsequent very fast intra-crystal recombination of a part of the electron-hole pairs. In order to inhibit this recombination and favor the silver reduction by photo-electrons, the AgX crystals were doped with the formate HCO 2 - as a specific hole scavenger. First, the dopant scavenges the photoinduced hole, thus enhancing the electron escape from the pair recombination. Second, the CO 2 ·- radical so formed transfers an electron to another silver cation, so that the PHI eff limit may be of 2Ag 0 per photon. This Photoinduced Bielectronic Transfer mechanism is strictly proportional to the light quanta absorbed and induces an exceptional efficiency for enhancing the radio- or photographic sensitivity insofar as it totally suppresses the electron-hole recombination

  17. Metal Enhanced Fluorescence on Super-Hydrophobic Clusters of Gold Nanoparticles

    Battista, Edmondo; Coluccio, Maria Laura; Alabastri, Alessandro; Barberio, Marianna; Causa, Filippo; Netti, Paolo Antonio; Di Fabrizio, Enzo M.; Gentile, Francesco

    2016-01-01

    We used optical lithography, electroless deposition and deep reactive ion etching techniques to realize arrays of super-hydrophobic gold nanoparticles arranged in a hierarchical structure. At the micro-scale, silicon-micro pillars in the chip permit to manipulate and concentrate biological solutions, at the nano-scale, gold nanoparticles enable metal enhanced fluorescence (MEF) effects, whereby fluorescence signal of fluorophores in close proximity to a rough metal surface is amplified by orders of magnitude. Here, we demonstrated the device in the analysis of fluorescein derived gold-binding peptides (GBP-FITC). While super-hydrophobic schemes and MEF effects have been heretofore used in isolation, their integration in a platform may advance the current state of fluorescence-based sensing technology in medical diagnostics and biotechnology. This scheme may be employed in protein microarrays where the increased sensitivity of the device may enable the early detection of cancer biomarkers or other proteins of biomedical interest.

  18. Metal Enhanced Fluorescence on Super-Hydrophobic Clusters of Gold Nanoparticles

    Battista, Edmondo

    2016-12-15

    We used optical lithography, electroless deposition and deep reactive ion etching techniques to realize arrays of super-hydrophobic gold nanoparticles arranged in a hierarchical structure. At the micro-scale, silicon-micro pillars in the chip permit to manipulate and concentrate biological solutions, at the nano-scale, gold nanoparticles enable metal enhanced fluorescence (MEF) effects, whereby fluorescence signal of fluorophores in close proximity to a rough metal surface is amplified by orders of magnitude. Here, we demonstrated the device in the analysis of fluorescein derived gold-binding peptides (GBP-FITC). While super-hydrophobic schemes and MEF effects have been heretofore used in isolation, their integration in a platform may advance the current state of fluorescence-based sensing technology in medical diagnostics and biotechnology. This scheme may be employed in protein microarrays where the increased sensitivity of the device may enable the early detection of cancer biomarkers or other proteins of biomedical interest.

  19. Formation of structured nanophases in halide crystals

    Kulveit, Jan; Demo, Pavel; Polák, Karel; Sveshnikov, Alexey; Kožíšek, Zdeněk

    2013-01-01

    Roč. 5, č. 6 (2013), s. 561-564 ISSN 2164-6627 R&D Projects: GA ČR GAP108/12/0891 Institutional support: RVO:68378271 Keywords : halide crystals * nucleation Subject RIV: BM - Solid Matter Physics ; Magnetism http://www.aspbs.com/asem.html#v5n6

  20. Complexes of alkylphenols with aluminium halides

    Golounin, A.V.

    1997-01-01

    Interaction of aluminium halides with alkylphenols is studied through the NMR method. The peculiarity of complex formation of pentamethylphenol with AlI 3 is revealed. By AlI 3 action on the pentamethylphenol the complexes are formed both of keto- and oxy form [ru

  1. luminescence in coloured alkali halide crystals

    have studied the effect of annealing in chlorine gas on the ML of X-rayed KCl crystals. ..... high temperature because of the thermal bleaching of the coloration in alkali halide ..... [31] J Hawkins, Ph.D. Thesis (University of Reading, 1976).

  2. Monocrystalline halide perovskite nanostructures for optoelectronic applications

    Khoram, P.

    2018-01-01

    Halide perovskites are a promising class of materials for incorporation in optoelectronics with higher efficiency and lower cost. The solution processability of these materials provides unique opportunities for simple nanostructure fabrication. In the first half of the thesis (chapter 2 and 3) we

  3. Molecular dynamics simulations with electronic stopping can reproduce experimental sputtering yields of metals impacted by large cluster ions

    Tian, Jiting; Zhou, Wei; Feng, Qijie; Zheng, Jian

    2018-03-01

    An unsolved problem in research of sputtering from metals induced by energetic large cluster ions is that molecular dynamics (MD) simulations often produce sputtering yields much higher than experimental results. Different from the previous simulations considering only elastic atomic interactions (nuclear stopping), here we incorporate inelastic electrons-atoms interactions (electronic stopping, ES) into MD simulations using a friction model. In this way we have simulated continuous 45° impacts of 10-20 keV C60 on a Ag(111) surface, and found that the calculated sputtering yields can be very close to the experimental results when the model parameter is appropriately assigned. Conversely, when we ignore the effect of ES, the yields are much higher, just like the previous studies. We further expand our research to the sputtering of Au induced by continuous keV C60 or Ar100 bombardments, and obtain quite similar results. Our study indicates that the gap between the experimental and the simulated sputtering yields is probably induced by the ignorance of ES in the simulations, and that a careful treatment of this issue is important for simulations of cluster-ion-induced sputtering, especially for those aiming to compare with experiments.

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

    Nakasuji, Toshiki, E-mail: t-nakasuji@iae.kyoto-u.ac.jp [Graduate School of Energy Science, Kyoto University, Uji, Kyoto 611-0011 (Japan); Morishita, Kazunori [Institute of Advanced Energy, Kyoto University, Uji, Kyoto 611-0011 (Japan); Ruan, Xiaoyong [Graduate School of Energy Science, Kyoto University, Uji, Kyoto 611-0011 (Japan)

    2017-02-15

    Highlights: • Monte-Carlo simulations were performed to investigate the nucleation process of copper-vacancy clusters in Fe. • Nucleation paths were obtained as a function of temperature and the damage rate. - Abstract: 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.

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

    Nakasuji, Toshiki; Morishita, Kazunori; Ruan, Xiaoyong

    2017-01-01

    Highlights: • Monte-Carlo simulations were performed to investigate the nucleation process of copper-vacancy clusters in Fe. • Nucleation paths were obtained as a function of temperature and the damage rate. - Abstract: 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.

  6. VizieR Online Data Catalog: Ages and metallicities for M31 star clusters (Fan+, 2016)

    Fan, Z.; de Grijs, R.; Chen, B.; Jiang, L.; Bian, F.; Li, Z.

    2017-05-01

    We have selected 22 confirmed M31 globular clusters from Peacock et al. 2010 (Cat. J/MNRAS/402/803). Spectroscopic observations were carried out with the 6.5m MMT/Red Channel Spectrograph from 2010 October 31 to 2010 November 2 and on 2011 November 4. The telescope is located on Mt. Hopkins in Arizona (USA) at an altitude of 2581m. The exposure times used ranged from 480-1800s, depending on the cluster brightness. The median seeing was ~0.98'' and we adopted a slit aperture of 0.75''*180''. The CCD's size is 450*1032 pixels2. It is characterized by a gain of 1.3e- ADU-1, with a readout noise of 3.5e-. A grating with 600l/mm with a blaze 1st/4800 was used. The spectral resolution was R=960 for a slit of 1'' and a central wavelength of 4701Å; the dispersion was 1.63Å/pixel. (7 data files).

