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Sample records for earth transition metal

  1. Method for treating rare earth-transition metal scrap

    Science.gov (United States)

    Schmidt, Frederick A.; Peterson, David T.; Wheelock, John T.; Jones, Lawrence L.

    1992-12-29

    Rare earth-transition metal (e.g., iron) scrap (e.g., Nd-Fe-B scrap) is flux (slag) remelted to reduce tramp non-metallic impurities, such as oxygen and nitrogen, and metallic impurities, such as Li, Na, Al, etc., picked up by the scrap from previous fabrication operations. The tramp impurities are reduced to concentrations acceptable for reuse of the treated alloy in the manufacture of end-use articles, such as permanent magnets. The scrap is electroslag or inductoslag melted using a prefused, rare earth fluoride-bearing flux of CaF.sub.2, CaCl.sub.2 or mixtures thereof or the slag resulting from practice of the thermite reduction process to make a rare earth-iron alloy.

  2. Growth of oriented rare-earth-transition-metal thin films

    Energy Technology Data Exchange (ETDEWEB)

    Fullerton, E.E.; Sowers, C.H.; Bader, S.D. [Argonne National Lab., IL (United States); Wu, X.Z. [Argonne National Lab., IL (United States)]|[Northern Illinois Univ., DeKalb, IL (United States)

    1996-04-01

    Rare-earth-transition-metal thin films are successfully grown by magnetron sputtering onto single-crystal MgO substrates with epitaxial W buffer layers. The use of epitaxial W buffer layers allows oriented single-phase films to be grown. Sm-Co films grown onto W(100), have strong in-plane anisotropy and coercivities exceeding 5 T at 5 K whereas Fe-Sm films have strong perpendicular anisotropy and are magnetically soft.

  3. Correlations in rare-earth transition-metal permanent magnets

    Energy Technology Data Exchange (ETDEWEB)

    Skomski, R., E-mail: rskomski@neb.rr.com; Manchanda, P. [Department of Physics and Astronomy and NCMN, University of Nebraska, Lincoln, Nebraska 68508 (United States); Kashyap, A. [School of Basic Science, IIT Mandi, Mandi, Himachal Pradesh (India)

    2015-05-07

    It is investigated how electron-electron correlations affect the intrinsic properties of rare-earth transition-metal magnets. Focusing on orbital moment and anisotropy, we perform model calculations for 3d-4f alloys and density-functional theory (DFT) calculations for NdCo{sub 5}. On an independent-electron level, the use of a single Slater determinant with broken spin symmetry introduces Hund's rule correlations, which govern the behavior of rare-earth ions and of alloys described by the local spin density approximation (LSDA) and LSDA + U approximations to DFT. By contrast, rare-earth ions in intermetallics involve configuration interactions between two or more Slater determinants and lead to phenomena such as spin-charge distribution. Analyzing DFT as a Legendre transformation and using Bethe's crystal-field theory, we show that the corresponding density functionals are very different from familiar LSDA-type expressions and outline the effect of spin-charge separation on the magnetocrystalline anisotropy.

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  5. Magnetic Behavior of Some Rare-Earth Transition-Metal Perovskite Oxide Systems

    Institute of Scientific and Technical Information of China (English)

    Kenji Yoshii; Akio Nakamura; Masaichiro Mizumaki; Naoshi Ikeda; Jun'ichiro Mizuki

    2004-01-01

    Magnetic properties were investigated for the rare-earth 3d-transition metal oxides with the perovskite structure. Intriguing magnetic phenomena were reviewed for a few systems:magnetization peak effect in the titanates, magnetization reversal in the chromites and metallic ferromagnetism in the cobaltites. The results suggest an important role of the rare-earth ions for the magnetic properties of such complex oxides.

  6. Adsorption of alkali, alkaline-earth, and 3d transition metal atoms on silicene

    Science.gov (United States)

    Sahin, H.; Peeters, F. M.

    2013-02-01

    The adsorption characteristics of alkali, alkaline-earth, and transition metal adatoms on silicene, a graphene-like monolayer structure of silicon are analyzed by means of first-principles calculations. In contrast to graphene, interaction between the metal atoms and the silicene surface is quite strong due to its highly reactive buckled hexagonal structure. In addition to structural properties, we also calculate the electronic band dispersion, net magnetic moment, charge transfer, work function, and dipole moment of the metal adsorbed silicene sheets. Alkali metals, Li, Na, and K, adsorb to hollow sites without any lattice distortion. As a consequence of the significant charge transfer from alkalis to silicene, metalization of silicene takes place. Trends directly related to atomic size, adsorption height, work function, and dipole moment of the silicene/alkali adatom system are also revealed. We found that the adsorption of alkaline-earth metals on silicene is entirely different from their adsorption on graphene. The adsorption of Be, Mg, and Ca turns silicene into a narrow gap semiconductor. Adsorption characteristics of eight transition metals Ti, V, Cr, Mn, Fe, Co, Mo, and W are also investigated. As a result of their partially occupied d orbital, transition metals show diverse structural, electronic, and magnetic properties. Upon the adsorption of transition metals, depending on the adatom type and atomic radius, the system can exhibit metal, half-metal, and semiconducting behavior. For all metal adsorbates, the direction of the charge transfer is from adsorbate to silicene, because of its high surface reactivity. Our results indicate that the reactive crystal structure of silicene provides a rich playground for functionalization at nanoscale.

  7. Maternal exposure to alkali, alkali earth, transition and other metals: Concentrations and predictors of exposure.

    Science.gov (United States)

    Hinwood, A L; Stasinska, A; Callan, A C; Heyworth, J; Ramalingam, M; Boyce, M; McCafferty, P; Odland, J Ø

    2015-09-01

    Most studies of metals exposure focus on the heavy metals. There are many other metals (the transition, alkali and alkaline earth metals in particular) in common use in electronics, defense industries, emitted via combustion and which are naturally present in the environment, that have received limited attention in terms of human exposure. We analysed samples of whole blood (172), urine (173) and drinking water (172) for antimony, beryllium, bismuth, cesium, gallium, rubidium, silver, strontium, thallium, thorium and vanadium using ICPMS. In general most metals concentrations were low and below the analytical limit of detection with some high concentrations observed. Few factors examined in regression models were shown to influence biological metals concentrations and explained little of the variation. Further study is required to establish the source of metals exposures at the high end of the ranges of concentrations measured and the potential for any adverse health impacts in children.

  8. Optimization of film synthesized rare earth transition metal permanent magnet systems

    Energy Technology Data Exchange (ETDEWEB)

    Cadieu, F.J.

    1992-01-01

    Progress is reported in three areas: high coercivity Sm-Fe-Ti-V, Sm-Fe-Zr, and two element Sm-Fe Sm{sub 5}(Fe,T){sub 17} type crystalline phases; ThMn{sub 12} type pseudobinary SmFe{sub 12-x}T{sub x}(0{le}{times}{le}1.5); and sputter process control for the synthesis of precisely textured rare earth-transition metal magnetic films. (DLC)

  9. High-pressure phase transitions in rare earth metal thulium to 195 GPa.

    Science.gov (United States)

    Montgomery, Jeffrey M; Samudrala, Gopi K; Tsoi, Georgiy M; Vohra, Yogesh K

    2011-04-20

    We have performed image plate x-ray diffraction studies on a heavy rare earth metal, thulium (Tm), in a diamond anvil cell to a pressure of 195 GPa and volume compression V/V₀ = 0.38 at room temperature. The rare earth crystal structure sequence, hcp →Sm-type→ dhcp →fcc → distorted fcc, is observed in Tm below 70 GPa with the exception of a pure fcc phase. The focus of our study is on the ultrahigh-pressure phase transition and Rietveld refinement of crystal structures in the pressure range between 70 and 195 GPa. The hexagonal hR-24 phase is seen to describe the distorted fcc phase between 70 and 124 GPa. Above 124 ± 4 GPa, a structural transformation from hR 24 phase to a monoclinic C 2/m phase is observed with a volume change of -1.5%. The equation of state data shows rapid stiffening above the phase transition at 124 GPa and is indicative of participation of f-electrons in bonding. We compare the behavior of Tm to other heavy rare-earths and heavy actinide metals under extreme conditions of pressure.

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

    Science.gov (United States)

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

    2011-09-18

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

  11. Low temperature route for the synthesis of rare earth transition metal borides and their hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Kramp, S.; Febri, M.; Joubert, J.C. [CNRS UMR 5628, Saint Martin d`Heres (France)

    1997-10-01

    Synthesis of rare earth-based alloys by the ORD technique consists in the reduction of rare earth oxides in a melt of calcium under argon, and simultaneous diffusion-reaction of the just formed rare earth metal with the other elements. This method has been applied with success to numerous ternary borides containing transition metals such as the magnetic alloys Y{sub 2}Co{sub 14}B, LnCo{sub 4}B, and YCo{sub 3}B{sub 2}. By using a small excess of Ca, boride particles grow in a viscous slurry media containing unreacted (melted) Ca and nanosize CaO particles. Single phase boride alloys can be obtained at 1000{degrees}C as loose micrometer-size particles of very high crystal quality as confirmed by the sharp diffraction peaks on the corresponding X-ray diagrams. Particles can be easily recovered by gentle wishing in diluted weak acid solution, and dried under vacuum at room temperature. This rather low temperature technique is particularly adapted to the synthesis of incongruent melting phases, as well as for the alloys containing volatile rare earth elements (Sm, Yb, Tb,...).

  12. A Low Temperature Route for the Synthesis of Rare Earth Transition Metal Borides and Their Hydrides

    Science.gov (United States)

    Kramp, S.; Febri, M.; Joubert, J. C.

    1997-10-01

    Synthesis of rare earth-based alloys by the ORD technique consists in the reduction of rare earth oxides in a melt of calcium under argon, and simultaneous diffusion-reaction of the just formed rare earth metal with the other elements. This method has been applied with success to numerous ternary borides containing transition metals such as the magnetic alloys Y2Co14B, LnCo4B, and YCo3B2. By using a small excess of Ca, boride particles grow in a viscous slurry media containing unreacted (melted) Ca and nanosize CaO particles. Single phase boride alloys can be obtained at 1000°C as loose micrometer-size particles of very high crystal quality as confirmed by the sharp diffraction peaks on the corresponding X-ray diagrams. Particles can be easily recovered by gentle washing in diluted weak acid solution, and dried under vacuum at room temperature. This rather low temperature technique is particularly adapted to the synthesis of incongruent melting phases, as well as for the alloys containing volatile rare earth elements (Sm, Yb, Tb,…).

  13. Rare-earth transition-metal intermetallics: Structure-bonding-property relationships

    Energy Technology Data Exchange (ETDEWEB)

    Han, M. K. [Iowa State Univ., Ames, IA (United States)

    2006-01-01

    The explorations of rare-earth, transition metal intermetallics have resulted in the synthesis and characterization, and electronic structure investigation, as well as understanding the structure-bonding property relationships. The work has presented the following results: (1) Understanding the relationship between compositions and properties in LaFe13-xSix system: A detailed structural and theoretical investigation provided the understanding of the role of a third element on stabilizing the structure and controlling the transformation of cubic NaZn{sub 13}-type structures to the tetragonal derivative, as well as the relationship between the structures and properties. (2) Synthesis of new ternary rare-earth iron silicides Re2-xFe4Si14-y and proposed superstructure: This compound offers complex structural challenges such as fractional occupancies and their ordering in superstructure. (3) Electronic structure calculation of FeSi2: This shows that the metal-semiconductor phase transition depends on the structure. The mechanism of band gap opening is described in terms of bonding and structural distortion. This result shows that the electronic structure calculations are an essential tool for understanding the relationship between structure and chemical bonding in these compounds. (4) Synthesis of new ternary rare-earth Zinc aluminides Tb3Zn3.6Al7.4: Partially ordered structure of Tb3Zn3.6Al7.4 compound provides new insights into the formation, composition and structure of rare-earth transition-metal intermetallics. Electronic structure calculations attribute the observed composition to optimizing metal-metal bonding in the electronegative (Zn, Al) framework, while the specific ordering is strongly influenced by specific orbital interactions. (5) Synthesis of new structure type of Zn39(CrxAl1-x)81

  14. Rare-Earth Transition-Metal Intermetallics: Structure-bonding-Property Relationships

    Energy Technology Data Exchange (ETDEWEB)

    Han, Mi-Kyung [Iowa State Univ., Ames, IA (United States)

    2006-01-01

    Our explorations of rare-earth, transition metal intermetallics have resulted in the synthesis and characterization, and electronic structure investigation, as well as understanding the structure-bonding-property relationships. Our work has presented the following results: (1) Understanding the relationship between compositions and properties in LaFe13-xSix system: A detailed structural and theoretical investigation provided the understanding of the role of a third element on stabilizing the structure and controlling the transformation of cubic NaZn13-type structures to the tetragonal derivative, as well as the relationship between the structures and properties. (2) Synthesis of new ternary rare-earth iron silicides RE2-xFe4Si14-y and proposed superstructure: This compound offers complex structural challenges such as fractional occupancies and their ordering in superstructure. (3) Electronic structure calculation of FeSi2: This shows that the metal-semiconductor phase transition depends on the structure. The mechanism of band gap opening is described in terms of bonding and structural distortion. This result shows that the electronic structure calculations are an essential tool for understanding the relationship between structure and chemical bonding in these compounds. (4) Synthesis of new ternary rare-earth Zinc aluminides Tb3Zn3.6Al7.4: Partially ordered structure of Tb3.6Zn13-xAl7.4 compound provides new insights into the formation, composition and structure of rare-earth transition-metal intermetallics. Electronic structure calculations attribute the observed composition to optimizing metal-metal bonding in the electronegative (Zn, Al) framework, while the specific ordering is strongly influenced by specific orbital interactions. (5) Synthesis of new structure type of Zn39(CrxAl1-x

  15. Synthesis and Structures of A Series of Novel Rare Earth Transition Metal Sulfates

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    Seven new rare earth transition metal sulfates were synthesized by hydrothermal reactions under conditions slightly above the critical point of water. Their crystal structures were determined from single crystal X-ray data. The compositions of the new compounds can be represented by two general formulae: REM(OH)3(SO4) and RE2M(OH)3(SO4)2F(H2O) with RE=Gd, Tb, Dy; M=Ni, Cu. Three different crystal structure types were found for the formula REM(OH)3(SO4). The structures of the new compounds all feature infinite chains of REOn coordination polyhedra, which are connected to chains of CuO6 or NiO6 octahedra. The limited size range of the rare earth cations observed in these compounds is most likely because of interactions between the octahedral chains and the chains of REOn polyhedra. The new compounds are closely related to the known yttrium transition metal sulfates.

  16. Theory of Temperature Dependence of the Magnetization in Rare-Earth-Transition-Metal Alloys

    DEFF Research Database (Denmark)

    Szpunar, B.; Lindgård, Per-Anker

    1977-01-01

    It is shown that the temperature dependence of the magnetic moments and Curie and ferrimagnetic compensation temperatures for Gdl-xTx (T = Co, Ni, and Fe) and Y1-xCox can be accounted for by a simple model assuming a RKKY interaction between the rare-earth moments and the transition-metal pseudo-spin......1-xCox durch ein einfaches Model1 erklärt werden können, das eine RKKY-Wechsel-wirkung zwischen den Momenten der Seltenen Erden und des Pseudo-Spins des Übergangsmetalls annimmt. Die Wechselwirkung wird durch ein effektives Legierungsmedium übermittelt, das mit der CPA-Theorie und elliptischen...

  17. Recording experiments on rare-earth transition-metal thin films studied with Lorentz microscopy

    Energy Technology Data Exchange (ETDEWEB)

    Greidanus, F.J.A.M.; Jacobs, B.A.J.; Spruit, J.H.M. (Philips Research Labs., Eindhoven (Netherlands)); Klahn, S. (Philips GmbH Forschungslaboratorium Hamburg, D-2000 Hamburg (DE))

    1989-09-01

    Domains written thermomagnetically under recording conditions in rare-earth transition-metal thin films are studied with Lorentz microscopy. New technique in which the magneto-optical layer is deposited on specially prepared silicon wafer disks, provided with Si/sub 3/N/sub 4/ windows is described. This technique allows direct observation of the written domain patterns in the electron microscope. It is demonstrated that the nucleation process plays a crucial role when writing in TbFeCo. Different compositions, having different temperature dependencies of the magnetic properties, lead to remarkably different domain-formation behaviour. With the detailed insight into the shape and structure of domains obtained by Lorentz microscopy, carrier and noise levels obtained from recording experiments can be understood. This is demonstrated with data on GdTbFe. It is shown that magnetic-field modulation, apart from the advantage of direct overwrite, offers the possibility of very high density recording.

  18. Structures of rare earth-transition metal rich compounds derived from CaCu5 type

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    The properties of materials have a close connect ion to their crystal structures. Rare earth (R)-transition metal (T) rich compo und are the focus of investigation in the search for new hard magnetic materials . As the basis for the study of stabilized effect of the third component on the fo rmation of RT5 derivative and its influence of the occupied sites on magnetic properties, in this paper, the possible derivative compounds based on the RT5 primitive unit cell of the CaCu5 structure type formed through the ordered or disordered substitution of dumbbell pair 2T atoms for the R atoms at some sit es, and the structural relationship between the derivatives and the prototype ar e summarized.

  19. Calculated Structural Phase-Transitions in the Alkaline-Earth Metals

    DEFF Research Database (Denmark)

    Skriver, Hans Lomholt

    1982-01-01

    The local-density approximation and the linear muffin-tin orbital method have been used within the atomic-sphere approximation to calculate structural energy differences for all the alkaline earth metals at zero temperature. At ordinary pressure the calculations predict the crystal structure...

  20. Optimization of film synthesized rare earth transition metal permanent magnet systems. Progress report, August 1, 1991--July 31, 1992

    Energy Technology Data Exchange (ETDEWEB)

    Cadieu, F.J.

    1992-08-01

    Progress is reported in three areas: high coercivity Sm-Fe-Ti-V, Sm-Fe-Zr, and two element Sm-Fe Sm{sub 5}(Fe,T){sub 17} type crystalline phases; ThMn{sub 12} type pseudobinary SmFe{sub 12-x}T{sub x}(0{le}{times}{le}1.5); and sputter process control for the synthesis of precisely textured rare earth-transition metal magnetic films. (DLC)

  1. High pressure phase transitions in the rare earth metal erbium to 151 GPa.

    Science.gov (United States)

    Samudrala, Gopi K; Thomas, Sarah A; Montgomery, Jeffrey M; Vohra, Yogesh K

    2011-08-10

    High pressure x-ray diffraction studies have been performed on the heavy rare earth metal erbium (Er) in a diamond anvil cell at room temperature to a pressure of 151 GPa and Er has been compressed to 40% of its initial volume. The rare earth crystal structure sequence hcp → Sm type → dhcp → distorted fcc (hcp: hexagonal close packed; fcc: face centered cubic; dhcp: double hcp) is observed in Er below 58 GPa. We have carried out Rietveld refinement of crystal structures in the pressure range between 58 GPa and 151 GPa. We have examined various crystal structures that have been proposed for the distorted fcc (dfcc) phase and the post-dfcc phase in rare earth metals. We find that the hexagonal hR 24 structure is the best fit between 58 and 118 GPa. Above 118 GPa, a structural transformation from hR 24 phase to a monoclinic C 2/m phase is observed with a volume change of - 1.9%. We have also established a clear trend for the pressure at which a post-dfcc phase is formed in rare earth metals and show that there is a monotonic increase in this pressure with the filling of 4f shell.

  2. Stabilization effects of third element on CaCu5 type derivatives of rare-earth transition-metal intermetallics

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    Part of the results of the key project "Search for novel rare-earth functional materials" supported by the National Natural Science Foundation of China is reviewed. In combination with reports in literature, the effects of the third element M on the formation and stability of La2(Co, M)17, R(Fe, M)12 and R3(Fe, M)29 intermetallic compounds are discussed by considering mixing enthalpy of M with rare-earth, Fe and Co, and atomic radius, electronegativity and electronic configurations, etc. It is concluded that the mixing en thalpy and atomic radius dominate the preferential sites and the minimum amount of M required to stabilize a structure, which ultimately affect the magnetic properties of a compound prominently. This review should provide some heuristic hints for exploiting novel rare-earth transition metal functional materials and for improving their performance.

  3. Synthesis and characterization of rare-earth oxide transition-metal arsenides and selenides

    Energy Technology Data Exchange (ETDEWEB)

    Peschke, Simon Friedrich

    2017-04-06

    oxyselenides were identifi ed and revealed unique structural building blocks that have not been observed in these systems before. The results of this thesis demonstrate not only the power of alternative preparation methods, but also the still increasing structural variety in the discussed quaternary systems. Strategic research in the field of transition-metal oxypnictides and oxychalcogenides, which still include a multiplicity of unknown materials, revealed numerous compounds with interesting physical properties and further investigations will probably uncover also new superconducting materials.

  4. Microstructure and composition of rare earth-transition metal-aluminium-magnesium alloys

    Directory of Open Access Journals (Sweden)

    Lia Maria Carlotti Zarpelon

    2008-03-01

    Full Text Available The determination of the microstructure and chemical composition of La0.7-xPr xMg0.3Al 0.3Mn0.4Co0.5 Ni3.8 (0 < x < 0.7 metal hydride alloys has been carried out using scanning electron microscopy (SEM, energy dispersive X ray analysis (EDX and X ray diffraction analysis (XRD. The substitution of La with Pr changed the grain structure from equiaxial to columnar. The relative atomic ratio of rare earth to (Al, Mn, Co, Ni in the matrix phase was 1:5 (LaNi5-type structure. Magnesium was detected only in two other phases present. A grey phase revealed 11 at.% Mg and the concentration ratios of other elements indicated the composition to be close to PrMgNi4. A dark phase was very heterogeneous in composition, attributed to the as-cast state of these alloys. The phases identified by XRD analysis in the La0.7Mg0.3Al0.3Mn0.4Co 0.5Ni3.8 alloy were: La(Ni,Co5, LaAl(Ni,Co4, La2(Ni,Co7 and AlMn(Ni,Co2. Praseodymium favors the formation of a phase with a PuNi3-type structure. Cobalt substituted Ni in the structures and yielded phases of the type: Pr(Ni,Co5 and Pr(Ni,Co3.

  5. Magnetic coupling at rare earth ferromagnet/transition metal ferromagnet interfaces: A comprehensive study of Gd/Ni.

    Science.gov (United States)

    Higgs, T D C; Bonetti, S; Ohldag, H; Banerjee, N; Wang, X L; Rosenberg, A J; Cai, Z; Zhao, J H; Moler, K A; Robinson, J W A

    2016-07-22

    Thin film magnetic heterostructures with competing interfacial coupling and Zeeman energy provide a fertile ground to study phase transition between different equilibrium states as a function of external magnetic field and temperature. A rare-earth (RE)/transition metal (TM) ferromagnetic multilayer is a classic example where the magnetic state is determined by a competition between the Zeeman energy and antiferromagnetic interfacial exchange coupling energy. Technologically, such structures offer the possibility to engineer the macroscopic magnetic response by tuning the microscopic interactions between the layers. We have performed an exhaustive study of nickel/gadolinium as a model system for understanding RE/TM multilayers using the element-specific measurement technique x-ray magnetic circular dichroism, and determined the full magnetic state diagrams as a function of temperature and magnetic layer thickness. We compare our results to a modified Stoner-Wohlfarth-based model and provide evidence of a thickness-dependent transition to a magnetic fan state which is critical in understanding magnetoresistance effects in RE/TM systems. The results provide important insight for spintronics and superconducting spintronics where engineering tunable magnetic inhomogeneity is key for certain applications.

  6. K2-111 b - a short period super-Earth transiting a metal poor, evolved old star

    Science.gov (United States)

    Fridlund, Malcolm; Gaidos, Eric; Barragán, Oscar; Persson, Carina M.; Gandolfi, Davide; Cabrera, Juan; Hirano, Teruyuki; Kuzuhara, Masayuki; Csizmadia, Sz.; Nowak, Grzegorz; Endl, Michael; Grziwa, Sascha; Korth, Judith; Pfaff, Jeremias; Bitsch, Bertram; Johansen, Anders; Mustill, Alexander J.; Davies, Melvyn B.; Deeg, Hans J.; Palle, Enric; Cochran, William D.; Eigmüller, Philipp; Erikson, Anders; Guenther, Eike; Hatzes, Artie P.; Kiilerich, Amanda; Kudo, Tomoyuki; MacQueen, Phillip; Narita, Norio; Nespral, David; Pätzold, Martin; Prieto-Arranz, Jorge; Rauer, Heike; Van Eylen, Vincent

    2017-07-01

    Context. From a light curve acquired through the K2 space mission, the star K2-111(EPIC 210894022) has been identified as possibly orbited by a transiting planet. Aims: Our aim is to confirm the planetary nature of the object and derive its fundamental parameters. Methods: We analyse the light curve variations during the planetary transit using packages developed specifically for exoplanetary transits. Reconnaissance spectroscopy and radial velocity observations have been obtained using three separate telescope and spectrograph combinations. The spectroscopic synthesis package SME has been used to derive the stellar photospheric parameters that were used as input to various stellar evolutionary tracks in order to derive the parameters of the system. The planetary transit was also validated to occur on the assumed host star through adaptive imaging and statistical analysis. Results: The star is found to be located in the background of the Hyades cluster at a distance at least 4 times further away from Earth than the cluster itself. The spectrum and the space velocities of K2-111 strongly suggest it to be a member of the thick disk population. The co-added high-resolution spectra show that that it is a metal poor ([Fe/H] = - 0.53 ± 0.05 dex) and α-rich somewhat evolved solar-like star of spectral type G3. We find Teff = 5730 ± 50 K, log g⋆ = 4.15 ± 0.1 cgs, and derive a radius of R⋆ = 1.3 ± 0.1 R⊙ and a mass of M⋆ = 0.88 ± 0.02 M⊙. The currently available radial velocity data confirms a super-Earth class planet with a mass of 8.6 ± 3.9 M⊕ and a radius of 1.9 ± 0.2 R⊕. A second more massive object with a period longer than about 120 days is indicated by a long-term radial velocity drift. Conclusions: The radial velocity detection together with the imaging confirms with a high level of significance that the transit signature is caused by a planet orbiting the star K2-111. This planet is also confirmed in the radial velocity data. A second more

  7. Alkaline earth metal thioindates

    Energy Technology Data Exchange (ETDEWEB)

    Ivanov-Ehmin, B.N.; Ivlieva, V.I.; Filatenko, L.A.; Zajtsev, B.E.; Kaziev, G.Z.; Sarabiya, M.G.

    1984-08-01

    Alkaline earth metal thioindates of MIn/sub 2/S/sub 4/ composition were synthesized by interaction of alkaline earth metal oxoindates with hydrogen sulfide during heating. Investigation into the compounds by X-ray analysis showed that calcium compound crystallizes in cubic crystal system and strontium and barium compounds in rhombic crystal system. Lattice parameters and the number of formula units were determined. Thioindates of M/sub 3/In/sub 2/S/sub 6/ composition were synthesized, their individuality was shown.

  8. Synchrotron Diffraction Studies of Spontaneous Magnetostriction in Rare Earth Transition Metal Compounds

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Ning [Iowa State Univ., Ames, IA (United States)

    2004-12-19

    Thermal expansion anomalies of R2Fe14B and R2Fe17Cx (x = 0,2) (R = Y, Nd, Gd, Tb, Er) stoichiometric compounds are studied with high-energy synchrotron X-ray powder diffraction using Debye-Schemer geometry in temperature range 10K to 1000K. Large spontaneous magnetostriction up to their Curie temperatures (Tc) is observed. The a-axes show relatively larger invar effects than c-axes in the R2Fe14B compounds whereas the R2Fe17Cx show the contrary anisotropies. The iron sub-lattice is shown to dominate the spontaneous magnetostriction of the compounds. The contribution of the rare earth sublattice is roughly proportional to the spin magnetic moment of the rare earth in the R2Fe14B compounds but in R2Fe17Cx, the rare earth sub-lattice contribution appears more likely to be dominated by the local bonding. The calculation of spontaneous magnetostrain of bonds shows that the bonds associated with Fe(j2) sites in R2Fe14B and the dumbbell sites in R2Fe17Cx have larger values, which is strongly related to their largest magnetic moment and Wigner-Seitz atomic cell volume. The roles of the carbon atoms in increasing the Curie temperatures of the R2Fe17 compounds are attributed to the increased separation of Fe hexagons. The R2Fe17 and R2Fe14B phases with magnetic rare earth ions also show anisotropies of thermal expansion above c. For R2Fe17 and R2Fe14B the a a/a c > 1 whereas the anisotropy is reversed with the interstitial carbon in R2Fe17. The average bond magnetostrain is shown to be a possible predictor of the magnetic moment of Fe sites in the compounds. Both of the theoretical and

  9. CO2 gasification reactivity of biomass char: catalytic influence of alkali, alkaline earth and transition metal salts.

    Science.gov (United States)

    Lahijani, Pooya; Zainal, Zainal Alimuddin; Mohamed, Abdul Rahman; Mohammadi, Maedeh

    2013-09-01

    This study investigates the influence of alkali (Na, K), alkaline earth (Ca, Mg) and transition (Fe) metal nitrates on CO2 gasification reactivity of pistachio nut shell (PNS) char. The preliminary gasification experiments were performed in thermogravimetric analyzer (TGA) and the results showed considerable improvement in carbon conversion; Na-char>Ca-char>Fe-char>K-char>Mg-char>raw char. Based on TGA studies, NaNO3 (with loadings of 3-7 wt%) was selected as the superior catalyst for further gasification studies in bench-scale reactor; the highest reactivity was devoted to 5 wt% Na loaded char. The data acquired for gasification rate of catalyzed char were fitted with several kinetic models, among which, random pore model was adopted as the best model. Based on obtained gasification rate constant and using the Arrhenius plot, activation energy of 5 wt% Na loaded char was calculated as 151.46 kJ/mol which was 53 kJ/mol lower than that of un-catalyzed char. Copyright © 2013 Elsevier Ltd. All rights reserved.

  10. Adsorption of alkali, alkaline-earth, simple and 3d transition metal, and nonmetal atoms on monolayer MoS2

    Directory of Open Access Journals (Sweden)

    X. D. Li

    2015-05-01

    Full Text Available Single adsorption of different atoms on pristine two-dimensional monolayer MoS2 have been systematically investigated by using density functional calculations with van der Waals correction. The adatoms cover alkali metals, alkaline earth metals, main group metal, 3d-transition metals, coinage metal and nonmetal atoms. Depending on the adatom type, metallic, semimetallic or semiconducting behavior can be found in direct bandgap monolayer MoS2. Additionally, local or long-range magnetic moments of two-dimensional MoS2 sheet can also attained through the adsorption. The detailed atomic-scale knowledge of single adsorption on MoS2 monolayer is important not only for the sake of a theoretical understanding, but also device level deposition technological application.

  11. Synthesis and characterization of rare earth and transition metal doped BaMgF{sub 4} nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Janssens, S. [Industrial Research Limited, PO Box 31310, Lower Hutt 5040 (New Zealand); MacDiarmid Institute, SCPS, Victoria University of Wellington, PO Box 600, Wellington 6012 (New Zealand); Williams, G.V.M., E-mail: grant.williams@vuw.ac.nz [MacDiarmid Institute, SCPS, Victoria University of Wellington, PO Box 600, Wellington 6012 (New Zealand); Clarke, D. [Industrial Research Limited, PO Box 31310, Lower Hutt 5040 (New Zealand)

    2013-02-15

    BaMgF{sub 4} nanoparticles doped with Ce{sup 3+}, Eu{sup 3+}, Mn{sup 2+}, and Nd{sup 3+} have been successfully synthesized using a reverse microemulsion method. They form nanorods that aggregate into 'moustache' shaped clusters. All doped samples show photoluminescence where the Ce{sup 3+} and Eu{sup 3+} photoluminescence spectra are consistent with substitution onto different crystal sites, while only a single site was found for the Mn{sup 2+} doped sample. Mn{sup 2+} was successfully sensitized by Ce{sup 3+} in BaMgF{sub 4}:Mn{sup 2+}:Ce{sup 3+} nanoparticles. The Ce{sup 3+} PL lifetimes are strongly wavelength dependent, which could be due to different Ce{sup 3+} sites with different PL lifetimes as well as energy transfer between Ce{sup 3+} sites. Transparent thick polymer films containing nanoparticles have been made. The appearance of photoluminescence in rare earth and transition metal doped BaMgF{sub 4} nanoparticles and the ability to make transparent thick films means that the BaMgF{sub 4} nanoparticles have a range of potential applications that include optical amplification. - Highlights: Black-Right-Pointing-Pointer BaMgF{sub 4} nanorods synthesized using a reverse microemulsion method. Black-Right-Pointing-Pointer BaMgF{sub 4} nanorods successfully doped with luminescent ions. Black-Right-Pointing-Pointer Ce{sup 3+} and Eu{sup 3+} ions occupy two distinct crystal sites. Black-Right-Pointing-Pointer Efficient energy transfer from Ce{sup 3+} to Mn{sup 2+} is observed. Black-Right-Pointing-Pointer Transparent nanoparticle/PMMA polymer films were made.

  12. Chelation ion chromatography of alkaline earth and transition metals a using monolithic silica column with bonded N-hydroxyethyliminodiacetic acid functional groups.

    Science.gov (United States)

    McGillicuddy, Nicola; Nesterenko, Ekaterina P; Nesterenko, Pavel N; Jones, Phil; Paull, Brett

    2013-02-08

    A commercially available porous silica monolithic column (Onyx Monolithic Si, 100 mm×4.6 mm I.D.) was 'in-column' covalently functionalised with 2-hydroxyethyliminodiacetic acid (HEIDA) groups, and applied to the simultaneous and rapid separation of alkaline earth and transition metal ions, using high-performance chelation ion chromatography (HPCIC). With a 0.3mM dipicolinic acid (DPA) containing eluent, the baseline separation of various common transition and heavy metal ions and the four alkaline earth metal ions could be achieved in under 14 min with a flow rate of just 0.8 mL/min. Detection was achieved using spectrophotometric detection at 540 nm after post-column reaction (PCR) with 4-(2-pyridylazo)-resorcinol (PAR). Significant effects from variation of eluent nature, concentration and temperature upon selectivity and retention were demonstrated with the new monolithic silica chelating phase. Under optimised conditions (0.165 M LiNO(3) eluent, pH 2.5), peak efficiencies of 54,000, 60,000 and 64,000 N/m, for Zn(2+), Mn(2+) and Cd(2+), respectively, were recorded, far exceeding that previously reported for IDA based chelation ion exchange columns.

  13. Oligocyclopentadienyl transition metal complexes

    Energy Technology Data Exchange (ETDEWEB)

    de Azevedo, Cristina G.; Vollhardt, K. Peter C.

    2002-01-18

    Synthesis, characterization, and reactivity studies of oligocyclopentadienyl transition metal complexes, namely those of fulvalene, tercyclopentadienyl, quatercyclopentadienyl, and pentacyclopentadienyl(cyclopentadienyl) are the subject of this account. Thermal-, photo-, and redox chemistries of homo- and heteropolynuclear complexes are described.

  14. Ground-state oxygen holes and the metal-insulator transition in the negative charge-transfer rare-earth nickelates

    Science.gov (United States)

    Bisogni, Valentina; Catalano, Sara; Green, Robert J.; Gibert, Marta; Scherwitzl, Raoul; Huang, Yaobo; Strocov, Vladimir N.; Zubko, Pavlo; Balandeh, Shadi; Triscone, Jean-Marc; Sawatzky, George; Schmitt, Thorsten

    2016-10-01

    The metal-insulator transition and the intriguing physical properties of rare-earth perovskite nickelates have attracted considerable attention in recent years. Nonetheless, a complete understanding of these materials remains elusive. Here we combine X-ray absorption and resonant inelastic X-ray scattering (RIXS) spectroscopies to resolve important aspects of the complex electronic structure of rare-earth nickelates, taking NdNiO3 thin film as representative example. The unusual coexistence of bound and continuum excitations observed in the RIXS spectra provides strong evidence for abundant oxygen holes in the ground state of these materials. Using cluster calculations and Anderson impurity model interpretation, we show that distinct spectral signatures arise from a Ni 3d8 configuration along with holes in the oxygen 2p valence band, confirming suggestions that these materials do not obey a conventional positive charge-transfer picture, but instead exhibit a negative charge-transfer energy in line with recent models interpreting the metal-insulator transition in terms of bond disproportionation.

  15. Superconductivity in transition metals.

    Science.gov (United States)

    Slocombe, Daniel R; Kuznetsov, Vladimir L; Grochala, Wojciech; Williams, Robert J P; Edwards, Peter P

    2015-03-13

    A qualitative account of the occurrence and magnitude of superconductivity in the transition metals is presented, with a primary emphasis on elements of the first row. Correlations of the important parameters of the Bardeen-Cooper-Schrieffer theory of superconductivity are highlighted with respect to the number of d-shell electrons per atom of the transition elements. The relation between the systematics of superconductivity in the transition metals and the periodic table high-lights the importance of short-range or chemical bonding on the remarkable natural phenomenon of superconductivity in the chemical elements. A relationship between superconductivity and lattice instability appears naturally as a balance and competition between localized covalent bonding and so-called broken covalency, which favours d-electron delocalization and superconductivity. In this manner, the systematics of superconductivity and various other physical properties of the transition elements are related and unified.

  16. Element Substitution Effect in Transition M et al Oxypnictide Re(O1-xFx)TAs (Re=rare earth, T=transition metal)

    Institute of Scientific and Technical Information of China (English)

    CHEN Gen-Fu; LI Zheng; WU Dan; DONG Jing; LI Gang; HU Wan-Zheng; ZHENG Ping; LUO Jian-Lin; WANG Nan-Lin

    2008-01-01

    Different element substitution effects in transition metal oxypnictide Re(O1-xFx)TAs, with Re=La, Ce, Nd, Eu, Gd, Tin, T=Fe, Ni, Ru, are studied. Similar to the La- or Ce-based systems, we find that the pure NdOFeAs shows a strong resistivity anomaly near 145 K, which is ascribed to the spin-density-wave instability. Electron doping by F increases Tc to about 50K. While in the case of Gd, Tc is reduced below 10K. The tetragonal ZrCuSiAs-type structure couM not be formed for Eu or Tm substitution in our preparing process. For the Ni-based case, although both pure and F-doped LaONiAs are superconducting, no superconductivity is found when La is replaced by Ce in both the cases, instead a ferromagnetic ordering transition is likely to form at low temperature in the undoped sample. We also synthesize LaO1-xFxRuAs and CeO1-xFx RuAs compounds. The metallic behaviour is observed down to 4 K.