  7. Spectroscopic investigation of indium halides as substitudes of mercury in low pressure discharges for lighting applications

    Briefi, Stefan

    2012-05-22

    Low pressure discharges with indium halides as radiator are discussed as substitutes for hazardous mercury in conventional fluorescent lamps. In this work, the applicability of InBr and InCl in a low pressure discharge light source is investigated. The aim is to identify and understand the physical processes which determine the discharge characteristics and the efficiency of the generated near-UV emission of the indium halide molecule and of the indium atom which is created due to dissociation processes in the plasma. As discharge vessels sealed cylindrical quartz glass tubes which contain a defined amount of indium halide and a rare gas are used. Preliminary investigations showed that for a controlled variation of the indium halide density a well-defined cold spot setup is mandatory. This was realized in the utilized experimental setup. The use of metal halides raises the issue, that power coupling by internal electrodes is not possible as the electrodes would quickly be eroded by the halides. The comparison of inductive and capacitive RF-coupling with external electrodes revealed that inductively coupled discharges provide higher light output and much better long term stability. Therefore, all investigations are carried out using inductive RF-coupling. The diagnostic methods optical emission and white light absorption spectroscopy are applied. As the effects of absorption-signal saturation and reabsorption of emitted radiation within the plasma volume could lead to an underestimation of the determined population densities by orders of magnitude, these effects are considered in the data evaluation. In order to determine the electron temperature and the electron density from spectroscopic measurements, an extended corona model as population model of the indium atom has been set up. A simulation of the molecular emission spectra has been implemented to investigate the rovibrational population processes of the indium halide molecules. The impact of the cold spot

  8. The emergence of nonbulk properties in supported metal clusters: negative thermal expansion and atomic disorder in Pt nanoclusters supported on gamma-Al2O3.

    Sanchez, Sergio I; Menard, Laurent D; Bram, Ariella; Kang, Joo H; Small, Matthew W; Nuzzo, Ralph G; Frenkel, Anatoly I

    2009-05-27

    The structural dynamics-cluster size and adsorbate-dependent thermal behaviors of the metal-metal (M-M) bond distances and interatomic order-of Pt nanoclusters supported on a gamma-Al(2)O(3) are described. Data from scanning transmission electron microscopy (STEM) and X-ray absorption spectroscopy (XAS) studies reveal that these materials possess a dramatically nonbulklike nature. Under an inert atmosphere small, subnanometer Pt/gamma-Al(2)O(3) clusters exhibit marked relaxations of the M-M bond distances, negative thermal expansion (NTE) with an average linear thermal expansion coefficient alpha = (-2.4 +/- 0.4) x 10(-5) K(-1), large static disorder and dynamical bond (interatomic) disorder that is poorly modeled within the constraints of classical theory. The data further demonstrate a significant temperature-dependence to the electronic structure of the Pt clusters, thereby suggesting the necessity of an active model to describe the cluster/support interactions mediating the cluster's dynamical structure. The quantitative dependences of these nonbulklike behaviors on cluster size (0.9 to 2.9 nm), ambient atmosphere (He, 4% H(2) in He or 20% O(2) in He) and support identity (gamma-Al(2)O(3) or carbon black) are systematically investigated. We show that the nonbulk structural, electronic and dynamical perturbations are most dramatically evidenced for the smallest clusters. The adsorption of hydrogen on the clusters leads to an increase of the Pt-Pt bondlengths (due to a lifting of the surface relaxation) and significant attenuation of the disorder present in the system. Oxidation of these same clusters has the opposite effect, leading to an increase in Pt-Pt bond strain and subsequent enhancement in nonbulklike thermal properties. The structural and electronic properties of Pt nanoclusters supported on carbon black contrast markedly with those of the Pt/gamma-Al(2)O(3) samples in that neither NTE nor comparable levels of atomic disorder are observed. The Pt

  9. MASS-TO-LIGHT RATIOS FOR M31 GLOBULAR CLUSTERS: AGE DATING AND A SURPRISING METALLICITY TREND

    Strader, Jay; Huchra, John P.; Smith, Graeme H.; Brodie, Jean P.; Larsen, Soeren

    2009-01-01

    We have obtained velocity dispersions from Keck high-resolution integrated spectroscopy of 10 M31 globular clusters (GCs), including three candidate intermediate-age GCs. We show that these candidates have the same V-band mass-to-light (M/L V ) ratios as the other GCs, implying that they are likely to be old. We also find a trend of derived velocity dispersion with wavelength, but cannot distinguish between a systematic error and a physical effect. Our new measurements are combined with photometric and spectroscopic data from the literature in a re-analysis of all M31 GC M/L V values. In a combined sample of 27 GCs, we show that the metal-rich GCs have lower M/L V than the metal-poor GCs, in conflict with predictions from stellar population models. Fragmentary data for other galaxies support this observation. The M31 GC fundamental plane is extremely tight, and we follow up an earlier suggestion by Djorgovski to show that the fundamental plane can be used to estimate accurate distances (potentially 10% or better).

  10. Basis set convergence on static electric dipole polarizability calculations of alkali-metal clusters

    Souza, Fabio A. L. de; Jorge, Francisco E.

    2013-01-01

    A hierarchical sequence of all-electron segmented contracted basis sets of double, triple and quadruple zeta valence qualities plus polarization functions augmented with diffuse functions for the atoms from H to Ar was constructed. A systematic study of basis sets required to obtain reliable and accurate values of static dipole polarizabilities of lithium and sodium clusters (n = 2, 4, 6 and 8) at their optimized equilibrium geometries is reported. Three methods are examined: Hartree-Fock (HF), second-order Moeller-Plesset perturbation theory (MP2), and density functional theory (DFT). By direct calculations or by fitting the directly calculated values through one extrapolation scheme, estimates of the HF, MP2 and DFT complete basis set limits were obtained. Comparison with experimental and theoretical data reported previously in the literature is done (author)

  11. Basis set convergence on static electric dipole polarizability calculations of alkali-metal clusters

    Souza, Fabio A. L. de; Jorge, Francisco E., E-mail: jorge@cce.ufes.br [Departamento de Fisica, Universidade Federal do Espirito Santo, 29060-900 Vitoria-ES (Brazil)

    2013-07-15

    A hierarchical sequence of all-electron segmented contracted basis sets of double, triple and quadruple zeta valence qualities plus polarization functions augmented with diffuse functions for the atoms from H to Ar was constructed. A systematic study of basis sets required to obtain reliable and accurate values of static dipole polarizabilities of lithium and sodium clusters (n = 2, 4, 6 and 8) at their optimized equilibrium geometries is reported. Three methods are examined: Hartree-Fock (HF), second-order Moeller-Plesset perturbation theory (MP2), and density functional theory (DFT). By direct calculations or by fitting the directly calculated values through one extrapolation scheme, estimates of the HF, MP2 and DFT complete basis set limits were obtained. Comparison with experimental and theoretical data reported previously in the literature is done (author)

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

    Scott, Carl D.; Smalley, Richard E.

    2003-01-01

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

  13. Structure and nature of the metal-support interface: characterization of iridium clusters on magnesium oxide by extended x-ray absorption fine structure spectroscopy

    Zon, van F.B.M.; Maloney, S.D.; Gates, B.C.; Koningsberger, D.C.

    1993-01-01

    X-ray absorption spectroscopy was used to characterize the metal-support interface in catalysts consisting of very small Ir clusters of nearly uniform nuclearity on the surface of MgO powder. [Ir4(CO)12] on MgO was converted in high yield into [HIr4(CO)11]- and sep. into [Ir6(CO)15]2-. EXAFS data

  14. How Does Boiling in the Earth's Crust Influence Metal Speciation and Transport?

    Kam, K.; Lemke, K.

    2014-12-01

    results from molecular simulations of metal halides that are aimed at characterizing the nature (i.e. relativistic structures and energies) of metal clusters in water vapor.