  17. Universal behavior of chalcogenides of rare-earth metals in the transition to a state with intermediate valence at high pressures

    Energy Technology Data Exchange (ETDEWEB)

    Tsiok, O. B.; Khvostantsev, L. G.; Brazhkin, V. V., E-mail: brazhkin@hppi.troitsk.ru [Russian Academy of Sciences, Vereshchagin Institute of High-Pressure Physics (Russian Federation)

    2015-06-15

    Precision measurements of resistivity, thermopower, and volume are performed for TmS, TmSe, and TmTe under a hydrostatic pressure up to 8 GPa. Comparison of the transport properties and volume of TmTe and SmTe in the valence transition region demonstrates a complete analogy up to quantitative coincidence. It is shown that the thermopower of all thulium and samarium chalcogenides in the lattice collapse region and in subsequent rearrangement of the electron spectrum in a wide range of pressures follow a universal dependence corresponding the passage of the Fermi level through the peak of the density of states (DOS). The results are considered in the context of ideas about the exciton nature of the intermediate valence in chalcogenides of rare-earth metals.

  18. Melting of Transition Metals

    Energy Technology Data Exchange (ETDEWEB)

    Ross, M; Japel, S; Boehler, R

    2005-04-11

    We review the transition melting studies carried out at Mainz, and describe a recently developed model used to explain that the relatively low melting slopes are due to the partially filled d-bands, and the persistence of the pressure induced s-d transition. The basic tenets of the model have now been reconfirmed by new measurements for Cu and Ni. The measurements show that Cu which has a filled 3d-band, has a melt slope that is about 2.5 greater than its neighbor Ni. In the case of Mo, the apparent discrepancy of DAC melting measurements with shock melting can be explained by accounting for the change in melt slope due to the bcc-cp transition observed in the shock studies. The Fe melt curve is revisited. The possible relevance of the Jahn-Teller effect and recently observed transition metal melts with Icosahedral Short-Range Order (ISRO) is discussed.

  19. Synthesis, characterization, antibacterial and antifungal studies of some transition and rare earth metal complexes of N-benzylidene-2-hydroxybenzohydrazide

    Directory of Open Access Journals (Sweden)

    T.K. Chondhekar

    2011-12-01

    Full Text Available The solid complexes of Cu(II, Co(II, Mn(II, La(III and Ce(III were prepared from bidentate Schiff base, N-benzylidene-2-hydroxybenzohydrazide. The Schiff base ligand was synthesized from 2-hyhdroxybenzohydrazide and benzaldehyde. These metal complexes were characterized by molar conductivity, magnetic susceptibility, thermal analysis, X-ray diffraction, FTIR, 1H-NMR, UV-Vis and mass spectroscopy. The analytical data of these metal complexes showed metal:ligand ratio of 1:2. The physico-chemical study supports the presence of square planar geometry around Cu(II and octahedral geometry around Mn(II, Co(II, La(III and Ce(III ions. The IR spectral data reveal that the ligand behaves as bidentate with ON donor atom sequence towards central metal ion. The molar conductance values of metal complexes suggest their non-electrolyte nature. The X-ray diffraction data suggest monoclinic crystal system for these complexes. Thermal behavior (TG/DTA and kinetic parameters calculated by Coats-Redfern method are suggestive of more ordered activated state in complex formation. The ligand and their metal complexes were screened for antibacterial activity against Staphylococcus aureus and Escherichia coli and fungicidal activity against Aspergillus niger and Trichoderma.

  20. Structural transition metal chemistry

    CERN Document Server

    Anderson, K M

    2002-01-01

    This thesis is divided up into five chapters as outlined below. Chapter 1 gives the background to the techniques used in this thesis including X-ray structure determination and ab initio methods. An overview of some recent studies using ab initio methods to study transition metal complexes is also given. Chapter 2 investigates structural trans influence in a number of transition metal and p-block complexes. The database and ab initio studies showed that the classical trans influence model based on Pt(II) chemistry does not always hold. For some systems (eg. d sup 1 sup 0 s sup 0 for Sb sup V and Sn sup I sup V) the cis influence is of similar magnitude to the trans influence. For other systems (d sup 0), the trans influence is not as powerful as usually assumed. Chapter 3 is an investigation into the bridging chloride unit. A database study was performed on three systems (M-CI-M', M-CI...H and M-CI...Li/Na/K). Reaction pathway analysis was carried out for the M-CI-M' case and showed that bond order is not con...

  1. Co-based alloys design based on first-principles calculations: Influence of transition metal and rare-earth alloying element on stacking fault energy

    Science.gov (United States)

    Achmad, Tria Laksana; Fu, Wenxiang; Chen, Hao; Zhang, Chi; Yang, Zhi-Gang

    2017-01-01

    The main idea of alloy design is to reduce costs and time required by the traditional (trial and error) method, then finding a new way to develop the efficiency of the alloy design is necessary. In this study, we proposed a new approach to the design of Co-based alloys. It is based on the concept that lowering the ratio of stable and unstable stacking fault energy (SFE) could bring a significant increase in the tendency of partial dislocation accumulation and FCC to HCP phase transformation then enhance mechanical properties. Through the advance development of the computing techniques, first-principles density-functional-theory (DFT) calculations are capable of providing highly accurate structural modeling at the atomic scale without any experimental data. The first-principles calculated results show that the addition of some transition metal (Cr, Mo, W, Re, Os, Ir) and rare-earth (Sc, Y, La, Sm) alloying elements would decrease both stable and unstable SFE of pure Co. The dominant deformation mechanism of binary Co-4.5 at.% X (X = alloying element) is extended partial dislocation. Our study reveals Re, W, Mo and La as the most promising alloying additions for the Co-based alloys design with superior performances. Furthermore, the underlying mechanisms for the SFE reduction can be explained regarding the electronic structure.

  2. Transition metals in carbohydrate chemistry

    DEFF Research Database (Denmark)

    Madsen, Robert

    1997-01-01

    This review describes the application of transition metal mediated reactions in carbohydrate synthesis. The different metal mediated transformations are divided into reaction types and illustrated by various examples on monosaccharide derivatives. Carbon-carbon bond forming reactions are further ...

  3. Transition metals in carbohydrate chemistry

    DEFF Research Database (Denmark)

    Madsen, Robert

    1997-01-01

    This review describes the application of transition metal mediated reactions in carbohydrate synthesis. The different metal mediated transformations are divided into reaction types and illustrated by various examples on monosaccharide derivatives. Carbon-carbon bond forming reactions are further...

  4. Transition Metal Compounds Towards Holography

    Directory of Open Access Journals (Sweden)

    Volker Dieckmann

    2012-06-01

    Full Text Available We have successfully proposed the application of transition metal compounds in holographic recording media. Such compounds feature an ultra-fast light-induced linkage isomerization of the transition-metal–ligand bond with switching times in the sub-picosecond regime and lifetimes from microseconds up to hours at room temperature. This article highlights the photofunctionality of two of the most promising transition metal compounds and the photophysical mechanisms that are underlying the hologram recording. We present the latest progress with respect to the key measures of holographic media assembled from transition metal compounds, the molecular embedding in a dielectric matrix and their impressive potential for modern holographic applications.

  5. Electrical Conductivity in Transition Metals

    Science.gov (United States)

    Talbot, Christopher; Vickneson, Kishanda

    2013-01-01

    The aim of this "Science Note" is to describe how to test the electron-sea model to determine whether it accurately predicts relative electrical conductivity for first-row transition metals. In the electron-sea model, a metal crystal is viewed as a three-dimensional array of metal cations immersed in a sea of delocalised valence…

  6. On the structural and magnetic properties of R{sub 2}Fe{sub 17-x}(A,T){sub x} (R=rare earth; A=Al, Si, Ga; T=transition metal) compounds

    Energy Technology Data Exchange (ETDEWEB)

    Rama Rao, K.V.S. [Technische Univ. Darmstadt (Germany). Inst. for Materials Science; Dept. of Physics, Indian Inst. of Tech. Madras, Chennai (India); Ehrenberg, H.; Fuess, H. [Technische Univ. Darmstadt (Germany). Inst. for Materials Science; Markandeyulu, G.; Murthy, V.S. [Dept. of Physics, Indian Inst. of Tech. Madras, Chennai (India); Varadaraju, U.V.; Venkatesan, M. [Indian Inst. of Tech., Madras (India). Materials Science Research Centre; Suresh, K.G. [Indian Inst. of Tech., Bombay (India). Dept. of Physics; Schmidt, P.C. [Technische Univ. Darmstadt (Germany). Inst. fuer Physikalische Chemie

    2002-02-16

    R{sub 2}Fe{sub 17} (R = rare earth) intermetallic compounds constitute one of the most important classes of materials identified as high-energy permanent magnet materials. They crystallize either in the rhombohedral Th{sub 2}Zn{sub 17} structure (for light R) or in the hexagonal Th{sub 2}Ni{sub 17} structure (for heavy R). In this article, we discuss the variations in the lattice parameters (unit cell volume), site occupancies and Curie temperature when non-transition and transition metals are substituted for Fe in R{sub 2}Fe{sub 17} compounds. (orig.)

  7. Selenophene transition metal complexes

    Energy Technology Data Exchange (ETDEWEB)

    White, Carter James [Iowa State Univ., Ames, IA (United States)

    1994-07-27

    This research shows that selenophene transition metal complexes have a chemistry that is similar to their thiophene analogs. Selenophene coordination has been demonstrated and confirmed by molecular structure in both the η5- and the η1(Se)-coordination modes. The reaction chemistry of selenophene complexes closely resembles that of the analogous thiophene complexes. One major difference, however, is that selenophene is a better donor ligand than thiophene making the selenophene complexes more stable than the corresponding thiophene complexes. The 77Se NMR chemical shift values for selenophene complexes fall within distinct regions primarily depending on the coordination mode of the selenophene ligand. In the final paper, the C-H bond activation of η1(S)-bound thiophenes, η1(S)-benzothiophene and η1(Se)-bound selenophenes has been demonstrated. The deprotonation and rearrangement of the η1(E)-bound ligand to the carbon bound L-yl complex readily occurs in the presence of base. Reprotonation with a strong acid gives a carbene complex that is unreactive towards nucleophilic attack at the carbene carbon and is stable towards exposure to air. The molecular structure of [Cp(NO)(PPh3)Re(2-benzothioenylcarbene)]O3SCF3 was determined and contains a Re-C bond with substantial double bond character. Methyl substitution for the thienylcarbene or selenylcarbene gives a carbene that rearranges thermally to give back the η1(E)-bound complex. Based on these model reactions, a new mechanism for the H/D exchange of thiophene over the hydrodesulfurization catalyst has been proposed.

  8. Rare Earth Metals: Resourcefulness and Recovery

    Science.gov (United States)

    Wang, Shijie

    2013-10-01

    When we appreciate the digital revolution carried over from the twentieth century with mobile communication and the Internet, and when we enjoy our high-tech lifestyle filled with iDevices, hybrid cars, wind turbines, and solar cells in this new century, we should also appreciate that all of these advanced products depend on rare earth metals to function. Although there are only 136,000 tons of annual worldwide demand, (Cho, Rare Earth Metals, Will We Have Enough?)1 rare earth metals are becoming such hot commodities on international markets, due to not only to their increasing uses, including in most critical military hardware, but also to Chinese growth, which accounts for 95% of global rare earth metal production. Hence, the 2013 technical calendar topic, planned by the TMS/Hydrometallurgy and Electrometallurgy Committee, is particularly relevant, with four articles (including this commentary) contributed to the JOM October Issue discussing rare earth metals' resourcefulness and recovery.

  9. Transits of Earth-Like Planets

    CERN Document Server

    Kaltenegger, L

    2009-01-01

    Transmission spectroscopy of Earth-like exoplanets is a potential tool for habitability screening. Transiting planets are present-day "Rosetta Stones" for understanding extrasolar planets because they offer the possibility to characterize giant planet atmospheres and should provide an access to biomarkers in the atmospheres of Earth-like exoplanets, once they are detected. Using the Earth itself as a proxy we show the potential and limits of the transiting technique to detect biomarkers on an Earth-analog exoplanet in transit. We quantify the Earths cross section as a function of wavelength, and show the effect of each atmospheric species, aerosol, and Rayleigh scattering. Clouds do not significantly affect this picture because the opacity of the lower atmosphere from aerosol and Rayleigh losses dominates over cloud losses. We calculate the optimum signal-to-noise ratio for spectral features in the primary eclipse spectrum of an Earth-like exoplanet around a Sun-like star and also M stars, for a 6.5-m telesco...

  10. Recovering heavy rare earth metals from magnet scrap

    Energy Technology Data Exchange (ETDEWEB)

    Ott, Ryan T.; McCallum, Ralph W.; Jones, Lawrence L.

    2017-08-08

    A method of treating rare earth metal-bearing permanent magnet scrap, waste or other material in a manner to recover the heavy rare earth metal content separately from the light rare earth metal content. The heavy rare earth metal content can be recovered either as a heavy rare earth metal-enriched iron based alloy or as a heavy rare earth metal based alloy.

  11. Structural and electronic properties of binary amorphous aluminum alloys with transition metals and rare earth metals; Strukturelle und elektronische Eigenschaften binaerer amorpher Aluminiumlegierungen mit Uebergangsmetallen und Metallen der Seltenen Erden

    Energy Technology Data Exchange (ETDEWEB)

    Stiehler, Martin

    2012-02-03

    The influence of the d-states of the transition metals on the structure formation in amorphous alloys has so far only been inadequately understood. The present work aims to elaborate additional contributions to the understanding of binary amorphous aluminum alloys with transition metals. Special emphasis was placed on alloys with a subgroup of the transition metals, the rare earth metals. Within the scope of the present work, layers of Al-Ce in the region of 15at% Ce-80at% Ce were produced by sequential flash evaporation at 4.2K in the high vacuum, and characterized electronically by electrical resistance and Hall effect measurements as well as structurally by transmission electron diffraction. In addition, studies of plasma resonance were carried out by means of electron energy loss spectroscopy. In the range of 25at% Ce-60at% Ce, homogeneous amorphous samples were obtained. Especially the structural investigations were made difficult by oxidation of the material. The influence of the Ce-4f electrons manifests itself mainly in the low-temperature and magnetoresistance, both of which are dominated by the Kondo effect. The Hall effect in Al-Ce is dominated by anomalous components over the entire temperature range (2K-320K), which are attributed to skew-scattering effects, also due to Ce-4f electrons. Down to 2K there was no macroscopic magnetic order. In the region 2K-20K, the existence of clusters of ordered magnetic moments is concluded. For T> 20K, paramagnetic behavior occurs. With regard to the structural and electronic properties, a-Al-Ce can be classified as a group with a-Al- (Sc, Y, La). In the sense of plasma resonance, a-Al-Ce is excellently arranged in a system known from other Al transition metal alloys. Furthermore, by increasing the results of binary amorphous Al transition metal alloys from the literature, it has been found that the structure formation in these systems is closely linked to a known but still unexplained structure-forming effect that

  12. Correlation-induced metal-insulator transitions in d{sup 0} magnetic superlattices based on alkaline-earth monoxides: Insights from ab initio calculations

    Energy Technology Data Exchange (ETDEWEB)

    Lu, Yi-Lin [Department of Applied Physics, Institute of Advanced Materials Physics, Tianjin Key Laboratory of Low Dimensional Materials Physics and Preparing Technology, Faculty of Science, Tianjin University, Tianjin 300072 (China); Dong, Shengjie [Department of Physics, Tianjin Normal University, Tianjin 300387 (China); Zhou, Baozeng [Department of Applied Physics, Institute of Advanced Materials Physics, Tianjin Key Laboratory of Low Dimensional Materials Physics and Preparing Technology, Faculty of Science, Tianjin University, Tianjin 300072 (China); Zhao, Hui [Department of Physics, Tianjin Normal University, Tianjin 300387 (China); Wu, Ping, E-mail: pingwu@tju.edu.cn [Department of Applied Physics, Institute of Advanced Materials Physics, Tianjin Key Laboratory of Low Dimensional Materials Physics and Preparing Technology, Faculty of Science, Tianjin University, Tianjin 300072 (China)

    2015-06-15

    Using first-principles density functional theory calculations, we have investigated the electronic structure and magnetic properties of four superlattices (MO){sub 1}/(MX){sub 1} (001) (M=Ca and Sr; X=N and C). Our results show that compared with standard GGA approach, the GGA plus effective U{sub eff} scheme can correct electronic structure and magnetic properties in some extent. With enhancing electronic correlation, for (CaO){sub 1}/(CaN){sub 1}, (SrO){sub 1}/(SrN){sub 1}, and (SrO){sub 1}/(SrC){sub 1}, the bands across Fermi level are divided into two parts and the shape of isotropic spherical spin atmosphere becomes anisotropic dumbbell-like with specific orientation, accompanying metal-insulator transitions. For (CaO){sub 1}/(CaC){sub 1}, the states just smearing with the Fermi level shift to lower energy region below Fermi level, indicating the transformation from a nearly half metal to an actual half metal occurs. The different behavior of (CaO){sub 1}/(CaC){sub 1} compared with three other compounds may be caused by the larger ionization energy of calcium than that of strontium and the smaller electronegativity of carbon than that of nitrogen. - Highlights: • The magnetic behaviors of four d{sup 0} superlattices are investigated. • The enhanced electronic correlation influences the magnetic properties. • (CaO){sub 1}/(CaC){sub 1} transforms from a nearly half metal to an actual half metal. • The other three compounds transform from half metals to magnetic insulators.

  13. Photochemistry of Transition Metal Hydrides.

    Science.gov (United States)

    Perutz, Robin N; Procacci, Barbara

    2016-08-10

    Photochemical reactivity associated with metal-hydrogen bonds is widespread among metal hydride complexes and has played a critical part in opening up C-H bond activation. It has been exploited to design different types of photocatalytic reactions and to obtain NMR spectra of dilute solutions with a single pulse of an NMR spectrometer. Because photolysis can be performed on fast time scales and at low temperature, metal-hydride photochemistry has enabled determination of the molecular structure and rates of reaction of highly reactive intermediates. We identify five characteristic photoprocesses of metal monohydride complexes associated with the M-H bond, of which the most widespread are M-H homolysis and R-H reductive elimination. For metal dihydride complexes, the dominant photoprocess is reductive elimination of H2. Dihydrogen complexes typically lose H2 photochemically. The majority of photochemical reactions are likely to be dissociative, but hydride complexes may be designed with equilibrated excited states that undergo different photochemical reactions, including proton transfer or hydride transfer. The photochemical mechanisms of a few reactions have been analyzed by computational methods, including quantum dynamics. A section on specialist methods (time-resolved spectroscopy, matrix isolation, NMR, and computational methods) and a survey of transition metal hydride photochemistry organized by transition metal group complete the Review.

  14. Transition-Metal-Free Biomolecule-Based Flexible Asymmetric Supercapacitors.

    Science.gov (United States)

    Yang, Yun; Wang, Hua; Hao, Rui; Guo, Lin

    2016-09-01

    A transition-metal-free asymmetric supercapacitor (ASC) is successfully fabricated based on an earth-abundant biomass derived redox-active biomolecule, named lawsone. Such an ASC exhibits comparable or even higher energy densities than most of the recently reported transition-metal-based ASCs, and this green ASC generation from renewable resources is promising for addressing current issues of electronic hazard processing, high cost, and unsustainability.

  15. Solvent Extraction of Alkaline Earth Metals with Alkylphosphorus Acids

    Institute of Scientific and Technical Information of China (English)

    XUXin; ZHUTun

    2002-01-01

    Solvent extraction equiliria of four main alkaline earth metals (magnesium, calcium, strontium and barium) with di(2-ethylhexyl) phosphoric acid (DEHPA), 2-ethylhexyl phosphonic acid mono-(2-ethylhexyl) ester, di(2,4,4-tri-methylpentyl) phosphinic acid and IR spectra of the extracts have been studied. The selectivity order is dependent of the e/r value and hydration energy of the metal ions. The minor shift of the P→O in IR absorption of the alkaline earth metal extracts indicates that the interaction between the metal ions and P→O is much weaker for alkaline earth metals than for transitional metals. The distribution of the four alkaline earth elements between aqueous solutions and solutions of DEHPA and neutral organophosphorus compunds, tri-n-butyl phosphate (TBP) or tri-octyl phosphine oxide (TOPO) in kerosene have been determined at varying ratio of TBP or TOPO to DEHPA and the positive synergism is observed. The synergic effects is explained by using IR spectra of the loaded organic phase.

  16. Vapor-liquid partitioning of alkaline earth and transition metals in NaCl-dominated hydrothermal fluids: An experimental study from 360 to 465 °C, near-critical to halite saturated conditions

    Science.gov (United States)

    Pester, Nicholas J.; Ding, Kang; Seyfried, William E.

    2015-11-01

    Multi-phase fluid flow is a common occurrence in magmatic hydrothermal systems; and extensive modeling efforts using currently established P-V-T-x properties of the NaCl-H2O system are impending. We have therefore performed hydrothermal flow experiments (360-465 °C) to observe vapor-liquid partitioning of alkaline earth and first row transition metals in NaCl-dominated source solutions. The data allow extraction of partition coefficients related to the intrinsic changes in both chlorinity and density along the two-phase solvus. The coefficients yield an overall decrease in vapor affinity in the order Cu(I) > Na > Fe(II) > Zn > Ni(II) ⩾ Mg ⩾ Mn(II) > Co(II) > Ca > Sr > Ba, distinguished with 95% confidence for vapor densities greater than ∼0.2 g/cm3. The alkaline earth metals are limited to purely electrostatic interactions with Cl ligands, resulting in an excellent linear correlation (R2 > 0.99) between their partition coefficients and respective ionic radii. Though broadly consistent with this relationship, relative behavior of the transition metals is not well resolved, being likely obscured by complex bonding processes and the potential participation of Na in the formation of tetra-chloro species. At lower densities (at/near halite saturation) partitioning behavior of all metals becomes highly non-linear, where M/Cl ratios in the vapor begin to increase despite continued decreases in chlorinity and density. We refer to this phenomenon as "volatility", which is broadly associated with substantial increases in the HCl/NaCl ratio (eventually to >1) due to hydrolysis of NaCl. Some transition metals (e.g., Fe, Zn) exhibit volatility prior to halite stability, suggesting a potential shift in vapor speciation relative to nearer critical regions of the vapor-liquid solvus. The chemistry of deep-sea hydrothermal fluids appears affected by this process during magmatic events, however, our results do not support suggestions of subseafloor halite precipitation

  17. Alkali metal and alkali earth metal gadolinium halide scintillators

    Energy Technology Data Exchange (ETDEWEB)

    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.

  18. The Transit Spectra of Earth and Jupiter

    CERN Document Server

    Irwin, Patrick G J; Bowles, Neil E; Fletcher, Leigh N; Aigrain, Suzanne; Lee, Jae-Min

    2014-01-01

    In recent years, a number of observations have been made of the transits of 'Hot Jupiters', such as HD 189733b, which have been modelled to derive atmospheric structure and composition. As measurement techniques improve, the transit spectra of 'Super-Earths' such as GJ 1214b are becoming better constrained, allowing model atmospheres to be fitted for this class of planet also. While it is not yet possible to constrain the atmospheric states of small planets such as the Earth or cold planets like Jupiter, this may become practical in the coming decades and if so, it is of interest to determine what we might infer from such measurements. Here we have constructed atmospheric models of the Solar System planets from 0.4 - 15.5 microns that are consistent with ground-based and satellite observations and from these calculate the primary transit and secondary eclipse spectra (with respect to the Sun and typical M-dwarfs) that would be observed by a 'remote observer', many light years away. From these spectra we test ...

  19. Metal-to-nonmetal transitions

    CERN Document Server

    Hensel, Friedrich; Holst, Bastian

    2010-01-01

    This book is devoted to nonmetal-to-metal transitions. The original ideas of Mott for such a transition in solids have been adapted to describe a broad variety of phenomena in condensed matter physics (solids, liquids, and fluids), in plasma and cluster physics, as well as in nuclear physics (nuclear matter and quark-gluon systems). The book gives a comprehensive overview of theoretical methods and experimental results of the current research on the Mott effect for this wide spectrum of topics. The fundamental problem is the transition from localized to delocalized states which describes the nonmetal-to-metal transition in these diverse systems. Based on the ideas of Mott, Hubbard, Anderson as well as Landau and Zeldovich, internationally respected scientists present the scientific challenges and highlight the enormous progress which has been achieved over the last years. The level of description is aimed to specialists in these fields as well as to young scientists who will get an overview for their own work...

  20. Transition metal (Cr{sup 3+}) and rare earth (Eu{sup 3+}, Dy{sup 3+}) ions used as a spectroscopic probe in compositional-dependent lead borate glasses

    Energy Technology Data Exchange (ETDEWEB)

    Pisarski, W.A., E-mail: Wojciech.Pisarski@us.edu.p [University of Silesia, Institute of Chemistry, Szkolna 9, 40-007 Katowice (Poland); Pisarska, J. [Silesian University of Technology, Department of Materials Science, Krasinskiego 8, 40-019 Katowice (Poland); Dominiak-Dzik, G.; Ryba-Romanowski, W. [Institute of Low Temperature and Structure Research, Polish Academy of Sciences, Okolna 2, 50-422 Wroclaw (Poland)

    2009-09-18

    Compositional-dependent lead borate glasses doped with transition metal and rare earth ions were studied using absorption and luminescence spectroscopy. The trivalent Cr{sup 3+}, Eu{sup 3+} and Dy{sup 3+} ions were used as a spectroscopic probe in glass samples with various PbO/B{sub 2}O{sub 3} ratios. Spectral analysis indicates that Cr{sup 3+} ions occupy intermediate field sites; the both sites coexist and emit from the {sup 4}T{sub 2} (low-field) and the {sup 2}E (high-field) states, respectively. The R and Y/B values due to {sup 5}D{sub 0}-{sup 7}F{sub 2}/{sup 5}D{sub 0}-{sup 7}F{sub 1} and {sup 4}F{sub 9/2}-{sup 6}H{sub 15/2}/{sup 4}F{sub 9/2}-{sup 6}H{sub 13/2} luminescence intensity ratios of Eu{sup 3+} and Dy{sup 3+} ions, respectively, increase with increasing heavy metal (PbO) content, suggesting higher asymmetry and more covalent bonding character between rare earth and oxygen ions.

  1. The DNA-binding and bioactivity of rare earth metal complexes.

    Science.gov (United States)

    Yang, Li; Wang, Bochu; Tan, Jun; Zhu, Liancai

    2013-08-01

    Recently more and more attention is paid to the rare earth metal complexes, because the properties of the rare earth metals are similar to those of the transition metals such as the similar atomic and the ionic radius. A large number of rare metal complexes were synthesized, and their bioactivities were also studied. This review highlights recent researches on the interaction of some rare earth metal complexes with DNA, analyzes how the configuration of the complexes influences the binding affinity, and focuses on the pharmacological activities of the complexes, such as anticancer, antibacterial, antioxidant, anti-inflammatory and anti-virus.

  2. Heterostructures of transition metal dichalcogenides

    KAUST Repository

    Amin, Bin

    2015-08-24

    The structural, electronic, optical, and photocatalytic properties of out-of-plane and in-plane heterostructures of transition metal dichalcogenides are investigated by (hybrid) first principles calculations. The out-of-plane heterostructures are found to be indirect band gap semiconductors with type-II band alignment. Direct band gaps can be achieved by moderate tensile strain in specific cases. The excitonic peaks show blueshifts as compared to the parent monolayer systems, whereas redshifts occur when the chalcogen atoms are exchanged along the series S-Se-Te. Strong absorption from infrared to visible light as well as excellent photocatalytic properties can be achieved.

  3. XANES spectra of transition metal compounds

    NARCIS (Netherlands)

    de Groot, F.M.F.|info:eu-repo/dai/nl/08747610X

    2009-01-01

    An overview is given of the interactions that determine the XANES spectral shapes of transition metal compounds. The interactions are divided into ground state effects, final state effects and transition effects. The metal L edges, metal K edges and ligand K edges are analysed with respect to these

  4. Biomass transition metal hydrogen-evolution electrocatalysts and electrodes

    Science.gov (United States)

    Chen, Wei-Fu; Iyer, Shweta; Iyer, Shilpa; Sasaki, Kotaro; Muckerman, James T.; Fujita, Etsuko

    2017-02-28

    A catalytic composition from earth-abundant transition metal salts and biomass is disclosed. A calcined catalytic composition formed from soybean powder and ammonium molybdate is specifically exemplified herein. Methods for making the catalytic composition are disclosed as are electrodes for hydrogen evolution reactions comprising the catalytic composition.

  5. Biomass transition metal hydrogen-evolution electrocatalysts and electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Wei-Fu; Iyer, Shweta; Iyer, Shilpa; Sasaki, Kotaro; Muckerman, James T.; Fujita, Etsuko

    2017-02-28

    A catalytic composition from earth-abundant transition metal salts and biomass is disclosed. A calcined catalytic composition formed from soybean powder and ammonium molybdate is specifically exemplified herein. Methods for making the catalytic composition are disclosed as are electrodes for hydrogen evolution reactions comprising the catalytic composition.

  6. 2D transition metal dichalcogenides

    Science.gov (United States)

    Manzeli, Sajedeh; Ovchinnikov, Dmitry; Pasquier, Diego; Yazyev, Oleg V.; Kis, Andras

    2017-08-01

    Graphene is very popular because of its many fascinating properties, but its lack of an electronic bandgap has stimulated the search for 2D materials with semiconducting character. Transition metal dichalcogenides (TMDCs), which are semiconductors of the type MX2, where M is a transition metal atom (such as Mo or W) and X is a chalcogen atom (such as S, Se or Te), provide a promising alternative. Because of its robustness, MoS2 is the most studied material in this family. TMDCs exhibit a unique combination of atomic-scale thickness, direct bandgap, strong spin-orbit coupling and favourable electronic and mechanical properties, which make them interesting for fundamental studies and for applications in high-end electronics, spintronics, optoelectronics, energy harvesting, flexible electronics, DNA sequencing and personalized medicine. In this Review, the methods used to synthesize TMDCs are examined and their properties are discussed, with particular attention to their charge density wave, superconductive and topological phases. The use of TMCDs in nanoelectronic devices is also explored, along with strategies to improve charge carrier mobility, high frequency operation and the use of strain engineering to tailor their properties.

  7. Tunable magnetocaloric effect in transition metal alloys.

    Science.gov (United States)

    Belyea, Dustin D; Lucas, M S; Michel, E; Horwath, J; Miller, Casey W

    2015-10-28

    The unpredictability of geopolitical tensions and resulting supply chain and pricing instabilities make it imperative to explore rare earth free magnetic materials. As such, we have investigated fully transition metal based "high entropy alloys" in the context of the magnetocaloric effect. We find the NiFeCoCrPdx family exhibits a second order magnetic phase transition whose critical temperature is tunable from 100 K to well above room temperature. The system notably displays changes in the functionality of the magnetic entropy change depending on x, which leads to nearly 40% enhancement of the refrigerant capacity. A detailed statistical analysis of the universal scaling behavior provides direct evidence that heat treatment and Pd additions reduce the distribution of exchange energies in the system, leading to a more magnetically homogeneous alloy. The general implications of this work are that the parent NiFeCoCr compound can be tuned dramatically with FCC metal additives. Together with their relatively lower cost, their superior mechanical properties that aid manufacturability and their relative chemical inertness that aids product longevity, NiFeCoCr-based materials could ultimately lead to commercially viable magnetic refrigerants.

  8. Tunable magnetocaloric effect in transition metal alloys

    Science.gov (United States)

    Belyea, Dustin D.; Lucas, M. S.; Michel, E.; Horwath, J.; Miller, Casey W.

    2015-10-01

    The unpredictability of geopolitical tensions and resulting supply chain and pricing instabilities make it imperative to explore rare earth free magnetic materials. As such, we have investigated fully transition metal based “high entropy alloys” in the context of the magnetocaloric effect. We find the NiFeCoCrPdx family exhibits a second order magnetic phase transition whose critical temperature is tunable from 100 K to well above room temperature. The system notably displays changes in the functionality of the magnetic entropy change depending on x, which leads to nearly 40% enhancement of the refrigerant capacity. A detailed statistical analysis of the universal scaling behavior provides direct evidence that heat treatment and Pd additions reduce the distribution of exchange energies in the system, leading to a more magnetically homogeneous alloy. The general implications of this work are that the parent NiFeCoCr compound can be tuned dramatically with FCC metal additives. Together with their relatively lower cost, their superior mechanical properties that aid manufacturability and their relative chemical inertness that aids product longevity, NiFeCoCr-based materials could ultimately lead to commercially viable magnetic refrigerants.

  9. Molecular precursor routes to transition metal sulfides

    Science.gov (United States)

    Dinnage, Christopher Walker

    This thesis is primarily concerned with the synthesis of homoleptic early transition meta thiolates and the subsequent preparation of bulk and thin-film metal disulfides from these compounds. Chapter 1 gives an introduction into the properties, preparation procedures and uses of bulk and thin-film transition metal disulfides as well as giving an overview of early transition metal thiolates synthesied so far in the literature (for titanium, zirconium, tantalum and niobium). Chapter 2 is concerned with the synthesis of a number of ionic and neutral transition metal thiolates. The main synthetic methodologies discussed in this chapter include substitution reactions of transition metal amides and alkyls with thiols, salt metathesis reactions of transition metal chlorides with alkali metal thiolates or with a base / thiol and the use of Grignard reagents. Chapter 3 discusses the preparation of bulk transition metal disulfides using the thiolates prepared in the previous chapter via a thio "sol-gel" route. The preparation of a range of bulk metal and mixed-metal disulfides using transition metal chlorides and hexamethyldisilathiane is also discussed in this chapter. Finally, chapter 4 is concerned with the attempted preparation of thin-films of some transition metal disulfides. Decomposition studies of some of the thiolates prepared in chapter 2 are discussed using thermal gravimetric analysis. Vapour-phase deposition studies are also explored in order to test the potential of the transition metal thiolates as precursors to the disulfides. Experiments using low-pressure chemical vapour deposition and aerosol-assisted chemical vapour deposition are also described.

  10. High-Tc Superconductivity and Raman Scattering Study of the phonon properties of electron doped (transition metal, rare-earth) - Oxygen-Free CaFeAsF and compared with RFeAsO system

    Science.gov (United States)

    Sasmal, Kalyan; Hadjiev, Viktor; Chu, C. W.(Paul)

    Quaternary CaFeAsF has ZrCuSiAs-type structure,(RO)δ+ layer in RFeAsO replaced by (CaF)δ+ layer,with tetragonal (P4/nmm)-orthorhombic (Cmma) phase transition at 134K,while magnetic order,SDW sets in at 114K. Partial replacement of Fe with Co/Ni is direct electron doping to (FeAs)δ+ layer.Tc ~15K in CaFe0.9Ni0.1AsF.Substitution of rare earth metal for alkaline earth metal suppresses anomaly in resistivity & induces superconductivity.Tc ~52K in Ca0.5Pr0.5FeAsF.Characterized by resistivity, susceptibility,XRD & EDX-SEM.Upper critical field estimated from magneto resistance.Bulk superconductivity proved by DC magnetization. Hall coefficient RH revealed hole-like charge carriers in parent compound CaFeAsF, while electron-type (RH in normal state is -Ve) for Ca0.5Pr0.5FeAsF.Evolution of Raman active phonons of Ca1-xPrxFeAsF measured with polarized Raman spectroscopy at room temperature from absurfaces of impurity-free microcrystals.Spectra exhibit sharp phonon lines on very weak electronic scattering background.Frequency and symmetry of Raman phonons involving out-of-plane atomic vibrations are found at 162.5 cm-1 (A1 g, Pr), 201 cm-1 (A1 g, As), 215.5 cm-1 (B1 g, Fe), 265 cm-1 (Eg, Fe) and 334 cm-1 (B1 g, F) for Ca0.5Pr0.5FeAsF.Observations are compared with RFeAsO unconventional superconductors also possibly related to magnetic fluctuations

  11. 稀土-过渡金属薄膜磁各向异性的理论研究%Theoretic studies on the magnetic anisotropy of rare-earth transition-metal thin films

    Institute of Scientific and Technical Information of China (English)

    何一鸣; 钱显毅; 黄致新

    2011-01-01

    The magnetic anisotropy of rare-earth transition-metal thin films is investigated in this paper. Based on the reference review and the analysis of thin film forming process by sputtering, the single ion model has been put foreword. With concrete computation, we found that when the composition of the film is R31Co69 and the rare-earth element is Tb, the magnetic anisotropy value can be as high as 3. 1×106 erg/cm3. And the Coulomb interactions between the non-S state rare-earth ion in non-spherical electric charge distribution with the deformed local crystalline field accounts for the major source of high perpendicular anisotropy of TbCo amorphous films.%对稀土-过渡金属薄膜的磁各向异性进行了理论分析研究.通过分析其它模型以及薄膜成膜过程的特点,建立了单离子模型,并进行了理论分析和计算.结果发现:组分为R31Co69薄膜中稀土元素R为Tb时的Ku值最大,接近3.1×106 erg/cm3.对于TbCo非晶垂直磁化膜而言,具有非球对称电荷分布的非S态离子Tb与局部电场的相互作用构成了其垂直磁各向异性的主要部分.

  12. Spinning around in Transition-Metal Chemistry

    OpenAIRE

    Swart, Marcel; Gruden-Pavlović, Maja

    2016-01-01

    Conspectus The great diversity and richness of transition metal chemistry, such as the features of an open d-shell, opened a way to numerous areas of scientific research and technological applications. Depending on the nature of the metal and its environment, there are often several energetically accessible spin states, and the progress in accurate theoretical treatment of this complicated phenomenon is presented in this Account. The spin state energetics of a transition metal complex can be ...

  13. Superconducting Metallic Glass Transition-Edge-Sensors

    Science.gov (United States)

    Hays, Charles C. (Inventor)

    2013-01-01

    A superconducting metallic glass transition-edge sensor (MGTES) and a method for fabricating the MGTES are provided. A single-layer superconducting amorphous metal alloy is deposited on a substrate. The single-layer superconducting amorphous metal alloy is an absorber for the MGTES and is electrically connected to a circuit configured for readout and biasing to sense electromagnetic radiation.