  15. Catalyst Architecture for Stable Single Atom Dispersion Enables Site-Specific Spectroscopic and Reactivity Measurements of CO Adsorbed to Pt Atoms, Oxidized Pt Clusters, and Metallic Pt Clusters on TiO2.

    DeRita, Leo; Dai, Sheng; Lopez-Zepeda, Kimberly; Pham, Nicholas; Graham, George W; Pan, Xiaoqing; Christopher, Phillip

    2017-10-11

    Oxide-supported precious metal nanoparticles are widely used industrial catalysts. Due to expense and rarity, developing synthetic protocols that reduce precious metal nanoparticle size and stabilize dispersed species is essential. Supported atomically dispersed, single precious metal atoms represent the most efficient metal utilization geometry, although debate regarding the catalytic activity of supported single precious atom species has arisen from difficulty in synthesizing homogeneous and stable single atom dispersions, and a lack of site-specific characterization approaches. We propose a catalyst architecture and characterization approach to overcome these limitations, by depositing ∼1 precious metal atom per support particle and characterizing structures by correlating scanning transmission electron microscopy imaging and CO probe molecule infrared spectroscopy. This is demonstrated for Pt supported on anatase TiO 2 . In these structures, isolated Pt atoms, Pt iso , remain stable through various conditions, and spectroscopic evidence suggests Pt iso species exist in homogeneous local environments. Comparing Pt iso to ∼1 nm preoxidized (Pt ox ) and prereduced (Pt metal ) Pt clusters on TiO 2 , we identify unique spectroscopic signatures of CO bound to each site and find CO adsorption energy is ordered: Pt iso ≪ Pt metal atoms bonded to TiO 2 and that Pt iso exhibits optimal reactivity because every atom is exposed for catalysis and forms an interfacial site with TiO 2 . This approach should be generally useful for studying the behavior of supported precious metal atoms.

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

    Lopez, M.J. [Valladolid Univ. (Spain). Dept. de Fisica Teorica; Jellinek, J. [Argonne National Lab., IL (United States)

    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.

  17. Graphene composites containing chemically bonded metal oxides

    the oxide layers are chemically bonded to graphene (Zhang ... sists of three glass chambers, one to contain the metal halide. (TiCl4, SiCl4 ... In this step, the metal halide reacts with the oxygen function- ... 1·0 g of FeCl3 were vigorously stirred in 30 ml of ethylene ... Reaction with water vapour results in hydrolysis of the un-.

  18. Silver nanoparticles from silver halide photography to plasmonics

    Tani, Tadaaki

    2015-01-01

    This book provides systematic knowledge and ideas on nanoparticles of Ag and related materials. While Ag and metal nanoparticles are essential for plasmonics, silver halide (AgX) photography relies to a great extent on nanoparticles of Ag and AgX which have the same crystal structure and have been studied extensively for many years. This book has been written to combine the knowledge of nanoparticles of Ag and related materials in plasmonics and AgX photography in order to provide new ideas for metal nanoparticles in plasmonics. Chapters 1–3 of this book describe the structure and formation of nanoparticles of Ag and related materials. Systematic descriptions of the structure and preparation of Ag, Au, and noble-metal nanoparticles for plasmonics are followed by and related to those of nanoparticles of Ag and AgX in AgX photography. Knowledge of the structure and preparation of Ag and AgX nanoparticles in photography covers nanoparticles with widely varying sizes, shapes, and structures, and formation proce...

  19. Morphology-Controlled Synthesis of Organometal Halide Perovskite Inverse Opals.

    Chen, Kun; Tüysüz, Harun

    2015-11-09

    The booming development of organometal halide perovskites in recent years has prompted the exploration of morphology-control strategies to improve their performance in photovoltaic, photonic, and optoelectronic applications. However, the preparation of organometal halide perovskites with high hierarchical architecture is still highly challenging and a general morphology-control method for various organometal halide perovskites has not been achieved. A mild and scalable method to prepare organometal halide perovskites in inverse opal morphology is presented that uses a polystyrene-based artificial opal as hard template. Our method is flexible and compatible with different halides and organic ammonium compositions. Thus, the perovskite inverse opal maintains the advantage of straightforward structure and band gap engineering. Furthermore, optoelectronic investigations reveal that morphology exerted influence on the conducting nature of organometal halide perovskites. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. EPR study of electron bombarded alkali- and alkaline-earth halide crystal surfaces

    Fryburg, G. C.; Lad, R. A.

    1975-01-01

    An EPR study of electron bombarded LiF, NaCl, KCl, CaF2 and BaF2 polycrystalline surfaces has shown that small metal particles are formed on the surfaces of the crystals. Identification was made from CESR signals. The symmetric line-shape of the signals, even at 77 K, indicated that the particles were less than 0.5 micron in diameter. Signals due to F centers were observed in LiF but not in the other halides. Implications to metal deposition are considered.

  1. Rapid Microwave-Assisted Copper-Catalyzed Nitration of Aromatic Halides with Nitrite Salts

    Paik, Seung Uk; Jung, Myoung Geun

    2012-01-01

    A rapid and efficient copper-catalyzed nitration of aryl halides has been established under microwave irradiation. The catalytic systems were found to be the most effective with 4-substituted aryl iodides leading to nearly complete conversions. Nitration of aromatic compounds is one of the important industrial processes as underlying intermediates in the manufacture of a wide range of chemicals such as dyes, pharmaceuticals, agrochemicals and explosives. General methods for the nitration of aromatic compounds utilize strongly acidic conditions employing nitric acid or a mixture of nitric and sulfuric acids, sometimes leading to problems with poor regioselectivity, overnitration, oxidized byproducts and excess acid waste in many cases of functionalized aromatic compounds. Several other nitrating agents or methods avoiding harsh reaction conditions have been explored using metal nitrates, nitrite salts, and ionic liquid-mediated or microwave-assisted nitrations. Recently, copper or palladium compounds have been successfully used as efficient catalysts for the arylation of amines with aryl halides under mild conditions

  2. Rapid Microwave-Assisted Copper-Catalyzed Nitration of Aromatic Halides with Nitrite Salts

    Paik, Seung Uk; Jung, Myoung Geun [Keimyung University, Daegu (Korea, Republic of)

    2012-02-15

    A rapid and efficient copper-catalyzed nitration of aryl halides has been established under microwave irradiation. The catalytic systems were found to be the most effective with 4-substituted aryl iodides leading to nearly complete conversions. Nitration of aromatic compounds is one of the important industrial processes as underlying intermediates in the manufacture of a wide range of chemicals such as dyes, pharmaceuticals, agrochemicals and explosives. General methods for the nitration of aromatic compounds utilize strongly acidic conditions employing nitric acid or a mixture of nitric and sulfuric acids, sometimes leading to problems with poor regioselectivity, overnitration, oxidized byproducts and excess acid waste in many cases of functionalized aromatic compounds. Several other nitrating agents or methods avoiding harsh reaction conditions have been explored using metal nitrates, nitrite salts, and ionic liquid-mediated or microwave-assisted nitrations. Recently, copper or palladium compounds have been successfully used as efficient catalysts for the arylation of amines with aryl halides under mild conditions.

  3. Physicochemical properties of mixed phosphorus halides

    Sladkov, I.B.; Tugarinova, N.S.