  14. Metal-semiconductor-metal transition in zigzag carbon nanoscrolls

    Science.gov (United States)

    Dong, Haixia; Zhang, Yang; Fang, Dangqi; Gong, Baihua; Zhang, Erhu; Zhang, Shengli

    2016-01-01

    Similar to rolling up paper, carbon nanoscrolls (CNSs) can be rolled from graphene nanoribbons (GNRs) using physical approaches. Owing to their peculiar one-dimensional nanostructures, CNSs have attracted great attention over the past few years. In this study, we have investigated the effects of bending deformation on the electronic properties of zigzag CNSs (ZCNSs) during the rolling process from zigzag GNRs (ZGNRs) by means of first-principles calculations. It is found that a metal-semiconductor-metal transition is observed. By analyzing charge density and density of states, the origin of this electronic property transition is discussed. Furthermore, we find that the metal-semiconductor-metal transition in ZCNSs is independent of ribbon width as well as spin-orbit interaction. Our results of the metal-semiconductor-metal transition in the ZCNSs are robust and may open potential applications in nano-electromechanical devices based on the ZCNSs.Similar to rolling up paper, carbon nanoscrolls (CNSs) can be rolled from graphene nanoribbons (GNRs) using physical approaches. Owing to their peculiar one-dimensional nanostructures, CNSs have attracted great attention over the past few years. In this study, we have investigated the effects of bending deformation on the electronic properties of zigzag CNSs (ZCNSs) during the rolling process from zigzag GNRs (ZGNRs) by means of first-principles calculations. It is found that a metal-semiconductor-metal transition is observed. By analyzing charge density and density of states, the origin of this electronic property transition is discussed. Furthermore, we find that the metal-semiconductor-metal transition in ZCNSs is independent of ribbon width as well as spin-orbit interaction. Our results of the metal-semiconductor-metal transition in the ZCNSs are robust and may open potential applications in nano-electromechanical devices based on the ZCNSs. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr07628

  15. HPTLC and magnetochromatography of new complexes of carboxylates with transition metals or rare earth elements and their ligands - study of lipophilicity.

    Science.gov (United States)

    Malinowska, Irena; Wronka, Agnieszka; Ferenc, Wiesława

    2016-10-18

    Nineteen new complexes of carboxylates with transition and rare elements as central ions and their ligands were characterized by chromatographic analyses. The parameter of relative lipophilicity (RM0 ) of the tested compounds was determined experimentally by the reversed-phase high-performance thin layer chromatography method with mixtures of various organic modifiers (acetonitrile, acetone, dioxane) and water as a mobile phase. The extrapolated RM0 values were compared with the logP values calculated from the molecular structures of tested solutes. Similarities between the lipophilicity indices were analysed by principal component analysis and linear regression. Thin-layer chromatography combined with a magnetic field has been proposed as a complementary method for determination of lipophilicity of the investigated compounds. The chromatograms in the field and outside it were developed simultaneously in two identical chromatographic chambers. One of them was placed in the external magnetic field of 0.4 T inductivity. We proved that chelation causes a drastic change in compound lipophilicity, but all complexes did not exhibit enhanced activity as compared with the parent ligand. Also in the magnetic field the retention of some complexes changed, which means that the presence of the field influences the physicochemical properties of the compounds and their interactions with the stationary phase.

  16. Some Rare Earth Metallic Organohydrides with Biindenyl as the Ligand

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    @@ Introduction It is well known that organometallic hydrides of rare earth metals are the catalysts and reducing reagents for the catalysis polymerization of alkenes and the catalysis hydrogenation of alkenoalkynes. There are four methods for the syntheses of organometallic hydrides of rare earth metals: (1) the thermal atomization of metals, I. E. , the interaction of a rare earth metal with alkenes with a terminal alkyne; (2) the Ln-C σ bond is broken with H2; (3) metallic hydride replacement[1], I. E., NaBH4, LiA1H4 and Na can be used to react with organometallic compounds of rare earth metals; (4) the elimination ofβ-H, I. E. , in the presence of LiC1, the elimination of theβ-H of the alkyl compounds of rare earth metals gives the target product. The organohydrides of biindenyl samarium, biindenyl gadolinium and biin denyl dysprosium were obtained with NaH reduction method.

  17. Global Earthing Systems: Characterization of Buried Metallic Parts

    OpenAIRE

    Tommasini, Riccardo; Colella, Pietro; Pons, Enrico

    2016-01-01

    International Standards IEC 61936-1 and EN 50522 define a Global Earthing System (GES) as the earthing network, created by the interconnection of local earthing systems, that should guarantee the absence of dangerous touch voltages. This is achieved through two effects: the division of the earth fault current between many earthing systems and the creation of a quasi equipotential surface. The second effect can be enhanced by the presence of buried metallic parts, such as light poles and water...

  18. Gyroscopic g factor of rare earth metals

    Science.gov (United States)

    Ogata, Y.; Chudo, H.; Ono, M.; Harii, K.; Matsuo, M.; Maekawa, S.; Saitoh, E.

    2017-02-01

    We develop the in situ magnetization measurement apparatus for observing the Barnett effect consisting of a fluxgate sensor, a high speed rotor with frequencies of up to 1.5 kHz, and a magnetic shield at room temperature. The effective magnetic field (Barnett field) in a sample arising from rotation magnetizes the sample and is proportional to the rotational frequency. The gyroscopic g factor, g ' , of rare earth metals, in particular, Gd, Tb, and Dy, was estimated to be 2.00 ± 0.08, 1.53 ± 0.17, and 1.15 ± 0.32, respectively, from the slopes of the rotation dependence of the Barnett field. This study provides a technique to determine the g ' factor even in samples where the spectroscopic method may not be available.

  19. The Search for Extraterrestrial Intelligence in Earth's Solar Transit Zone

    CERN Document Server

    Heller, René

    2016-01-01

    Over the past few years, astronomers have detected thousands of planets and planet candidates by observing their periodic transits in front of their host stars. A related transit method, called transit spectroscopy, might soon allow studies of the chemical imprints of life in extrasolar planetary atmospheres. We here address the reciprocal question, namely, from where is Earth detectable by extrasolar observers using similar methods. Thus, we explore the Earth's transit zone (ETZ), the projection of a band around the Earth's ecliptic onto the celestial plane, where observers can detect Earth transits across the Sun. The ETZ is between $0.520^\\circ$ and $0.537^\\circ$ wide due to the non-circular Earth orbit. The restricted ETZ (rETZ), where the Earth transits the Sun less than 0.5 solar radii from its center, is about $0.262^\\circ$ wide. We compile a target list of 45 K and 37 G dwarf stars inside the rETZ and within 1 kiloparsec (about 3260 lightyears). We construct an analytic galactic disk model and find th...

  20. Properties of Transition Metal Doped Alumina

    Science.gov (United States)

    Nykwest, Erik; Limmer, Krista; Brennan, Ray; Blair, Victoria; Ramprasad, Rampi

    Crystallographic texture can have profound effects on the properties of a material. One method of texturing is through the application of an external magnetic field during processing. While this method works with highly magnetic systems, doping is required to couple non-magnetic systems with the external field. Experiments have shown that low concentrations of rare earth (RE) dopants in alumina powders have enabled this kind of texturing. The magnetic properties of RE elements are directly related to their f orbital, which can have as many as 7 unpaired electrons. Since d-block elements can have as many as 5 unpaired electrons the effects of substitutional doping of 3d transition metals (TM) for Al in alpha (stable) and theta (metastable) alumina on the local structure and magnetic properties, in addition to the energetic cost, have been calculated by performing first-principles calculations based on density functional theory. This study has led to the development of general guidelines for the magnetic moment distribution at and around the dopant atom, and the dependence of this distribution on the dopant atom type and its coordination environment. It is anticipated that these findings can aid in the selection of suitable dopants help to guide parallel experimental efforts. This project was supported in part by an internship at the Army Research Laboratory, administered by the Oak Ridge Institute for Science and Education, along with a grant of computer time from the DoD High Performance Computing Modernization Program.

  1. Quantum phase transition in a common metal.

    Science.gov (United States)

    Yeh, A; Soh, Yeong-Ah; Brooke, J; Aeppli, G; Rosenbaum, T F; Hayden, S M

    2002-10-03

    The classical theory of solids, based on the quantum mechanics of single electrons moving in periodic potentials, provides an excellent description of substances ranging from semiconducting silicon to superconducting aluminium. Over the last fifteen years, it has become increasingly clear that there are substances for which the conventional approach fails. Among these are certain rare earth compounds and transition metal oxides, including high-temperature superconductors. A common feature of these materials is complexity, in the sense that they have relatively large unit cells containing heterogeneous mixtures of atoms. Although many explanations have been put forward for their anomalous properties, it is still possible that the classical theory might suffice. Here we show that a very common chromium alloy has some of the same peculiarities as the more exotic materials, including a quantum critical point, a strongly temperature-dependent Hall resistance and evidence for a 'pseudogap'. This implies that complexity is not a prerequisite for unconventional behaviour. Moreover, it should simplify the general task of explaining anomalous properties because chromium is a relatively simple system in which to work out in quantitative detail the consequences of the conventional theory of solids.

  2. Plasmons in metallic monolayer and bilayer transition metal dichalcogenides

    DEFF Research Database (Denmark)

    Andersen, Kirsten; Thygesen, Kristian S.

    2013-01-01

    We study the collective electronic excitations in metallic single-layer and bilayer transition metal dichalcogenides (TMDCs) using time dependent density functional theory in the random phase approximation. For very small momentum transfers (below q≈0.02 Å−1), the plasmon dispersion follows the √q...

  3. Transition metal catalysis in confined spaces.

    Science.gov (United States)

    Leenders, Stefan H A M; Gramage-Doria, Rafael; de Bruin, Bas; Reek, Joost N H

    2015-01-21

    Transition metal catalysis plays an important role in both industry and in academia where selectivity, activity and stability are crucial parameters to control. Next to changing the structure of the ligand, introducing a confined space as a second coordination sphere around a metal catalyst has recently been shown to be a viable method to induce new selectivity and activity in transition metal catalysis. In this review we focus on supramolecular strategies to encapsulate transition metal complexes with the aim of controlling the selectivity via the second coordination sphere. As we will discuss, catalyst confinement can result in selective processes that are impossible or difficult to achieve by traditional methods. We will describe the template-ligand approach as well as the host-guest approach to arrive at such supramolecular systems and discuss how the performance of the catalyst is enhanced by confining it in a molecular container.

  4. Transition metal contacts to graphene

    Energy Technology Data Exchange (ETDEWEB)

    Politou, Maria, E-mail: Maria.Politou@imec.be; De Gendt, Stefan; Heyns, Marc [KU Leuven, 3001 Leuven (Belgium); imec, Kapeldreef 75, 3001 Leuven (Belgium); Asselberghs, Inge; Radu, Iuliana; Conard, Thierry; Richard, Olivier; Martens, Koen; Huyghebaert, Cedric; Tokei, Zsolt [imec, Kapeldreef 75, 3001 Leuven (Belgium); Lee, Chang Seung [SAIT, Samsung Electronics Co., Suwon 443-803 (Korea, Republic of); Sayan, Safak [imec, Kapeldreef 75, 3001 Leuven (Belgium); Intel Corporation, 2200 Mission College Blvd, Santa Clara, California 95054 (United States)

    2015-10-12

    Achieving low resistance contacts to graphene is a common concern for graphene device performance and hybrid graphene/metal interconnects. In this work, we have used the circular Transfer Length Method (cTLM) to electrically characterize Ag, Au, Ni, Ti, and Pd as contact metals to graphene. The consistency of the obtained results was verified with the characterization of up to 72 cTLM structures per metal. Within our study, the noble metals Au, Ag and Pd, which form a weaker bond with graphene, are shown to result in lower contact resistance (Rc) values compared to the more reactive Ni and Ti. X-ray Photo Electron Spectroscopy and Transmission Electron Microscopy characterization for the latter have shown the formation of Ti and Ni carbides. Graphene/Pd contacts show a distinct intermediate behavior. The weak carbide formation signature and the low Rc values measured agree with theoretical predictions of an intermediate state of weak chemisorption of Pd on graphene.

  5. Microwave-assisted synthesis of transition metal phosphide

    Science.gov (United States)

    Viswanathan, Tito

    2014-12-30

    A method of synthesizing transition metal phosphide. In one embodiment, the method has the steps of preparing a transition metal lignosulfonate, mixing the transition metal lignosulfonate with phosphoric acid to form a mixture, and subjecting the mixture to a microwave radiation for a duration of time effective to obtain a transition metal phosphide.

  6. The Metallicities of Stars With and Without Transiting Planets

    CERN Document Server

    Buchhave, Lars A

    2015-01-01

    Host star metallicities have been used to infer observational constraints on planet formation throughout the history of the exoplanet field. The giant planet metallicity correlation has now been widely accepted, but questions remain as to whether the metallicity correlation extends to the small terrestrial-sized planets. Here, we report metallicities for a sample of 518 stars in the Kepler field that have no detected transiting planets and compare their metallicity distribution to a sample of stars that hosts small planets (Rp < 1.7 R_Earth). Importantly, both samples have been analyzed in a homogeneous manner using the same set of tools (Stellar Parameters Classification tool; SPC). We find the average metallicity of the sample of stars without detected transiting planets to be [m/H]_SNTP,dwarf = -0.02 +- 0.02 dex and the sample of stars hosting small planets to be [m/H]_STP = -0.02 +- 0.02 dex. The average metallicities of the two samples are indistinguishable within the uncertainties, and the two-sample...

  7. Alkane Soluble Transition Metal Complexes.

    Science.gov (United States)

    1983-10-01

    and decomposition of any intermediate, complexes. Cloro - L~r. spectra were recorded in the range 4 000-200 cm𔃻 form solutions of the phosphine PAr5...netathesis quickly showed that the lo~o-complez Is less stable than its cloro -malogue. A detailed Investigatiom of the preparation, charecterlstion and...solvent extraction of products that are believed to be a mixture of several metals, as stationary phases in gas chromatography. isomers of the ortho

  8. Cascade morphology transition in bcc metals.

    Science.gov (United States)

    Setyawan, Wahyu; Selby, Aaron P; Juslin, Niklas; Stoller, Roger E; Wirth, Brian D; Kurtz, Richard J

    2015-06-10

    Energetic atom collisions in solids induce shockwaves with complex morphologies. In this paper, we establish the existence of a morphological transition in such cascades. The order parameter of the morphology is defined as the exponent, b, in the defect production curve as a function of cascade energy (N(F) ~ E(MD)(b)). Response of different bcc metals can be compared in a consistent energy domain when the energy is normalized by the transition energy, μ, between the high- and the low-energy regime. Using Cr, Fe, Mo and W data, an empirical formula of μ as a function of displacement threshold energy, E(d), is presented for bcc metals.

  9. Earth's Atmospheric Electricity Parameter Response During Venus Transit

    Directory of Open Access Journals (Sweden)

    Syam Sundar De

    2015-01-01

    Full Text Available Venus transited across the Sun on 06 June 2012, introducing significant contribution to the tidal characteristics of the solar atmosphere. _ atmosphere was perturbed due to an anomalous Coronal Mass Ejection (CME and γ-radiationγ-radiation influenced by the solar tide due to Venus transit, thereby the Earth-ionosphere waveguide characteristics were changed. In this anomalous situation we measured some atmospheric electricity parameters such as Schumann resonance (SR amplitude, very low frequency (VLF sferics, subionospheric transmitted signals and the point discharge current (PDC along with the vertical electrical potential gradient (PG at the ground surface on the day of transit. The results showed some remarkable variations during the transit as well as pre- and post-transit periods. The observed anomalies in the recorded data were interpreted in terms of the anomalous solar tidal effects initiated due to Venus transit.

  10. Transition metal-catalyzed functionalization of pyrazines

    NARCIS (Netherlands)

    Nikishkin, N.; Huskens, Jurriaan; Verboom, Willem

    2013-01-01

    Transition metal-catalyzed reactions are generally used for carbon–carbon bond formation on pyrazines and include, but are not limited to, classical palladium-catalyzed reactions like Sonogashira, Heck, Suzuki, and Stille reactions. Also a few examples of carbon–heteroatom bond formation in

  11. Transition metal-catalyzed functionalization of pyrazines

    NARCIS (Netherlands)

    Nikishkin, Nicolai I.; Huskens, Jurriaan; Verboom, Willem

    2013-01-01

    Transition metal-catalyzed reactions are generally used for carbon–carbon bond formation on pyrazines and include, but are not limited to, classical palladium-catalyzed reactions like Sonogashira, Heck, Suzuki, and Stille reactions. Also a few examples of carbon–heteroatom bond formation in pyrazine

  12. Fluid metals the liquid-vapor transition of metals

    CERN Document Server

    Hensel, Friedrich

    2014-01-01

    This is a long-needed general introduction to the physics and chemistry of the liquid-vapor phase transition of metals. Physicists and physical chemists have made great strides understanding the basic principles involved, and engineers have discovered a wide variety of new uses for fluid metals. Yet there has been no book that brings together the latest ideas and findings in the field or that bridges the conceptual gap between the condensed-matter physics relevant to a dense metallic liquid and the molecular chemistry relevant to a dilute atomic vapor. Friedrich Hensel and William Warren seek

  13. Mesoporous Transition Metal Oxides for Supercapacitors

    Science.gov (United States)

    Wang, Yan; Guo, Jin; Wang, Tingfeng; Shao, Junfeng; Wang, Dong; Yang, Ying-Wei

    2015-01-01

    Recently, transition metal oxides, such as ruthenium oxide (RuO2), manganese dioxide (MnO2), nickel oxides (NiO) and cobalt oxide (Co3O4), have been widely investigated as electrode materials for pseudo-capacitors. In particular, these metal oxides with mesoporous structures have become very hot nanomaterials in the field of supercapacitors owing to their large specific surface areas and suitable pore size distributions. The high specific capacities of these mesoporous metal oxides are resulted from the effective contacts between electrode materials and electrolytes as well as fast transportation of ions and electrons in the bulk of electrode and at the interface of electrode and electrolyte. During the past decade, many achievements on mesoporous transition metal oxides have been made. In this mini-review, we select several typical nanomaterials, such as RuO2, MnO2, NiO, Co3O4 and nickel cobaltite (NiCo2O4), and briefly summarize the recent research progress of these mesoporous transition metal oxides-based electrodes in the field of supercapacitors.

  14. Mesoporous Transition Metal Oxides for Supercapacitors

    Directory of Open Access Journals (Sweden)

    Yan Wang

    2015-10-01

    Full Text Available Recently, transition metal oxides, such as ruthenium oxide (RuO2, manganese dioxide (MnO2, nickel oxides (NiO and cobalt oxide (Co3O4, have been widely investigated as electrode materials for pseudo-capacitors. In particular, these metal oxides with mesoporous structures have become very hot nanomaterials in the field of supercapacitors owing to their large specific surface areas and suitable pore size distributions. The high specific capacities of these mesoporous metal oxides are resulted from the effective contacts between electrode materials and electrolytes as well as fast transportation of ions and electrons in the bulk of electrode and at the interface of electrode and electrolyte. During the past decade, many achievements on mesoporous transition metal oxides have been made. In this mini-review, we select several typical nanomaterials, such as RuO2, MnO2, NiO, Co3O4 and nickel cobaltite (NiCo2O4, and briefly summarize the recent research progress of these mesoporous transition metal oxides-based electrodes in the field of supercapacitors.

  15. Transition metal based borohydrides for hydrogen storage

    Science.gov (United States)

    Jayanthi, Chakram; Liu, Jianjun; Wei, Suhuai; Zhao, Yufeng

    2010-03-01

    Using ab-initio studies based on the density-functional theory, we have calculated binding energies per hydrogen molecule for decomposition reactions of transition metal borohydrides MHxB12H12 to MB12 structures, where M corresponds to Sc, Ti, or V. Depending on the valence of the transition metal, x can be 1, 2, or 3. Crystal structures considered for MB12 included both hypothetical and those found in the international crystallographic structural database. On the other hand, the crystal structure considered for MHxB12H12 belongs to C2/c (space group 15) structure as reported in a previous study [V. Ozolins et al. JACS, 131, 230 (2009)]. Among the structures investigated, Titanium-based metal borohydride structure has the lowest binding energy per hydrogen molecule relative to the cubic TiB12 structure (˜0.37 eV/H2). Our finding should be contrasted with the binding energy/H2 for simple metal based borohydrides (e.g., CaB12H12 ), which has a value of ˜ 1.5 eV/H2, suggesting that transition metals play a significant role in lowering the H2 binding energy in borohydrides.

  16. Transitioning Unmanned Technologies for Earth Science Applications

    Science.gov (United States)

    Wardell, L. J.; Douglas, J.

    2008-12-01

    Development of small unmanned aerial systems (UAS) has progressed dramatically in recent years along with miniaturization of sensor technology. This confluence of development paths has resulted in greater capability in smaller, less expensive platforms allowing research to be performed where manned airborne platforms are impractical or dangerous. Recent applications include small UAS for studies involving hurricanes, volcanic activity, sea ice changes, glacier melt, biological monitoring of land and sea species, wildfire monitoring, and others. However, the majority of UAS employed in these investigations were originally developed for non-civilian applications and many of the required interfaces are locked behind proprietary specifications, requiring expensive customization by the manufacturer to transform a military UAS into one suitable for civilian work. A small UAS for scientific research should be standards-based, low-cost, user friendly, field serviceable, and be designed to accept a range of payloads. The AV8R UAS is one example of an unmanned system that has been developed for specific application to earth observation missions. This system is designed to be operated by the user with difficult environmental conditions and field logistics in mind. Numerous features and innovations that advance this technology as a research tool as well as its planned science missions will be presented. Most importantly, all interfaces to the system required for successful design and integration of various payloads will be openly available. The environment of open, standards based development allow the small technologies companies that serve as the backbone for much of the technology development to participate in the rapid development of industry capabilities. This is particularly true with UAS technologies. Programs within the USA such as the STTR foster collaborations with small businesses and university researchers. Other innovations related to autonomous unmanned systems

  17. The Effect of Recent Venus Transit on Earths Atmosphere

    OpenAIRE

    H. P. Sardar; Mandal, S. K.; Mandal, P. K.; Guha, A.; Sarkar, S. K.; Sarkar, B. K.; Adhikari, S. K.; De, B. K.; S S; Ray, M.

    2006-01-01

    Some experiments on June 8, 2004, the day of transit of Venus across the Sun, were undertaken at Kolkata (latitude: 23034? N) to observe effect, if any, of transit of Venus on FWF, ELF and VLF amplitudes. The result shows good correlation between their temporal variations during the transit. The observation was unbelievable as the Venus subtends only 1/32th of the cone subtended by Sun on Earth. This anomaly may be explained on the assumption that the height of Venusian atmosphere with high c...

  18. The effect of recent Venus transit on Earths atmosphere

    OpenAIRE

    H. P. Sardar; Mandal, S. K.; Mandal, P. K.; Guha, A.; Sarkar, S. K.; Sarkar, B. K.; Adhikari, S. K.; De, B. K.; S S; Ray, M.

    2006-01-01

    Some experiments on June 8, 2004, the day of transit of Venus across the Sun, were undertaken at Kolkata (latitude: 22°34lN) to observe the effect, if any, of transit of Venus on FWF, ELF and VLF amplitudes. The result shows a good correlation between their temporal variations during the transit. The observation was unbelievable as the Venus subtends only 1/32th of the cone subtended by Sun on Earth. This anomaly may be explained on the assumption that the height of Venusian atmosphere with h...

  19. The Search for Extraterrestrial Intelligence in Earth's Solar Transit Zone.

    Science.gov (United States)

    Heller, René; Pudritz, Ralph E

    2016-04-01

    Over the past few years, astronomers have detected thousands of planets and candidate planets by observing their periodic transits in front of their host stars. A related method, called transit spectroscopy, might soon allow studies of the chemical imprints of life in extrasolar planetary atmospheres. Here, we address the reciprocal question, namely, from where is Earth detectable by extrasolar observers using similar methods. We explore Earth's transit zone (ETZ), the projection of a band around Earth's ecliptic onto the celestial plane, where observers can detect Earth transits across the Sun. ETZ is between 0.520° and 0.537° wide due to the noncircular Earth orbit. The restricted Earth transit zone (rETZ), where Earth transits the Sun less than 0.5 solar radii from its center, is about 0.262° wide. We first compile a target list of 45 K and 37 G dwarf stars inside the rETZ and within 1 kpc (about 3260 light-years) using the Hipparcos catalogue. We then greatly enlarge the number of potential targets by constructing an analytic galactic disk model and find that about 10(5) K and G dwarf stars should reside within the rETZ. The ongoing Gaia space mission can potentially discover all G dwarfs among them (several 10(4)) within the next 5 years. Many more potentially habitable planets orbit dim, unknown M stars in ETZ and other stars that traversed ETZ thousands of years ago. If any of these planets host intelligent observers, they could have identified Earth as a habitable, or even as a living, world long ago, and we could be receiving their broadcasts today. The K2 mission, the Allen Telescope Array, the upcoming Square Kilometer Array, or the Green Bank Telescope might detect such deliberate extraterrestrial messages. Ultimately, ETZ would be an ideal region to be monitored by the Breakthrough Listen Initiatives, an upcoming survey that will constitute the most comprehensive search for extraterrestrial intelligence so far.

  20. Spin doping using transition metal phthalocyanine molecules

    Science.gov (United States)

    Atxabal, A.; Ribeiro, M.; Parui, S.; Urreta, L.; Sagasta, E.; Sun, X.; Llopis, R.; Casanova, F.; Hueso, L. E.

    2016-12-01

    Molecular spins have become key enablers for exploring magnetic interactions, quantum information processes and many-body effects in metals. Metal-organic molecules, in particular, let the spin state of the core metal ion to be modified according to its organic environment, allowing localized magnetic moments to emerge as functional entities with radically different properties from its simple atomic counterparts. Here, using and preserving the integrity of transition metal phthalocyanine high-spin complexes, we demonstrate the magnetic doping of gold thin films, effectively creating a new ground state. We demonstrate it by electrical transport measurements that are sensitive to the scattering of itinerant electrons with magnetic impurities, such as Kondo effect and weak antilocalization. Our work expands in a simple and powerful way the classes of materials that can be used as magnetic dopants, opening a new channel to couple the wide range of molecular properties with spin phenomena at a functional scale.

  1. Detection of Earth-mass and Super-Earth Trojan Planets Using Transit Timing Variation Method

    CERN Document Server

    Haghighipour, Nader; Hinse, Tobias C

    2013-01-01

    We have carried out an extensive study of the possibility of the detection of Earth-mass and super-Earth Trojan planets using transit timing variation method with the Kepler space telescope. We have considered a system consisting of a transiting Jovian-type planet in a short period orbit, and determined the induced variations in its transit timing due to an Earth-mass/super-Earth Trojan planet. We mapped a large section of the phase space around the 1:1 mean-motion resonance and identified regions corresponding to several other mean-motion resonances where the orbit of the planet would be stable. We calculated TTVs for different values of the mass and orbital elements of the transiting and perturbing bodies as well as the mass of central star, and identified orbital configurations of these objects (ranges of their orbital elements and masses) for which the resulted TTVs would be within the range of the variations of the transit timing of Kepler's planetary candidates. Results of our study indicate that in gen...

  2. First-row transition metal hydrogenation and hydrosilylation catalysts

    Science.gov (United States)

    Trovitch, Ryan J.; Mukhopadhyay, Tufan K.; Pal, Raja; Levin, Hagit Ben-Daat; Porter, Tyler M.; Ghosh, Chandrani

    2017-07-18

    Transition metal compounds, and specifically transition metal compounds having a tetradentate and/or pentadentate supporting ligand are described, together with methods for the preparation thereof and the use of such compounds as hydrogenation and/or hydrosilylation catalysts.

  3. A Transition to Metallic Hydrogen: Evidence of the Plasma Phase Transition

    Science.gov (United States)

    Silvera, Isaac; Zaghoo, Mohamed; Salamat, Ashkan

    The insulator-metal transition in hydrogen is one of the most outstanding problems in condensed matter physics. The high-pressure metallic phase is now predicted to be liquid atomic from T =0 K to very high temperatures. We have conducted measurements of optical properties of hot dense hydrogen in the region of 1.1-1.7 Mbar and up to 2200 K in a diamond anvil cell using pulsed laser heating of the sample. We present evidence in two forms: a plateau in the heating curves (average laser power vs temperature) characteristic of a first-order phase transition with latent heat, and changes in transmittance and reflectance characteristic of a metal for temperatures above the plateau temperature. For thick films the reflectance saturates at ~0.5. The phase line of this transition has a negative slope in agreement with theories of the so-called plasma phase transition. The NSF, Grant DMR-1308641, the DOE Stockpile Stewardship Academic Alliance Program, Grant DE-FG52-10NA29656, and NASA Earth and Space Science Fellowship Program, Award NNX14AP17H supported this research.

  4. Electronic structure of hcp transition metals

    DEFF Research Database (Denmark)

    Jepsen, O.; Andersen, O. Krogh; Mackintosh, A. R.

    1975-01-01

    Using the linear muffin-tin-orbital method described in the previous paper, we have calculated the electronic structures of the hcp transition metals, Zr, Hf, Ru, and Os. We show how the band structures of these metals may be synthesized from the sp and d bands, and illustrate the effects...... mRy. Very small pieces of Fermi surface, which have not yet been observed experimentally, are predicted for Os. The limited amount of experimental information available for Zr can be fairly satisfactorily interpreted if the calculated d bands are raised by about 10-20 mRy relative to the sp bands...

  5. Insulator to Metal Transition in Fluid Hydrogen

    Energy Technology Data Exchange (ETDEWEB)

    Hood, R Q; Galli, G

    2003-06-15

    The authors have investigated the insulator to metal transition (ITM) in fluid hydrogen using first principles simulations. Both density functional and quantum Monte Carlo calculations show that the electronic energy gap of the liquid vanishes at about 9 fold compression and 3000 K. At these conditions the computed conductivity values are characteristic of a poor metal. These findings are consistent with those of recent shock wave experiments but the computed conductivity is larger than the measured value. From the ab-initio results they conclude that the ITM is driven by molecular dissociation rather than disorder and that both temperature and pressure play a key role in determining structural changes in the fluid.

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  7. Lattice Location of Transition Metals in Semiconductors

    CERN Multimedia

    2002-01-01

    %IS366 %title\\\\ \\\\Transition metals (TMs) in semiconductors have been the subject of considerable research for nearly 40 years. This is due both to their role as important model impurities for deep centers in semiconductors, and to their technological impact as widespread contaminants in Si processing, where the miniaturization of devices requires to keep their sheet concentration below 10$^{10}$ cm$^{-2}$. As a consequence of the low TM solubility, conventional ion beam methods for direct lattice location have failed completely in identifying the lattice sites of isolated transition metals. Although electron paramagnetic resonance (EPR) has yielded valuable information on a variety of TM centers, it has been unable to detect certain defects considered by theory, e.g., isolated interstitial or substitutional Cu in Si. The proposed identity of other EPR centers such as substitutional Fe in Si, still needs confirmation by additional experimental methods. As a consequence, the knowledge on the structural propert...

  8. Thermodynamic Hydricity of Transition Metal Hydrides.

    Science.gov (United States)

    Wiedner, Eric S; Chambers, Matthew B; Pitman, Catherine L; Bullock, R Morris; Miller, Alexander J M; Appel, Aaron M

    2016-08-10

    Transition metal hydrides play a critical role in stoichiometric and catalytic transformations. Knowledge of free energies for cleaving metal hydride bonds enables the prediction of chemical reactivity, such as for the bond-forming and bond-breaking events that occur in a catalytic reaction. Thermodynamic hydricity is the free energy required to cleave an M-H bond to generate a hydride ion (H(-)). Three primary methods have been developed for hydricity determination: the hydride transfer method establishes hydride transfer equilibrium with a hydride donor/acceptor pair of known hydricity, the H2 heterolysis method involves measuring the equilibrium of heterolytic cleavage of H2 in the presence of a base, and the potential-pKa method considers stepwise transfer of a proton and two electrons to give a net hydride transfer. Using these methods, over 100 thermodynamic hydricity values for transition metal hydrides have been determined in acetonitrile or water. In acetonitrile, the hydricity of metal hydrides spans a range of more than 50 kcal/mol. Methods for using hydricity values to predict chemical reactivity are also discussed, including organic transformations, the reduction of CO2, and the production and oxidation of hydrogen.

  9. Defect-Tolerant Monolayer Transition Metal Dichalcogenides

    DEFF Research Database (Denmark)

    Pandey, Mohnish; Rasmussen, Filip Anselm; Kuhar, Korina;

    2016-01-01

    -principles investigation of defect tolerance in 29 monolayer transition metal dichalcogenides (TMDs) of interest for nanoscale optoelectronics. We find that the TMDs based on group VI and X metals form deep gap states upon creation of a chalcogen (S, Se, Te) vacancy, while the TMDs based on group IV metals form only...... shallow defect levels and are thus predicted to be defect-tolerant. Interestingly, all the defect sensitive TMDs have valence and conduction bands with a very similar orbital composition. This indicates a bonding/antibonding nature of the gap, which in turn suggests that dangling bonds will fall inside...... the gap. These ideas are made quantitative by introducing a descriptor that measures the degree of similarity of the conduction and valence band manifolds. Finally, the study is generalized to nonpolar nanoribbons of the TMDs where we find that only the defect sensitive materials form edge states within...

  10. Spinning around in Transition-Metal Chemistry.

    Science.gov (United States)

    Swart, Marcel; Gruden, Maja

    2016-12-20

    The great diversity and richness of transition metal chemistry, such as the features of an open d-shell, opened a way to numerous areas of scientific research and technological applications. Depending on the nature of the metal and its environment, there are often several energetically accessible spin states, and the progress in accurate theoretical treatment of this complicated phenomenon is presented in this Account. The spin state energetics of a transition metal complex can be predicted theoretically on the basis of density functional theory (DFT) or wave function based methodology, where DFT has advantages since it can be applied routinely to medium-to-large-sized molecules and spin-state consistent density functionals are now available. Additional factors such as the effect of the basis set, thermochemical contributions, solvation, relativity, and dispersion, have been investigated by many researchers, but challenges in unambiguous assignment of spin states still remain. The first DFT studies showed intrinsic spin-state preferences of hybrid functionals for high spin and early generalized gradient approximation functionals for low spin. Progress in the development of density functional approximations (DFAs) then led to a class of specially designed DFAs, such as OPBE, SSB-D, and S12g, and brought a very intriguing and fascinating observation that the spin states of transition metals and the SN2 barriers of organic molecules are somehow intimately linked. Among the many noteworthy results that emerged from the search for the appropriate description of the complicated spin state preferences in transition metals, we mainly focused on the examination of the connection between the spin state and the structures or coordination modes of the transition metal complexes. Changes in spin states normally lead only to changes in the metal-ligand bond lengths, but to the best of our knowledge, the dapsox ligand showed the first example of a transition-metal complex where a

  11. Origin of Transitions between Metallic and Insulating States in Simple Metals

    Science.gov (United States)

    Naumov, Ivan I.; Hemley, Russell J.

    2015-04-01

    Unifying principles that underlie recently discovered transitions between metallic and insulating states in elemental solids under pressure are developed. Using group theory arguments and first-principles calculations, we show that the electronic properties of the phases involved in these transitions are controlled by symmetry principles. The valence bands in these systems are described by simple and composite band representations constructed from localized Wannier functions centered on points unoccupied by atoms, and which are not necessarily all symmetrical. The character of the Wannier functions is closely related to the degree of s -p (-d ) hybridization and reflects multicenter chemical bonding in these insulating states. The conditions under which an insulating state is allowed for structures having an integer number of atoms per primitive unit cell as well as reentrant (i.e., metal-insulator-metal) transition sequences are detailed, resulting in predictions of behavior such as phases having band-contact lines. The general principles developed are tested and applied to the alkali and alkaline earth metals, including elements where high-pressure insulating phases have been reported (e.g., Li, Na, and Ca).

  12. Laser materials based on transition metal ions

    Science.gov (United States)

    Moncorgé, Richard

    2017-01-01

    The purpose of this presentation is to review the spectroscopic properties of the main laser materials based on transition metal ions which lead to noticeable laser performance at room temperature and, for very few cases, because of unique properties, when they are operated at cryogenic temperatures. The description also includes the materials which are currently being used as saturable absorbers for passive-Q-switching of a variety of other near- and mid-infrared solid state lasers. A substantial part of the article is devoted first to the description of the energy levels and of the absorption and emission transitions of the transition metal ions in various types of environments by using the well-known Tanabe-Sugano diagrams. It is shown in particular how these diagrams can be used along with other theoretical considerations to understand and describe the spectroscopic properties of ions sitting in crystal field environments of near-octahedral or near-tetrahedral symmetry. The second part is then dedicated to the description (positions and intensities) of the main absorption and emission features which characterize the different types of materials.