    1996-01-01

    Certain physicochemical properties (thermodynamic characteristics at boiling point, critical constants, density of liquid on the saturation line) of mixed phosphorus halides (PI 3 , PI 2 F, PIF 2 , PI 2 Cl, PICl 2 , PI 1 Br, PIBr 2 , PIClF, PIBrCl, etc.) are determined by means of approximate methods. Reliability of the results obtained is confirmed by comparison of calculated and experimental data for phosphorus compounds of the same type. 7 refs., 3 figs., 4 tabs

  4. Unraveling halide hydration: A high dilution approach.

    Migliorati, Valentina; Sessa, Francesco; Aquilanti, Giuliana; D'Angelo, Paola

    2014-07-28

    The hydration properties of halide aqua ions have been investigated combining classical Molecular Dynamics (MD) with Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy. Three halide-water interaction potentials recently developed [M. M. Reif and P. H. Hünenberger, J. Chem. Phys. 134, 144104 (2011)], along with three plausible choices for the value of the absolute hydration free energy of the proton (ΔG [minus sign in circle symbol]hyd[H+]), have been checked for their capability to properly describe the structural properties of halide aqueous solutions, by comparing the MD structural results with EXAFS experimental data. A very good agreement between theory and experiment has been obtained with one parameter set, namely LE, thus strengthening preliminary evidences for a ΔG [minus sign in circle symbol]hyd[H] value of -1100 kJ mol(-1) [M. M. Reif and P. H. Hünenberger, J. Chem. Phys. 134, 144104 (2011)]. The Cl(-), Br(-), and I(-) ions have been found to form an unstructured and disordered first hydration shell in aqueous solution, with a broad distribution of instantaneous coordination numbers. Conversely, the F(-) ion shows more ordered and defined first solvation shell, with only two statistically relevant coordination geometries (six and sevenfold complexes). Our thorough investigation on the effect of halide ions on the microscopic structure of water highlights that the perturbation induced by the Cl(-), Br(-), and I(-) ions does not extend beyond the ion first hydration shell, and the structure of water in the F(-) second shell is also substantially unaffected by the ion.

  5. Thermomechanical measurements of lead halide single crystals

    Nitsch, Karel; Rodová, Miroslava

    2002-01-01

    Roč. 234, č. 2 (2002), s. 701-709 ISSN 0370-1972 R&D Projects: GA AV ČR IAA2010926 Institutional research plan: CEZ:AV0Z1010914 Keywords : PbX 2 (X=Cl, Br, I) * coefficients of linear thermal expansion * polymorphism in lead halides Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 0.930, year: 2002

  6. Spatial clustering of metal and metalloid mixtures in unregulated water sources on the Navajo Nation - Arizona, New Mexico, and Utah, USA.

    Hoover, Joseph H; Coker, Eric; Barney, Yolanda; Shuey, Chris; Lewis, Johnnye

    2018-08-15

    Contaminant mixtures are identified regularly in public and private drinking water supplies throughout the United States; however, the complex and often correlated nature of mixtures makes identification of relevant combinations challenging. This study employed a Bayesian clustering method to identify subgroups of water sources with similar metal and metalloid profiles. Additionally, a spatial scan statistic assessed spatial clustering of these subgroups and a human health metric was applied to investigate potential for human toxicity. These methods were applied to a dataset comprised of metal and metalloid measurements from unregulated water sources located on the Navajo Nation, in the southwest United States. Results indicated distinct subgroups of water sources with similar contaminant profiles and that some of these subgroups were spatially clustered. Several profiles had metal and metalloid concentrations that may have potential for human toxicity including arsenic, uranium, lead, manganese, and selenium. This approach may be useful for identifying mixtures in water sources, spatially evaluating the clusters, and help inform toxicological research investigating mixtures. Copyright © 2018 The Authors. Published by Elsevier B.V. All rights reserved.

  7. Gaussian free field in the background of correlated random clusters, formed by metallic nanoparticles

    Cheraghalizadeh, Jafar; Najafi, Morteza N.; Mohammadzadeh, Hossein

    2018-05-01

    The effect of metallic nano-particles (MNPs) on the electrostatic potential of a disordered 2D dielectric media is considered. The disorder in the media is assumed to be white-noise Coulomb impurities with normal distribution. To realize the correlations between the MNPs we have used the Ising model with an artificial temperature T that controls the number of MNPs as well as their correlations. In the T → 0 limit, one retrieves the Gaussian free field (GFF), and in the finite temperature the problem is equivalent to a GFF in iso-potential islands. The problem is argued to be equivalent to a scale-invariant random surface with some critical exponents which vary with T and correspondingly are correlation-dependent. Two type of observables have been considered: local and global quantities. We have observed that the MNPs soften the random potential and reduce its statistical fluctuations. This softening is observed in the local as well as the geometrical quantities. The correlation function of the electrostatic and its total variance are observed to be logarithmic just like the GFF, i.e. the roughness exponent remains zero for all temperatures, whereas the proportionality constants scale with T - T c . The fractal dimension of iso-potential lines ( D f ), the exponent of the distribution function of the gyration radius ( τ r ), and the loop lengths ( τ l ), and also the exponent of the loop Green function x l change in terms of T - T c in a power-law fashion, with some critical exponents reported in the text. Importantly we have observed that D f ( T) - D f ( T c ) 1/√ ξ( T), in which ξ( T) is the spin correlation length in the Ising model.

  8. Metallic oxide nano-clusters synthesis by ion implantation in high purity Fe10Cr alloy

    Zheng, Ce

    2015-01-01

    ODS (Oxide Dispersed Strengthened) steels, which are reinforced with metal dispersions of nano-oxides (based on Y, Ti and O elements), are promising materials for future nuclear reactors. The detailed understanding of the mechanisms involved in the precipitation of these nano-oxides would improve manufacturing and mechanical properties of these ODS steels, with a strong economic impact for their industrialization. To experimentally study these mechanisms, an analytical approach by ion implantation is used, to control various parameters of synthesis of these precipitates as the temperature and concentration. This study demonstrated the feasibility of this method and concerned the behaviour of alloys models (based on aluminium oxide) under thermal annealing. High purity Fe-10Cr alloys were implanted with Al and O ions at room temperature. Transmission electron microscopy observations showed that the nano-oxides appear in the Fe-10Cr matrix upon ion implantation at room temperature without subsequent annealing. The mobility of implanted elements is caused by the defects created during ion implantation, allowing the nucleation of these nanoparticles, of a few nm in diameter. These nanoparticles are composed of aluminium and oxygen, and also chromium. The high-resolution experiments show that their crystallographic structure is that of a non-equilibrium compound of aluminium oxide (cubic γ-Al 2 O 3 type). The heat treatment performed after implantation induces the growth of the nano-sized oxides, and a phase change that tends to balance to the equilibrium structure (hexagonal α-Al 2 O 3 type). These results on model alloys are fully applicable to industrial materials: indeed ion implantation reproduces the conditions of milling and heat treatments are at equivalent temperatures to those of thermo-mechanical treatments. A mechanism involving the precipitation of nano-oxide dispersed in ODS alloys is proposed in this manuscript based on the obtained experimental results

  9. Investigation of surface halide modification of nitrile butadiene rubber

    Sukhareva, K. V.; Mikhailov, I. A.; Andriasyan, Yu O.; Mastalygina, E. E.; Popov, A. A.

    2017-12-01

    The investigation is devoted to the novel technology of surface halide modification of rubber samples based on nitrile butadiene rubber (NBR). 1,1,2-trifluoro-1,2,2-trichlorethane was used as halide modifier. The developed technology is characterized by production stages reduction to one by means of treating the rubber compound with a halide modifier. The surface halide modification of compounds based on nitrile butadiene rubber (NBR) was determined to result in increase of resistance to thermal oxidation and aggressive media. The conducted research revealed the influence of modification time on chemical resistance and physical-mechanical properties of rubbers under investigation.

  10. Lanthanide doped strontium-barium cesium halide scintillators

    Bizarri, Gregory; Bourret-Courchesne, Edith; Derenzo, Stephen E.; Borade, Ramesh B.; Gundiah, Gautam; Yan, Zewu; Hanrahan, Stephen M.; Chaudhry, Anurag; Canning, Andrew

    2015-06-09

    The present invention provides for a composition comprising an inorganic scintillator comprising an optionally lanthanide-doped strontium-barium, optionally cesium, halide, useful for detecting nuclear material.