  13. Ultrafast photophysics of transition metal complexes.

    Science.gov (United States)

    Chergui, Majed

    2015-03-17

    The properties of transition metal complexes are interesting not only for their potential applications in solar energy conversion, OLEDs, molecular electronics, biology, photochemistry, etc. but also for their fascinating photophysical properties that call for a rethinking of fundamental concepts. With the advent of ultrafast spectroscopy over 25 years ago and, more particularly, with improvements in the past 10-15 years, a new area of study was opened that has led to insightful observations of the intramolecular relaxation processes such as internal conversion (IC), intersystem crossing (ISC), and intramolecular vibrational redistribution (IVR). Indeed, ultrafast optical spectroscopic tools, such as fluorescence up-conversion, show that in many cases, intramolecular relaxation processes can be extremely fast and even shorter than time scales of vibrations. In addition, more and more examples are appearing showing that ultrafast ISC rates do not scale with the magnitude of the metal spin-orbit coupling constant, that is, that there is no heavy-atom effect on ultrafast time scales. It appears that the structural dynamics of the system and the density of states play a crucial role therein. While optical spectroscopy delivers an insightful picture of electronic relaxation processes involving valence orbitals, the photophysics of metal complexes involves excitations that may be centered on the metal (called metal-centered or MC) or the ligand (called ligand-centered or LC) or involve a transition from one to the other or vice versa (called MLCT or LMCT). These excitations call for an element-specific probe of the photophysics, which is achieved by X-ray absorption spectroscopy. In this case, transitions from core orbitals to valence orbitals or higher allow probing the electronic structure changes induced by the optical excitation of the valence orbitals, while also delivering information about the geometrical rearrangement of the neighbor atoms around the atom of

  14. Metal-insulator and charge ordering transitions in oxide nanostructures

    Science.gov (United States)

    Singh, Sujay Kumar

    Strongly correlated oxides are a class of materials wherein interplay of various degrees of freedom results in novel electronic and magnetic phenomena. Vanadium oxides are widely studied correlated materials that exhibit metal-insulator transitions (MIT) in a wide temperature range from 70 K to 380 K. In this Thesis, results from electrical transport measurements on vanadium dioxide (VO2) and vanadium oxide bronze (MxV 2O5) (where M: alkali, alkaline earth, and transition metal cations) are presented and discussed. Although the MIT in VO2 has been studied for more than 50 years, the microscopic origin of the transition is still debated since a slew of external parameters such as light, voltage, and strain are found to significantly alter the transition. Furthermore, recent works on electrically driven switching in VO2 have shown that the role of Joule heating to be a major cause as opposed to electric field. We explore the mechanisms behind the electrically driven switching in single crystalline nanobeams of VO2 through DC and AC transport measurements. The harmonic analysis of the AC measurement data shows that non-uniform Joule heating causes electronic inhomogeneities to develop within the nanobeam and is responsible for driving the transition in VO2. Surprisingly, field assisted emission mechanisms such as Poole-Frenkel effect is found to be absent and the role of percolation is also identified in the electrically driven transition. This Thesis also provides a new insight into the mechanisms behind the electrolyte gating induced resistance modulation and the suppression of MIT in VO2. We show that the metallic phase of VO2 induced by electrolyte gating is due to an electrochemical process and can be both reversible and irreversible under different conditions. The kinetics of the redox processes increase with temperature; a complete suppression of the transition and the stabilization of the metallic phase are achievable by gating in the rutile metallic phase

  15. Switchable Metal-Insulator Phase Transition Metamaterials.

    Science.gov (United States)

    Hajisalem, Ghazal; Nezami, Mohammadreza S; Gordon, Reuven

    2017-05-10

    We investigate the switching of a gap plasmon tunnel junction between conducting and insulating states. Hysteresis is observed in the second and the third harmonic generation power dependence, which arises by thermally induced disorder ("melting") of a two-carbon self-assembled monolayer between an ultraflat gold surface and metal nanoparticles. The hysteresis is observed for a variety of nanoparticle sizes, but not for larger tunnel junctions where there is no appreciable tunneling. By combining quantum corrected finite-difference time-domain simulations with nonlinear scattering theory, we calculate the changes in the harmonic generation between the tunneling and the insulating states, and good agreement is found with the experiments. This paves the way to a new class of metal-insulator phase transition switchable metamaterials, which may provide next-generation information processing technologies.

  16. Large gem diamonds from metallic liquid in Earth's deep mantle.

    Science.gov (United States)

    Smith, Evan M; Shirey, Steven B; Nestola, Fabrizio; Bullock, Emma S; Wang, Jianhua; Richardson, Stephen H; Wang, Wuyi

    2016-12-16

    The redox state of Earth's convecting mantle, masked by the lithospheric plates and basaltic magmatism of plate tectonics, is a key unknown in the evolutionary history of our planet. Here we report that large, exceptional gem diamonds like the Cullinan, Constellation, and Koh-i-Noor carry direct evidence of crystallization from a redox-sensitive metallic liquid phase in the deep mantle. These sublithospheric diamonds contain inclusions of solidified iron-nickel-carbon-sulfur melt, accompanied by a thin fluid layer of methane ± hydrogen, and sometimes majoritic garnet or former calcium silicate perovskite. The metal-dominated mineral assemblages and reduced volatiles in large gem diamonds indicate formation under metal-saturated conditions. We verify previous predictions that Earth has highly reducing deep mantle regions capable of precipitating a metallic iron phase that contains dissolved carbon and hydrogen.

  17. Catabolism of hyaluronan: involvement of transition metals

    OpenAIRE

    Šoltés, Ladislav; Kogan, Grigorij

    2009-01-01

    One of the very complex structures in the vertebrates is the joint. The main component of the joint is the synovial fluid with its high-molar-mass glycosaminoglycan hyaluronan, which turnover is approximately twelve hours. Since the synovial fluid does not contain any hyaluronidases, the fast hyaluronan catabolism is caused primarily by reductive-oxidative processes. Eight transition metals – V23, Mn25, Fe26, Co27, Ni28, Cu29, Zn30, and Mo42 – naturally occurring in living organism are essent...

  18. Electrical conduction in transition-metal salts

    Energy Technology Data Exchange (ETDEWEB)

    Grado-Caffaro, M.A.; Grado-Caffaro, M. [Scientific Consultants, Madrid (Spain)

    2016-08-01

    We predict that a given transition-metal salt as, for example, a K{sub 2}CuCl{sub 4}.2H{sub 2}O-type compound, can behave as an electrical conductor in the paramagnetic case. In fact, we determine the electrical conductance in a salt of this type. This conductance is found to be quantised in agreement with previous well-known results. Related mathematical expressions in the context of superexchange interaction are obtained. In addition, we determine the corresponding (macroscopically viewed) current density and the associated electron wave functions.

  19. Magnetic correlations in doped transition metal oxides

    Energy Technology Data Exchange (ETDEWEB)

    Aeppli, G. [AT and T Bell Labs., Murray Hill, NJ (United States); Bao, W.; Broholm, C. [Johns Hopkins Univ., Baltimore, MD (United States)] [and others

    1995-02-15

    The authors review recent reactor- and spallation-source-based neutron scattering experiments on the magnetic fluctuations and order in a variety of doped transition metal oxides. In particular, data are shown for the NiO chain compound, Y{sub 2{minus}x}Ca{sub x}BaNiO{sub 5}, the two-dimensional cuprate superconductors La{sub 2{minus}x}Sr{sub x}CuO{sub 4} and YBa{sub 2}Cu{sub 3} O{sub 6+x}, and the classical three-dimensional ``Mott-Hubbard`` system V{sub 2{minus}y}O{sub 3}.

  20. Electronic and Magnetic Properties of Rare-Earth Metals Doped ZnO Monolayer

    Directory of Open Access Journals (Sweden)

    Changlong Tan

    2015-01-01

    Full Text Available The structural, electronic, and magnetic properties of rare-earth metals doped ZnO monolayer have been investigated using the first-principles calculations. The induced spin polarization is confirmed for Ce, Eu, Gd, and Dy dopings while the induced spin polarization is negligible for Y doping. The localized f states of rare-earth atoms respond to the introduction of a magnetic moment. ZnO monolayer undergoes transition from semiconductor to metal in the presence of Y, Ce, Gd, and Dy doping. More interestingly, Eu doped ZnO monolayer exhibits half-metallic behavior. Our result demonstrates that the RE-doping is an efficient route to modify the magnetic and electronic properties in ZnO monolayer.

  1. The transmission spectrum of Earth-size transiting planets

    CERN Document Server

    Ehrenreich, D; Etangs, A L; Vidal-Madjar, A; Selsis, F; Ehrenreich, David; Tinetti, Giovanna; Etangs, Alain Lecavelier Des; Vidal-Madjar, Alfred; Selsis, Franck

    2005-01-01

    A variety of terrestrial planets with different physical parameters and exotic atmospheres might plausibly exist outside our Solar System, waiting to be detected by the next generation of space-exploration missions. Some of these planets might transit their parent star. We present here the first study of atmospheric signatures of transiting Earth-size exoplanets. We focus on a limited number of significant examples, for which we discuss the detectability of some of the possible molecules present in their atmospheres, such as water, carbon dioxide, ozone or molecular oxygen. To this purpose, we developed a model to simulate transmission spectra of Earth-size exoplanets from the ultraviolet to the near infrared. According to our calculations, the signatures of planetary atmospheres represent an absorption of a few parts-per-million (ppm) in the stellar flux. The atmospheres of a few Earth-like planets can be detected with a 30-40m telescope. The detection of the extensive atmospheres of tens of small satellites...

  2. Role of thermal heating on the voltage induced insulator-metal transition in VO2.

    Science.gov (United States)

    Zimmers, A; Aigouy, L; Mortier, M; Sharoni, A; Wang, Siming; West, K G; Ramirez, J G; Schuller, Ivan K

    2013-02-01

    We show that the main mechanism for the dc voltage or dc current induced insulator-metal transition in vanadium dioxide VO(2) is due to local Joule heating and not a purely electronic effect. This "tour de force" experiment was accomplished by using the fluorescence spectra of rare-earth doped micron sized particles as local temperature sensors. As the insulator-metal transition is induced by a dc voltage or dc current, the local temperature reaches the transition temperature indicating that Joule heating plays a predominant role. This has critical implications for the understanding of the dc voltage or dc current induced insulator-metal transition and has a direct impact on applications which use dc voltage or dc current to externally drive the transition.

  3. High-Pressure Thermodynamic Properties of f-electron Metals, Transition Metal Oxides, and Half-Metallic Magnets

    Energy Technology Data Exchange (ETDEWEB)

    Richard T. Scalettar; Warren E. Pickett

    2005-08-02

    This project involves research into the thermodynamic properties of f-electron metals, transition metal oxides, and half-metallic magnets at high pressure. These materials are ones in which the changing importance of electron-electron interactions as the distance between atoms is varied can tune the system through phase transitions from localized to delocalized electrons, from screened to unscreened magnetic moments, and from normal metal to one in which only a single spin specie can conduct. Three main thrusts are being pursued: (i) Mott transitions in transition metal oxides, (ii) magnetism in half-metallic compounds, and (iii) large volume-collapse transitions in f-band metals.

  4. Detection of a Transiting Low-Density Super-Earth

    CERN Document Server

    Henry, Gregory W; Marcy, Geoffrey W; Fischer, Debra A; Johnson, John Asher

    2011-01-01

    We present evidence for photometric transits of the low-mass planet HD 97658b across the disk of its host star, an early K dwarf. This planet was previously discovered in radial velocities (RVs) from Keck/HIRES as part of the Eta-Earth Survey. Using photometry from the Automated Photometric Telescopes at Fairborn Observatory, we detected four separate planetary egress events at times predicted from the RV orbit. We measured a transit depth of 1470 +/- 260 ppm, a result that should be confirmed and refined with space-based photometry. We also collected additional Keck-HIRES RV measurements that refined the transit ephemeris and planet mass. With an orbital period of 9.4957 +/- 0.0022 days, HD 97658b is a close-in planet that had been classified as a `super-Earth' based on its mass of 6.4 +/- 0.7 Mearth. However, the planet radius of 2.93 +/- 0.28 Rearth implies a density of 1.40 g/cc and suggests `sub-Neptune' status. The low density can be explained by an extended atmosphere of volatiles such as hydrogen, hel...

  5. Improved Laboratory Transition Probabilities for Ce II, Application to the Cerium Abundances of the Sun and Five r-process Rich, Metal-Poor Stars, and Rare Earth Lab Data

    CERN Document Server

    Lawler, J E; Cowan, J J; Ivans, I I; Hartog, E A Den

    2009-01-01

    Recent radiative lifetime measurements accurate to +/- 5% using laser-induced fluorescence (LIF) on 43 even-parity and 15 odd-parity levels of Ce II have been combined with new branching fractions measured using a Fourier transform spectrometer (FTS) to determine transition probabilities for 921 lines of Ce II. This improved laboratory data set has been used to determine a new solar photospheric Ce abundance, log epsilon = 1.61 +/- 0.01 (sigma = 0.06 from 45 lines), a value in excellent agreement with the recommended meteoritic abundance, log epsilon = 1.61 +/- 0.02. Revised Ce abundances have also been derived for the r-process-rich metal-poor giant stars BD+17 3248, CS 22892-052, CS 31082-001, HD 115444 and HD 221170. Between 26 and 40 lines were used for determining the Ce abundance in these five stars, yielding a small statistical uncertainty of 0.01 dex similar to the Solar result. The relative abundances in the metal-poor stars of Ce and Eu, a nearly pure r-process element in the Sun, matches r-process ...

  6. Methyl Complexes of the Transition Metals.

    Science.gov (United States)

    Campos, Jesús; López-Serrano, Joaquín; Peloso, Riccardo; Carmona, Ernesto

    2016-05-01

    Organometallic chemistry can be considered as a wide area of knowledge that combines concepts of classic organic chemistry, that is, based essentially on carbon, with molecular inorganic chemistry, especially with coordination compounds. Transition-metal methyl complexes probably represent the simplest and most fundamental way to view how these two major areas of chemistry combine and merge into novel species with intriguing features in terms of reactivity, structure, and bonding. Citing more than 500 bibliographic references, this review aims to offer a concise view of recent advances in the field of transition-metal complexes containing M-CH3 fragments. Taking into account the impressive amount of data that are continuously provided by organometallic chemists in this area, this review is mainly focused on results of the last five years. After a panoramic overview on M-CH3 compounds of Groups 3 to 11, which includes the most recent landmark findings in this area, two further sections are dedicated to methyl-bridged complexes and reactivity.

  7. Janus monolayers of transition metal dichalcogenides

    KAUST Repository

    Lu, Ang-Yu

    2017-05-15

    Structural symmetry-breaking plays a crucial role in determining the electronic band structures of two-dimensional materials. Tremendous efforts have been devoted to breaking the in-plane symmetry of graphene with electric fields on AB-stacked bilayers or stacked van der Waals heterostructures. In contrast, transition metal dichalcogenide monolayers are semiconductors with intrinsic in-plane asymmetry, leading to direct electronic bandgaps, distinctive optical properties and great potential in optoelectronics. Apart from their in-plane inversion asymmetry, an additional degree of freedom allowing spin manipulation can be induced by breaking the out-of-plane mirror symmetry with external electric fields or, as theoretically proposed, with an asymmetric out-of-plane structural configuration. Here, we report a synthetic strategy to grow Janus monolayers of transition metal dichalcogenides breaking the out-of-plane structural symmetry. In particular, based on a MoS2 monolayer, we fully replace the top-layer S with Se atoms. We confirm the Janus structure of MoSSe directly by means of scanning transmission electron microscopy and energy-dependent X-ray photoelectron spectroscopy, and prove the existence of vertical dipoles by second harmonic generation and piezoresponse force microscopy measurements.

  8. Transition Metal Catalysis Using Functionalized Dendrimers.

    Science.gov (United States)

    Oosterom, G. Eric; Reek, Joost N. H.; Kamer, Paul C. J.; van Leeuwen, Piet W. N. M.

    2001-05-18

    Dendrimers are well-defined hyperbranched macromolecules with characteristic globular structures for the larger systems. These novel polymers have inspired many chemists to develop new materials and several applications have been explored, catalysis being one of them. The recent impressive strides in synthetic procedures increased the accessibility of functionalized dendrimers, resulting in a rapid development of dendrimer chemistry. The position of the catalytic site(s) as well as the spatial separation of the catalysts appears to be of crucial importance. Dendrimers that are functionalized with transition metals in the core potentially can mimic the properties of enzymes, their efficient natural counterparts, whereas the surface-functionalized systems have been proposed to fill the gap between homogeneous and heterogeneous catalysis. This might yield superior catalysts with novel properties, that is, special reactivity or stability. Both the core and periphery strategies lead to catalysts that are sufficiently larger than most substrates and products, thus separation by modern membrane separation techniques can be applied. These novel homogeneous catalysts can be used in continuous membrane reactors, which will have major advantages particularly for reactions that benefit from low substrate concentrations or suffer from side reactions of the product. Here we review the recent progress and breakthroughs made with these promising novel transition metal functionalized dendrimers that are used as catalysts, and we will discuss the architectural concepts that have been applied.

  9. Earth Science Markup Language: Transitioning From Design to Application

    Science.gov (United States)

    Moe, Karen; Graves, Sara; Ramachandran, Rahul

    2002-01-01

    The primary objective of the proposed Earth Science Markup Language (ESML) research is to transition from design to application. The resulting schema and prototype software will foster community acceptance for the "define once, use anywhere" concept central to ESML. Supporting goals include: 1. Refinement of the ESML schema and software libraries in cooperation with the user community. 2. Application of the ESML schema and software libraries to a variety of Earth science data sets and analysis tools. 3. Development of supporting prototype software for enhanced ease of use. 4. Cooperation with standards bodies in order to assure ESML is aligned with related metadata standards as appropriate. 5. Widespread publication of the ESML approach, schema, and software.

  10. Peruvian perovskite Between Transition-metal to PGM/PlatinumGroupMetal Catalytic Fusion

    Science.gov (United States)

    Maksoed, Wh-

    2016-11-01

    Strongly correlated electronic materials made of simple building blocks, such as a transition-metal ion in an octahedral oxygen cage forming a perovskite structure- Dagotto & Tokura for examples are the high-temperature superconductivity & the CMR/Colossal Magnetoresistance . Helium-4 denotes from LC Case,ScD: "Catalytic Fusion of Deuterium into Helium-4"- 1998 dealt with gaseous D2- "contacted with a supported metallic catalyst at superatmospheric pressure". The catalyst is a platinum-group metal, at about 0.5% - 1% by weight, on activated C. Accompanies Stephen J Geier, 2010 quotes "transition metal complexes", the Energy thus produced is enormous, and because the deuterium is very cheap in the form of heavy water (less than US 1/g), the fuel cost is very low (<<1 %/KwH). "The oceans contain enough deuterium to satisfy the Earth's energy needs for many millions of year" to keep "maria"/Latin name of seas &Deuteronomy to be eternally preserves. Heartfelt Gratitudes to HE. Mr. Prof. Ir. HANDOJO.

  11. Electrons and Spin Waves in Heavy Rare Earth Metals

    DEFF Research Database (Denmark)

    Mackintosh, A. R.

    1972-01-01

    Although the main principles governing the magnetic interactions and magnetic ordering in rare earth metals have been qualitatively understood for some time, it is only relatively recently that a sufficiently detailed study has been made of their electronic and magnetic excitations to place this ...

  12. Recognition- and reactivity-based fluorescent probes for studying transition metal signaling in living systems.

    Science.gov (United States)

    Aron, Allegra T; Ramos-Torres, Karla M; Cotruvo, Joseph A; Chang, Christopher J

    2015-08-18

    Metals are essential for life, playing critical roles in all aspects of the central dogma of biology (e.g., the transcription and translation of nucleic acids and synthesis of proteins). Redox-inactive alkali, alkaline earth, and transition metals such as sodium, potassium, calcium, and zinc are widely recognized as dynamic signals, whereas redox-active transition metals such as copper and iron are traditionally thought of as sequestered by protein ligands, including as static enzyme cofactors, in part because of their potential to trigger oxidative stress and damage via Fenton chemistry. Metals in biology can be broadly categorized into two pools: static and labile. In the former, proteins and other macromolecules tightly bind metals; in the latter, metals are bound relatively weakly to cellular ligands, including proteins and low molecular weight ligands. Fluorescent probes can be useful tools for studying the roles of transition metals in their labile forms. Probes for imaging transition metal dynamics in living systems must meet several stringent criteria. In addition to exhibiting desirable photophysical properties and biocompatibility, they must be selective and show a fluorescence turn-on response to the metal of interest. To meet this challenge, we have pursued two general strategies for metal detection, termed "recognition" and "reactivity". Our design of transition metal probes makes use of a recognition-based approach for copper and nickel and a reactivity-based approach for cobalt and iron. This Account summarizes progress in our laboratory on both the development and application of fluorescent probes to identify and study the signaling roles of transition metals in biology. In conjunction with complementary methods for direct metal detection and genetic and/or pharmacological manipulations, fluorescent probes for transition metals have helped reveal a number of principles underlying transition metal dynamics. In this Account, we give three recent

  13. Magnetic endohedral transition-metal-doped semiconducting-nanoclusters.

    Science.gov (United States)

    Matxain, Jon M; Formoso, Elena; Mercero, Jose M; Piris, Mario; Lopez, Xabier; Ugalde, Jesus M

    2008-01-01

    Endohedral first-row transition-metal-doped TM@Zn(i)S(i) nanoclusters, in which TM stands for the first-row transition-metals from Sc to Zn, and i=12, 16, have been characterized. In these structures the dopant metals are trapped inside spheroidal hollow semiconducting nanoclusters. It is observed that some of the transition metals are trapped in the center of mass of the cluster, whereas others are found to be displaced from that center, leading to structures in which the transition metals display a complex dynamical behavior upon encapsulation. This fact was confirmed by quantum molecular dynamics calculations, which further confirmed the thermal stability of endohedral compounds. In the endohedrally-doped nanoclusters in which the transition-metal atom sits on the center of mass, the host hollow cluster structure remains undistorted after dopant encapsulation. Conversely, if the encapsulated transition-metal atom is displaced from the center of mass, the host hollow cluster structure suffers a very tiny distortion. Additionally, it is found that there is negligible charge transfer between the dopant transition-metal atom and its hollow cluster host and, after encapsulation, the spin densities remain localized on the transition-metal atom. This allows for the atomic-like behavior of the trapped transition-metal atom, which gives rise to their atomic-like magnetic properties. The encapsulation free energies are negative, suggesting that these compounds are thermodynamically stable.

  14. Temperate Earth-sized planets transiting a nearby ultracool dwarf star

    Science.gov (United States)

    Gillon, Michaël; Jehin, Emmanuël; Lederer, Susan M.; Delrez, Laetitia; de Wit, Julien; Burdanov, Artem; Van Grootel, Valérie; Burgasser, Adam; Triaud, Amaury H. M. J.; Opitom, Cyrielle; Demory, Brice-Olivier; Sahu, Devendra K.; Bardalez Gagliuffi, Daniella; Magain, Pierre; Queloz, Didier

    2017-01-01

    Stellar-like objects with effective temperatures of 2700K and below are referred to as “ultracool dwarfs”1. This heterogeneous group includes both extremely low-mass stars and brown dwarfs (substellar objects not massive enough to sustain hydrogen fusion), and represents about 15% of the stellar-like objects in the vicinity of the Sun2. Based on the small masses and sizes of their protoplanetary disks3,4, core-accretion theory for ultracool dwarfs predicts a large, but heretofore undetected population of close-in terrestrial planets5, ranging from metal-rich Mercury-sized planets6 to more hospitable volatile-rich Earth-sized planets7. Here we report the discovery of three short-period Earth-sized planets transiting an ultracool dwarf star 12 parsecs away using data collected by the TRAPPIST8 telescope as part of an ongoing prototype transit survey9. The inner two planets receive four and two times the irradiation of Earth, respectively, placing them close to the inner edge of the habitable zone of the star10. Eleven orbits remain possible for the third planet based on our data, the most likely resulting in an irradiation significantly smaller than Earth's. The infrared brightness of the host star combined with its Jupiter-like size offer the possibility of thoroughly characterizing the components of this nearby planetary system. PMID:27135924

  15. High pressure behavior of 3d transition metal carbonates

    Science.gov (United States)

    Farfan, G. A.; Wang, S.; Boulard, E.; Mao, W. L.

    2012-12-01

    Understanding the behavior of carbon-rich phases in Earth's lower mantle is critical for modeling the global carbon cycle since the lower mantle may be the major repository for carbon in our planet. We were interested in the behavior of carbonates containing 3d transition metals, which can exhibit unusual properties at extreme conditions. Thus, we studied siderite (FeCO3) and rhodochrosite (MnCO3) at high pressure using a diamond anvil cell coupled with Raman spectroscopy, X-ray diffraction (XRD) and X-ray emission spectroscopy. In siderite we observed a high to low spin transition and associated volume collapse at approximately 46 GPa which is consistent with previous reports. Our Raman data show that the C-O bonds soften when the Fe2+ volume collapses (Farfan et al, 2012). In contrast, our XES results indicate that the Mn2+ in rhodochrosite does not undergo a spin transition like siderite up to 50 GPa. We observed a new Raman peak emerging above 48 GPa, which is a similar pressure at which a new structure was found in a previous XRD study.

  16. Electronic entanglement in late transition metal oxides.

    Science.gov (United States)

    Thunström, Patrik; Di Marco, Igor; Eriksson, Olle

    2012-11-01

    We present a study of the entanglement in the electronic structure of the late transition metal monoxides--MnO, FeO, CoO, and NiO--obtained by means of density-functional theory in the local density approximation combined with dynamical mean-field theory. The impurity problem is solved through exact diagonalization, which grants full access to the thermally mixed many-body ground state density operator. The quality of the electronic structure is affirmed through a direct comparison between the calculated electronic excitation spectrum and photoemission experiments. Our treatment allows for a quantitative investigation of the entanglement in the electronic structure. Two main sources of entanglement are explicitly resolved through the use of a fidelity based geometrical entanglement measure, and additional information is gained from a complementary entropic entanglement measure. We show that the interplay of crystal field effects and Coulomb interaction causes the entanglement in CoO to take a particularly intricate form.

  17. Recovery of rare earth metals through biosorption:An overview

    Institute of Scientific and Technical Information of China (English)

    Nilanjana Das; Devlina Das

    2013-01-01

    Rare earth metals (REMs) are a series of 17 elements that have widespread and unique applications in high technology, power generation, communications, and defense industries. These resources are also pivotal to emergent sustainable energy and car-bon alternative technologies. Recovery of REMs is interesting due to its high market prices along with various industrial applications. Conventional technologies, viz. precipitation, filtration, liquid-liquid extraction, solid-liquid extraction, ion exchange, super critical extraction, electrowinning, electrorefining, electroslag refining, etc., which have been developed for the recovery of REMs, are not economically attractive. Biosorption represents a biotechnological innovation as well as a cost effective excellent tool for the recovery of rare earth metals from aqueous solutions. A variety of biomaterials such as algae, fungi, bacteria, resin, activated carbon, etc., have been reported to serve as potential adsorbents for the recovery of REMs. The metal binding mechanisms, as well as the parameters in-fluencing the uptake of rare earth metals and isotherm modeling are presented here. This article provides an overview of past achievements and current scenario of the biosorption studies carried out using some promising biosorbents which could serve as an economical means for recovering REMs. The experimental findings reported by different workers will provide insights into this re-search frontier.

  18. Chemoselective single-site Earth-abundant metal catalysts at metal-organic framework nodes

    Science.gov (United States)

    Manna, Kuntal; Ji, Pengfei; Lin, Zekai; Greene, Francis X.; Urban, Ania; Thacker, Nathan C.; Lin, Wenbin

    2016-08-01

    Earth-abundant metal catalysts are critically needed for sustainable chemical synthesis. Here we report a simple, cheap and effective strategy of producing novel earth-abundant metal catalysts at metal-organic framework (MOF) nodes for broad-scope organic transformations. The straightforward metalation of MOF secondary building units (SBUs) with cobalt and iron salts affords highly active and reusable single-site solid catalysts for a range of organic reactions, including chemoselective borylation, silylation and amination of benzylic C-H bonds, as well as hydrogenation and hydroboration of alkenes and ketones. Our structural, spectroscopic and kinetic studies suggest that chemoselective organic transformations occur on site-isolated, electron-deficient and coordinatively unsaturated metal centres at the SBUs via σ-bond metathesis pathways and as a result of the steric environment around the catalytic site. MOFs thus provide a novel platform for the development of highly active and affordable base metal catalysts for the sustainable synthesis of fine chemicals.

  19. Density functional theory based screening of ternary alkali-transition metal borohydrides: A computational material design project

    DEFF Research Database (Denmark)

    Hummelshøj, Jens Strabo; Landis, David; Voss, Johannes

    2009-01-01

    We present a computational screening study of ternary metal borohydrides for reversible hydrogen storage based on density functional theory. We investigate the stability and decomposition of alloys containing 1 alkali metal atom, Li, Na, or K (M1); and 1 alkali, alkaline earth or 3d/4d transition...

  20. Solution thermodynamics of rare-earth metal ions - physicochemical study-

    Energy Technology Data Exchange (ETDEWEB)

    Amerkhanova, Sh K; Shlyapov, R M; Uali, A S [Buketov Karaganda state university, University str., 28, Karaganda, 100028 (Kazakhstan)], E-mail: amerkhanova_sh@mail.ru

    2009-02-01

    The results of the studying of interactions in multicomponent systems 'polyvinyl alcohol (PVA) - rare-earth element ion - nitrate of sodium - water' are represented. It is established that for rubidium (I) ions temperature and ionic strength is render destroying action, and for yttrium (III) ions the influence of these factors has return character which is connected with features of an electronic structure of metal ion. It is revealed that a dominating role of non-electrostatic formation composed, hence, the formation of donor-acceptor connection of 'metal - ligand' occurs through atom of oxygen.

  1. Luminescence enhancement of rare earth ions by metal nanostructures

    Institute of Scientific and Technical Information of China (English)

    G.A.Denisenko

    2009-01-01

    Well-ordered metal structures,i.e.arrays of nanosized tips on silver surface for studies of the luminescence enhancement of absorbed media with rare earth ions were used.These arrays were prepared by the metal evaporation on track membranes.Calculations of resonance frequencies of tips regarded as semispheroids were done taking into account the interaction between dipoles of tips.They were used to discuss experimental results for media with Eu(NO3)3·6H2O salt basing on data for bulk silver dielectric function.

  2. Electronic Structure of Rare-Earth Metals. II. Positron Annihilation

    DEFF Research Database (Denmark)

    Williams, R. W.; Mackintosh, Allan

    1968-01-01

    The angular correlation of the photons emitted when positrons annihilate with electrons has been studied in single crystals of the rare-earth metals Y, Gd, Tb, Dy, Ho, and Er, and in a single crystal of an equiatomic alloy of Ho and Er. A comparison of the results for Y with the calculations...... of Loucks shows that the independent-particle model gives a good first approximation to the angular distribution, although correlation effects probably smear out some of the structure. The angular distributions from the heavy rare-earth metals are very similar to that from Y and can be understood...... qualitatively in terms of the relativistic augmented-plane-wave calculations by Keeton and Loucks. The angular distributions in the c direction in the paramagnetic phases are characterized by a rapid drop at low angles followed by a hump, and these features are associated with rather flat regions of Fermi...

  3. Nanostructured transition metal oxides useful for water oxidation catalysis

    Science.gov (United States)

    Frei, Heinz M; Jiao, Feng

    2013-12-24

    The present invention provides for a composition comprising a nanostructured transition metal oxide capable of oxidizing two H.sub.2O molecules to obtain four protons. In some embodiments of the invention, the composition further comprises a porous matrix wherein the nanocluster of the transition metal oxide is embedded on and/or in the porous matrix.

  4. Trends in Ionization Energy of Transition-Metal Elements

    Science.gov (United States)

    Matsumoto, Paul S.

    2005-01-01

    A rationale for the difference in the periodic trends in the ionization energy of the transition-metal elements versus the main-group elements is presented. The difference is that in the transition-metal elements, the electrons enter an inner-shell electron orbital, while in the main-group elements, the electrons enter an outer-shell electron…

  5. Surface segregation energies in transition-metal alloys

    DEFF Research Database (Denmark)

    Ruban, Andrei; Skriver, Hans Lomholt; Nørskov, Jens Kehlet

    1999-01-01

    We present a database of 24 x 24 surface segregation energies of single transition metal impurities in transition-metal hosts obtained by a Green's-function linear-muffin-tin-orbitals method in conjunction with the coherent potential and atomic sphere approximations including a multipole correction...

  6. Isotopic fractionation of alkali earth metals during carbonate precipitation

    Science.gov (United States)

    Yotsuya, T.; Ohno, T.; Muramatsu, Y.; Shimoda, G.; Goto, K. T.

    2014-12-01

    The alkaline earth metals such as magnesium, calcium and strontium play an important role in a variety of geochemical and biological processes. The element ratios (Mg/Ca and Sr/Ca) in marine carbonates have been used as proxies for reconstruction of the past environment. Recently several studies suggested that the study for the isotopic fractionation of the alkaline earth metals in marine carbonates has a potentially significant influence in geochemical research fields (e.g. Eisenhauer et al., 2009). The aim of this study is to explore the influence of carbonate polymorphs (Calcite and Aragonite) and environmental factors (e.g., temperature, precipitation rate) on the level of isotopic fractionation of the alkaline earth metals. We also examined possible correlations between the level of isotopic fractionation of Ca and that of other alkaline earth metals during carbonate precipitation. In order to determine the isotope fractionation factor of Mg, Ca and Sr during carbonate precipitation, calcite and aragonite were synthesized from calcium bicarbonate solution in which the amount of magnesium was controlled based on Kitano method. Calcium carbonates were also prepared from the mixture of calcium chlorite and sodium hydrogen carbonate solutions. The isotope fractionation factors were measured by MC-ICPMS. Results suggested that the level of isotopic fractionation of Mg during carbonate precipitation was correlated with that of Sr and that the change of the carbonate crystal structure could make differences of isotopic fractionations of Mg and Ca, however no difference was found in the case of Sr. In this presentation, the possible mechanism will be discussed.

  7. Metal sulfide and rare-earth phosphate nanostructures and methods of making same

    Science.gov (United States)

    Wong, Stanislaus; Zhang, Fen

    2016-06-28

    The present invention provides a method of producing a crystalline rare earth phosphate nanostructure. The method comprising: providing a rare earth metal precursor solution and providing a phosphate precursor solution; placing a porous membrane between the metal precursor solution and the phosphate precursor solution, wherein metal cations of the metal precursor solution and phosphate ions of the phosphate precursor solution react, thereby producing a crystalline rare earth metal phosphate nanostructure.

  8. Nutritional immunity: transition metals at the pathogen-host interface.

    Science.gov (United States)

    Hood, M Indriati; Skaar, Eric P

    2012-07-16

    Transition metals occupy an essential niche in biological systems. Their electrostatic properties stabilize substrates or reaction intermediates in the active sites of enzymes, and their heightened reactivity is harnessed for catalysis. However, this heightened activity also renders transition metals toxic at high concentrations. Bacteria, like all living organisms, must regulate their intracellular levels of these elements to satisfy their physiological needs while avoiding harm. It is therefore not surprising that the host capitalizes on both the essentiality and toxicity of transition metals to defend against bacterial invaders. This Review discusses established and emerging paradigms in nutrient metal homeostasis at the pathogen-host interface.

  9. Critical behavior in the hydrogen insulator-metal transition

    Science.gov (United States)

    Hemley, R. J.; Mao, H. K.

    1990-01-01

    The vibrational Raman spectrum of solid hydrogen has been measured from 77 to 295 K in the vicinity of the recently observed insulator-metal transition and low-temperature phase transition at 150 gigapascals. The measurements provide evidence for a critical point in the pressure-temperature phase boundary of the low-temperature transition. The result suggests that below the critical temperature the insulator-metal transition changes from continuous to discontinuous, consistent with the general criteria originally proposed by Mott (1949) for metallization by band-gap closure. The effect of temperature on hydrogen metallization closely resembles that of the lower-pressure insulator-metal transitions in doped V2O3 alloys.

  10. Three 2012 Transits of Venus: From Earth, Jupiter, and Saturn

    Science.gov (United States)

    Pasachoff, Jay M.; Schneider, G.; Babcock, B. A.; Lu, M.; Edelman, E.; Reardon, K.; Widemann, T.; Tanga, P.; Dantowitz, R.; Silverstone, M. D.; Ehrenreich, D.; Vidal-Madjar, A.; Nicholson, P. D.; Willson, R. C.; Kopp, G. A.; Yurchyshyn, V. B.; Sterling, A. C.; Scherrer, P. H.; Schou, J.; Golub, L.; McCauley, P.; Reeves, K.

    2013-01-01

    We observed the 2012 June 6/5 transit seen from Earth (E/ToV), simultaneously with Venus Express and several other spacecraft not only to study the Cytherean atmosphere but also to provide an exoplanet-transit analog. From Haleakala, the whole transit was visible in coronal skies; among our instruments was one of the world-wide Venus Twilight Experiment's nine coronagraphs. Venus's atmosphere became visible before first contact. SacPeak/IBIS provided high-resolution images at Hα/carbon-dioxide. Big Bear's NST also provided high-resolution observations of the Cytherean atmosphere and black-drop evolution. Our liaison with UH's Mees Solar Observatory scientists provided magneto-optical imaging at calcium and potassium. Solar Dynamics Observatory's AIA and HMI, and the Solar Optical Telescope (SOT) and X-ray Telescope (XRT) on Hinode, and total-solar-irradiance measurements with ACRIMSAT and SORCE/TIM, were used to observe the event as an exoplanet-transit analog. On September 20, we imaged Jupiter for 14 Hubble Space Telescope orbits, centered on a 10-hour ToV visible from Jupiter (J/ToV), as an exoplanet-transit analog in our own solar system, using Jupiter as an integrating sphere. Imaging was good, although much work remains to determine if we can detect the expected 0.01% solar irradiance decrease at Jupiter and the even slighter differential effect between our violet and near-infrared filters caused by Venus's atmosphere. We also give a first report on our currently planned December 21 Cassini UVIS observations of a transit of Venus from Saturn (S/ToV). Our E/ToV expedition was sponsored by the Committee for Research and Exploration/National Geographic Society; supplemented: NASA/AAS's Small Research Grant Program. We thank Rob Ratkowski, Stan Truitt, Rob Lucas, Aram Friedman, and Eric Pilger '82 at Haleakala, and Joseph Gangestad '06 at Big Bear for assistance, and Lockheed Martin Solar and Astrophysics Lab and Hinode science and operations teams for support

  11. Temperate Earth-sized planets transiting a nearby ultracool dwarf star.

    Science.gov (United States)

    Gillon, Michaël; Jehin, Emmanuël; Lederer, Susan M; Delrez, Laetitia; de Wit, Julien; Burdanov, Artem; Van Grootel, Valérie; Burgasser, Adam J; Triaud, Amaury H M J; Opitom, Cyrielle; Demory, Brice-Olivier; Sahu, Devendra K; Bardalez Gagliuffi, Daniella; Magain, Pierre; Queloz, Didier

    2016-05-12

    Star-like objects with effective temperatures of less than 2,700 kelvin are referred to as 'ultracool dwarfs'. This heterogeneous group includes stars of extremely low mass as well as brown dwarfs (substellar objects not massive enough to sustain hydrogen fusion), and represents about 15 per cent of the population of astronomical objects near the Sun. Core-accretion theory predicts that, given the small masses of these ultracool dwarfs, and the small sizes of their protoplanetary disks, there should be a large but hitherto undetected population of terrestrial planets orbiting them--ranging from metal-rich Mercury-sized planets to more hospitable volatile-rich Earth-sized planets. Here we report observations of three short-period Earth-sized planets transiting an ultracool dwarf star only 12 parsecs away. The inner two planets receive four times and two times the irradiation of Earth, respectively, placing them close to the inner edge of the habitable zone of the star. Our data suggest that 11 orbits remain possible for the third planet, the most likely resulting in irradiation significantly less than that received by Earth. The infrared brightness of the host star, combined with its Jupiter-like size, offers the possibility of thoroughly characterizing the components of this nearby planetary system.