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

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

    2017-05-01

    Context. The radial metallicity distribution in the Galactic thin disc represents a crucial constraint for modelling disc formation and evolution. Open star clusters allow us to derive both the radial metallicity distribution and its evolution over time. Aims: In this paper we perform the first investigation of the present-day radial metallicity distribution based on [Fe/H] determinations in late type members of pre-main-sequence clusters. Because of their youth, these clusters are therefore essential for tracing the current interstellar medium metallicity. Methods: We used the products of the Gaia-ESO Survey analysis of 12 young regions (age ages is not easily explained by the models. Our results reveal a complex interplay of several processes (e.g. star formation activity, initial mass function, supernova yields, gas flows) that controlled the recent evolution of the Milky Way. Based on observations made with the ESO/VLT, at Paranal Observatory, under program 188.B-3002 (The Gaia-ESO Public Spectroscopic Survey).Full Table 1 is only available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (http://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/601/A70

  12. INTERRELATION OF ACIDITY-BASICITY, SOLUBILITY AND ABILITY TO INTERACTION OF HALIDES OF MX AND M'X2 (M - Li ÷ Cs, M' - Be ÷ Ba, X - Cl ÷ I TYPES

    V. F. Zinchenko

    2015-11-01

    Full Text Available The size-charge factor of basicity for definition of the acid-base properties of alkaline both alkaline-earth metals and Be halides is offered. The certain interrelation of the specified factor, and also the magnitudes connected with energy of a crystal lattice (temperature of boiling and enthalpy of evaporation of salt with its solubility in water, and also with enthalpy of hydration is established. It is shown that the minimum solubility possess alkaline metals halides (KCl for chlorides, RbBr for Rubidium halides and CsI for alkaline metals halides as a whole at which value of the factor of basicity is equal to 0.83, i.e. it is slightly less than 1. Among alkaline-earth metals halides the lowest solubility has BaCl2 with the highest value of the factor of basicity (0.4. An absolute value of enthalpy of hydration for salts crystal-hydrates possesses tens kJ/mol H2O and increases with reduction of the factor of basicity at transition from metals chlorides to iodides, and also at cationic substitution by easier analogue. Qualitative correlation between a difference of basicity of binary halides and their ability to interaction with formation of complex compounds of various degree of durability is established. At an average difference of basicities 0.4 in halide systems are formed incongruently melting, and at 0.6-0.8 and more – congruently melting compounds. Forecasting of solubility of complex halide of CsSrCl3 composition on the basis of its value of equalized basicity is carried out.

  13. First-principles thermodynamics study of phase stability in inorganic halide perovskite solid solutions

    Bechtel, Jonathon S.; Van der Ven, Anton

    2018-04-01

    Halide substitution gives rise to a tunable band gap as a function of composition in halide perovskite materials. However, photoinduced phase segregation, observed at room temperature in mixed halide A Pb (IxBr1-x) 3 systems, limits open circuit voltages and decreases photovoltaic device efficiencies. We investigate equilibrium phase stability of orthorhombic P n m a γ -phase CsM (XxY1-x) 3 perovskites where M is Pb or Sn, and X and Y are Br, Cl, or I. Finite-temperature phase diagrams are constructed using a cluster expansion effective Hamiltonian parameterized from first-principles density-functional-theory calculations. Solid solution phases for CsM (IxBr1-x) 3 and CsM (BrxCl1-x) 3 are predicted to be stable well below room temperature while CsM (IxCl1-x) 3 systems have miscibility gaps that extend above 400 K. The height of the miscibility gap correlates with the difference in volume between end members. Also layered ground states are found on the convex hull at x =2 /3 for CsSnBr2Cl ,CsPbI2Br , and CsPbBrCl2. The impact of these ground states on the finite temperature phase diagram is discussed in the context of the experimentally observed photoinduced phase segregation.

  14. Comparison of single-use and reusable metal laryngoscope blades for orotracheal intubation during rapid sequence induction of anesthesia: a multicenter cluster randomized study.

    Amour, Julien; Le Manach, Yannick Le; Borel, Marie; Lenfant, François; Nicolas-Robin, Armelle; Carillion, Aude; Ripart, Jacques; Riou, Bruno; Langeron, Olivier

    2010-02-01

    Single-use metal laryngoscope blades are cheaper and carry a lower risk of infection than reusable metal blades. The authors compared single-use and reusable metal blades during rapid sequence induction of anesthesia in a multicenter cluster randomized trial. One thousand seventy-two adult patients undergoing general anesthesia under emergency conditions and requiring rapid sequence induction were randomly assigned on a weekly basis to either single-use or reusable metal blades (cluster randomization). After induction, a 60-s period was allowed to complete intubation. In the case of failed intubation, a second attempt was performed using the opposite type of blade. The primary endpoint was the rate of failed intubation, and the secondary endpoints were the incidence of complications (oxygen desaturation, lung aspiration, and/or oropharynx trauma) and the Cormack and Lehane score. Both groups were similar in their main characteristics, including the risk factors for difficult intubation. The rate of failed intubation was significantly decreased with single-use metal blades at the first attempt compared with reusable blades (2.8 vs. 5.4%, P < 0.05). In addition, the proportion of grades III and IV in Cormack and Lehane score were also significantly decreased with single-use metal blades (6 vs. 10%, P < 0.05). The global complication rate did not reach statistical significance, although the same trend was noted (6.8% vs. 11.5%, P = not significant). An investigator survey and a measure of illumination pointed that illumination might have been responsible for this result. The single-use metal blade was more efficient than a reusable metal blade in rapid sequence induction of anesthesia.

  15. Influence of stacking fault energies on the size distribution and character of defect clusters formed by collision cascades in face-centered cubic metals

    Y. Yang

    2016-12-01

    Full Text Available Molecular dynamics simulations are performed to evaluate the influence of the stacking fault energy (SFE as a single variable parameter on defect formation by collision cascades in face-centered cubic metals. The simulations are performed for energies of a primary knock-on atom (EPKA up to 50keV at 100K by using six sets of the recently developed embedded atom method–type potentials. Neither the number of residual defects nor their clustering behavior is found to be affected by the SFE, except for the mean size of the vacancy clusters at EPKA=50keV. The mean size increases as the SFE decreases because of the enhanced formation of large vacancy clusters, which prefer to have stacking faults inside them. On the other hand, the ratio of glissile self-interstitial atom (SIA clusters decreases as the SFE increases. At higher SFEs, both the number of Frank loops and number of perfect loops tend to decrease; instead, three-dimensional irregular clusters with higher densities appear, most of which are sessile. The effect of SFE on the number of Frank loops becomes apparent only at a high EPKA of 50keV, where comparably large SIA clusters can be formed with a higher density.

  16. White-Light Emission from Layered Halide Perovskites.

    Smith, Matthew D; Karunadasa, Hemamala I

    2018-03-20

    With nearly 20% of global electricity consumed by lighting, more efficient illumination sources can enable massive energy savings. However, effectively creating the high-quality white light required for indoor illumination remains a challenge. To accurately represent color, the illumination source must provide photons with all the energies visible to our eye. Such a broad emission is difficult to achieve from a single material. In commercial white-light sources, one or more light-emitting diodes, coated by one or more phosphors, yield a combined emission that appears white. However, combining emitters leads to changes in the emission color over time due to the unequal degradation rates of the emitters and efficiency losses due to overlapping absorption and emission energies of the different components. A single material that emits broadband white light (a continuous emission spanning 400-700 nm) would obviate these problems. In 2014, we described broadband white-light emission upon near-UV excitation from three new layered perovskites. To date, nine white-light-emitting perovskites have been reported by us and others, making this a burgeoning field of study. This Account outlines our work on understanding how a bulk material, with no obvious emissive sites, can emit every color of the visible spectrum. Although the initial discoveries were fortuitous, our understanding of the emission mechanism and identification of structural parameters that correlate with the broad emission have now positioned us to design white-light emitters. Layered hybrid halide perovskites feature anionic layers of corner-sharing metal-halide octahedra partitioned by organic cations. The narrow, room-temperature photoluminescence of lead-halide perovskites has been studied for several decades, and attributed to the radiative recombination of free excitons (excited electron-hole pairs). We proposed that the broad white emission we observed primarily stems from exciton self-trapping. Here, the

  17. Electronic structure and geometries of small compound metal clusters: Progress report, August 1, 1987-July 31, 1988

    Jena, P.; Rao, B.K.; Khanna, S.N.