  12. The Intriguing Properties of Transition Metal Oxides

    Science.gov (United States)

    Hoch, Michael J. R.

    2007-05-01

    Since the discovery of high-temperature superconductivity in the cuprates twenty years ago, there has been a resurgence of interest in the transition metal oxides. Work on these systems has been driven both by the fascinating properties that these materials exhibit and by potential applications in technology. A brief general review of the perovskites and their electronic structures is given. This is followed by a discussion of the properties of magnetic oxide systems ABO3 (A=La; B=Mn or Co), specifically focusing on the doped manganites (e.g. La1-x SrxMnO3) and cobaltites (e.g. La1-xSrxCoO3), in which mixed valence states and double exchange are important. Competing electron localizing and delocalizing effects result in rich phase diagrams and interesting transport properties with large magnetoresistance effects. Nanoscale phase separation has been found for a range of x values using a variety of techniques, such as nuclear magnetic resonance and neutron scattering. These discoveries have provided an increased understanding of the role of the interacting magnetic, electronic and lattice structures in these systems.

  13. Energetic characteristics of transition metal complexes.

    Science.gov (United States)

    Wojewódka, Andrzej; Bełzowski, Janusz; Wilk, Zenon; Staś, Justyna

    2009-11-15

    Ten transition metal nitrate and perchlorate complexes of hydrazine and ethylenediamine were synthesized, namely [Cu(EN)(2)](ClO(4))(2), [Co(EN)(3)](ClO(4))(3), [Ni(EN)(3)](ClO(4))(2), [Hg(EN)(2)](ClO(4))(2), [Cr(N(2)H(4))(3)](ClO(4))(3), [Cd(N(2)H(4))(3)](ClO(4))(2), [Ni(N(2)H(4))(3)](NO(3))(2), [Co(N(2)H(4))(3)](NO(3))(3), [Zn(N(2)H(4))(3)](NO(3))(2), and [Cd(N(2)H(4))(3)](NO(3))(2) based on the lines of the literature reported methods. All of them were tested with applying underwater detonation test and further compared to the typical blasting explosives: RDX, HMX, TNT and PETN. From the above presented complexes [Ni(N(2)H(4))(3)](NO(3))(2) (called NHN) and [Co(N(2)H(4))(3)](NO(3))(3) (called CoHN) are known as primary explosives and can be used as the standard explosives. Explosion parameters, such as shock wave overpressure, shock wave energy equivalent and bubble energy equivalent, were determined. Evaluated energetic characteristics of the tested compounds are comparable to those of the classic high explosives and are even enhanced in some cases.

  14. Transition metal-free olefin polymerization catalyst

    Science.gov (United States)

    Sen, Ayusman; Wojcinski, II, Louis M.; Liu, Shengsheng

    2001-01-01

    Ethylene and/or propylene are polymerized to form high molecular weight, linear polymers by contacting ethylene and/or propylene monomer, in the presence of an inert reaction medium, with a catalyst system which consists essentially of (1) an aluminum alkyl component, such as trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-octylaluminum and diethylaluminum hydride and (2) a Lewis acid or Lewis acid derivative component, such as B (C.sub.6 F.sub.5).sub.3, [(CH.sub.3).sub.2 N (H) (C.sub.6 H.sub.5)].sup.+ [B (C.sub.6 F.sub.5)4].sup.-, [(C.sub.2 H.sub.5).sub.3 NH].sup.+ [B C.sub.6 F.sub.5).sub.4 ],.sup.-, [C(C.sub.6 F.sub.5).sub.3 ].sup.+ [B(C.sub.6 F.sub.5).sub.4 ].sup.-, (C.sub.2 H.sub.5).sub.2 Al(OCH.sub.3), (C.sub.2 H.sub.5).sub.2 Al(2,6-di-t-butyl-4-methylphenoxide), (C.sub.2 H.sub.5)Al(2,6 -di-t-butylphenoxide).sub.2, (C.sub.2 H.sub.5).sub.2 Al(2,6-di-t-butylphonoxide) , 2,6 -di-t-butylphenol.multidot.methylaluminoxane or an alkylaluminoxane, and which may be completely free any transition metal component(s).

  15. Transition-Metal Hydride Radical Cations.

    Science.gov (United States)

    Hu, Yue; Shaw, Anthony P; Estes, Deven P; Norton, Jack R

    2016-08-10

    Transition-metal hydride radical cations (TMHRCs) are involved in a variety of chemical and biochemical reactions, making a more thorough understanding of their properties essential for explaining observed reactivity and for the eventual development of new applications. Generally, these species may be treated as the ones formed by one-electron oxidation of diamagnetic analogues that are neutral or cationic. Despite the importance of TMHRCs, the generally sensitive nature of these complexes has hindered their development. However, over the last four decades, many more TMHRCs have been synthesized, characterized, isolated, or hypothesized as reaction intermediates. This comprehensive review focuses on experimental studies of TMHRCs reported through the year 2014, with an emphasis on isolated and observed species. The methods used for the generation or synthesis of TMHRCs are surveyed, followed by a discussion about the stability of these complexes. The fundamental properties of TMHRCs, especially those pertaining to the M-H bond, are described, followed by a detailed treatment of decomposition pathways. Finally, reactions involving TMHRCs as intermediates are described.

  16. Solid-solid phase transitions via melting in metals

    Science.gov (United States)

    Pogatscher, S.; Leutenegger, D.; Schawe, J. E. K.; Uggowitzer, P. J.; Löffler, J. F.

    2016-04-01

    Observing solid-solid phase transitions in-situ with sufficient temporal and spatial resolution is a great challenge, and is often only possible via computer simulations or in model systems. Recently, a study of polymeric colloidal particles, where the particles mimic atoms, revealed an intermediate liquid state in the transition from one solid to another. While not yet observed there, this finding suggests that such phenomena may also occur in metals and alloys. Here we present experimental evidence for a solid-solid transition via the formation of a metastable liquid in a `real' atomic system. We observe this transition in a bulk glass-forming metallic system in-situ using fast differential scanning calorimetry. We investigate the corresponding transformation kinetics and discuss the underlying thermodynamics. The mechanism is likely to be a feature of many metallic glasses and metals in general, and may provide further insight into phase transition theory.

  17. The local structure of transition metal doped semiconducting boron carbides

    Energy Technology Data Exchange (ETDEWEB)

    Liu Jing; Dowben, P A [Department of Physics and Astronomy and the Nebraska Center for Materials and Nanoscience, Behlen Laboratory of Physics, University of Nebraska-Lincoln, PO Box 880111, Lincoln, NE 68588-0111 (United States); Luo Guangfu; Mei Waining [Department of Physics, University of Nebraska at Omaha, Omaha, NE 68182-0266 (United States); Kizilkaya, Orhan [J. Bennett Johnston Sr. Center for Advanced Microstructures and Devices, Louisiana State University, 6980 Jefferson Hwy., Baton Rouge LA 70806 (United States); Shepherd, Eric D; Brand, J I [College of Engineering, and the Nebraska Center for Materials and Nanoscience, N209 Walter Scott Engineering Center, 17th and Vine Streets, University of Nebraska-Lincoln, Lincoln, NE 68588-0511 (United States)

    2010-03-03

    Transition metal doped boron carbides produced by plasma enhanced chemical vapour deposition of orthocarborane (closo-1,2-C{sub 2}B{sub 10}H{sub 12}) and 3d metal metallocenes were investigated by performing K-edge extended x-ray absorption fine structure and x-ray absorption near edge structure measurements. The 3d transition metal atom occupies one of the icosahedral boron or carbon atomic sites within the icosahedral cage. Good agreement was obtained between experiment and models for Mn, Fe and Co doping, based on the model structures of two adjoined vertex sharing carborane cages, each containing a transition metal. The local spin configurations of all the 3d transition metal doped boron carbides, Ti through Cu, are compared using cluster and/or icosahedral chain calculations, where the latter have periodic boundary conditions.

  18. Model for continuous thermal metal to insulator transition

    Science.gov (United States)

    Jian, Chao-Ming; Bi, Zhen; Xu, Cenke

    2017-09-01

    We propose a d -dimensional interacting Majorana fermion model with quenched disorder, which gives us a continuous quantum phase transition between a diffusive thermal metal phase with a finite entropy density to an insulator phase with zero entropy density. This model is based on coupled Sachdev-Ye-Kitaev model clusters, and hence has a controlled large-N limit. The metal-insulator transition is accompanied by a spontaneous time-reversal symmetry breaking. We perform controlled calculations to show that the energy diffusion constant jumps to zero discontinuously at the metal-insulator transition, while the time-reversal symmetry-breaking order parameter increases continuously.

  19. Controlled charge exchange between alkaline earth metals and their ions

    Science.gov (United States)

    Gacesa, Marko; Côté, Robin

    2015-05-01

    We theoretically investigate the prospects of realizing controlled charge exchange via magnetic Feshbach resonances in cold and ultracold collisions of atoms and ions. In particular, we focus on near-resonant charge exchange in heteroisotopic combinations of alkaline earth metals, such as 9Be++10 Be9 Be+10Be+ , which exhibit favorable electronic and hyperfine structure. The quantum scattering calculations are performed for a range of initial states and experimentally attainable magnetic fields in standard coupled-channel Feshbach projection formalism, where higher-order corrections such as the mass-polarization term are explicitely included. In addition, we predict a number of magnetic Feshbach resonances for different heteronuclear isotopic combinations of the listed and related alkaline earth elements. Our results imply that near-resonant charge-exchange could be used to realize atom-ion quantum gates, as well as controlled charge transfer in optically trapped cold quantum gases. This work is partially supported by ARO.

  20. Catalysis by alkali and alkaline-earth metal ions in nucleophilic attack of methoxide ion on crown ethers bearing an intra-annular acetoxy group

    NARCIS (Netherlands)

    Cacciapaglia, Roberta; Lucente, Silvia; Mandolini, Luigi; Doorn, van Arie R.; Reinhoudt, David N.; Verboom, Willem

    1989-01-01

    Rates of reaction of methoxide ion with crown ethers bearing an intra-annular acetoxy group are markedly enhanced by alkali and alkaline-earth metal bromides as a result of much stronger interactions of the metal ions with transition states than with reactants. Rates of reactions of methoxide ion w

  1. Ultrafast Transient Absorption Spectroscopy of Polymer-Based Organophotoredox Catalysts Mimicking Transition-Metal Complexes

    Science.gov (United States)

    Jamhawi, Abdelqader; Paul, Anam C.; Smith, Justin D.; Handa, Sachin; Liu, Jinjun

    2017-06-01

    Transition-metal complexes of rare earth metals including ruthenium and iridium are most commonly employed as visible-light photocatalysts. Despite their highly important and broad applications, they have many disadvantages including high cost associated with low abundance in earth crust, potential toxicity, requirement of specialized ligands for desired activity, and difficulty in recycling of metal contents as well as associated ligands. Polymer-based organophotoredox catalysts are promising alternatives and possess unique advantages such as easier synthesis from inexpensive starting material, longer excited state life time, broad range of activity, sustainability, and recyclability. In this research talk, time-resolved photoluminescence and femtosecond transient absorption (TA) spectroscopy measurements of three novel polymer-based organophotoredox catalysts will be presented. By our synthetic team, their catalytic activity has been proven in some highly valuable chemical transformations, that otherwise require transition metal complexes. Time-resolved spectroscopic investigations have demonstrated that photoinduced processes in these catalysts are similar to the transition metal complexes. Especially, intramolecular vibrational relaxation, internal conversion, and intersystem crossing from the S1 state to the T1 state all occur on a sub-picosecond timescale. The long lifetime of the T1 state ( 2-3 microsecond) renders these polymers potent oxidizing and reducing agents. A spectroscopic and kinetic model has been developed for global fitting of TA spectra in both the frequency and time domains. Implication of the current ultrafast spectroscopy studies of these novel molecules to their roles in photocatalysis will be discussed.

  2. Tethered Transition Metals Promoted Photocatalytic System for Efficient Hydrogen Evolutions

    KAUST Repository

    Takanabe, Kazuhiro

    2015-03-05

    The present invention is directed, at least in part, to a process for improving the efficiency of a photocatalyst (a semiconductor photocatalyst) by tethering (depositing) a metal (e.g., metal ions of a late transition metal, such as nickel) to the semiconductor (photocatalyst) surface through the use of an organic ligand. More specifically, 1,2-ethanedithiol (EDT) functions as an excellent molecular linker (organic ligand) to attach a transition metal complex (e.g., nickel (Ni.sup.2+ ions)) to the semiconductor surface, which can be in the form of a cadmium sulfide surface. The photocatalyst has particular utility in generating hydrogen from H.sub.2S.

  3. Structural variations in layered alkaline earth metal cyclohexyl phosphonates

    Indian Academy of Sciences (India)

    Ramaswamy Murugavel; Nayanmoni Gogoi

    2009-06-01

    Two series of alkaline earth metal cyclohexyl phosphonates, M(C6H11PO3H)2(H2O) (M = Ca, Sr and Ba) (1–3) and M(C6H11PO3)(H2O) (M = Mg, Ca, Sr, and Ba) (4–7) have been synthesized under mild reaction conditions. All new compounds have been characterized using elemental analysis, IR, TGA and powder X-ray diffraction techniques. The molecular structure of compound 2 determined using single crystal X-ray diffraction technique reveals a layered polymeric structure.

  4. Electron-phonon coupling in the rare-earth metals

    DEFF Research Database (Denmark)

    Skriver, Hans Lomholt; Mertig, I.

    1990-01-01

    We have estimated the strength of the mass enhancement of the conduction electrons due to electron-phonon interaction in the rare metals Sc, Y, and La–Lu. The underlying self-consistent energy bands were obtained by means of the scalar relativistic linear-muffin-tin-orbital method, and the electron......-phonon parameters were calculated within the Gaspari-Gyorffy formulation. For the heavier rare earths Gd–Tm spin polarization was included both in the band-structure calculations and in the treatment of the electron-phonon coupling to take into account the spin splitting of the conduction electrons induced by the 4...

  5. Synthesis and luminescence of some rare earth metal complexes

    Science.gov (United States)

    Bochkarev, Mikhail N.; Pushkarev, Anatoly P.

    2016-12-01

    In the present paper the synthesis, photoand electroluminescent properties of new rare earth metal complexes prepared and studied at the Razuvaev Institute of Organometallic Chemistry during the last decade are reviewed. The obtained compounds give luminescence in UV, visible and NIR regions. The substituted phenolates, naphtholates, mercaptobenzothiazolate, 8-oxyquinolinolate, polyfluorinated alcoholates and chalcogenophosphinates were used as ligands. The synthesis and structure of unusual three-nuclear sulfidenitride clusters of Nd and Dy are described. The new excitation mechanism of ytterbium phenolates and naphtholates, which includes the stage of reversible reduction of Yb to divalent state and oxidation of the ligands in the excitation process, is discussed.

  6. Quantum computing with alkaline-Earth-metal atoms.

    Science.gov (United States)

    Daley, Andrew J; Boyd, Martin M; Ye, Jun; Zoller, Peter

    2008-10-24

    We present a complete scheme for quantum information processing using the unique features of alkaline-earth-metal atoms. We show how two completely independent lattices can be formed for the 1S0 and 3P0 states, with one used as a storage lattice for qubits encoded on the nuclear spin, and the other as a transport lattice to move qubits and perform gate operations. We discuss how the 3P2 level can be used for addressing of individual qubits, and how collisional losses from metastable states can be used to perform gates via a lossy blockade mechanism.

  7. The metallicities of stars with and without transiting planets

    DEFF Research Database (Denmark)

    Buchhave, Lars A.; Latham, David W.

    2015-01-01

    Host star metallicities have been used to infer observational constraints on planet formation throughout the history of the exoplanet field. The giant planet metallicity correlation has now been widely accepted, but questions remain as to whether the metallicity correlation extends to the small...... terrestrial-sized planets. Here, we report metallicities for a sample of 518 stars in the Kepler field that have no detected transiting planets and compare their metallicity distribution to a sample of stars that hosts small planets (). Importantly, both samples have been analyzed in a homogeneous manner...... using the same set of tools (Stellar Parameters Classification tool). We find the average metallicity of the sample of stars without detected transiting planets to be and the sample of stars hosting small planets to be . The average metallicities of the two samples are indistinguishable within...

  8. Transit and radial velocity survey efficiency comparison for a habitable zone Earth

    Energy Technology Data Exchange (ETDEWEB)

    Burke, Christopher J. [SETI Institute/NASA Ames Research Center, Moffett Field, CA 94035 (United States); McCullough, P. R., E-mail: christopher.j.burke@nasa.gov [Space Telescope Science Institute, 3700 San Martin Drive, Baltimore, MD 21218 (United States)

    2014-09-01

    Transit and radial velocity searches are two techniques for identifying nearby extrasolar planets to Earth that transit bright stars. Identifying a robust sample of these exoplanets around bright stars for detailed atmospheric characterization is a major observational undertaking. In this study we describe a framework that answers the question of whether a transit or radial velocity survey is more efficient at finding transiting exoplanets given the same amount of observing time. Within the framework we show that a transit survey's window function can be approximated using the hypergeometric probability distribution. We estimate the observing time required for a transit survey to find a transiting Earth-sized exoplanet in the habitable zone (HZ) with an emphasis on late-type stars. We also estimate the radial velocity precision necessary to detect the equivalent HZ Earth-mass exoplanet that also transits when using an equal amount of observing time as the transit survey. We find that a radial velocity survey with σ{sub rv} ∼ 0.6 m s{sup –1} precision has comparable efficiency in terms of observing time to a transit survey with the requisite photometric precision σ{sub phot} ∼ 300 ppm to find a transiting Earth-sized exoplanet in the HZ of late M dwarfs. For super-Earths, a σ{sub rv} ∼ 2.0 m s{sup –1} precision radial velocity survey has comparable efficiency to a transit survey with σ{sub phot} ∼ 2300 ppm.

  9. Temperate Earth-sized planets transiting a nearby ultracool dwarf star

    CERN Document Server

    Gillon, Michael; Lederer, Susan M; Delrez, Laetitia; de Wit, Julien; Burdanov, Artem; Van Grootel, Valerie; Burgasser, Adam J; Triaud, Amaury H M J; Opitom, Cyrielle; Demory, Brice-Olivier; Sahu, Devendra K; Gagliuffi, Daniella Bardalez; Magain, Pierre; Queloz, Didier

    2016-01-01

    Star-like objects with effective temperatures of less than 2,700 kelvin are referred to as ultracool dwarfs. This heterogeneous group includes stars of extremely low mass as well as brown dwarfs (substellar objects not massive enough to sustain hydrogen fusion), and represents about 15 per cent of the population of astronomical objects near the Sun. Core-accretion theory predicts that, given the small masses of these ultracool dwarfs, and the small sizes of their protoplanetary disk, there should be a large but hitherto undetected population of terrestrial planets orbiting them - ranging from metal-rich Mercury-sized planets to more hospitable volatile-rich Earth-sized planets. Here we report observations of three short-period Earth-sized planets transiting an ultracool dwarf star only 12 parsecs away. The inner two planets receive four times and two times the irradiation of Earth, respectively, placing them close to the inner edge of the habitable zone of the star. Our data suggest that 11 orbits remain poss...

  10. Mechanisms of transition-metal gettering in silicon

    Energy Technology Data Exchange (ETDEWEB)

    MYERS JR.,SAMUEL M.; SEIBT,M.; SCHROTER,W.

    2000-03-23

    The atomic process, kinetics, and equilibrium thermodynamics underlying the gettering of transition-metal impurities in Si are reviewed from a mechanistic perspective. Methods for mathematical modeling of gettering are reviewed and illustrated. Needs for further research are discussed.

  11. On metal-insulator transition in cubic fullerides

    Science.gov (United States)

    Iwahara, Naoya; Chibotaru, Liviu

    The interplay between degenerate orbital and electron correlation is a key to characterize the electronic phases in, for example, transition metal compounds and alkali-doped fullerides. Besides, the degenerate orbital couples to spin and lattice degrees of freedom ,giving rise to exotic phenomena. Here, we develop the self-consistent Gutzwiller approach for the simultaneous treatment of the Jahn-Teller effect and electron correlation, and apply the methodology to reveal the nature of the ground electronic state of fullerides. For small Coulomb repulsion on site U, the fulleride is quasi degenerate correlated metal. With increase of U, we found the quantum phase transition from the metallic phase to JT split phase. In the latter, the Mott transition (MT) mainly develops in the half-filled subband, whereas the empty and the completely filled subbands are almost uninvolved. Therefore, we can qualify the metal-insulator transition in fullerides as an orbital selective MT induced by JT effect.

  12. studies on transition metal complexes of herbicidal compounds. ii

    African Journals Online (AJOL)

    a

    II: TRANSITION METAL COMPLEXES OF DERIVATIZED 2-CHLORO-4- ... Several compounds of this class like atrazine, simazine, prometryn, aziprotryn, etc. .... dissolve in water and most of the common polar organic solvents. ... coordination.

  13. Trends in catalytic NO decomposition over transition metal surfaces

    DEFF Research Database (Denmark)

    Falsig, Hanne; Bligaard, Thomas; Rass-Hansen, Jeppe

    2007-01-01

    The formation of NOx from combustion of fossil and renewable fuels continues to be a dominant environmental issue. We take one step towards rationalizing trends in catalytic activity of transition metal catalysts for NO decomposition by combining microkinetic modelling with density functional...... theory calculations. We show specifically why the key problem in using transition metal surfaces to catalyze direct NO decomposition is their significant relative overbinding of atomic oxygen compared to atomic nitrogen....

  14. Transition metal mediated transformations of small molecules

    Energy Technology Data Exchange (ETDEWEB)

    Sen, Ayusman [Pennsylvania State Univ., University Park, PA (United States)

    2017-03-08

    Catalysis at metal centers is of great scientific, as well as practical, importance because of the high efficiency, high specificity, and low energy demands often associated with such systems. The two major themes of our research are (a) the design of metal-based systems for the synthesis of novel classes of polymers and (b) the identification of new metal-catalyzed systems for the conversion of biomass to fuels and chemicals, and related “green” chemical processes.

  15. Homometallic rare-Earth metal phosphinidene clusters: synthesis and reactivity.

    Science.gov (United States)

    Wang, Kai; Luo, Gen; Hong, Jianquan; Zhou, Xigeng; Weng, Linhong; Luo, Yi; Zhang, Lixin

    2014-01-20

    Two new trinuclear μ3 -bridged rare-earth metal phosphinidene complexes, [{L(Ln)(μ-Me)}3 (μ3 -Me)(μ3 -PPh)] (L=[PhC(NC6 H4 iPr2 -2,6)2 ](-) , Ln=Y (2 a), Lu (2 b)), were synthesized through methane elimination of the corresponding carbene precursors with phenylphosphine. Heating a toluene solution of 2 at 120 °C leads to an unprecedented ortho CH bond activation of the PhP ligand to form the bridged phosphinidene/phenyl complexes. Reactions of 2 with ketones, thione, or isothiocyanate show clear phospha-Wittig chemistry, giving the corresponding organic phosphinidenation products and oxide (sulfide) complexes. Reaction of 2 with CS2 leads to the formation of novel trinuclear rare-earth metal thione dianion clusters, for which a possible pathway was determined by DFT calculation. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. The impact of transition metals on bacterial plant disease.

    Science.gov (United States)

    Fones, Helen; Preston, Gail M

    2013-07-01

    Metals play essential roles in many biological processes but are toxic when present in excess. This makes their transport and homoeostatic control of particular importance to living organisms. Within the context of plant-pathogen interactions the availability and toxicity of transition metals can have a substantial impact on disease development. Metals are essential for defensive generation of reactive oxygen species and other plant defences and can be used directly to limit pathogen growth. Metal-based antimicrobials are used in agriculture to control plant disease, and there is increasing evidence that metal hyperaccumulating plants use accumulated metal to limit pathogen growth. Pathogens and hosts compete for available metals, with plants possessing mechanisms to withhold essential metals from invading microbes. Pathogens, meanwhile, use low-metal conditions as a signal to recognise and respond to the host environment. Consequently, metal-sensing systems such as fur (iron) and zur (zinc) regulate the expression of pathogenicity and virulence genes; and pathogens have developed sophisticated strategies to acquire metal during growth in plant tissues, including the production of multiple siderophores. This review explores the impact of transition metals on the processes that determine the outcome of bacterial infection in plants, with a particular emphasis on zinc, iron and copper. © 2012 Federation of European Microbiological Societies. Published by Blackwell Publishing Ltd. All rights reserved.

  17. Long-range interacting many-body systems with alkaline-earth-metal atoms

    CERN Document Server

    Olmos, B; Singh, Y; Schreck, F; Bongs, K; Lesanovsky, I

    2012-01-01

    Alkaline-earth-metal atoms exhibit long-range dipolar interactions, which are generated via the coherent exchange of photons on the 3P_0-3D_1-transition of the triplet manifold. In case of bosonic strontium, which we discuss here, this transition has a wavelength of 2.7 \\mu m and a dipole moment of 2.46 Debye, and there exists a magic wavelength permitting the creation of optical lattices that are identical for the states 3P_0 and 3D_1. This interaction enables the realization and study of mixtures of hard-core lattice bosons featuring long-range hopping, with tuneable disorder and anisotropy. We derive the many-body Master equation, investigate the dynamics of excitation transport and analyze spectroscopic signatures stemming from coherent long-range interactions and collective dissipation. Our results show that lattice gases of alkaline-earth-metal atoms permit the creation of long-lived collective atomic states and constitute a simple and versatile platform for the exploration of many-body systems with lon...

  18. High-pressure phase transition of alkali metal-transition metal deuteride Li2PdD2

    Science.gov (United States)

    Yao, Yansun; Stavrou, Elissaios; Goncharov, Alexander F.; Majumdar, Arnab; Wang, Hui; Prakapenka, Vitali B.; Epshteyn, Albert; Purdy, Andrew P.

    2017-06-01

    A combined theoretical and experimental study of lithium palladium deuteride (Li2PdD2) subjected to pressures up to 50 GPa reveals one structural phase transition near 10 GPa, detected by synchrotron powder x-ray diffraction, and metadynamics simulations. The ambient-pressure tetragonal phase of Li2PdD2 transforms into a monoclinic C2/m phase that is distinct from all known structures of alkali metal-transition metal hydrides/deuterides. The structure of the high-pressure phase was characterized using ab initio computational techniques and from refinement of the powder x-ray diffraction data. In the high-pressure phase, the PdD2 complexes lose molecular integrity and are fused to extended [PdD2]∞ chains. The discovered phase transition and new structure are relevant to the possible hydrogen storage application of Li2PdD2 and alkali metal-transition metal hydrides in general.

  19. Green's function approach to edge states in transition metal dichalcogenides

    NARCIS (Netherlands)

    Farmanbar Gelepordsari, M.; Amlaki, T.; Brocks, G.

    2016-01-01

    The semiconducting two-dimensional transition metal dichalcogenides MX 2 show an abundance of one-dimensional metallic edges and grain boundaries. Standard techniques for calculating edge states typically model nanoribbons, and require the use of supercells. In this paper, we formulate a Green's fun

  20. Direct NO decomposition over stepped transition-metal surfaces

    DEFF Research Database (Denmark)

    Falsig, Hanne; Bligaard, Thomas; Christensen, Claus H.

    2007-01-01

    We establish the full potential energy diagram for the direct NO decomposition reaction over stepped transition-metal surfaces by combining a database of adsorption energies on stepped metal surfaces with known Bronsted-Evans-Polanyi (BEP) relations for the activation barriers of dissociation...

  1. The transition to the metallic state in low density hydrogen.

    Science.gov (United States)

    McMinis, Jeremy; Morales, Miguel A; Ceperley, David M; Kim, Jeongnim

    2015-11-21

    Solid atomic hydrogen is one of the simplest systems to undergo a metal-insulator transition. Near the transition, the electronic degrees of freedom become strongly correlated and their description provides a difficult challenge for theoretical methods. As a result, the order and density of the phase transition are still subject to debate. In this work, we use diffusion quantum Monte Carlo to benchmark the transition between paramagnetic and anti-ferromagnetic body centered cubic atomic hydrogen in its ground state. We locate the density of the transition by computing the equation of state for these two phases and identify the phase transition order by computing the band gap near the phase transition. These benchmark results show that the phase transition is continuous and occurs at a Wigner-Seitz radius of rs = 2.27(3) a0. We compare our results to previously reported density functional theory, Hedin's GW approximation, and dynamical mean field theory results.

  2. Thermal metal-insulator transition in a helical topological superconductor

    OpenAIRE

    Fulga, I. C.; Akhmerov, A. R.; Tworzydło, J.; Béri, B.; Beenakker, C. W. J.

    2012-01-01

    Two-dimensional superconductors with time-reversal symmetry have a Z_2 topological invariant, that distinguishes phases with and without helical Majorana edge states. We study the topological phase transition in a class-DIII network model, and show that it is associated with a metal-insulator transition for the thermal conductance of the helical superconductor. The localization length diverges at the transition with critical exponent nu approx 2.0, about twice the known value in a chiral supe...

  3. Two-dimensional transition metal dichalcogenide nanomaterials for solar water splitting

    Science.gov (United States)

    Andoshe, Dinsefa M.; Jeon, Jong-Myeong; Kim, Soo Young; Jang, Ho Won

    2015-05-01

    Recently, 2-dimensional (2D) transition metal dichalcogenides (TMDs) have received great attention for solar water splitting and electrocatalysis. In addition to their wide variety of electronic and microstructural properties, their promising catalytic activities for hydrogen production make 2D TMDs as earth-abundant and inexpensive catalysts that can replace noble metals. This paper reviews the electronic, structural, and optical properties of 2D TMDs. We highlight the various synthetic methods for 2D TMDs and their applications in hydrogen evolution based on photoelectrochemical and electrocatalytic cells. We also discuss perspectives and challenges of 2D TMDs for hydrogen production and artificial photosynthesis.[Figure not available: see fulltext.

  4. Density functional theory studies of transition metal nanoparticles in catalysis

    DEFF Research Database (Denmark)

    Greeley, Jeffrey Philip; Rankin, Rees; Zeng, Zhenhua

    2013-01-01

    Periodic Density Functional Theory calculations are capable of providing powerful insights into the structural, energetics, and electronic phenomena that underlie heterogeneous catalysis on transition metal nanoparticles. Such calculations are now routinely applied to single crystal metal surfaces...... and to subnanometer metal clusters. Descriptions of catalysis on truly nanosized structures, however, are generally not as well developed. In this talk, I will illustrate different approaches to analyzing nanocatalytic phenomena with DFT calculations. I will describe case studies from heterogeneous catalysis...

  5. High-Field Magnetization of Light Rare-Earth Metals

    DEFF Research Database (Denmark)

    McEwen, K.A.; Cock, G.J.; Roeland, L.W.;

    1973-01-01

    The magnetization of single crystals of Eu, Sm, Nd, Pr, and Pr-Nd alloys has been measured in fields up to 37 T (370 kG). The results give new information on the magnetic properties of these metals. Of particular interest is a first-order transition from a nonmagnetic to a metamagnetic phase...... in double-hexagonal close-packed Pr, due to the crossing of crystal-field levels, when a field of about 32 T is applied in the hard direction at low temperatures....

  6. Molecular rare-earth-metal hydrides in non-cyclopentadienyl environments.

    Science.gov (United States)

    Fegler, Waldemar; Venugopal, Ajay; Kramer, Mathias; Okuda, Jun

    2015-02-02

    Molecular hydrides of the rare-earth metals play an important role as homogeneous catalysts and as counterparts of solid-state interstitial hydrides. Structurally well-characterized non-metallocene-type hydride complexes allow the study of elementary reactions that occur at rare-earth-metal centers and of catalytic reactions involving bonds between rare-earth metals and hydrides. In addition to neutral hydrides, cationic derivatives have now become available.

  7. K-CO on Transition Metals: A Local Ionic Interaction.

    Science.gov (United States)

    1987-05-01

    A-Rli8t 342 K-CO ON TRANSITION METALS- A LOCAL IONIC INTERACTION i/i (U) PENNSYLVANIA UNIV PHILADELPHIA DEPT OF PHYSICS C H PATTERSON ET AL MAY 87 TR...CO on Transition Metals: A Local Ionic Interaction by Charles H. Patterson, Peter A. Schultz, and Richard P. Messmer Abstract Submitted for the...administrator. 87 9 1 011 K-CO on Transition Metalss A Local Ionic Interaction Charles H. Patterson and 0 Peter A. Schultz III Department of Physics (a) D

  8. Melting of bcc Transition Metals and Icosahedral Clustering

    Energy Technology Data Exchange (ETDEWEB)

    Ross, M; Boehler, R; Japel, S

    2006-05-26

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

  9. Metal-Insulator Transition in C60-Polymers

    CERN Document Server

    Harigaya, K

    1995-01-01

    Variations in the band structures of C60-polymers are studied, when pi-conjugation conditions are changed. We look at band structures in order to discuss a metal-insulator transition, using a semi-empirical model with the Su-Schrieffer-Heeger type electron-phonon interactions. We find that electronic structures change among direct-gap insulators and the metal, depending on the degree of pi-conjugations. High pressure experiments could observe such pressure-induced metal-insulator transitions.

  10. CHARACTERIZING K2 PLANET DISCOVERIES: A SUPER-EARTH TRANSITING THE BRIGHT K DWARF HIP 116454

    Energy Technology Data Exchange (ETDEWEB)

    Vanderburg, Andrew; Montet, Benjamin T.; Johnson, John Asher; Buchhave, Lars A.; Zeng, Li; Latham, David W.; Angus, Ruth; Bieryla, Allyson; Charbonneau, David [Harvard-Smithsonian Center for Astrophysics, Cambridge, MA 02138 (United States); Pepe, Francesco; Udry, Stéphane; Lovis, Christophe [Observatoire Astronomique de l' Université de Genève, 51 chemin des Maillettes, CH-1290 Versoix (Switzerland); Cameron, Andrew Collier [SUPA, School of Physics and Astronomy, University of St Andrews, North Haugh, St Andrews, Fife KY16 9SS (United Kingdom); Molinari, Emilio; Boschin, Walter [INAF-Fundación Galileo Galilei, Rambla José Ana Fernández Pérez, 7, E-38712 Breña Baja (Spain); Matthews, Jaymie M. [University of British Columbia, Vancouver, BC V6T1Z1 (Canada); Cameron, Chris [Cape Breton University, 1250 Grand Lake Road, Sydney NS B1P 6L2 (Canada); Law, Nicholas [University of North Carolina at Chapel Hill, Chapel Hill, NC 27599 (United States); Bowler, Brendan P. [California Institute of Technology, Pasadena, CA 91125 (United States); Baranec, Christoph, E-mail: avanderburg@cfa.harvard.edu [University of Hawai' i at Mānoa, Hilo, HI 96720 (United States); and others

    2015-02-10

    We report the first planet discovery from the two-wheeled Kepler (K2) mission: HIP 116454 b. The host star HIP 116454 is a bright (V = 10.1, K = 8.0) K1 dwarf with high proper motion and a parallax-based distance of 55.2 ± 5.4 pc. Based on high-resolution optical spectroscopy, we find that the host star is metal-poor with [Fe/H] =–0.16 ± 0.08 and has a radius R {sub *} = 0.716 ± 0.024 R {sub ☉} and mass M {sub *} = 0.775 ± 0.027 M {sub ☉}. The star was observed by the Kepler spacecraft during its Two-Wheeled Concept Engineering Test in 2014 February. During the 9 days of observations, K2 observed a single transit event. Using a new K2 photometric analysis technique, we are able to correct small telescope drifts and recover the observed transit at high confidence, corresponding to a planetary radius of R{sub p} = 2.53 ± 0.18 R {sub ⊕}. Radial velocity observations with the HARPS-N spectrograph reveal a 11.82 ± 1.33 M {sub ⊕} planet in a 9.1 day orbit, consistent with the transit depth, duration, and ephemeris. Follow-up photometric measurements from the MOST satellite confirm the transit observed in the K2 photometry and provide a refined ephemeris, making HIP 116454 b amenable for future follow-up observations of this latest addition to the growing population of transiting super-Earths around nearby, bright stars.

  11. Ground-state oxygen holes and the metal–insulator transition in the negative charge-transfer rare-earth nickelates

    OpenAIRE

    Bisogni, Valentina; Catalano, Sara; Green, Robert J.; Gibert, Marta; Scherwitzl, Raoul; Huang, Yaobo; Strocov, Vladimir N.; Zubko, Pavlo; Balandeh, Shadi; Triscone, Jean-Marc; Sawatzky, George; Schmitt, Thorsten

    2016-01-01

    The metal-insulator transitions and the intriguing physical properties of rare-earth perovskite nickelates have attracted considerable attention in recent years. Nonetheless, a complete understanding of these materials remains elusive. Here, taking a NdNiO3 thin film as a representative example, we utilize a combination of x-ray absorption and resonant inelastic x-ray scattering (RIXS) spectroscopies to resolve important aspects of the complex electronic structure of the rare-earth nickelates...

  12. Maximum solid solubility of transition metals in vanadium solvent

    Institute of Scientific and Technical Information of China (English)

    ZHANG Jin-long; FANG Shou-shi; ZHOU Zi-qiang; LIN Gen-wen; GE Jian-sheng; FENG Feng

    2005-01-01

    Maximum solid solubility (Cmax) of different transition metals in metal solvent can be described by a semi-empirical equation using function Zf that contains electronegativity difference, atomic diameter and electron concentration. The relation between Cmax and these parameters of transition metals in vanadium solvent was studied.It is shown that the relation of Cmax and function Zf can be expressed as ln Cmax = Zf = 7. 316 5-2. 780 5 (△X)2 -71. 278δ2 -0. 855 56n2/3. The factor of atomic size parameter has the largest effect on the Cmax of the V binary alloy;followed by the factor of electronegativity difference; the electrons concentration has the smallest effect among the three bond parameters. Function Zf is used for predicting the unknown Cmax of the transition metals in vanadium solvent. The results are compared with Darken-Gurry theorem, which can be deduced by the obtained function Zf in this work.

  13. How Does Boiling in the Earth's Crust Influence Metal Speciation and Transport?

    Science.gov (United States)

    Kam, K.; Lemke, K.