    1988-04-01

    Our research during this reporting period has focused on studying electronic structure and properties of both gas-phase clusters and clusters as models of crystals and defects. We have also concentrated on developing new theoretical techniques that can allow us to study large clusters in a computationally effective manner. Following is a summary of results

  18. Electronic structure and geometries of small compound metal clusters: Progress report, August 1, 1988--July 31, 1989

    Jena, P.; Rao, B.K.; Khanna, S.N.

    1989-04-01

    Our research during this reporting period has focused on the following two aspects of cluster research. Electronic structure and stability of charged clusters and studies of evolution of magnetic properties with increasing cluster size. Following is a summary of our results

  19. Vibrational Spectra of Discrete UO22+ Halide Complexes in the Gas Phase

    Groenewold, G.S.; Van Stipdonk, Michael J.; Oomens, Jos; De Jong, Wibe A.; Gresham, Garold L.; Mcilwain, Michael

    2010-01-01

    The intrinsic binding of halide ions to the metal center in the uranyl molecule is a topic of ongoing research interest in both the actinide separations and theoretical communities. Investigations of structure in the condensed phases is frequently obfuscated by solvent interactions that can alter ligand binding and spectroscopic properties. The approach taken in this study is to move the uranyl halide complexes into the gas phase where they are free from solvent interactions, and then interrogate their vibrational spectroscopy using infrared multiple photon dissociation (IRMPD). The spectra of cationic coordination complexes having the composition (UO 2 (X)(ACO) 3 ) + (where X = F, Cl, Br and I; ACO = acetone) were acquired using electrospray for ion formation, and monitoring the ion signal from the photoelimination of ACO ligands. The studies showed that the asymmetric ν 3 UO 2 frequency was insensitive to halide identity as X was varied from Cl to I, suggesting that in these pseudo-octahedral complexes, changing the nucleophilicity of the halide did not appreciably alter its binding in the complex. The ν 3 peak in the spectrum of the F-containing complex was 9 cm -1 lower indicating stronger coordination in this complex. Similarly the ACO carbonyl stretches showed that the C=O frequency was relatively insensitive to the identity of the halide, although a modest shift to higher wavenumber was seen for the complexes with the more nucleophilic anions, consistent with the idea that they loosen solvent binding. Surprisingly, the ν 1 stretch was activated when the softer anions Cl, Br and I were present in the complexes. IR studies of the anionic complexes (UO 2 X 3 ) - (where X = Cl - , Br - and I - ) compared the ν 3 UO 2 modes versus halide, and showed that the ν 3 values decreased with increasing anion nucleophilicity. This observation was consistent with DFT calculations that indicated that (UO 2 X 2 ) - -X, and (UO 2 X 2 )·-X - dissociation energies

  20. High Pressure Optical Studies of the Thallous Halides and of Charge-Transfer Complexes

    Jurgensen, Charles Willard

    High pressure was used to study the insulator -to-metal transition in sulfur and the thallous halides and to study the intermolecular interactions in charge -transfer complexes. The approach to the band overlap insulator -to-metal transition was studied in three thallous halides and sulfur by optical absorption measurements of the band gap as a function of pressure. The band gap of sulfur continuously decreases with pressure up to the insulator -to-metal transition which occurs between 450 and 485 kbars. The results on the thallous halides indicate that the indirect gap decreases more rapidly than the direct gap; the closing of the indirect gap is responsible for the observed insulator -to-metal transitions. High pressure electronic and vibrational spectroscopic measurements on the solid-state complexes of HMB-TCNE were used to study the intermolecular interactions of charge -transfer complexes. The vibrational frequency shifts indicate that the degree of charge transfer increases with pressure which is independently confirmed by an increase in the molar absorptivity of the electronic charge-transfer peak. Induction and dispersion forces contribute towards a red shift of the charge-transfer peak; however, charge-transfer resonance contributes toward a blue shift and this effect is dominant for the HMB-TCNE complexes. High pressure electronic spectra were used to study the effect of intermolecular interactions on the electronic states of TCNQ and its complexes. The red shifts with pressure of the electronic spectra of TCNQ and (TCNQ)(' -) in polymer media and of crystalline TCNQ can be understood in terms of Van der Waals interactions. None of the calculations which considered intradimer distance obtained the proper behavior for either the charge-transfer of the locally excited states of the complexes. The qualitative behavior of both states can be interpreted as the effect of increased mixing of the locally excited and charge transfer states.

  1. The coacervation of aqueous solutions of tetraalkylammonium halides

    Mugnier de Trobriand, Anne.

    1979-09-01

    The coacervation of aqueous solutions of tatraalkylammonium halides in the presence of not of inorganic halides and acids has been studied, considering thermodynamic and spectroscopic aspects. The importance of dispersion forces as well as forces resulting from hydrophobic hydration has been assessed. The analogy between these systems and anionic ion exchange resins has been shown especially for Uranium VI extraction [fr

  2. Lead Halide Perovskite Nanocrystals in the Research Spotlight: Stability and Defect Tolerance

    2017-01-01

    This Perspective outlines basic structural and optical properties of lead halide perovskite colloidal nanocrystals, highlighting differences and similarities between them and conventional II–VI and III–V semiconductor quantum dots. A detailed insight into two important issues inherent to lead halide perovskite nanocrystals then follows, namely, the advantages of defect tolerance and the necessity to improve their stability in environmental conditions. The defect tolerance of lead halide perovskites offers an impetus to search for similar attributes in other related heavy metal-free compounds. We discuss the origins of the significantly blue-shifted emission from CsPbBr3 nanocrystals and the synthetic strategies toward fabrication of stable perovskite nanocrystal materials with emission in the red and infrared parts of the optical spectrum, which are related to fabrication of mixed cation compounds guided by Goldschmidt tolerance factor considerations. We conclude with the view on perspectives of use of the colloidal perovskite nanocrystals for applications in backlighting of liquid-crystal TV displays. PMID:28920080

  3. Radiation damage in the alkali halide crystals

    Diller, K.M.

    1975-10-01

    A general review is given of the experimental data on radiation damage in the alkali halide crystals. A report is presented of an experimental investigation of irradiation produced interstitial dislocation loops in NaCl. These loops are found to exhibit the usual growth and coarsening behaviour during thermal annealing which operates by a glide and self-climb mechanism. It is shown that the recombination of defects in these crystals is a two stage process, and that the loss of interstitials stabilized at the loops is caused by extrinsic vacancies. The theoretical techniques used in simulating point defects in ionic crystals are described. Shell model potentials are derived for all the alkali halide crystals by fitting to bulk crystal data. The fitting is supplemented by calculations of the repulsive second neighbour interactions using methods based on the simple electron gas model. The properties of intrinsic and substitutional impurity defects are calculated. The HADES computer program is used in all the defect calculations. Finally the report returns to the problems of irradiation produced interstitial defects. The properties of H centres are discussed; their structure, formation energies, trapping at impurities and dimerization. The structure, formation energies and mobility of the intermediate and final molecular defects are then discussed. The thermodynamics of interstitial loop formation is considered for all the alklai halide crystals. The nucleation of interstitial loops in NaCl and NaBr is discussed, and the recombination of interstitial and vacancy defects. The models are found to account for all the main features of the experimental data. (author)

  4. Density functional investigation of mercury and arsenic adsorption on nitrogen doped graphene decorated with palladium clusters: A promising heavy metal sensing material in farmland