    2014-12-01

    The presence of large quantities of precious metals, such as gold and copper, near the Earth's surface (upper crust) is commonly attributed to transport in aqueous solution and precipitation upon variations in temperature and pressure. As a consequence, gold exploration is closely linked to solution chemistry, i.e. hydrothermal processes involving aqueous fluids with densities of around unity. However, as crustal fluids buoyantly ascend, boiling produces a coexisting low-density aqueous liquid with fundamentally different physical and chemical properties, and a, most importantly, a high affinity for coinage metals (Heinrich et al., Econ Geol., 1992, 87, 1566). From recent experimental studies of Au (Hurtig and Williams-Jones, 2014, Geochim. Cosmochim. Acta,, 127, 304), we know that metal speciation in this low-density phase differs fundamentally from that observed in bulk solution, clearly, with important implications for Au, and metal speciation in general, transport and ore concentrations processes (these processes would also be operable in industrial geothermal plants given the quite special solvent properties of steam). In brief, this study focuses on the speciation of select metal halides in bulk solution as well as in water vapor, and is driven by our need to understand the solvent properties of around 2.0x109 cubic kilometers of free water (or 2,500 times as much water as stored in all lakes and rivers) present in the Earth's crust. The scope of this study has particular applications in the geothermal and oil industries, as both deal with high temperature low-density aqueous fluids. Understanding how metal halide species behave upon boiling can also provide insight into how metals, such as copper and silver, coat turbine equipment and steam piping in geothermal plants, ultimately rendering these components inoperable. This study will also provide preliminary results from mass spectrometric experiments of transition metal halides, and will be augmented with

  14. Supramolecular structures constructed from three novel rare earth metal complexes

    Indian Academy of Sciences (India)

    Huaze Dong; Xiaojun Feng; Xia Liu; BiN Zheng; Jianhong Bi; Yan Xue; Shaohua Gou; Yanping Wang

    2015-05-01

    Three rare earth metal supramolecular complexes, {[Tb(2)4](ClO4)3·2H2O(1), [Eu(2)2(H2O)5] (ClO4)3(2) and [Gd(NO3)3(2)2]·2CH3CH2OH(3) ( 2 = 3-Dimethylamino-1-pyridin-2-yl-propenone), have been synthesized and characterized by elemental analysis, IR and single crystal X-ray diffraction. The crystal structure analysis reveals that the coordination numbers of three complexes (1–3) are 8, 9 and 10, respectively. Three complexes assembled into 3D frameworks based on C-H⋯O, O-H⋯O hydrogen bond linkages.

  15. Metal selectivity determinants in a family of transition metal transporters.

    Science.gov (United States)

    Podar, Dorina; Scherer, Judith; Noordally, Zeenat; Herzyk, Pawel; Nies, Dietrich; Sanders, Dale

    2012-01-27

    Metal tolerance proteins (MTPs) are plant members of the cation diffusion facilitator (CDF) transporter family involved in cellular metal homeostasis. Members of the CDF family are ubiquitously found in all living entities and show principal selectivity for Zn(2+), Mn(2+), and Fe(2+). Little is known regarding metal selectivity determinants of CDFs. We identified a novel cereal member of CDFs in barley, termed HvMTP1, that localizes to the vacuolar membrane. Unlike its close relative AtMTP1, which is highly selective for Zn(2+), HvMTP1 exhibits selectivity for both Zn(2+) and Co(2+) as assessed by its ability to suppress yeast mutant phenotypes for both metals. Expression of HvMTP1/AtMTP1 chimeras in yeast revealed a five-residue sequence within the AtMTP1 N-segment of the His-rich intracytoplasmic loop that confines specificity to Zn(2+). Furthermore, mutants of AtMTP1 generated through random mutagenesis revealed residues embedded within transmembrane domain 3 that additionally specify the high degree of Zn(2+) selectivity. We propose that the His-rich loop, which might play a role as a zinc chaperone, determines the identity of the metal ions that are transported. The residues within transmembrane domain 3 can also influence metal selectivity, possibly through conformational changes induced at the cation transport site located within the membrane or at the cytoplasmic C-terminal domain.

  16. Flexible metallic seal for transition duct in turbine system

    Science.gov (United States)

    Flanagan, James Scott; LeBegue, Jeffrey Scott; McMahan, Kevin Weston; Dillard, Daniel Jackson; Pentecost, Ronnie Ray

    2014-04-22

    A turbine system is disclosed. In one embodiment, the turbine system includes a transition duct. The transition duct includes an inlet, an outlet, and a passage extending between the inlet and the outlet and defining a longitudinal axis, a radial axis, and a tangential axis. The outlet of the transition duct is offset from the inlet along the longitudinal axis and the tangential axis. The transition duct further includes an interface member for interfacing with a turbine section. The turbine system further includes a flexible metallic seal contacting the interface member to provide a seal between the interface member and the turbine section.

  17. New transition metal-rich rare-earth palladium/platinum aluminides with RET{sub 5}Al{sub 2} composition. Structure, magnetism and {sup 27}Al NMR spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Benndorf, Christopher [Muenster Univ. (Germany). Inst. fuer Anorganische und Analytische Chemie; Muenster Univ. (Germany). Inst. fuer Physikalische Chemie; Stegemann, Frank; Janka, Oliver [Muenster Univ. (Germany). Inst. fuer Anorganische und Analytische Chemie; Eckert, Hellmut [Muenster Univ. (Germany). Inst. fuer Physikalische Chemie

    2015-06-01

    REPd{sub 5}Al{sub 2} compounds with RE = Ce-Gd as well as Y and Lu have been previously synthesized. Although some compounds with the small lanthanides also exist, the compounds with intermediate-sized rare-earth elements (RE = Tb-Yb) had not been prepared. We report on the missing members of the REPd{sub 5}Al{sub 2} (RE = Tb-Yb) series as well as on the new REPt{sub 5}Al{sub 2} (RE = Y, Gd-Tm, Lu) series, which we have synthesized and structurally as well as magnetically characterized. All members crystallize isostructurally in the ZrNi{sub 2}Al{sub 5} type with an anti-arrangement of the T = Pd/Pt and Al atoms. YPd{sub 5}Al{sub 2} and LuPd{sub 5}Al{sub 2}, as well as the respective platinum homologs, YPt{sub 5}Al{sub 2} and LuPt{sub 5}Al{sub 2}, have been characterized also by {sup 27}Al magic-angle spinning nuclear magnetic resonance spectroscopy. Consistent with the XRD analysis, the spectra indicate the existence of only one distinct Al site in the structure.

  18. Stable isotopes of transition and post-transition metals as tracers in environmental studies

    Science.gov (United States)

    Bullen, Tomas D.; Baskaran, Mark

    2011-01-01

    The transition and post-transition metals, which include the elements in Groups 3–12 of the Periodic Table, have a broad range of geological and biological roles as well as industrial applications and thus are widespread in the environment. Interdisciplinary research over the past decade has resulted in a broad understanding of the isotope systematics of this important group of elements and revealed largely unexpected variability in isotope composition for natural materials. Significant kinetic and equilibrium isotope fractionation has been observed for redox sensitive metals such as iron, chromium, copper, molybdenum and mercury, and for metals that are not redox sensitive in nature such as cadmium and zinc. In the environmental sciences, the isotopes are increasingly being used to understand important issues such as tracing of metal contaminant sources and fates, unraveling metal redox cycles, deciphering metal nutrient pathways and cycles, and developing isotope biosignatures that can indicate the role of biological activity in ancient and modern planetary systems.

  19. Baotou Becomes Pilot City for Transition & Upgrading of the National Rare Earth Industry

    Institute of Scientific and Technical Information of China (English)

    2015-01-01

    The Ministry of Industry and Information Technology and the Ministry of Finance recently approved transition&upgrading; pilot plan for Baotou City rare earth industry,Baotou City has been identified as pilot city for

  20. Syntheses and structures of new rare-earth metal tetracyanidoborates

    Energy Technology Data Exchange (ETDEWEB)

    Falk, Fanni; Hackbarth, Liisa; Koeckerling, Martin [Anorganische Festkoerperchemie, Institut fuer Chemie, Universitaet Rostock, Albert-Einstein-Str. 3a, 18059, Rostock (Germany); Herkert, Lorena; Mueller-Buschbaum, Klaus; Finze, Maik [Institut fuer Anorganische Chemie, Institut fuer nachhaltige Chemie and Katalyse mit Bor (ICB), Julius-Maximilians-Universitaet Wuerzburg, Am Hubland, 97074, Wuerzburg (Germany)

    2017-05-04

    Six new rare-earth metal tetracyanidoborates were prepared and characterized by single-crystal X-ray diffraction. Crystals of these salts contain co-crystallized solvent molecules, such as water, acetone, ethanol, or diethyl ether. In [La(EtOH){sub 3}(H{sub 2}O){sub 2}{B(CN)_4}{sub 3}] (1), [La(EtOH)(H{sub 2}O){sub 4}{B(CN)_4}{sub 3}].Et{sub 2}O (2), and [Y(EtOH)(H{sub 2}O){sub 4}{B(CN)_4}{sub 3}].EtOH (6) the tetracyanidoborate anions are all or in part bonded to the RE{sup 3+} ions, whereas in [Pr(H{sub 2}O){sub 9}][B(CN){sub 4}]{sub 3}.(CH{sub 3}){sub 2}CO (3), [Er(H{sub 2}O){sub 8}][B(CN){sub 4}]{sub 3}.(CH{sub 3}){sub 2}CO (4), and [Lu(EtOH)(H{sub 2}O){sub 7}][B(CN){sub 4}]{sub 3}.EtOH.0.5H{sub 2}O (5) the [B(CN){sub 4}]{sup -} anions are not coordinated to the central metal atoms. Only in 1, one of the three crystallographically independent [B(CN){sub 4}]{sup -} anions acts as a bridging ligand. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  1. A simple model for /f-->d transitions of rare-earth ions in crystals

    Science.gov (United States)

    Duan, C. K.; Reid, M. F.

    2003-02-01

    Theoretical simulation and interpretation of f→ d transitions of rare earth ions in crystals are more difficult than for f→ f transitions, because f→ d transitions involve many more energy levels and are further complicated by strong vibronic transitions, so the experimental spectra contain many fewer resolvable peaks. In order to better understand the structure of the spectra, a simple model is developed to take into account the main interactions in the fN-1 d configuration. This model leads to quantum numbers characterizing the states and the associated transition selection rules. Relative transition intensities can be quantitatively estimated. The model is applied to Eu 2+ and Sm 3+ ions in crystals.

  2. Transition metal-substituted cobalt ferrite nanoparticles for biomedical applications.

    Science.gov (United States)

    Sanpo, Noppakun; Berndt, Christopher C; Wen, Cuie; Wang, James

    2013-03-01

    Transition metals of copper, zinc, chromium and nickel were substituted into cobalt ferrite nanoparticles via a sol-gel route using citric acid as a chelating agent. The microstructure and elemental composition were characterized using scanning electron microscopy combined with energy-dispersive X-ray spectroscopy. Phase analysis of transition metal-substituted cobalt ferrite nanoparticles was performed via X-ray diffraction. Surface wettability was measured using the water contact angle technique. The surface roughness of all nanoparticles was measured using profilometry. Moreover, thermogravimetric analysis and differential scanning calorimetry were performed to determine the temperature at which the decomposition and oxidation of the chelating agents took place. Results indicated that the substitution of transition metals influences strongly the microstructure, crystal structure and antibacterial property of the cobalt ferrite nanoparticles.

  3. Elastic phase transitions in metals at high pressures.

    Science.gov (United States)

    Krasilnikov, O M; Vekilov, Yu Kh; Mosyagin, I Yu; Isaev, E I; Bondarenko, N G

    2012-04-19

    The elastic phase transitions of cubic metals at high pressures are investigated within the framework of Landau theory. It is shown that at pressures comparable with the magnitude of the bulk modulus the phase transition is connected with the loss of stability relative to uniform deformation of the crystalline lattice. Discontinuity of the order parameter at the transition point and its equilibrium value are expressed through the second- to fourth-order elastic constants. The second-,third- and fourth-order elastic constants and phonon dispersion curves of vanadium under hydrostatic pressure are obtained by first-principles calculations. Structural transformation in vanadium under pressure is studied using the obtained results. It is shown that the experimentally observed at P ≈ 69 GPa phase transition in vanadium is the first-order phase transition close to a second-order phase transition.

  4. Synthesis of some novel divalent transition metal complexes as antimicrobials

    Institute of Scientific and Technical Information of China (English)

    Kaushal K. Oza; Paresh N. Patel; Hasmukh S. Patel

    2011-01-01

    A novel series of transition metal complexes have been synthesized from the reaction of 5-((3-(methylthio)-5-(pyridin-4-yl)-4H-1,2,4-triazol-4-ylamino)methyl)quinolin-8-ol with transition metal salts. The structures of these compounds have been elucidated by elemental and spectral analysis. Furthermore, compounds were screened for in vitro antimicrobial activity against the representative panel of two Gram-positive and two Gram-negative bacteria and two strains of fungus. The various compounds show potent inhibitory action against test organisms.

  5. Integrating Transition Metals into Nanomaterials: Strategies and Applications

    KAUST Repository

    Fhayli, Karim

    2016-04-14

    Transition metals complexes have been involved in various catalytic, biomedical and industrial applications, but only lately they have been associated with nanomaterials to produce innovative and well-defined new hybrid systems. The introduction of transition metals into nanomaterials is important to bear the advantages of metals to nanoscale and also to raise the stability of nanomaterials. In this dissertation, we study two approaches of associating transition metals into nanomaterials. The first approach is via spontaneous self-organization based assembly of small molecule amphiphiles and bulky hydrophilic polymers to produce organic-inorganic hybrid materials that have nanoscale features and can be precisely controlled depending on the experimental conditions used. These hybrid materials can successfully act as templates to design new porous material with interesting architecture. The second approach studied is via electroless reduction of transition metals on the surface of nanocarbons (nanotubes and nanodiamonds) without using any reducing agents or catalysts. The synthesis of these systems is highly efficient and facile resulting in stable and mechanically robust new materials with promising applications in catalysis.

  6. Quantum critical transport at a continuous metal-insulator transition

    OpenAIRE

    Haldar, P.; Laad, M. S.; Hassan, S. R.

    2016-01-01

    In contrast to the first-order correlation-driven Mott metal-insulator transition (MIT), contin- uous disorder-driven transitions are intrinsically quantum critical. Here, we investigate transport quantum criticality in the Falicov-Kimball model, a representative of the latter class in the "strong disorder" category. Employing cluster-dynamical mean-field theory (CDMFT), we find clear and anomalous quantum critical scaling behavior manifesting as perfect mirror symmetry of scaling curves on b...

  7. Spatiotemporal Analysis of Heavy Metal Water Pollution in Transitional China

    OpenAIRE

    Huixuan Li; Yingru Li; Ming-Kuo Lee; Zhongwei Liu; Changhong Miao

    2015-01-01

    China’s socioeconomic transitions have dramatically accelerated its economic growth in last three decades, but also companioned with continuous environmental degradation. This study will advance the knowledge of heavy metal water pollution in China from a spatial–temporal perspective. Specifically, this study addressed the following: (1) spatial patterns of heavy metal water pollution levels were analyzed using data of prefecture-level cities from 2004 to 2011; and (2) spatial statistical met...

  8. Volume variation of Gruneisen parameters of fcc transition metals

    Indian Academy of Sciences (India)

    C V Pandya; P R Vyas; T C Pandya; V B Gohel

    2002-02-01

    The volume variation of the Gruneisen parameters of ten fcc transition metals, up to 40% compression, has been studied on the basis of a model approach proposed by Antonov et al. The results are reasonably good for six metals except for Rh, Ag, Au and Ni when compared with available experimental and other theoretical values. The model requires an appropriate modification for Rh, Ag, Au and Ni.

  9. Microstructure of N—Picolylpolyurethane Transition Metal Complexes

    Institute of Scientific and Technical Information of China (English)

    Qun-DongShen; Tian-DouHu; 等

    1999-01-01

    Spectroscopic methods are used to investigate coordination structure of N-picolylpolyurethane transition metal complexes(PUPYM,M=Co2+ and Ni2+) .Geometrical arrangement of ligands in first-shell coordination sphere of metal ions is postulated to be tetrahedral CoL2Cl2 and octahedral NiL2-Cl2Z2.where L is the picolyl group and Z is a hydrate.From extended X-ray absorption fine structure (EXAFS) analysis,bond lengths for metal-chlorine and metal-ligand of PUPYM are similar to those of small molecular weight transition metal complexes.A two-phase model of PUPYM which best describes the experimental data of DMTA and SAXS.is proposed.One microphase is the hard domain of self segregated haed segments brought about by metal-ligand interaction.and the other phase is the matrix of soft segments.Transition metal ion-ligand moieties and their interactions dominate the macroscopic thermal behavior of PUPYM.The ligand field stabilization energy difference(ΔLFSE) between mteal d-electrons in complexes with two picolyl ligands in the coordination sphere of metal ions and complexes maintaining one picolyl ligand as coordination pendent group is calculated on the basis of observed coordination structure,and it represents the energy supplied to split coordination cross-links.ΔLFSE of polyurethane nickel(II) complex is larger than that of the cobalt(II) complex,Since the mobility of hard segments is in inverse proportion to the strength of coordination cross-links.a higher α-transition temperature of PUPYNi2+ with respect to PUPYCo2+ is found as expected.

  10. Spatiotemporal Analysis of Heavy Metal Water Pollution in Transitional China

    OpenAIRE

    Huixuan Li; Yingru Li; Ming-Kuo Lee; Zhongwei Liu; Changhong Miao

    2015-01-01

    China’s socioeconomic transitions have dramatically accelerated its economic growth in last three decades, but also companioned with continuous environmental degradation. This study will advance the knowledge of heavy metal water pollution in China from a spatial–temporal perspective. Specifically, this study addressed the following: (1) spatial patterns of heavy metal water pollution levels were analyzed using data of prefecture-level cities from 2004 to 2011; and (2) spatial statistical met...

  11. Rare-earth metal prices in the USA ca. 1960 to 1994

    Science.gov (United States)

    Hedrick, James B.

    1997-01-01

    Rare-earth metal prices were compiled from the late 1950s and early 1960s through 1994. Although commercial demand for rare-earth metals began in 1908, as the alloy mischmetal, commercial quantities of a wide range of individual rare-earth metals were not available until the late 1950s. The discovery of a large, high-grade rare-earth deposit at Mountain Pass. CA, USA, in 1949, was significant because it led to the production of commercial quantities or rare-earth elements that reduced prices and encouraged wider application of the materials. The availability of ore from Mountain Pass, and other large rare-earth deposits, especially those in Australia and China, has provided the world with abundant resources for rare-earth metal production. This availability, coupled with improved technology from Government and private-sector metallurgical research, has resulted in substantial decreases in rare-earth metal prices since the late 1950s and early 1960s. Price series for the individual rare-earth metals (except promethium) are quoted on a kilogram basis from the late 1950s and early 1960s through 1994. Prices are given in US dollars on an actual and constant dollar basis. Industrial and economic factors affecting prices during this time period are examined.

  12. Nitridomanganates of alkaline-earth metals. Synthesis, structure, and physical properties

    Energy Technology Data Exchange (ETDEWEB)

    Ovchinnikov, Alexander

    2016-12-02

    The main goal of the present work was the synthesis of alkaline-earth nitridomanganates (AE{sub x}Mn{sub y}N{sub z}) with extended anionic structures and the characterization of their electronic and magnetic properties. Up to now, only compounds with isolated nitridomanganate anions have been reported in the discussed ternary systems. A systematic exploratory synthesis, employing high-temperature treatment of AE nitrides and Mn under controlled N2 pressure, yielded more than ten new nitridomanganates. Their crystal structures contain anionic building blocks of different dimensionalities, ranging from isolated species to three-dimensional frameworks. In general, the formation of Mn-rich compositions was found to be driven by the emergence of Mn-Mn interactions, which creates a link between nitridometalates and transition-metal-rich binary nitrides. The obtained nitridomanganates display a plethora of interesting phenomena, such as large spin-orbit coupling, magnetic frustration, quenching of magnetism due to Mn-Mn interactions, and metal-insulator transition.

  13. Magnetic ordering temperatures in rare earth metal dysprosium under ultrahigh pressures

    Science.gov (United States)

    Samudrala, Gopi K.; Tsoi, Georgiy M.; Weir, Samuel T.; Vohra, Yogesh K.

    2014-04-01

    Magnetic ordering temperatures in heavy rare earth metal dysprosium (Dy) have been studied using an ultrasensitive electrical transport measurement technique in a designer diamond anvil cell to a pressure of 69 GPa and a temperature of 10 K. Previous studies using magnetic susceptibility measurements at high pressures were able to track magnetic ordering temperature only till 7 GPa in the hexagonal close packed (hcp) phase of Dy. Our studies indicate that the magnetic ordering temperature shows an abrupt drop of 80 K at the hcp-Sm phase transition followed by a gradual decrease that continues till 17 GPa. This is followed by a rapid increase in the magnetic ordering temperatures in the double hcp phase and finally leveling off in the distorted face centered cubic phase of Dy. Our studies reaffirm that 4f-shell remains localized in Dy and there is no loss of magnetic moment or 4f-shell delocalization for pressures up to 69 GPa.

  14. Growth of transition metals on cerium tungstate model catalyst layers

    Science.gov (United States)

    Skála, T.; Tsud, N.; Stetsovych, V.; Mysliveček, J.; Matolín, V.

    2016-10-01

    Two model catalytic metal/oxide systems were investigated by photoelectron spectroscopy and scanning tunneling microscopy. The mixed-oxide support was a cerium tungstate epitaxial thin layer grown in situ on the W(1 1 0) single crystal. Active particles consisted of palladium and platinum 3D islands deposited on the tungstate surface at 300 K. Both metals were found to interact weakly with the oxide support and the original chemical state of both support and metals was mostly preserved. Electronic and morphological changes are discussed during the metal growth and after post-annealing at temperatures up to 700 K. Partial transition-metal coalescence and self-cleaning from the CO and carbon impurities were observed.

  15. Observation of the Wigner-Huntington transition to metallic hydrogen

    Science.gov (United States)

    Dias, Ranga P.; Silvera, Isaac F.

    2017-02-01

    Producing metallic hydrogen has been a great challenge in condensed matter physics. Metallic hydrogen may be a room-temperature superconductor and metastable when the pressure is released and could have an important impact on energy and rocketry. We have studied solid molecular hydrogen under pressure at low temperatures. At a pressure of 495 gigapascals, hydrogen becomes metallic, with reflectivity as high as 0.91. We fit the reflectance using a Drude free-electron model to determine the plasma frequency of 32.5 ± 2.1 electron volts at a temperature of 5.5 kelvin, with a corresponding electron carrier density of 7.7 ± 1.1 × 1023 particles per cubic centimeter, which is consistent with theoretical estimates of the atomic density. The properties are those of an atomic metal. We have produced the Wigner-Huntington dissociative transition to atomic metallic hydrogen in the laboratory.

  16. Transition metal catalysed ammonia-borane dehydrogenation in ionic liquids.

    Science.gov (United States)

    Wright, William R H; Berkeley, Emily R; Alden, L R; Baker, R Tom; Sneddon, Larry G

    2011-03-21

    Significant advantages result from combining the disparate hydrogen release pathways for ammonia-borane (AB) dehydrogenation using ionic liquids (ILs) and transition metal catalysts. With the RuCl(2)(PMe(3))(4) catalyst precursor, AB dehydrogenation selectivity and extent are maximized in an IL with a moderately coordinating ethylsulfate anion.

  17. Superconductivity Series in Transition Metal Dichalcogenides by Ionic Gating

    NARCIS (Netherlands)

    Shi, Wu; Ye, Jianting; Zhang, Yijin; Suzuki, Ryuji; Yoshida, Masaro; Miyazaki, Jun; Inoue, Naoko; Saito, Yu; Iwasa, Yoshihiro

    2015-01-01

    Functionalities of two-dimensional (2D) crystals based on semiconducting transition metal dichalcogenides (TMDs) have now stemmed from simple field effect transistors (FETs) to a variety of electronic and opto-valleytronic devices, and even to superconductivity. Among them, superconductivity is the

  18. Spin, Charge, and Bonding in Transition Metal Mono Silicides

    NARCIS (Netherlands)

    Marel, D. van der; Damascelli, A.; Schulte, K.; Menovsky, A. A.

    1997-01-01

    Published in: Physica B 244 (1998) 138-147 citations recorded in [Science Citation Index] Abstract: We review some of the relevant physical properties of the transition metal mono-silicides with the FeSi structure (CrSi, MnSi, FeSi, CoSi, NiSi, etc) and explore the relation between their structural

  19. Disorder- and correlation-driven metal-insulator transitions

    OpenAIRE

    Balzer, Matthias; Potthoff, Michael

    2004-01-01

    Metal-insulator transitions driven by disorder (Delta) and/or by electron correlations (U) are investigated within the Anderson-Hubbard model with local binary-alloy disorder using a simple but consistent mean-field approach. The Delta-U phase diagram is derived and discussed for T=0 and finite temperatures.

  20. Luminescent molecular rods - transition-metal alkynyl complexes.

    Science.gov (United States)

    Yam, Vivian Wing-Wah; Wong, Keith Man-Chung

    2005-01-01

    A number of transition-metal complexes have been reported to exhibit rich luminescence, usually originating from phosphorescence. Such luminescence properties of the triplet excited state with a large Stoke's shift, long lifetime, high luminescence quantum yield as well as lower excitation energy, are envisaged to serve as an ideal candidate in the area of potential applications for chemosensors, dye-sensitized solar cells, flat panel displays, optics, new materials and biological sciences. Organic alkynes (poly-ynes), with extended or conjugatedπ-systems and rigid structure with linear geometry, have become a significant research area due to their novel electronic and physical properties and their potential applications in nanotechnology. Owing to the presence of unsaturated sp-hybridized carbon atoms, the alkynyl unit can serve as a versatile building block in the construction of alkynyl transition-metal complexes, not only throughσ-bonding but also viaπ-bonding interactions. By incorporation of linear alkynyl groups into luminescent transition-metal complexes, the alkynyl moiety with goodσ-donor,π-donor andπ-acceptor abilities is envisaged to tune or perturb the emission behaviors, including emission energy (color), intensity and lifetime by its role as an auxiliary ligand as well as to govern the emission origin from its direct involvement. This review summarizes recent efforts on the synthesis of luminescent rod-like alkynyl complexes with different classes of transition metals and details the effects of the introduction of alkynyl groups on the luminescence properties of the complexes.

  1. Cooperative catalysis with first-row late transition metals

    NARCIS (Netherlands)

    J.I. van der Vlugt

    2012-01-01

    Cooperative catalysis with first-row transition metals holds much promise for future developments regarding sustainable, selective transformations, including e.g. alkenes, dienes and a variety of small molecules such as CO2, N2 and water. This non-exhaustive analysis of the current state-of-the-art

  2. The Electrochemical Synthesis of Transition-Metal Acetylacetonates

    Science.gov (United States)

    Long, S. R.; Browning, S. R.; Lagowski, J. J.

    2008-01-01

    The electrochemical synthesis of transition-metal acetylacetonates described here can form the basis of assisting in the transformation of an entry-level laboratory course into a research-like environment where all members of a class are working on the same problem, but where each member has a personal responsibility for the synthesis and…

  3. Monolayer transition metal disulfide:Synthesis, characterization and applications

    Institute of Scientific and Technical Information of China (English)

    Qi Fu; Bin Xiang

    2016-01-01

    Two-dimensional transition metal dichalcogenides (2D TMDCs) has aroused tremendous attention in recent years, because of their remarkable properties originated from their unique structure. In this re-view we report the synthesis, characterization and applications of monolayer MoS2 and WS2.

  4. Well-defined transition metal hydrides in catalytic isomerizations.

    Science.gov (United States)

    Larionov, Evgeny; Li, Houhua; Mazet, Clément

    2014-09-07

    This Feature Article intends to provide an overview of a variety of catalytic isomerization reactions that have been performed using well-defined transition metal hydride precatalysts. A particular emphasis is placed on the underlying mechanistic features of the transformations discussed. These have been categorized depending upon the nature of the substrate and in most cases discussed following a chronological order.

  5. Electrocatalysis using transition metal carbide and oxide nanocrystals

    Science.gov (United States)

    Regmi, Yagya N.

    Carbides are one of the several families of transition metal compounds that are considered economic alternatives to catalysts based on noble metals and their compounds. Phase pure transition metal carbides of group 4-6 metals, in the first three periods, were synthesized using a common eutectic salt flux synthesis method, and their electrocatalytic activities compared under uniform electrochemical conditions. Mo2C showed highest hydrogen evolution reaction (HER) and oxygen reduction reaction (ORR) activities among the nine metal carbides investigated, but all other metal carbides also showed substantial activities. All the metal carbides showed remarkable enhancement in catalytic activities as supports, when compared to traditional graphitic carbon as platinum support. Mo2C, the most active transition metal carbide electrocatalyst, was prepared using four different synthesis routes, and the synthesis route dependent activities compared. Bifunctional Mo 2C that is HER as well as oxygen evolution reaction (OER) active, was achieved when the carbide was templated on a multiwalled carbon nanotube using carbothermic reduction method. Bimetallic carbides of Fe, Co, and Ni with Mo or W were prepared using a common carbothermic reduction method. Two different stoichiometries of bimetallic carbides were obtained for each system within a 60 °C temperature window. While the bimetallic carbides showed relatively lower electrocatalytic activities towards HER and ORR in comparison to Mo2C and WC, they revealed remarkably higher OER activities than IrO2 and RuO2, the state-of-the-art OER catalysts. Bimetallic oxides of Fe, Co, and Ni with Mo and W were also prepared using a hydrothermal synthesis method and they also revealed OER activities that are much higher than RuO2 and IrO2. Additionally, the OER activities were dependent on the degree and nature of hydration in the bimetallic oxide crystal lattice, with the completely hydrated, as synthesized, cobalt molybdate and nickel

  6. On the thermodynamics of phase transitions in metal hydrides

    Science.gov (United States)

    Vita, Andrea

    2012-02-01

    Metal hydrides are solutions of hydrogen in a metal, where phase transitions may occur depending on temperature, pressure etc. We apply Le Chatelier's principle of thermodynamics to a particular phase transition in TiHx, which can approximately be described as a second-order phase transition. We show that the fluctuations of the order parameter correspond to fluctuations both of the density of H+ ions and of the distance between adjacent H+ ions. Moreover, as the system approaches the transition and the correlation radius increases, we show -with the help of statistical mechanics-that the statistical weight of modes involving a large number of H+ ions (`collective modes') increases sharply, in spite of the fact that the Boltzmann factor of each collective mode is exponentially small. As a result, the interaction of the H+ ions with collective modes makes a tiny suprathermal fraction of the H+ population appear. Our results hold for similar transitions in metal deuterides, too. A violation of an -insofar undisputed-upper bound on hydrogen loading follows.

  7. Covalent bonds against magnetism in transition metal compounds.

    Science.gov (United States)

    Streltsov, Sergey V; Khomskii, Daniel I

    2016-09-20

    Magnetism in transition metal compounds is usually considered starting from a description of isolated ions, as exact as possible, and treating their (exchange) interaction at a later stage. We show that this standard approach may break down in many cases, especially in 4d and 5d compounds. We argue that there is an important intersite effect-an orbital-selective formation of covalent metal-metal bonds that leads to an "exclusion" of corresponding electrons from the magnetic subsystem, and thus strongly affects magnetic properties of the system. This effect is especially prominent for noninteger electron number, when it results in suppression of the famous double exchange, the main mechanism of ferromagnetism in transition metal compounds. We study this mechanism analytically and numerically and show that it explains magnetic properties of not only several 4d-5d materials, including Nb2O2F3 and Ba5AlIr2O11, but can also be operative in 3d transition metal oxides, e.g., in CrO2 under pressure. We also discuss the role of spin-orbit coupling on the competition between covalency and magnetism. Our results demonstrate that strong intersite coupling may invalidate the standard single-site starting point for considering magnetism, and can lead to a qualitatively new behavior.

  8. Disorder-Driven Metal-Insulator Transitions in Deformable Lattices

    Science.gov (United States)

    Di Sante, Domenico; Fratini, Simone; Dobrosavljević, Vladimir; Ciuchi, Sergio

    2017-01-01

    We show that, in the presence of a deformable lattice potential, the nature of the disorder-driven metal-insulator transition is fundamentally changed with respect to the noninteracting (Anderson) scenario. For strong disorder, even a modest electron-phonon interaction is found to dramatically renormalize the random potential, opening a mobility gap at the Fermi energy. This process, which reflects disorder-enhanced polaron formation, is here given a microscopic basis by treating the lattice deformations and Anderson localization effects on the same footing. We identify an intermediate "bad insulator" transport regime which displays resistivity values exceeding the Mott-Ioffe-Regel limit and with a negative temperature coefficient, as often observed in strongly disordered metals. Our calculations reveal that this behavior originates from significant temperature-induced rearrangements of electronic states due to enhanced interaction effects close to the disorder-driven metal-insulator transition.

  9. Transition Metal Nitrides for Electrocatalytic Energy Conversion: Opportunities and Challenges.

    Science.gov (United States)

    Xie, Junfeng; Xie, Yi

    2016-03-07

    Electrocatalytic energy conversion has been considered as one of the most efficient and promising pathways for realizing energy storage and energy utilization in modern society. To improve electrocatalytic reactions, specific catalysts are needed to lower the overpotential. In the search for efficient alternatives to noble metal catalysts, transition metal nitrides have attracted considerable interest due to their high catalytic activity and unique electronic structure. Over the past few decades, numerous nitride-based catalysts have been explored with respect to their ability to drive various electrocatalytic reactions, such as the hydrogen evolution reaction and the oxygen evolution reaction to achieve water splitting and the oxygen reduction reaction coupled with the methanol oxidation reaction to construct fuel cells or rechargeable Li-O2 batteries. This Minireview provides a brief overview of recent progress on electrocatalysts based on transition metal nitrides, and outlines the current challenges and future opportunities.

  10. Metal-insulator transition in films of doped semiconductor nanocrystals.

    Science.gov (United States)

    Chen, Ting; Reich, K V; Kramer, Nicolaas J; Fu, Han; Kortshagen, Uwe R; Shklovskii, B I

    2016-03-01

    To fully deploy the potential of semiconductor nanocrystal films as low-cost electronic materials, a better understanding of the amount of dopants required to make their conductivity metallic is needed. In bulk semiconductors, the critical concentration of electrons at the metal-insulator transition is described by the Mott criterion. Here, we theoretically derive the critical concentration nc for films of heavily doped nanocrystals devoid of ligands at their surface and in direct contact with each other. In the accompanying experiments, we investigate the conduction mechanism in films of phosphorus-doped, ligand-free silicon nanocrystals. At the largest electron concentration achieved in our samples, which is half the predicted nc, we find that the localization length of hopping electrons is close to three times the nanocrystals diameter, indicating that the film approaches the metal-insulator transition.

  11. The transition to the metallic state in low density hydrogen

    Energy Technology Data Exchange (ETDEWEB)

    McMinis, Jeremy; Morales, Miguel A. [Lawrence Livermore National Laboratory, Livermore, California 94550 (United States); Ceperley, David M. [Department of Physics, University of Illinois, Urbana, Illinois 61801 (United States); Kim, Jeongnim [Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831 (United States)

    2015-11-21

    Solid atomic hydrogen is one of the simplest systems to undergo a metal-insulator transition. Near the transition, the electronic degrees of freedom become strongly correlated and their description provides a difficult challenge for theoretical methods. As a result, the order and density of the phase transition are still subject to debate. In this work, we use diffusion quantum Monte Carlo to benchmark the transition between paramagnetic and anti-ferromagnetic body centered cubic atomic hydrogen in its ground state. We locate the density of the transition by computing the equation of state for these two phases and identify the phase transition order by computing the band gap near the phase transition. These benchmark results show that the phase transition is continuous and occurs at a Wigner-Seitz radius of r{sub s} = 2.27(3) a{sub 0}. We compare our results to previously reported density functional theory, Hedin’s GW approximation, and dynamical mean field theory results.

  12. GLANCING VIEWS OF THE EARTH: FROM A LUNAR ECLIPSE TO AN EXOPLANETARY TRANSIT

    Energy Technology Data Exchange (ETDEWEB)

    Garcia Munoz, A.; Barrena, R.; Montanes-Rodriguez, P.; Palle, E. [Instituto de Astrofisica de Canarias, C/Via Lactea s/n, E-38205 La Laguna, Tenerife (Spain); Zapatero Osorio, M. R.; Martin, E. L., E-mail: tonhingm@gmail.com [Centro de Astrobiologia, CSIC-INTA, Ctra. de Torrejon a Ajalvir, km 4, E-28550 Madrid (Spain)

    2012-08-20

    It has been posited that lunar eclipse observations may help predict the in-transit signature of Earth-like extrasolar planets. However, a comparative analysis of the two phenomena addressing in detail the transport of stellar light through the planet's atmosphere has not yet been presented. Here, we proceed with the investigation of both phenomena by making use of a common formulation. Our starting point is a set of previously unpublished near-infrared spectra collected at various phases during the 2008 August lunar eclipse. We then take the formulation to the limit of an infinitely distant observer in order to investigate the in-transit signature of the Earth-Sun system as being observed from outside our solar system. The refraction bending of sunlight rays that pass through Earth's atmosphere is a critical factor in the illumination of the eclipsed Moon. Likewise, refraction will have an impact on the in-transit transmission spectrum for specific planet-star systems depending on the refractive properties of the planet's atmosphere, the stellar size, and the planet's orbital distance. For the Earth-Sun system, at mid-transit, refraction prevents the remote observer's access to the lower {approx}12-14 km of the atmosphere and, thus, also to the bulk of the spectroscopically active atmospheric gases. We demonstrate that the effective optical radius of the Earth in-transit is modulated by refraction and varies by {approx}12 km from mid-transit to internal contact. The refractive nature of atmospheres, a property which is rarely accounted for in published investigations, will pose additional challenges to the characterization of Earth-like extrasolar planets. Refraction may have a lesser impact for Earth-like extrasolar planets within the habitable zone of some M-type stars.

  13. A super-Earth transiting a nearby low-mass star

    CERN Document Server

    Charbonneau, David; Irwin, Jonathan; Burke, Christopher J; Nutzman, Philip; Buchhave, Lars A; Lovis, Christophe; Bonfils, Xavier; Latham, David W; Udry, Stephane; Murray-Clay, Ruth A; Holman, Matthew J; Falco, Emilio E; Winn, Joshua N; Queloz, Didier; Pepe, Francesco; Mayor, Michel; Delfosse, Xavier; Forveille, Thierry

    2009-01-01

    A decade ago, the detection of the first transiting extrasolar planet provided a direct constraint on its composition and opened the door to spectroscopic investigations of extrasolar planetary atmospheres. As such characterization studies are feasible only for transiting systems that are both nearby and for which the planet-to-star radius ratio is relatively large, nearby small stars have been surveyed intensively. Doppler studies and microlensing have uncovered a population of planets with minimum masses of 1.9-10 times the Earth's mass (M_Earth), called super-Earths. The first constraint on the bulk composition of this novel class of planets was afforded by CoRoT-7b, but the distance and size of its star preclude atmospheric studies in the foreseeable future. Here we report observations of the transiting planet GJ 1214b, which has a mass of 6.55 M_Earth and a radius 2.68 times Earth's radius (R_Earth), indicating that it is intermediate in stature between Earth and the ice giants of the Solar System. We fi...

  14. Self-assembly of noble metal monolayers on transition metal carbide nanoparticle catalysts.

    Science.gov (United States)

    Hunt, Sean T; Milina, Maria; Alba-Rubio, Ana C; Hendon, Christopher H; Dumesic, James A; Román-Leshkov, Yuriy

    2016-05-20

    We demonstrated the self-assembly of transition metal carbide nanoparticles coated with atomically thin noble metal monolayers by carburizing mixtures of noble metal salts and transition metal oxides encapsulated in removable silica templates. This approach allows for control of the final core-shell architecture, including particle size, monolayer coverage, and heterometallic composition. Carbon-supported Ti(0.1)W(0.9)C nanoparticles coated with Pt or bimetallic PtRu monolayers exhibited enhanced resistance to sintering and CO poisoning, achieving an order of magnitude increase in specific activity over commercial catalysts for methanol electrooxidation after 10,000 cycles. These core-shell materials provide a new direction to reduce the loading, enhance the activity, and increase the stability of noble metal catalysts.

  15. High pressure and microwave based synthesis of transition metal pnictides

    Energy Technology Data Exchange (ETDEWEB)

    Pobel, Roman Rupert

    2016-04-11

    The goal of this thesis was to explore the possibilities of synthetic methods that are not very common in current transition metal pnictide research. The substitution of the Ca-site in CaFe{sub 2}As{sub 2} with rare earth elements such as Pr the has been reported to induce superconductivity. However, some inconsistencies in the data suggested a non-intrinsic origin of the observed diamagnetic signal. Furthermore a solubility limit of 13% was found when prepared in an electrical furnace thus leaving a huge part of the physical phase diagram inaccessible. A high pressure/high temperature synthesis was developed to allow access to the whole doping range and an in-depth characterization of this compound was carried out. During the experiments concerning the high pressure synthesis of Ca{sub 1-x}Pr{sub x}Fe{sub 2}As{sub 2} the new ternary iron arsenide CaFe{sub 5}As{sub 3} was identified and classified as a member of the Ca{sub n(n+1)/2}(Fe{sub 1-x}M{sub x}){sub (2+3n)}M'{sub n(n-1)/2}As{sub (n+1)(n+2)/2} (n = 1-3; M =Nb, Pd, Pt; M' = □, Pd, Pt) family. The complete solid solution Ca{sub 1-x}Pr{sub x}Fe{sub 5}As{sub 3} (O ≤ x ≤ 1) was prepared and physically characterized. Furthermore, several useful techniques were developed to aid in future high pressure based investigations of transition metal pnictides. The second part of this thesis concerns a completely different, but equally promising synthetic approach. Microwave based synthesis is a well-established technique in many solution based fields, such as organic, medicinal or nano chemistry. For solid state and materials research several parameters and particularities have to be considered. But when successful, it allows for the reduction of reaction time by several orders of magnitude. It has very rarely been applied in the preparation of pnictides and on1y once in the context of pnictide superconductor research. The possibilities of this method were explored and employed in the preparation of several

  16. Bioactive luminescent transition-metal complexes for biomedical applications.

    Science.gov (United States)

    Ma, Dik-Lung; He, Hong-Zhang; Leung, Ka-Ho; Chan, Daniel Shiu-Hin; Leung, Chung-Hang

    2013-07-22

    The serendipitous discovery of the anticancer drug cisplatin cemented medicinal inorganic chemistry as an independent discipline in the 1960s. Luminescent metal complexes have subsequently been widely applied for sensing, bio-imaging, and in organic light-emitting diode applications. Transition-metal complexes possess a variety of advantages that make them suitable as therapeutics and as luminescent probes for biomolecules. It is thus highly desirable to develop new luminescent metal complexes that either interact with DNA through different binding modes or target alternative cellular machinery such as proteins as well as to provide a more effective means of monitoring disease progression. In this Review, we highlight recent examples of biologically active luminescent metal complexes that can target and probe a specific biomolecule, and offer insights into the future potential of these compounds for the investigation and treatment of human diseases.

  17. sup 29 Si magic angle spinning NMR spectra of alkali metal, alkaline earth metal, and rare earth metal ion exchanged Y zeolites

    Energy Technology Data Exchange (ETDEWEB)

    Chao, Kueijung; Chern, Jeryoung (Tsinghua Univ., Taiwan (China))

    1989-02-23

    The variation of the extraframework cation location in groups IA and IIA metals and rare earth metal (RE) Y zeolites as a function of the dehydration and the rehydration is monitored by {sup 29}Si MAS NMR. Unheated hydrated zeolites give similar {sup 29}Si spectra as they present the similar cation distributions. Upon dehydration a high-field shift is observed which correlates with the distortion of bond angles in silicon-oxygen tetrahedra. The line shapes of {sup 29}Si spectra depend on the nature and the location of the exchangeable cations and the occupancy of the different sites in dehydrated and rehydrated states. The correlation between the line shape of {sup 29}Si spectra and the migration of cations from the supercages to the sodalite cages after heating treatment was studied. The results of {sup 29}Si NMR agree with the known structure data.

  18. Vibrational energy transfer dynamics in ruthenium polypyridine transition metal complexes.

    Science.gov (United States)

    Fedoseeva, Marina; Delor, Milan; Parker, Simon C; Sazanovich, Igor V; Towrie, Michael; Parker, Anthony W; Weinstein, Julia A

    2015-01-21

    Understanding the dynamics of the initial stages of vibrational energy transfer in transition metal complexes is a challenging fundamental question which is also of crucial importance for many applications, such as improving the performance of solar devices or photocatalysis. The present study investigates vibrational energy transport in the ground and the electronic excited state of Ru(4,4'-(COOEt)2-2,2-bpy)2(NCS)2, a close relative of the efficient "N3" dye used in dye-sensitized solar cells. Using the emerging technique of ultrafast two-dimensional infrared spectroscopy, we show that, similarly to other transition-metal complexes, the central Ru heavy atom acts as a "bottleneck" making the energy transfer from small ligands with high energy vibrational stretching frequencies less favorable and thereby affecting the efficiency of vibrational energy flow in the complex. Comparison of the vibrational relaxation times in the electronic ground and excited state of Ru(4,4'-(COOEt)2-2,2-bpy)2(NCS)2 shows that it is dramatically faster in the latter. We propose to explain this observation by the intramolecular electrostatic interactions between the thiocyanate group and partially oxidised Ru metal center, which increase the degree of vibrational coupling between CN and Ru-N modes in the excited state thus reducing structural and thermodynamic barriers that slow down vibrational relaxation and energy transport in the electronic ground state. As a very similar behavior was earlier observed in another transition-metal complex, Re(4,4'-(COOEt)2-2,2'-bpy)(CO)3Cl, we suggest that this effect in vibrational energy dynamics might be common for transition-metal complexes with heavy central atoms.

  19. Transition metal catalysis in the generation of petroleum and natural gas. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Mango, F.D.

    1997-01-21

    This project originated on the premise that natural gas could be formed catalytically in the earth rather than thermally as commonly believed. The intention was to test this hypothetical view and to explore generally the role of sedimentary metals in the generation of light hydrocarbons (C1 - C9). We showed the metalliferous source rocks are indeed catalytic in the generation of natural gas. Various metal compounds in the pure state show the same levels of catalytic activity as sedimentary rocks and the products are identical. Nickel is particularly active among the early transition metals and is projected to remain catalytically robust at all stages of catagenesis. Nickel oxide promotes the formation of n-alkanes in addition to natural gas (NG), demonstrating the full scope of the hypothetical catalytic process: The composition of catalytic gas duplicates the entire range of natural gas, from so-called wet gas to dry gas (60 to 95+ wt % methane), while gas generated thermally is consistently depleted in methane (10 to 60 wt % methane). These results support the view that metal catalysis is a major pathway through which natural gas is formed in the earth.

  20. An Alternative Approach to the Teaching of Systematic Transition Metal Chemistry.

    Science.gov (United States)

    Hathaway, Brian

    1979-01-01

    Presents an alternative approach to teaching Systematic Transition Metal Chemistry with the transition metal chemistry skeleton features of interest. The "skeleton" is intended as a guide to predicting the chemistry of a selected compound. (Author/SA)

  1. Effects of transition metal oxide doping on the structure of sodium metaphosphate glasses

    Energy Technology Data Exchange (ETDEWEB)

    Zotov, N.; Kirfel, A.; Beuneu, B.; Delaplane, R.; Hohlwein, D.; Reinauer, F.; Glaum, R

    2004-07-15

    Neutron diffraction measurements of transition metal-oxide-doped sodium metaphosphate glasses and melts show an anomalous increase of the first sharp diffraction peak both with increasing transition metal content and temperature due to progressive increase of the structural disorder.

  2. A superconductor to superfluid phase transition in liquid metallic hydrogen.

    Science.gov (United States)

    Babaev, Egor; Sudbø, Asle; Ashcroft, N W

    2004-10-07

    Although hydrogen is the simplest of atoms, it does not form the simplest of solids or liquids. Quantum effects in these phases are considerable (a consequence of the light proton mass) and they have a demonstrable and often puzzling influence on many physical properties, including spatial order. To date, the structure of dense hydrogen remains experimentally elusive. Recent studies of the melting curve of hydrogen indicate that at high (but experimentally accessible) pressures, compressed hydrogen will adopt a liquid state, even at low temperatures. In reaching this phase, hydrogen is also projected to pass through an insulator-to-metal transition. This raises the possibility of new state of matter: a near ground-state liquid metal, and its ordered states in the quantum domain. Ordered quantum fluids are traditionally categorized as superconductors or superfluids; these respective systems feature dissipationless electrical currents or mass flow. Here we report a topological analysis of the projected phase of liquid metallic hydrogen, finding that it may represent a new type of ordered quantum fluid. Specifically, we show that liquid metallic hydrogen cannot be categorized exclusively as a superconductor or superfluid. We predict that, in the presence of a magnetic field, liquid metallic hydrogen will exhibit several phase transitions to ordered states, ranging from superconductors to superfluids.

  3. A new N-hydroxyethyliminodiacetic acid modified core-shell silica phase for chelation ion chromatography of alkaline earth, transition and rare earth elements.

    Science.gov (United States)

    McGillicuddy, Nicola; Nesterenko, Ekaterina P; Nesterenko, Pavel N; Stack, Elaine M; Omamogho, Jesse O; Glennon, Jeremy D; Paull, Brett

    2013-12-20

    Bare core-shell silica (1.7μm) has been modified with iminodiacetic acid functional groups via standard silane chemistry, forming a new N-hydroxyethyliminodiacetic acid (HEIDA) functionalised core-shell stationary phase. The column was applied in high-performance chelation ion chromatography and evaluated for the retention of alkaline earth, transition and heavy metal cations. The influence of nitric acid eluent concentration, addition of complexing agent dipicolinic acid, eluent pH and column temperature on the column performance was investigated. The efficiencies obtained for transition and heavy metal cations (and resultant separations) were comparable or better than those previously obtained for alternative fully porous silica based chelation stationary phases, and a similarly modified monolithic silica column, ranging from ∼15 to 56μm HETP. Increasing the ionic strength of the eluent with the addition of KNO3 (0.75M) and increasing the column temperature (70°C) facilitated the isocratic separation of a mixture of 14 lanthanides and yttrium in under 12min, with HETP averaging 18μm (7μm for Ce(III)). Copyright © 2013 Elsevier B.V. All rights reserved.

  4. Transition metal doped arsenene: A first-principles study

    Science.gov (United States)

    Sun, Minglei; Wang, Sake; Du, Yanhui; Yu, Jin; Tang, Wencheng

    2016-12-01

    Using first-principles calculations, we investigate the structural, electronic, and magnetic properties of 3d transition metal (TM) atoms substitutional doping of an arsenene monolayer. Based on the binding energy, the TM-substituted arsenene systems were found to be robust. Magnetic states were obtained for Ti, V, Cr, Mn and Fe doping. More importantly, a half-metallic state resulted from Ti and Mn doping, while the spin-polarized semiconducting state occurred with V, Cr and Fe doping. Our studies demonstrated the potential applications of TM-substituted arsenene for spintronics and magnetic storage devices.

  5. New synthesis route for ternary transition metal amides as well as ultrafast amide-hydride hydrogen storage materials.

    Science.gov (United States)

    Cao, Hujun; Santoru, Antonio; Pistidda, Claudio; Richter, Theresia M M; Chaudhary, Anna-Lisa; Gizer, Gökhan; Niewa, Rainer; Chen, Ping; Klassen, Thomas; Dornheim, Martin

    2016-04-14

    K2[Mn(NH2)4] and K2[Zn(NH2)4] were successfully synthesized via a mechanochemical method. The mixture of K2[Mn(NH2)4] and LiH showed excellent rehydrogenation properties. In fact, after dehydrogenation K2[Mn(NH2)4]-8LiH fully rehydrogenates within 60 seconds at ca. 230 °C and 5 MPa of H2. This is one of the fastest rehydrogenation rates in amide-hydride systems known to date. This work also shows a strategy for the synthesis of transition metal nitrides by decomposition of the mixtures of M[M'(NH2)n] (where M is an alkali or alkaline earth metal and M' is a transition metal) and metal hydrides.

  6. Process optimization and kinetics for leaching of rare earth metals from the spent Ni-metal hydride batteries.

    Science.gov (United States)

    Meshram, Pratima; Pandey, B D; Mankhand, T R

    2016-05-01

    Nickel-metal hydride batteries (Ni-MH) contain not only the base metals, but valuable rare earth metals (REMs) viz. La, Sm, Nd, Pr and Ce as well. In view of the importance of resource recycling and assured supply of the contained metals in such wastes, the present study has focussed on the leaching of the rare earth metals from the spent Ni-MH batteries. The conditions for the leaching of REMs from the spent batteries were optimized as: 2M H2SO4, 348K temperature and 120min of time at a pulp density (PD) of 100g/L. Under this condition, the leaching of 98.1% Nd, 98.4% Sm, 95.5% Pr and 89.4% Ce was achieved. Besides the rare earth metals, more than 90% of base metals (Ni, Co, Mn and Zn) were also leached out in this condition. Kinetic data for the dissolution of all the rare earth metals showed the best fit to the chemical control shrinking core model. The leaching of metals followed the mechanism involving the chemical reaction proceeding on the surface of particles by the lixiviant, which was corroborated by the XRD phase analysis and SEM-EDS studies. The activation energy of 7.6, 6.3, 11.3 and 13.5kJ/mol was acquired for the leaching of neodymium, samarium, praseodymium and cerium, respectively in the temperature range 305-348K. From the leach liquor, the mixed rare earth metals were precipitated at pH∼1.8 and the precipitated REMs was analyzed by XRD and SEM studies to determine the phases and the morphological features.

  7. Spitzer Transits of the Super-Earth GJ1214b and Implications for Its Atmosphere

    CERN Document Server

    Fraine, Jonathan D; Gillon, Michaël; Jehin, Emmanuël; Demory, Brice-Olivier; Benneke, Bjoern; Seager, Sara; Lewis, Nikole K; Knutson, Heather; Desert, Jean-Michel

    2013-01-01

    We observed the transiting super-Earth exoplanet GJ1214b using Warm Spitzer at 4.5 microns wavelength during a 20-day quasi-continuous sequence in May 2011. The goals of our long observation were to accurately define the infrared transit radius of this nearby super-Earth, to search for the secondary eclipse, and to search for other transiting planets in the habitable zone of GJ1214. We here report results from the transit monitoring of GJ1214b, including a re-analysis of previous transit observations by Desert et al. (2011). In total, we analyse 14 transits of GJ1214b at 4.5 microns, 3 transits at 3.6 microns, and 7 new ground-based transits in the I+z band. Our new Spitzer data by themselves eliminate cloudless solar composition atmospheres for GJ1214b, and methane-rich models from Howe & Burrows (2012). Using our new Spitzer measurements to anchor the observed transit radii of GJ1214b at long wavelengths, and adding new measurements in I+z, we evaluate models from Benneke & Seager (2012) and Howe &a...

  8. Adsorption of rare earth metal ion by algae. Sorui ni yoru kidorui ion no kyuchaku

    Energy Technology Data Exchange (ETDEWEB)

    Kuwabara, T.; Yazawa, A. (Miyagi National College of Technology, Miyagi (Japan))

    1994-02-25

    This paper reports the result of investigations on adsorption of rare earth metal ion by using algae, and adsorption of different metal ions by using egg white and soy bean protein. Rare earth metal ion is adsorbed at a considerably high rate with alga powder of different kinds. The adsorption has been judged to be cation exchange reactive adsorption, while with use of spirulina and chlorella a maximum value of adsorption rate has been observed at pH from 3 to 4.5. Therefore, selective adsorption and separation of metal ions other than rare earth metal ion has become possible. When the blue pigment extracted from spirulina, the spirulina blue, is used, the rare earth metal ion had its selective adsorption and separation performance improved higher than using spirulina itself at pH from 3 to 4.5. As a result of adsorption experiment using egg white and soy bean protein, it has been found that the metal ion adsorption behavior of the spirulina blue depends on coagulative action of protein structure to some extent. However, the sharp selective adsorption performance on rare earth metal ion due to particular pH strength has been found because of actions unique to the pigment structure of phycocyanin, a major component in the spirulina blue. 7 refs., 19 figs.

  9. Spin Transport in Single Layer Transition Metal Dichalcogenides

    Science.gov (United States)

    Phillips, Michael; Aji, Vivek

    Inversion symmetry breaking and strong spin orbit coupling in two dimensional transition metal dichalcogenides leads to interesting new phenomena such as the valley hall and spin hall effects. The nontrivial Berry curvature of the bands yields transverse spin currents in applied field. In this talk we characterize the spin transport in hole-doped systems. Due to the large spin-splitting, time-reversal invariance, and the large separation of hole pockets in momentum space, spin flip scattering involves inter-valley processes with large momentum. As such, one expects large spin life times and a large spin hall angle. We analyze the robustness of the phenomena to various scattering processes and explore the viability of transition metal dichalcogenides for spintronic applications. We acknowledge the support of the NSF via Grant NSF DMR-1506707.

  10. Laser Assisted Additively Manufactured Transition Metal Coating on Aluminum

    Science.gov (United States)

    Vora, Hitesh D.; Rajamure, Ravi Shanker; Roy, Anurag; Srinivasan, S. G.; Sundararajan, G.; Banerjee, Rajarshi; Dahotre, Narendra B.

    2016-07-01

    Various physical and chemical properties of surface and subsurface regions of Al can be improved by the formation of transition metal intermetallic phases (Al x TM y ) via coating of the transition metal (TM). The lower equilibrium solid solubility of TM in Al (laser-aided additive manufacturing approach can effectively synthesize TM intermetallic coatings on the surface of Al. The focus of the present work included the development of process control to achieve thermodynamic and kinetic conditions necessary for desirable physical, microstructural and compositional attributes. A multiphysics finite element model was developed to predict the temperature profile, cooling rate, melt depth, dilution of W in Al matrix and corresponding micro-hardness in the coating, and the interface between the coating and the base material and the base material.

  11. Engineering skyrmions in transition-metal multilayers for spintronics

    Science.gov (United States)

    Dupé, B.; Bihlmayer, G.; Böttcher, M.; Blügel, S.; Heinze, S.

    2016-06-01

    Magnetic skyrmions are localized, topologically protected spin structures that have been proposed for storing or processing information due to their intriguing dynamical and transport properties. Important in terms of applications is the recent discovery of interface stabilized skyrmions as evidenced in ultra-thin transition-metal films. However, so far only skyrmions at interfaces with a single atomic layer of a magnetic material were reported, which greatly limits their potential for application in devices. Here we predict the emergence of skyrmions in [4d/Fe2/5d]n multilayers, that is, structures composed of Fe biatomic layers sandwiched between 4d and 5d transition-metal layers. In these composite structures, the exchange and the Dzyaloshinskii-Moriya interactions that control skyrmion formation can be tuned separately by the two interfaces. This allows engineering skyrmions as shown based on density functional theory and spin dynamics simulations.

  12. Engineering skyrmions in transition-metal multilayers for spintronics.

    Science.gov (United States)

    Dupé, B; Bihlmayer, G; Böttcher, M; Blügel, S; Heinze, S

    2016-06-03

    Magnetic skyrmions are localized, topologically protected spin structures that have been proposed for storing or processing information due to their intriguing dynamical and transport properties. Important in terms of applications is the recent discovery of interface stabilized skyrmions as evidenced in ultra-thin transition-metal films. However, so far only skyrmions at interfaces with a single atomic layer of a magnetic material were reported, which greatly limits their potential for application in devices. Here we predict the emergence of skyrmions in [4d/Fe2/5d]n multilayers, that is, structures composed of Fe biatomic layers sandwiched between 4d and 5d transition-metal layers. In these composite structures, the exchange and the Dzyaloshinskii-Moriya interactions that control skyrmion formation can be tuned separately by the two interfaces. This allows engineering skyrmions as shown based on density functional theory and spin dynamics simulations.

  13. Quantum critical transport at a continuous metal-insulator transition

    Science.gov (United States)

    Haldar, P.; Laad, M. S.; Hassan, S. R.

    2016-08-01

    In contrast to the first-order correlation-driven Mott metal-insulator transition, continuous disorder-driven transitions are intrinsically quantum critical. Here, we investigate transport quantum criticality in the Falicov-Kimball model, a representative of the latter class in the strong disorder category. Employing cluster-dynamical mean-field theory, we find clear and anomalous quantum critical scaling behavior manifesting as perfect mirror symmetry of scaling curves on both sides of the MIT. Surprisingly, we find that the beta function β (g ) scales as log(g ) deep into the bad-metallic phase as well, providing a sound unified basis for these findings. We argue that such strong localization quantum criticality may manifest in real three-dimensional systems where disorder effects are more important than electron-electron interactions.

  14. Comparison between methods for predicting maximum solid solubility of transition metals in solvent metal

    Institute of Scientific and Technical Information of China (English)

    周自强; 方守狮; 冯锋

    2003-01-01

    It is important to know the maximum solid solubility(Cmax) of various transition metals in a metal when one designs multi-component alloys. There have been several semi-empirical approaches to qualitatively predict the Cmax, such as Darken-Gurry(D-G) theorem, Miedema-Chelikowsky(M-C) theorem, electron concentration rule and the bond-parameter rule. However, they are not particularly valid for the prediction of Cmax. It was developed on the basis of energetics of alloys as a new method to predict Cmax of different transition metals in metal Ti, which can be described as a semi-empirical equation using the atomic parameters, i e, electronegativity difference, atomic diameter and electron concentration. It shows that the present method can be used to explain and deduce D-G theorem, M-C theorem and electron concentration rule.

  15. Examination of Solubility Models for the Determination of Transition Metals within Liquid Alkali Metals

    Directory of Open Access Journals (Sweden)

    Jeremy Isler

    2016-06-01

    Full Text Available The experimental solubility of transition metals in liquid alkali metal was compared to the modeled solubility calculated using various equations for solubility. These equations were modeled using the enthalpy calculations of the semi-empirical Miedema model and various entropy calculations. The accuracy of the predicted solubility compared to the experimental data is more dependent on which liquid alkali metal is being examined rather than the transition metal solute examined. For liquid lithium the calculated solubility by the model was generally larger than experimental values, while for liquid cesium the modeling solubility was significantly smaller than the experimental values. For liquid sodium, potassium, and rubidium the experimental solubilities were within the range calculated by this study. Few data approached the predicted temperature dependence of solubility and instead most data exhibited a less pronounced temperature dependence.

  16. Methanol Oxidation on Model Elemental and Bimetallic Transition Metal Surfaces

    DEFF Research Database (Denmark)

    Tritsaris, G. A.; Rossmeisl, J.

    2012-01-01

    Direct methanol fuel cells are a key enabling technology for clean energy conversion. Using density functional theory calculations, we study the methanol oxidation reaction on model electrodes. We discuss trends in reactivity for a set of monometallic and bimetallic transition metal surfaces, flat...... sites on the surface and to screen for novel bimetallic surfaces of enhanced activity. We suggest platinum copper surfaces as promising anode catalysts for direct methanol fuel cells....

  17. Preparation of nanocomposites containing nanoclusters of transition metals

    Energy Technology Data Exchange (ETDEWEB)

    Milne, S.B.; Lukehart, C.M., Wittig, J.E. [Vanderbilt Univ., Nashville, TN (United States)] [and others

    1996-10-01

    New nanocomposites containing nanoclusters of transition metals have been prepared and characterized by TEM, XRD, and energy dispersive spectroscopy. Organometallic or other coordination compounds functionalized with trialkoxysilyl groups have been synthesized and covalently incorporated into silica xerogels using standard sol-gel techniques. Thermal oxidative treatment of these xerogels in air followed by reduction in hydrogen yielded the desired nanocomposite phases. Using these methods, Mo, Re, Fe, Ru, Os, Pd, Pt, Cu. and Ag nanocomposites have been prepared.

  18. Exciton ionization in multilayer transition-metal dichalcogenides

    DEFF Research Database (Denmark)

    Pedersen, Thomas Garm; Latini, Simone; Thygesen, Kristian Sommer;

    2016-01-01

    Photodetectors and solar cells based on materials with strongly bound excitons rely crucially on field-assisted exciton ionization. We study the ionization process in multilayer transition-metal dichalcogenides (TMDs) within the Mott-Wannier model incorporating fully the pronounced anisotropy......-principles material parameters, an analysis of several important TMDs reveals WSe2 and MoSe2 to be superior for applications relying on ionization of direct and indirect excitons, respectively....

  19. Cointercalation of titanium dichalcogenides with transition metals and copper

    Science.gov (United States)

    Titov, A. A.; Titov, A. N.; Titova, S. G.; Pryanichnikov, S. V.; Chezganov, D. S.

    2017-01-01

    Cointercalated materials are studied, obtained by introducing copper into a TiSe2 lattice preintercalated with transition metals M = Mn, Fe, Co, or Ni. The analysis of the state of cointercalated systems at 950°C shows that copper reduces manganese and iron, but it is incapable of reducing cobalt or nickel. To explain the results, the values of the binding energy of hybrid states M3d/Ti3 d are compared.

  20. Unique reactivity of fluorinated molecules with transition metals.

    Science.gov (United States)

    Catalán, Silvia; Munoz, Sócrates B; Fustero, Santos

    2014-01-01

    Organofluorine and organometallic chemistry by themselves constitute two potent areas in organic synthesis. Thus, the combination of both offers many chemical possibilities and represents a powerful tool for the design and development of new synthetic methodologies leading to diverse molecular structures in an efficient manner. Given the importance of the selective introduction of fluorine atoms into organic molecules and the effectiveness of transition metals in C-C and C-heteroatom bond formation, this review represents an interesting read for this aim.

  1. Zwitterionic Group VIII transition metal initiators supported by olefin ligands

    Science.gov (United States)

    Bazan, Guillermo C.; Chen, Yaofeng

    2011-10-25

    A zwitterionic Group VIII transition metal complex containing the simple and relatively small 3-(arylimino)-but-1-en-2-olato ligand that catalyzes the formation of polypropylene and high molecular weight polyethylene. A novel feature of this catalyst is that the active species is stabilized by a chelated olefin adduct. The present invention also provides methods of polymerizing olefin monomers using zwitterionic catalysts, particularly polypropylene and high molecular weight polyethylene.

  2. Applications of Transition Metals in Organic Synthesis and Polymerization

    Institute of Scientific and Technical Information of China (English)

    Praveen; K.Tandon; Manish; Srivastava; Santosh; B.Singh

    2007-01-01

    1 Results Classic oxidants require rigorous control of the experimental conditions added with the problem of lack of selectivity. Catalysis by transition metals with environmentally safe oxidants provides synthetic routes to minimize pollution by giving environmental benign by-products. Fe (Ⅵ) is a powerful and a selective oxidant with Fe(Ⅲ) as a by-product, while hydrogen peroxide is clean with water as the only by-product. Separation of sodium or potassium ferrates requires tedious processes. Associat...

  3. The energetics of ordered intermetallic alloys (of the transition metals)

    Energy Technology Data Exchange (ETDEWEB)

    Watson, R.E.; Weinert, M.; Davenport, J.W. (Brookhaven National Lab., Upton, NY (United States)); Fernando, G.W. (Connecticut Univ., Storrs, CT (United States). Dept. of Physics); Bennett, L.H. (National Inst. of Standards and Technology, Gaithersburg, MD (United States). Metallurgy Div.)

    1992-01-01

    The atomically ordered phases in ordered transition metal alloys are discussed. This chapter is divided into: physical parameters controlling phase stability (Hume-Rothery, structural maps, Miedema Hamiltonian), wave functions band theory, comment on entropy terms, cohesive energies (electron promotion energies, Hund's rule on orbital effects), structural energies/stabilities of elemental solids, total energies and atomic positions, charge transfer (Au alloys, charge tailing), heats of formation of ordered compounds.

  4. The energetics of ordered intermetallic alloys (of the transition metals)

    Energy Technology Data Exchange (ETDEWEB)

    Watson, R.E.; Weinert, M.; Davenport, J.W. [Brookhaven National Lab., Upton, NY (United States); Fernando, G.W. [Connecticut Univ., Storrs, CT (United States). Dept. of Physics; Bennett, L.H. [National Inst. of Standards and Technology, Gaithersburg, MD (United States). Metallurgy Div.

    1992-10-01

    The atomically ordered phases in ordered transition metal alloys are discussed. This chapter is divided into: physical parameters controlling phase stability (Hume-Rothery, structural maps, Miedema Hamiltonian), wave functions & band theory, comment on entropy terms, cohesive energies (electron promotion energies, Hund`s rule on orbital effects), structural energies/stabilities of elemental solids, total energies and atomic positions, charge transfer (Au alloys, charge tailing), heats of formation of ordered compounds.

  5. Current noise in some transition-metal compounds

    NARCIS (Netherlands)

    Kleinpenning, Th.G.M.

    1972-01-01

    Measurements are reported on current noise in some single crystals of transition-metal compounds, namely: reduced Al-doped rutile (TiO2), Li-doped NiO, Li-doped CoO and Ga-doped CdCr2Se4. Also results obtained with polycrystalline Ga-doped CdCr2Se4 are reported. The current-noise spectra of the mate

  6. THE TRANSFER OF ALKALINE EARTH-METAL ION AT W/NB INTERFACE FACILITATED BY JOSAMYCIN

    Institute of Scientific and Technical Information of China (English)

    范瑞溪; 狄俊伟

    1991-01-01

    This paper describes the invesligation of the transfer behaviour of the alkaline earth-metal cations across the water/nitrobenzene interface facilitated by josamycin in the nitrobenzene phase using semi-differential cyclic voltammetry .The peak height is directly proportional to the concentration of josaycin (nb) and to the potential scan rate.The complexes formed from alkaline earth-metal ions and josamycin at the w/nb interface are ML22+ ion.

  7. The development of a biological interface for transition metal implants

    Science.gov (United States)

    Melton, Kim R.

    The specific goal of this research was to develop an in vitro model for a root-form endosseous dental implant that contains a periodontal ligament and that is biologically integratable into alveolar bone. This objective was based on the following two hypotheses. (1) The chemical attachment of extracellular matrix proteins to the surface of transition metals increases the number of fibroblast cells attached to the surface of the metal. (2) The chemical attachment of extracellular matrix proteins to the surface of transition metals increases the strength of the fibroblast cell attachment to the surface of the metal. The model needed to have a well-controlled surface that was reproducible. Thus, a layer of Au was deposited over a Ti base, and dithiobis(succinimidylpropionate) (DSP) a chemical containing disulfide groups was adsorbed to the Au. Next, extracellular matrix proteins which are periodontal ligament components were attached to the free end group of the chemical that was adsorbed to the Au. This surface served as an attachment substrate on which additional periodontal ligament components such as fibroblast cells could grow. From this model a new implant interface may be developed. This model was tested using the following polypeptides; collagen type I, collagen type IV, fibronectin, and poly-D-lysine. L929 cells were grown on Ti, Ti + Au, Ti + Au + polypeptide, and Ti + Au + DSP + polypeptide. After 72 hours, the live cells were stained with neutral red. The substrates were then subjected to increasing centrifugal forces. The viable stained cells were fixed onto the substrates and cells were counted. The hypotheses were proven for three polypeptides: fibronectin, collagen type I, and poly-D-lysine. The strongest attachment was found with collagen type I. Collagen type IV did not provide any advantage for attachment over uncoated transition metals.

  8. A Spitzer search for transits of radial velocity detected super-Earths

    Energy Technology Data Exchange (ETDEWEB)

    Kammer, J. A.; Knutson, H. A.; Desert, J.-M. [Division of Geological and Planetary Sciences, California Institute of Technology, Pasadena, CA 91125 (United States); Howard, A. W. [Institute for Astronomy, University of Hawaii, Honolulu, HI 96822 (United States); Laughlin, G. P.; Fortney, J. J. [Department of Astronomy and Astrophysics, University of California at Santa Cruz, Santa Cruz, CA 95064 (United States); Deming, D. [Department of Astronomy, University of Maryland at College Park, College Park, MD 20742 (United States); Todorov, K. O. [Institute for Astronomy, ETH Zürich, CH-8093 Zürich (Switzerland); Agol, E. [Department of Astronomy, University of Washington, Seattle, WA 98195 (United States); Burrows, A. [Department of Astrophysical Sciences, Princeton University, Princeton, NJ 08544 (United States); Showman, A. P. [Lunar and Planetary Laboratory, University of Arizona, Tucson, AZ 85721 (United States); Lewis, N. K., E-mail: jkammer@caltech.edu [Department of Earth, Atmospheric, and Planetary Sciences, Massachusetts Institute of Technology, Cambridge, MA 02139 (United States)

    2014-02-01

    Unlike hot Jupiters or other gas giants, super-Earths are expected to have a wide variety of compositions, ranging from terrestrial bodies like our own to more gaseous planets like Neptune. Observations of transiting systems, which allow us to directly measure planet masses and radii and constrain atmospheric properties, are key to understanding the compositional diversity of the planets in this mass range. Although Kepler has discovered hundreds of transiting super-Earth candidates over the past 4 yr, the majority of these planets orbit stars that are too far away and too faint to allow for detailed atmospheric characterization and reliable mass estimates. Ground-based transit surveys focus on much brighter stars, but most lack the sensitivity to detect planets in this size range. One way to get around the difficulty of finding these smaller planets in transit is to start by choosing targets that are already known to host super-Earth sized bodies detected using the radial velocity (RV) technique. Here we present results from a Spitzer program to observe six of the most favorable RV-detected super-Earth systems, including HD 1461, HD 7924, HD 156668, HIP 57274, and GJ 876. We find no evidence for transits in any of their 4.5 μm flux light curves, and place limits on the allowed transit depths and corresponding planet radii that rule out even the most dense and iron-rich compositions for these objects. We also observed HD 97658, but the observation window was based on a possible ground-based transit detection that was later ruled out; thus the window did not include the predicted time for the transit detection recently made by the Microvariability and Oscillations of Stars space telescope.

  9. Theory of the pairbreaking superconductor-metal transition in nanowires

    Science.gov (United States)

    Sachdev, Subir

    2009-03-01

    We present a detailed description of a zero temperature phase transition between superconducting and diffusive metallic states in very thin wires due to a Cooper pair breaking mechanism. The dissipative critical theory contains current reducing fluctuations in the guise of both quantum and thermally activated phase slips. A full cross-over phase diagram is computed via an expansion in the inverse number of complex components of the superconducting order parameter (one in the physical case). The fluctuation corrections to the electrical (σ) and thermal (κ) conductivities are determined, and we find that σ has a non-monotonic temperature dependence in the metallic phase which may be consistent with recent experimental results on ultra-narrow wires. In the quantum critical regime, the ratio of the thermal to electrical conductivity displays a linear temperature dependence and thus the Wiedemann-Franz law is obeyed, with a new universal experimentally verifiable Lorenz number. We also examined the influence of quenched disorder on the superconductor-metal transition. The self-consistent pairing eigenmodes of a quasi-one dimensional wire were determined numerically. Our results support the proposal by Hoyos et al./ (Phys. Rev. Lett. 99, 230601 (2007)) that the transition is described by the same strong disorder fixed point describing the onset of ferromagnetism in the quantum Ising model in a transverse field.

  10. Pressure induced structural phase transition in IB transition metal nitrides compounds

    Energy Technology Data Exchange (ETDEWEB)

    Soni, Shubhangi; Kaurav, Netram, E-mail: netramkaurav@yahoo.co.uk; Jain, A. [Department of Physics, Govt. Holkar Science college, A. B. Road, Indore-452001 India (India); Shah, S. [Department of Physics, P. M. B. Gujarati Science College, Indore-452001 (India); Choudhary, K. K. [Department of Physics, National Defence Academy, Khadakwasla, Pune-411 0231 India (India)

    2015-06-24

    Transition metal mononitrides are known as refractory compounds, and they have, relatively, high hardness, brittleness, melting point, and superconducting transition temperature, and they also have interesting optical, electronic, catalytic, and magnetic properties. Evolution of structural properties would be an important step towards realizing the potential technological scenario of this material of class. In the present study, an effective interionic interaction potential (EIOP) is developed to investigate the pressure induced phase transitions in IB transition metal nitrides TMN [TM = Cu, Ag, and Au] compounds. The long range Coulomb, van der Waals (vdW) interaction and the short-range repulsive interaction upto second-neighbor ions within the Hafemeister and Flygare approach with modified ionic charge are properly incorporated in the EIOP. The vdW coefficients are computed following the Slater-Kirkwood variational method, as both the ions are polarizable. The estimated value of the phase transition pressure (Pt) and the magnitude of the discontinuity in volume at the transition pressure are consistent as compared to the reported data.