    Zhao, Chunjiang, E-mail: zhaocj_nercita@163.com [National Engineering Research Center for Information Technology in Agriculture, Beijing 100097 (China); Beijing Research Center for Information Technology in Agriculture, Beijing Academy of Agriculture and Forestry Sciences, Beijing 100097 (China); Key Laboratory for Information Technologies in Agriculture, Ministry of Agriculture, Beijing100097 (China); Wu, Huarui, E-mail: wuhrnercita@163.com [National Engineering Research Center for Information Technology in Agriculture, Beijing 100097 (China); Beijing Research Center for Information Technology in Agriculture, Beijing Academy of Agriculture and Forestry Sciences, Beijing 100097 (China); Key Laboratory for Information Technologies in Agriculture, Ministry of Agriculture, Beijing100097 (China)

    2017-03-31

    Highlights: • PNG can be acted as micro-sensor for monitoring heavy metal in agriculture. • The most favorable adsorption site of Pd atom or cluster on PNG is the vacancy site. • The Pd atom or cluster enhance the reactivity of PNG toward Hg and AsH{sub 3} adsorption. • The efficiency of a sorbent can be tuned by tailoring the ε{sub d} of adsorbed metals. - Abstract: Density functional theory calculations are carried out to study the adsorption of mercury and arsenic on Pd{sub n} (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 AsH{sub 3} adsorption on PNG. The adsorption ability of Hg on Pd{sub n} decorated PNG is found to be related to the d-band center (ε{sub d}) of the Pd{sub n}, in which the closer ε{sub d} of Pd{sub n} to the Fermi level, the higher adsorption strength for Hg on Pd{sub n} decorated PNG. Moreover, the charge transfer between Pd{sub n} and arsenic may constitute arsenic adsorption on Pd{sub n} decorated PNG. Further design of highly efficient carbon based sorbents for heavy metals removal should be focused on tailoring ε{sub d} of adsorbed metals.

  5. Density functional investigation of mercury and arsenic adsorption on nitrogen doped graphene decorated with palladium clusters: A promising heavy metal sensing material in farmland

    Zhao, Chunjiang; Wu, Huarui

    2017-01-01

    Highlights: • PNG can be acted as micro-sensor for monitoring heavy metal in agriculture. • The most favorable adsorption site of Pd atom or cluster on PNG is the vacancy site. • The Pd atom or cluster enhance the reactivity of PNG toward Hg and AsH_3 adsorption. • The efficiency of a sorbent can be tuned by tailoring the ε_d of adsorbed metals. - Abstract: Density functional theory calculations are carried out to study the adsorption of mercury and arsenic on Pd_n (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 AsH_3 adsorption on PNG. The adsorption ability of Hg on Pd_n decorated PNG is found to be related to the d-band center (ε_d) of the Pd_n, in which the closer ε_d of Pd_n to the Fermi level, the higher adsorption strength for Hg on Pd_n decorated PNG. Moreover, the charge transfer between Pd_n and arsenic may constitute arsenic adsorption on Pd_n decorated PNG. Further design of highly efficient carbon based sorbents for heavy metals removal should be focused on tailoring ε_d of adsorbed metals.

  6. Research Update: Luminescence in lead halide perovskites

    Ajay Ram Srimath Kandada

    2016-09-01

    Full Text Available Efficiency and dynamics of radiative recombination of carriers are crucial figures of merit for optoelectronic materials. Following the recent success of lead halide perovskites in efficient photovoltaic and light emitting technologies, here we review some of the noted literature on the luminescence of this emerging class of materials. After outlining the theoretical formalism that is currently used to explain the carrier recombination dynamics, we review a few significant works which use photoluminescence as a tool to understand and optimize the operation of perovskite based optoelectronic devices.

  7. Exciton-relaxation dynamics in lead halides

    Iwanaga, Masanobu; Hayashi, Tetsusuke

    2003-01-01

    We survey recent comprehensive studies of exciton relaxation in the crystals of lead halides. The luminescence and electron-spin-resonance studies have revealed that excitons in lead bromide spontaneously dissociate and both electrons and holes get self-trapped individually. Similar relaxation has been also clarified in lead chloride. The electron-hole separation is ascribed to repulsive correlation via acoustic phonons. Besides, on the basis of the temperature profiles of self-trapped states, we discuss the origin of luminescence components which are mainly induced under one-photon excitation into the exciton band in lead fluoride, lead chloride, and lead bromide

  8. Large polarons in lead halide perovskites

    Miyata, Kiyoshi; Meggiolaro, Daniele; Trinh, M. Tuan; Joshi, Prakriti P.; Mosconi, Edoardo; Jones, Skyler C.; De Angelis, Filippo; Zhu, X.-Y.

    2017-01-01

    Lead halide perovskites show marked defect tolerance responsible for their excellent optoelectronic properties. These properties might be explained by the formation of large polarons, but how they are formed and whether organic cations are essential remain open questions. We provide a direct time domain view of large polaron formation in single-crystal lead bromide perovskites CH3NH3PbBr3 and CsPbBr3. We found that large polaron forms predominantly from the deformation of the PbBr3 ? framewor...

  9. The alkali halide disk technique in infra-red spectrometry : Anomalous behaviour of some samples dispersed in alkali halide disks

    Tolk, A.

    1961-01-01

    Some difficulties encountered in the application of the alkali halide disk technique in infra-red spectrometry are discussed. Complications due to interaction of the sample with the alkali halide have been studied experimentally. It was found that the anomalous behaviour of benzoic acid, succinic

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

    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. Copyright © 2015. Published by Elsevier Inc.

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

    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.

  12. Transport, Optical, and Magnetic Properties of the Conducting Halide Perovskite CH 3NH 3SnI 3

    Mitzi, D. B.; Feild, C. A.; Schlesinger, Z.; Laibowitz, R. B.

    1995-01-01

    A low-temperature ( T ≤ 100°C) solution technique is described for the preparation of polycrystalline and single crystal samples of the conducting halide perovskite, CH 3NH 3SnI 3. Transport, Hall effect, magnetic, and optical properties are examined over the temperature range 1.8-300 K, confirming that this unusual conducting halide perovskite is a low carrier density p-type metal with a Hall hole density, 1/ RHe ≃ 2 × 10 19 cm -3. The resistivity of pressed pellet samples decreases with decreasing temperature with resistivity ratio ρ(300 K)/ρ(2 K) ≃ 3 and room temperature resistivity ρ(300 K) ≃ 7 mΩ-cm. A free-carrier infrared reflectivity spectrum with a plasma edge observed at approximately 1600 cm -1 further attests to the metallic nature of this compound and suggests a small optical effective mass, m* ≃ 0.2.

  13. The effect of metal cluster deposition route on structure and photocatalytic activity of mono- and bimetallic nanoparticles supported on TiO{sub 2} by radiolytic method

    Klein, Marek [Department of Chemical Technology, Faculty of Chemistry, Gdansk University of Technology, 80-233 Gdansk (Poland); Institute of Fluid-Flow Machinery, Polish Academy of Sciences, 80-231 Gdansk (Poland); Nadolna, Joanna, E-mail: joanna.nadolna@ug.edu.pl [Department of Chemical Technology, Faculty of Chemistry, Gdansk University of Technology, 80-233 Gdansk (Poland); Department of Environmental Technology, University of Gdansk, 80-308 Gdansk (Poland); Gołąbiewska, Anna [Department of Chemical Technology, Faculty of Chemistry, Gdansk University of Technology, 80-233 Gdansk (Poland); Mazierski, Paweł [Department of Environmental Technology, University of Gdansk, 80-308 Gdansk (Poland); Klimczuk, Tomasz [Department of Solid State Physics, Faculty of Applied Physics and Mathematics, Gdansk University of Technology, 80-233 Gdansk (Poland); Remita, Hynd [Laboratoire de Chimie Physique, CNRS-UMR 8000, Université Paris-Sud, Université Paris-Saclay, 91405 Orsay (France); CNRS, Laboratoire de Chimie Physique, UMR 8000, 91405 Orsay (France); Zaleska-Medynska, Adriana [Department of Chemical Technology, Faculty of Chemistry, Gdansk University of Technology, 80-233 Gdansk (Poland); Department of Environmental Technology, University of Gdansk, 80-308 Gdansk (Poland)

    2016-08-15

    Highlights: • Pd-Pt decorated TiO{sub 2} shows the highest activity under visible light among all. • Concurrent addition of metal precursors results in rise of BNPs size and Vis-activity. • Subsequent addition of metal precursors enhances UV–vis stability of modified TiO{sub 2}. • Superoxide radicals are responsible for pollutants degradation over BNPs-TiO{sub 2}. - Abstract: TiO{sub 2} (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 TiO{sub 2} 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 TiO{sub 2} surface and enhances the Vis-induced activity of Ag/Pd-TiO{sub 2} 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

  14. Finding New Perovskite Halides via Machine learning

    Ghanshyam ePilania

    2016-04-01

    Full Text Available Advanced materials with improved properties have the potential to fuel future technological advancements. However, identification and discovery of these optimal materials for a specific application is a non-trivial task, because of the vastness of the chemical search space with enormous compositional and configurational degrees of freedom. Materials informatics provides an efficient approach towards rational design of new materials, via learning from known data to make decisions on new and previously unexplored compounds in an accelerated manner. Here, we demonstrate the power and utility of such statistical learning (or machine learning via building a support vector machine (SVM based classifier that uses elemental features (or descriptors to predict the formability of a given ABX3 halide composition (where A and B represent monovalent and divalent cations, respectively, and X is F, Cl, Br or I anion in the perovskite crystal structure. The classification model is built by learning from a dataset of 181 experimentally known ABX3 compounds. After exploring a wide range of features, we identify ionic radii, tolerance factor and octahedral factor to be the most important factors for the classification, suggesting that steric and geometric packing effects govern the stability of these halides. The trained and validated models then predict, with a high degree of confidence, several novel ABX3 compositions with perovskite crystal structure.

  15. Finding New Perovskite Halides via Machine learning

    Pilania, Ghanshyam; Balachandran, Prasanna V.; Kim, Chiho; Lookman, Turab

    2016-04-01

    Advanced materials with improved properties have the potential to fuel future technological advancements. However, identification and discovery of these optimal materials for a specific application is a non-trivial task, because of the vastness of the chemical search space with enormous compositional and configurational degrees of freedom. Materials informatics provides an efficient approach towards rational design of new materials, via learning from known data to make decisions on new and previously unexplored compounds in an accelerated manner. Here, we demonstrate the power and utility of such statistical learning (or machine learning) via building a support vector machine (SVM) based classifier that uses elemental features (or descriptors) to predict the formability of a given ABX3 halide composition (where A and B represent monovalent and divalent cations, respectively, and X is F, Cl, Br or I anion) in the perovskite crystal structure. The classification model is built by learning from a dataset of 181 experimentally known ABX3 compounds. After exploring a wide range of features, we identify ionic radii, tolerance factor and octahedral factor to be the most important factors for the classification, suggesting that steric and geometric packing effects govern the stability of these halides. The trained and validated models then predict, with a high degree of confidence, several novel ABX3 compositions with perovskite crystal structure.

  16. Local polar fluctuations in lead halide perovskites

    Tan, Liang; Yaffe, Omer; Guo, Yinsheng; Brus, Louis; Rappe, Andrew; Egger, David; Kronik, Leeor

    The lead halide perovskites have recently attracted much attention because of their large and growing photovoltaic power conversion efficiencies. However, questions remain regarding the temporal and spatial correlations of the structural fluctuations, their atomistic nature, and how they affect electronic and photovoltaic properties. To address these questions, we have performed a combined ab initio molecular dynamics (MD) and density functional theory (DFT) study on CsPbBr3. We have observed prevalent anharmonic motion in our MD trajectories, with local polar fluctuations involving head-to-head motion of A-site Cs cations coupled with Br window opening. We calculate Raman spectra from the polarizability auto-correlation functions obtained from these trajectories and show that anharmonic A-site cation motion manifests as a broad central peak in the Raman spectrum, which increases in intensity with temperature. A comparison of the experimental Raman spectrum of hybrid organometallic MAPbBr3 and fully inorganic CsPbBr3 suggests that structural fluctuations in lead-halide perovskites is more general than rotation of polar organic cations and is intimately coupled to the inorganic framework.

  17. Large polarons in lead halide perovskites

    Miyata, Kiyoshi; Meggiolaro, Daniele; Trinh, M. Tuan; Joshi, Prakriti P.; Mosconi, Edoardo; Jones, Skyler C.; De Angelis, Filippo; Zhu, X.-Y.

    2017-01-01

    Lead halide perovskites show marked defect tolerance responsible for their excellent optoelectronic properties. These properties might be explained by the formation of large polarons, but how they are formed and whether organic cations are essential remain open questions. We provide a direct time domain view of large polaron formation in single-crystal lead bromide perovskites CH3NH3PbBr3 and CsPbBr3. We found that large polaron forms predominantly from the deformation of the PbBr3− frameworks, irrespective of the cation type. The difference lies in the polaron formation time, which, in CH3NH3PbBr3 (0.3 ps), is less than half of that in CsPbBr3 (0.7 ps). First-principles calculations confirm large polaron formation, identify the Pb-Br-Pb deformation modes as responsible, and explain quantitatively the rate difference between CH3NH3PbBr3 and CsPbBr3. The findings reveal the general advantage of the soft [PbX3]− sublattice in charge carrier protection and suggest that there is likely no mechanistic limitations in using all-inorganic or mixed-cation lead halide perovskites to overcome instability problems and to tune the balance between charge carrier protection and mobility. PMID:28819647

  18. Formation of transition metal cluster adducts on the surface of single-walled carbon nanotubes: HRTEM studies

    Kalinina, Irina V.; Bekyarova, Elena B.; Wang, Qingxiao; Al-Hadeethi, Yas Fadel; Zhang, Xixiang; Al-Agel, Faisel; Al-Marzouki, Fahad M.; Yaghmour, Saud Jamil; Haddon, Robert C.

    2014-01-01

    We report the formation of chromium clusters on the outer walls of single-walled carbon nanotubes (SWNTs). The clusters were obtained by reacting purified SWNTs with chromium hexacarbonyl in dibutyl ether at 100°C. The functionalized SWNTs were

  19. Synthesis, Reactivity and Stability of Aryl Halide Protecting Groups towards Di-Substituted Pyridines

    Ptoton Mnangat Brian

    2016-03-01

    Full Text Available This paper reports the synthesis and reactivity of different Benzyl derivative protecting groups. The synthesis and stability of Benzyl halides, 4-methoxybenzyl halides, 3,5-dimethoxybenzyl halides, 3,4-dimethoxybenzyl halides, 3,4,5-trimethoxybenzyl halide protecting groups and their reactivity towards nitrogen atom of a di-substituted pyridine ring in formation of pyridinium salts is also reported.

  20. Influence of clusters in melt on the subsequent glass-formation and crystallization of Fe–Si–B metallic glasses

    Shaoxiong Zhou

    2015-04-01

    Full Text Available The liquid structure of seven representative Fe–Si–B alloys has been investigated by ab initio molecular dynamics simulation focusing on the role of clusters in terms of glass-forming ability (GFA and crystallization. It is demonstrated that the type of primary phase precipitated from amorphous state under heat treatment is determined by the relative fraction and role of various clusters in melt. The alloy melt shows higher stability and resultantly larger GFA when there is no dominant cluster or several clusters coexist, which explains the different GFAs and crystallization processes at various ratios of Si and B in the Fe–Si–B system. The close correlation among clusters, crystalline phase and GFA is also studied.