  11. Synthesis and Characterization of some First Row Transition Metal Picrates

    Directory of Open Access Journals (Sweden)

    R. C. Aggarwal

    1975-10-01

    Full Text Available Transition metal picrates of the empirical compositions Ti(Picrate CI/Sub3, Ti (Picrate/Sub2CI/Sub2, Cr (OH (H/Sub2O/Sub6 (Pierate/Sub2 and M(H/Sub2Ox (Picrate/Sub2 (where M=Mn (II, Fe (II, Co(II, Ni(II, Cu(II and Zn(II and x=4for Cu(II, 8 for Fe(II & 6 for others have been prepared and characterized by elemental analysis, molar conductance, magnetic susceptibility measurements, infrared and electronic spectral studies. Molar conductances and molecular weights of the soluble metal picrates show that TiCI/Sub2 (Picrate/Sub2 is non electrolyte whereas others are 1:2 electrolytes. Magnetic susceptibility and electronic spectral I studies indicate that(II picrate is square planar, whereas those of Cr(III Mn(II0, Fe(II,Co(II and NI(II are spin free octahedral. The infrared spectral studies of the hydrated and anhydrous metal picrates show: (i that phenolic group of the picric acid is involved in bounding with the metals;(ii the water molecules in the hydrated metal picrates coordinated and (iii the-NO/Sub2 groups do not participate in bonding with the metals.

  12. Metal-insulator transition: the Mott criterion and coherence length

    CERN Document Server

    Pergament, A

    2003-01-01

    On the basis of the Mott criterion for metal-insulator transition (MIT), an expression for the correlation length, identical to that for the coherence length in the theory of superconductivity, is obtained. This correlation length characterizes the size of an electron-hole pair (in an excitonic insulator) or the effective Bohr radius (as, e.g., in doped semiconductors). The relation obtained is used for calculation of the coherence length in vanadium dioxide. The presence of two characteristic coherence lengths (xi sub 1 approx 20 A and xi sub 2 approx 2 A) is found. This is associated with the specific features of the transition mechanism in VO sub 2 : this mechanism represents a combination of the purely electronic Mott-Hubbard contribution and the structural (Peierls-like) one. It is shown, however, that the driving force of the MIT in VO sub 2 is the electron-correlation Mott-Hubbard transition.

  13. Spatiotemporal Analysis of Heavy Metal Water Pollution in Transitional China

    Directory of Open Access Journals (Sweden)

    Huixuan Li

    2015-07-01

    Full Text Available China’s socioeconomic transitions have dramatically accelerated its economic growth in last three decades, but also companioned with continuous environmental degradation. This study will advance the knowledge of heavy metal water pollution in China from a spatial–temporal perspective. Specifically, this study addressed the following: (1 spatial patterns of heavy metal water pollution levels were analyzed using data of prefecture-level cities from 2004 to 2011; and (2 spatial statistical methods were used to examine the underlying socioeconomic and physical factors behind water pollution including socioeconomic transitions (industrialization, urbanization, globalization and economic development, and environmental characteristic (natural resources, hydrology and vegetation coverage. The results show that only Cr pollution levels increased over the years. The individual pollution levels of the other four heavy metals, As, Cd, Hg, and Pb, declined. High heavy metal water pollution levels are closely associated with both anthropogenic activities and physical environments, in particular abundant mineral resources and industrialization prosperity. On the other hand, economic development and urbanization play important roles in controlling water pollution problems. The analytical findings will provide valuable information for policy-makers to initiate and adjust protocols and strategies for protecting water sources and controlling water pollution; thus improving the quality of living environments.

  14. Metal-insulator transition in oriented poly(p-phenylenevinylene)

    Science.gov (United States)

    Ahlskog, M.; Menon, Reghu; Heeger, A. J.; Noguchi, T.; Ohnishi, T.

    1997-03-01

    The transport properties of H2 SO4 -doped, tensile drawn, and oriented poly(phenylenevinylene) have been studied in the metallic, critical, and insulating regimes of the disorder-induced metal-insulator transition (M-I) transition. The temperature dependence of the conductivity, σ(T) and the magnetoconductance (MC) were investigated between room temperature and 1.3 K and in magnetic fields up to 8 T, in freshly doped samples and in samples during controlled dedoping (aging). A complete set of measurements were carried out on a single, fully doped sample that was followed during ageing from the metallic state through the critical regime into the insulting state. The transport properties are characterized as a function of the resistivity ratio (ρr), where ρr=[ρ(1.3 K)/ρ(200 K)]. In the metallic regime (ρr50), ρ(T)~exp(T0/T)x indicating variable-range-hopping transport. Although anisotropic, the field and temperature dependences of the transport are similar both parallel and perpendicular to the chain axis, implying that oriented conducting polymers are anisotropic three-dimensional conductors.

  15. Thermophysical Property Measurements of Silicon-Transition Metal Alloys

    Science.gov (United States)

    Banish, R. Michael; Erwin, William R.; Sansoucie, Michael P.; Lee, Jonghyun; Gave, Matthew A.

    2014-01-01

    Metals and metallic alloys often have high melting temperatures and highly reactive liquids. Processing reactive liquids in containers can result in significant contamination and limited undercooling. This is particularly true for molten silicon and it alloys. Silicon is commonly termed "the universal solvent". The viscosity, surface tension, and density of several silicon-transition metal alloys were determined using the Electrostatic Levitator system at the Marshall Space Flight Center. The temperature dependence of the viscosity followed an Arrhenius dependence, and the surface tension followed a linear temperature dependence. The density of the melts, including the undercooled region, showed a linear behavior as well. Viscosity and surface tension values were obtain for several of the alloys in the undercooled region.

  16. Transition-metal prion protein attachment: Competition with copper

    Science.gov (United States)

    Hodak, Miroslav; Bernholc, Jerry

    2012-02-01

    Prion protein, PrP, is a protein capable of binding copper ions in multiple modes depending on their concentration. Misfolded PrP is implicated in a group of neurodegenerative diseases, which include ``mad cow disease'' and its human form, variant Creutzfeld-Jacob disease. An increasing amount of evidence suggests that attachment of non-copper metal ions to PrP triggers transformations to abnormal forms similar to those observed in prion diseases. In this work, we use hybrid Kohn-Sham/orbital-free density functional theory simulations to investigate copper replacement by other transition metals that bind to PrP, including zinc, iron and manganese. We consider all known copper binding modes in the N-terminal domain of PrP. Our calculations identify modes most susceptible to copper replacement and reveal metals that can successfully compete with copper for attachment to PrP.

  17. Quantum-based Atomistic Simulation of Transition Metals

    Energy Technology Data Exchange (ETDEWEB)

    Moriarty, J A; Benedict, L X; Glosli, J N; Hood, R Q; Orlikowski, D A; Patel, M V; Soderlind, P; Streitz, F H; Tang, M; Yang, L H

    2005-08-29

    First-principles generalized pseudopotential theory (GPT) provides a fundamental basis for transferable multi-ion interatomic potentials in d-electron transition metals within density-functional quantum mechanics. In mid-period bcc metals, where multi-ion angular forces are important to structural properties, simplified model GPT or MGPT potentials have been developed based on canonical d bands to allow analytic forms and large-scale atomistic simulations. Robust, advanced-generation MGPT potentials have now been obtained for Ta and Mo and successfully applied to a wide range of structural, thermodynamic, defect and mechanical properties at both ambient and extreme conditions of pressure and temperature. Recent algorithm improvements have also led to a more general matrix representation of MGPT beyond canonical bands allowing increased accuracy and extension to f-electron actinide metals, an order of magnitude increase in computational speed, and the current development of temperature-dependent potentials.

  18. Thermal transport across a continuous metal-insulator transition

    Science.gov (United States)

    Haldar, P.; Laad, M. S.; Hassan, S. R.

    2017-09-01

    The celebrated Wiedemann-Franz (WF) law is believed to be robust in metals as long as interactions between electrons preserve their fermion-quasiparticle character. We study thermal transport and the fate of the WF law close to a continuous metal-insulator transition (MIT) in the Falicov-Kimball model (FKM) using cluster-dynamical mean-field theory (CDMFT). Surprisingly, as for electrical transport, we find robust and novel quantum critical scaling in thermal transport across the MIT. We unearth the deeper reasons for these novel findings in terms of (i) the specific structure of energy-current correlations for the FKM and (ii) the microscopic electronic processes which facilitate energy transport while simultaneously blocking charge transport close to the MIT. However, within (C)DMFT, we also find that the WF law survives at T ⟶0 in the incoherent metal right up to the MIT, even in absence of Landau quasiparticles.

  19. The effects of refraction on transit transmission spectroscopy: application to Earth-like exoplanets

    Energy Technology Data Exchange (ETDEWEB)

    Misra, Amit; Meadows, Victoria [Astronomy Department, University of Washington, Box 351580, Seattle, WA 98195 (United States); Crisp, Dave, E-mail: amit0@astro.washington.edu [NAI Virtual Planetary Laboratory, Seattle, WA (United States)

    2014-09-01

    We quantify the effects of refraction in transit transmission spectroscopy on spectral absorption features and on temporal variations that could be used to obtain altitude-dependent spectra for planets orbiting stars of different stellar types. We validate our model against altitude-dependent transmission spectra of the Earth from ATMOS and against lunar eclipse spectra from Pallé et al. We perform detectability studies to show the potential effects of refraction on hypothetical observations of Earth analogs with the James Webb Space Telescope NIRSPEC. Due to refraction, there will be a maximum tangent pressure level that can be probed during transit for each given planet-star system. We show that because of refraction, for an Earth-analog planet orbiting in the habitable zone of a Sun-like star only the top 0.3 bars of the atmosphere can be probed, leading to a decrease in the signal-to-noise ratio (S/N) of absorption features by 60%, while for an Earth-analog planet orbiting in the habitable zone of an M5V star it is possible to probe almost the entire atmosphere with minimal decreases in S/N. We also show that refraction can result in temporal variations in the transit transmission spectrum which may provide a way to obtain altitude-dependent spectra of exoplanet atmospheres. Additionally, the variations prior to ingress and subsequent to egress provide a way to probe pressures greater than the maximum tangent pressure that can be probed during transit. Therefore, probing the maximum range of atmospheric altitudes, and in particular the near-surface environment of an Earth-analog exoplanet, will require looking at out-of-transit refracted light in addition to the in-transit spectrum.

  20. Alkali cation specific adsorption onto fcc(111) transition metal electrodes.

    Science.gov (United States)

    Mills, J N; McCrum, I T; Janik, M J

    2014-07-21

    The presence of alkali cations in electrolyte solutions is known to impact the rate of electrocatalytic reactions, though the mechanism of such impact is not conclusively determined. We use density functional theory (DFT) to examine the specific adsorption of alkali cations to fcc(111) electrode surfaces, as specific adsorption may block catalyst sites or otherwise impact surface catalytic chemistry. Solvation of the cation-metal surface structure was investigated using explicit water models. Computed equilibrium potentials for alkali cation adsorption suggest that alkali and alkaline earth cations will specifically adsorb onto Pt(111) and Pd(111) surfaces in the potential range of hydrogen oxidation and hydrogen evolution catalysis in alkaline solutions.

  1. Polaronic Transport in Phosphate Glasses Containing Transition Metal Ions

    Science.gov (United States)

    Henderson, Mark

    The goal of this dissertation is to characterize the basic transport properties of phosphate glasses containing various amounts of TIs and to identify and explain any electronic phase transitions which may occur. The P2 O5-V2O5-WO3 (PVW) glass system will be analyzed to find the effect of TI concentration on conduction. In addition, the effect of the relative concentrations of network forming ions (SiO2 and P2O5) on transport will be studied in the P2O5-SiO2-Fe2O 3 (PSF) system. Also presented is a numerical study on a tight-binding model adapted for the purposes of modelling Gaussian traps, mimicking TI's, which are arranged in an extended network. The results of this project will contribute to the development of fundamental theories on the electronic transport in glasses containing mixtures of transition oxides as well as those containing multiple network formers without discernible phase separation. The present study on the PVW follows up on previous investigation into the effect on mixed transition ions in oxide glasses. Past research has focused on glasses containing transition metal ions from the 3d row. The inclusion of tungsten, a 5d transition metal, adds a layer of complexity through the mismatch of the energies of the orbitals contributing to localized states. The data have indicated that a transition reminiscent of a metal-insulator transition (MIT) occurs in this system as the concentration of tungsten increases. As opposed to some other MIT-like transitions found in phosphate glass systems, there seems to be no polaron to bipolaron conversion. Instead, the individual localization parameter for tungsten noticeably decreases dramatically at the transition point as well as the adiabaticity. Another distinctive feature of this project is the study of the PSF system, which contains two true network formers, phosphorous pentoxide (P2O 5) and silicon dioxide (SiO2). It is not usually possible to do a reliable investigation of the conduction properties of

  2. Rare Earth Application in Sealing Anodized Al-Based Metal Matrix Composites

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    A new method for corrosion protection of Al-based metal matrixcomposites (MMC) was developed using two-step process, which involves anodizing in H2SO4 solution and sealing in rare earth solution. Corrosion resistance of the treated surface was evaluated with polarization curves.The results showed that the effect of the protection using rare earth sealing is equivalent to that using chromate sealing for Al6061/SiCp. The rare earth metal salt can be an alternative to the toxic chromate for sealing anodized Al MMC.

  3. Role of alkali metal promoter in enhancing lateral growth of monolayer transition metal dichalcogenides

    Science.gov (United States)

    Kim, Hyun; Han, Gang Hee; Yun, Seok Joon; Zhao, Jiong; Keum, Dong Hoon; Jeong, Hye Yun; Hue Ly, Thuc; Jin, Youngjo; Park, Ji-Hoon; Moon, Byoung Hee; Kim, Sung-Wng; Lee, Young Hee

    2017-09-01

    Synthesis of monolayer transition metal dichalcogenides (TMDs) via chemical vapor deposition relies on several factors such as precursor, promoter, substrate, and surface treatment of substrate. Among them, the use of promoter is crucial for obtaining uniform and large-area monolayer TMDs. Although promoters have been speculated to enhance adhesion of precursors to the substrate, their precise role in the growth mechanism has rarely been discussed. Here, we report the role of alkali metal promoter in growing monolayer TMDs. The growth occurred via the formation of sodium metal oxides which prevent the evaporation of metal precursor. Furthermore, the silicon oxide substrate helped to decrease the Gibbs free energy by forming sodium silicon oxide compounds. The resulting sodium metal oxide was anchored within such concavities created by corrosion of silicon oxide. Consequently, the wettability of the precursors to silicon oxide was improved, leading to enhance lateral growth of monolayer TMDs.

  4. Potentiometric and spectroscopic study of the interaction of 3d transition metal ions with inositol hexakisphosphate

    Science.gov (United States)

    Veiga, Nicolás; Macho, Israel; Gómez, Kerman; González, Gabriel; Kremer, Carlos; Torres, Julia

    2015-10-01

    Among myo-inositol phosphates, the most abundant in nature is the myo-inositol hexakisphosphate, InsP6. Although it is known to be vital to cell functioning, the biochemical research into its metabolism needs chemical and structural analysis of all the protonation, complexation and precipitation processes that it undergoes in the biological media. In view of its high negative charge at physiological level, our group has been leading a thorough research into the InsP6 chemical and structural behavior in the presence of the alkali and alkaline earth metal ions essential for life. The aim of this article is to extend these studies, dealing with the chemical and structural features of the InsP6 interaction with biologically relevant 3d transition metal ions (Fe(II), Fe(III), Mn(II), Co(II), Ni(II), Cu(II) and Zn(II)), in a non-interacting medium and under simulated physiological conditions. The metal-complex stability constants were determined by potentiometry, showing under ligand-excess conditions the formation of mononuclear species in different protonation states. Under metal ion excess, polymetallic species were detected for Fe(II), Fe(III), Zn(II) and Cu(II). Additionally, the 31P NMR and UV-vis spectroscopic studies provided interesting structural aspects of the strong metal ion-InsP6 interaction.

  5. High-temperature corrosion of metals in the salt and metallic melts containing rare earths

    Science.gov (United States)

    Karpov, V. V.; Abramov, A. V.; Zhilyakov, A. Yu.; Belikov, S. V.; Volkovich, V. A.; Polovov, I. B.; Rebrin, O. I.

    2016-09-01

    A complex of independent methods was employed to study the corrosion resistance of molybdenum, zirconium, tantalum and tungsten in chloride, chloride-fluoride and fluoride-oxide melts based on LiCl, CaCl2, NaCl- KCl, LiF, and containing rare earths. Tests were conducted for 30 h at 750-1050 °C. The metals showed excellent corrosion resistance in fused chlorides (the corrosion rates were below 0.0005 g/(m2 h). Despite the presence of chemically active fluoride ions in the chloride-fluoride melts, the metals studied also showed very low corrosion rates, except molybdenum, for which the rate of corrosion was 0,8 g/(m2 h). The corrosion resistance of tantalum was considerably reduced in the fluoride-oxide melts; the corrosion rate was over 1 g/(m2 h) corresponding to the 8-th grade of stability and placing tantalum to the group of "low stability" materials.

  6. Study on leaching rare earths from bastnaesite treated by calcification transition

    Institute of Scientific and Technical Information of China (English)

    黄宇坤; 张廷安; 豆志河; 刘江; 唐方方

    2014-01-01

    Extracting rare earths from bastnaesite concentrate treated by calcification transition was studied through the single factor test and XRD patterns of bastnaesite after calcification and slags after leaching in HCl solution. And the effects of the main calcified parameters such as temperature, liquid/solid and calcified time on transition performance of bastnaesite were investigated. It was found that under the optimal conditions of calcification temperature of 250 ºC, liquid/solid of 20 mL/g, calcification time of 180 min, the highest leaching rate of rare earth were obtained, with the leaching ratio of rare earths 83.70%and Ce 77.01%, La 90.55%, Nd 92.03%, respectively;loss rates of fluorine with different calcification conditions were always less than 1%and XRD patterns of cal-cification slags and leaching slags showed that fluorine existed in the form of CaF2.

  7. High-purity rare-earth metals: preparation, properties, and application

    Institute of Scientific and Technical Information of China (English)

    Kol'chugina; N.; B.; Burkhanov; G.; S.; Chistyakov; O.; D.; Burkhanov; Yu.; S.

    2005-01-01

    In recent years, the ever-growing interest of investigators to the study of rare-earth metals REM) is observed owing to unique properties of the metals and potential uses in electronics, laser technology, space technology, medicine, and many other high-technology applications.……

  8. High-purity rare-earth metals: preparation, properties, and application

    Institute of Scientific and Technical Information of China (English)

    2005-01-01

    @@ In recent years, the ever-growing interest of investigators to the study of rare-earth metals REM) is observed owing to unique properties of the metals and potential uses in electronics, laser technology, space technology, medicine, and many other high-technology applications.

  9. 40 CFR 421.270 - Applicability: Description of the primary rare earth metals subcategory.

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 28 2010-07-01 2010-07-01 true Applicability: Description of the primary rare earth metals subcategory. 421.270 Section 421.270 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) EFFLUENT GUIDELINES AND STANDARDS NONFERROUS METALS MANUFACTURING POINT...

  10. Disorder and metal-insulator transitions in Weyl semimetals

    Science.gov (United States)

    Jiang, Hua; Chen, Chui-Zhen; Song, Juntao; Sun, Qing-Feng; Wang, Ziqiang; Xie, X. C.

    The Weyl semimetal (WSM) is a newly proposed quantum state of matter. It has Weyl nodes in bulk excitations and Fermi arcs surface states. We study the effects of disorder and localization in WSMs and find three novel phase transitions.(I) Two Weyl nodes near the Brillouin zone boundary can be annihilated pairwise by disorder scattering, resulting in the opening of a topologically nontrivial gap and a transition from a WSM to a three-dimensional (3D) quantum anomalous Hall state. (II) When the two Weyl nodes are well separated in momentum space, the emergent bulk extended states can give rise to a direct transition from a WSM to a 3D diffusive anomalous Hall metal. (III) Two Weyl nodes can emerge near the zone center when an insulating gap closes with increasing disorder, enabling a direct transition from a normal band insulator to a WSM. We determine the phase diagram by numerically computing the localization length and the Hall conductivity, and propose that the novel phase transitions can be realized on a photonic lattice.

  11. Reconstructing Earth's Surface Oxidation Across The Archean- Proterozoic Transition

    Science.gov (United States)

    Kaufman, A. J.; Guo, Q.; Strauss, H.; Schröder, S.; Gutzmer, J.; Wing, B. A.; Baker, M.; Bekker, A.; Jin, Q.; Kim, S.; Farquhar, J.

    2010-12-01

    The Archean-Proterozoic transition is characterized by the widespread deposition of organic-rich shale, sedimentary iron formation, glacial diamictite, and marine carbonates recording profound carbon isotope anomalies, but notably lacks bedded evaporites. All deposits reflect environmental changes in oceanic and atmospheric redox states, in part associated with Earth’s earliest ice ages. Time-series data for multiple sulfur isotopes from carbonate associated sulfate as well as sulfides in the glaciogenic Duitschland Formation of the Transvaal Supergroup, South Africa, capture the concomitant buildup of sulfate in the ocean and the loss of mass independent sulfur isotope fractionation. This is arguably associated with the atmospheric rise of oxygen (as well as the protective ozone layer) coincident with profound changes in ocean chemistry and biology. The loss of the MIF signal within the Duitschland succession is in phase with the earliest recorded positive carbon isotope anomaly, convincingly linking these environmental perturbations to the Great Oxidation Event (ca. 2.3 Ga). The emergence of cyanobacteria and oxygenic photosynthesis may be associated with a geochemical “whiff of oxygen” recorded in 2.5 Ga sediments. If true, the delay in the GOE can then be understood in terms of a finite sink for molecular oxygen - ferrous iron, which was abundant in deep Neoarchean seawater and sequestered in a worldwide episode of iron formation deposition ending shortly before accumulation of the Duitschland Formation. Insofar as early Paleoproterozoic glaciation is associated with oxygenation of a methane-rich atmosphere, we conclude that Earth’s earliest ice age(s) and the onset of a modern and far more energetic carbon cycle are directly related to the global expansion of cyanobacteria that released oxygen to the environment, and of eukaryotes that respired it.

  12. Enabling the transition towards Earth Observation Science 2.0

    Science.gov (United States)

    Mathieu, Pierre-Philippe; Desnos, Yves-Louis

    2015-04-01

    Science 2.0 refers to the rapid and systematic changes in doing Research and organising Science driven by the rapid advances in ICT and digital technologies combined with a growing demand to do Science for Society (actionable research) and in Society (co-design of knowledge). Nowadays, teams of researchers around the world can easily access a wide range of open data across disciplines and remotely process them on the Cloud, combining them with their own data to generate knowledge, develop information products for societal applications, and tackle complex integrative complex problems that could not be addressed a few years ago. Such rapid exchange of digital data is fostering a new world of data-intensive research, characterized by openness, transparency, and scrutiny and traceability of results, access to large volume of complex data, availability of community open tools, unprecedented level of computing power, and new collaboration among researchers and new actors such as citizen scientists. The EO scientific community is now facing the challenge of responding to this new paradigm in science 2.0 in order to make the most of the large volume of complex and diverse data delivered by the new generation of EO missions, and in particular the Sentinels. In this context, ESA - in particular within the framework of the Scientific Exploitation of Operational Missions (SEOM) element - is supporting a variety of activities in partnership with research communities to ease the transition and make the most of the data. These include the generation of new open tools and exploitation platforms, exploring new ways to exploit data on cloud-based platforms, dissiminate data, building new partnership with citizen scientists, and training the new generation of data scientists. The paper will give a brief overview of some of ESA activities aiming to facilitate the exploitation of large amount of data from EO missions in a collaborative, cross-disciplinary, and open way, from science to

  13. Transition metal co-precipitation mechanisms in silicon

    Energy Technology Data Exchange (ETDEWEB)

    Buonassisi, T. [Department of Materials Science and Engineering, University of California, Berkeley and Materials Science Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720 (United States)], E-mail: buonassisi@alumni.nd.edu; Heuer, M.; Istratov, A.A.; Pickett, M.D. [Department of Materials Science and Engineering, University of California, Berkeley and Materials Science Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720 (United States); Marcus, M.A. [Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, CA 94720 (United States); Lai, B.; Cai, Z.; Heald, S.M. [Advanced Photon Source, Argonne National Laboratory, Argonne, IL 60439 (United States); Weber, E.R. [Department of Materials Science and Engineering, University of California, Berkeley and Materials Science Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720 (United States)

    2007-10-15

    Formation mechanisms of precipitates containing multiple-metal species in silicon are elucidated by nano-scale morphology and phase investigations performed by synchrotron-based X-ray microprobe techniques. Precipitates formed at low (655 deg. C) and high (1200 deg. C+) temperatures exhibit distinguishing features indicative of unique formation mechanisms. After lower-temperature annealing, co-localized single-metal silicide phases are observed, consistent with classical models predicting that dissolved, supersaturated metal atoms will precipitate into solid second-phase particles. Precise precipitate morphologies are found to depend on the local crystallographic environment. In precipitates formed during slow cooling from higher-temperature anneals, nano-scale phase separation and intermetallic phases are evident, suggestive of a high-temperature transition through a liquid phase. Based on experimental results and phase diagram information, it is proposed that under certain conditions, liquid metal-silicon droplets may form within the silicon matrix, possibly with the potential to getter additional metal atoms via liquid-solid segregation.

  14. X-ray Emission Spectroscopy in Magnetic 3d-Transition Metals

    Energy Technology Data Exchange (ETDEWEB)

    Iota, V; Park, J; Baer, B; Yoo, C; Shen, G

    2003-11-18

    The application of high pressure affects the band structure and magnetic interactions in solids by modifying nearest-neighbor distances and interatomic potentials. While all materials experience electronic changes with increasing pressure, spin polarized, strongly electron correlated materials are expected to undergo the most dramatic transformations. In such materials, (d and f-electron metals and compounds), applied pressure reduces the strength of on-site correlations, leading to increased electron delocalization and, eventually, to loss of its magnetism. In this ongoing project, we study the electronic and magnetic properties of Group VIII, 3d (Fe, Co and Ni) magnetic transition metals and their compounds at high pressures. The high-pressure properties of magnetic 3d-transition metals and compounds have been studied extensively over the years, because of iron being a major constituent of the Earth's core and its relevance to the planetary modeling to understand the chemical composition, internal structure, and geomagnetism. However, the fundamental scientific interest in the high-pressure properties of magnetic 3d-electron systems extends well beyond the geophysical applications to include the electron correlation-driven physics. The role of magnetic interactions in the stabilization of the ''non-standard'' ambient pressure structures of Fe, Co and Ni is still incompletely understood. Theoretical studies have predicted (and high pressure experiments are beginning to show) strong correlations between the electronic structure and phase stability in these materials. The phase diagrams of magnetic 3d systems reflect a delicate balance between spin interactions and structural configuration. At ambient conditions, the crystal structures of {alpha}-Fe(bcc) and {var_epsilon}-Co(hcp) phases depart from the standard sequence (hcp {yields} bcc{yields} hcp {yields} fcc), as observed in all other non-magnetic transition metals with increasing the d

  15. A temperate rocky super-Earth transiting a nearby cool star.

    Science.gov (United States)

    Dittmann, Jason A; Irwin, Jonathan M; Charbonneau, David; Bonfils, Xavier; Astudillo-Defru, Nicola; Haywood, Raphaëlle D; Berta-Thompson, Zachory K; Newton, Elisabeth R; Rodriguez, Joseph E; Winters, Jennifer G; Tan, Thiam-Guan; Almenara, Jose-Manuel; Bouchy, François; Delfosse, Xavier; Forveille, Thierry; Lovis, Christophe; Murgas, Felipe; Pepe, Francesco; Santos, Nuno C; Udry, Stephane; Wünsche, Anaël; Esquerdo, Gilbert A; Latham, David W; Dressing, Courtney D

    2017-04-19

    M dwarf stars, which have masses less than 60 per cent that of the Sun, make up 75 per cent of the population of the stars in the Galaxy. The atmospheres of orbiting Earth-sized planets are observationally accessible via transmission spectroscopy when the planets pass in front of these stars. Statistical results suggest that the nearest transiting Earth-sized planet in the liquid-water, habitable zone of an M dwarf star is probably around 10.5 parsecs away. A temperate planet has been discovered orbiting Proxima Centauri, the closest M dwarf, but it probably does not transit and its true mass is unknown. Seven Earth-sized planets transit the very low-mass star TRAPPIST-1, which is 12 parsecs away, but their masses and, particularly, their densities are poorly constrained. Here we report observations of LHS 1140b, a planet with a radius of 1.4 Earth radii transiting a small, cool star (LHS 1140) 12 parsecs away. We measure the mass of the planet to be 6.6 times that of Earth, consistent with a rocky bulk composition. LHS 1140b receives an insolation of 0.46 times that of Earth, placing it within the liquid-water, habitable zone. With 90 per cent confidence, we place an upper limit on the orbital eccentricity of 0.29. The circular orbit is unlikely to be the result of tides and therefore was probably present at formation. Given its large surface gravity and cool insolation, the planet may have retained its atmosphere despite the greater luminosity (compared to the present-day) of its host star in its youth. Because LHS 1140 is nearby, telescopes currently under construction might be able to search for specific atmospheric gases in the future.

  16. Silylation of C-H bonds in aromatic heterocycles by an Earth-abundant metal catalyst

    Science.gov (United States)

    Toutov, Anton A.; Liu, Wen-Bo; Betz, Kerry N.; Fedorov, Alexey; Stoltz, Brian M.; Grubbs, Robert H.

    2015-02-01

    Heteroaromatic compounds containing carbon-silicon (C-Si) bonds are of great interest in the fields of organic electronics and photonics, drug discovery, nuclear medicine and complex molecule synthesis, because these compounds have very useful physicochemical properties. Many of the methods now used to construct heteroaromatic C-Si bonds involve stoichiometric reactions between heteroaryl organometallic species and silicon electrophiles or direct, transition-metal-catalysed intermolecular carbon-hydrogen (C-H) silylation using rhodium or iridium complexes in the presence of excess hydrogen acceptors. Both approaches are useful, but their limitations include functional group incompatibility, narrow scope of application, high cost and low availability of the catalysts, and unproven scalability. For this reason, a new and general catalytic approach to heteroaromatic C-Si bond construction that avoids such limitations is highly desirable. Here we report an example of cross-dehydrogenative heteroaromatic C-H functionalization catalysed by an Earth-abundant alkali metal species. We found that readily available and inexpensive potassium tert-butoxide catalyses the direct silylation of aromatic heterocycles with hydrosilanes, furnishing heteroarylsilanes in a single step. The silylation proceeds under mild conditions, in the absence of hydrogen acceptors, ligands or additives, and is scalable to greater than 100 grams under optionally solvent-free conditions. Substrate classes that are difficult to activate with precious metal catalysts are silylated in good yield and with excellent regioselectivity. The derived heteroarylsilane products readily engage in versatile transformations enabling new synthetic strategies for heteroaromatic elaboration, and are useful in their own right in pharmaceutical and materials science applications.

  17. Progress of Study on Application of Rare Earth Metals in Steels

    Institute of Scientific and Technical Information of China (English)

    Wang Longmei; Lin Qin; Ji Jingwen; Lan Denian

    2004-01-01

    With the improvement of the clean steel by degrees, the functions of rare earth metals in steel are more focused on modification of inclusions and micro alloying.The new study concerning the application of RE metals in clean steels were investigated by ICP, metallographic examination, SEM, EDS, EPMA, TEM and IMMA.The mechanism of corrosion resistance in the weather resistance steel was clarified.The mechanism of abrasion resistance and the life of fatigue enhanced in the RE - heavy rails steel were discussed.Progress in study of application of rare earth metals in steels (including weather resistance steel, low alloy steel, and heavy rails steel) was covered in this paper.

  18. Enhancing conductivity of metallic carbon nanotube networks by transition metal adsorption

    Science.gov (United States)

    Ketolainen, T.; Havu, V.; Puska, M. J.

    2015-02-01

    The conductivity of carbon nanotube thin films is mainly determined by carbon nanotube junctions, the resistance of which can be reduced by several different methods. We investigate electronic transport through carbon nanotube junctions in a four-terminal configuration, where two metallic single-wall carbon nanotubes are linked by a group 6 transition metal atom. The transport calculations are based on the Green's function method combined with the density-functional theory. The transition metal atom is found to enhance the transport through the junction near the Fermi level. However, the size of the nanotube affects the improvement in the conductivity. The enhancement is related to the hybridization of chromium and carbon atom orbitals, which is clearly reflected in the character of eigenstates near the Fermi level. The effects of chromium atoms and precursor molecules remaining adsorbed on the nanotubes outside the junctions are also examined.

  19. Enhancing conductivity of metallic carbon nanotube networks by transition metal adsorption

    Energy Technology Data Exchange (ETDEWEB)

    Ketolainen, T., E-mail: tomi.ketolainen@aalto.fi; Havu, V.; Puska, M. J. [COMP, Department of Applied Physics, Aalto University, P.O. Box 11100, FI-00076 Aalto (Finland)

    2015-02-07

    The conductivity of carbon nanotube thin films is mainly determined by carbon nanotube junctions, the resistance of which can be reduced by several different methods. We investigate electronic transport through carbon nanotube junctions in a four-terminal configuration, where two metallic single-wall carbon nanotubes are linked by a group 6 transition metal atom. The transport calculations are based on the Green’s function method combined with the density-functional theory. The transition metal atom is found to enhance the transport through the junction near the Fermi level. However, the size of the nanotube affects the improvement in the conductivity. The enhancement is related to the hybridization of chromium and carbon atom orbitals, which is clearly reflected in the character of eigenstates near the Fermi level. The effects of chromium atoms and precursor molecules remaining adsorbed on the nanotubes outside the junctions are also examined.

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

    Science.gov (United States)

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

    2016-02-01

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

  1. Cohesion and coordination effects on transition metal surface energies

    Science.gov (United States)

    Ruvireta, Judit; Vega, Lorena; Viñes, Francesc

    2017-10-01

    Here we explore the accuracy of Stefan equation and broken-bond model semiempirical approaches to obtain surface energies on transition metals. Cohesive factors are accounted for either via the vaporization enthalpies, as proposed in Stefan equation, or via cohesive energies, as employed in the broken-bond model. Coordination effects are considered including the saturation degree, as suggested in Stefan equation, employing Coordination Numbers (CN), or as the ratio of broken bonds, according to the bond-cutting model, considering as well the square root dependency of the bond strength on CN. Further, generalized coordination numbers CN bar are contemplated as well, exploring a total number of 12 semiempirical formulations on the three most densely packed surfaces of 3d, 4d, and 5d Transition Metals (TMs) displaying face-centered cubic (fcc), body-centered cubic (bcc), or hexagonal close-packed (hcp) crystallographic structures. Estimates are compared to available experimental surface energies obtained extrapolated to zero temperature. Results reveal that Stefan formula cohesive and coordination dependencies are only qualitative suited, but unadvised for quantitative discussion, as surface energies are highly overestimated, favoring in addition the stability of under-coordinated surfaces. Broken-bond cohesion and coordination dependencies are a suited basis for quantitative comparison, where square-root dependencies on CN to account for bond weakening are sensibly worse. An analysis using Wulff shaped averaged surface energies suggests the employment of broken-bond model using CN to gain surface energies for TMs, likely applicable to other metals.

  2. Crystal Fields in Dilute Rare-Earth Metals Obtained from Magnetization Measurements on Dilute Rare-Earth Alloys

    DEFF Research Database (Denmark)

    Touborg, P.; Høg, J.

    1974-01-01

    Crystal field parameters of Tb, Dy, and Er in Sc, Y, and Lu are summarized. These parameters are obtained from magnetization measurements on dilute single crystals, and successfully checked by a number of different methods. The crystal field parameters vary unpredictably with the rare-earth solute....... B40, B60, and B66 are similar in Y and Lu. Crystal field parameters for the pure metals Tb, Dy, and Er are estimated from the crystal fields in Y and Lu....

  3. SPITZER TRANSITS OF THE SUPER-EARTH GJ1214b AND IMPLICATIONS FOR ITS ATMOSPHERE

    Energy Technology Data Exchange (ETDEWEB)

    Fraine, Jonathan D.; Deming, Drake [Department of Astronomy, University of Maryland, College Park, MD 20742 (United States); Gillon, Michaeel; Jehin, Emmanueel [Institute d' Astrophysique et de Geophysique, Universite de Liege, Liege (Belgium); Demory, Brice-Olivier; Benneke, Bjoern; Seager, Sara [Department of Earth, Atmospheric and Planetary Sciences, and Department of Physics, Massachusetts Institute of Technology, Cambridge, MA 02139 (United States); Lewis, Nikole K. [Department of Planetary Sciences and Lunar and Planetary Laboratory, University of Arizona, Tucson, AZ 85721 (United States); Knutson, Heather [Division of Geological and Planetary Sciences, California Institute of Technology, Pasadena, CA 91125 (United States); Desert, Jean-Michel, E-mail: jfraine@astro.umd.edu [Harvard-Smithsonian Center for Astrophysics, 60 Garden St., Cambridge, MA 02138 (United States)

    2013-03-10

    We observed the transiting super-Earth exoplanet GJ1214b using warm Spitzer at 4.5 {mu}m wavelength during a 20 day quasi-continuous sequence in 2011 May. The goals of our long observation were to accurately define the infrared transit radius of this nearby super-Earth, to search for the secondary eclipse, and to search for other transiting planets in the habitable zone of GJ1214. We here report results from the transit monitoring of GJ1214b, including a reanalysis of previous transit observations by Desert et al. In total, we analyze 14 transits of GJ1214b at 4.5 {mu}m, 3 transits at 3.6 {mu}m, and 7 new ground-based transits in the I+z band. Our new Spitzer data by themselves eliminate cloudless solar composition atmospheres for GJ1214b, and methane-rich models from Howe and Burrows. Using our new Spitzer measurements to anchor the observed transit radii of GJ1214b at long wavelengths, and adding new measurements in I+z, we evaluate models from Benneke and Seager and Howe and Burrows using a {chi}{sup 2} analysis. We find that the best-fit model exhibits an increase in transit radius at short wavelengths due to Rayleigh scattering. Pure water atmospheres are also possible. However, a flat line (no atmosphere detected) remains among the best of the statistically acceptable models, and better than pure water atmospheres. We explore the effect of systematic differences among results from different observational groups, and we find that the Howe and Burrows tholin-haze model remains the best fit, even when systematic differences among observers are considered.

  4. Spin-exchange interaction between transition metals and metalloids in soft-ferromagnetic metallic glasses

    Science.gov (United States)

    Das, Santanu; Choudhary, Kamal; Chernatynskiy, Aleksandr; Choi Yim, Haein; Bandyopadhyay, Asis K.; Mukherjee, Sundeep

    2016-06-01

    High-performance magnetic materials have immense industrial and scientific importance in wide-ranging electronic, electromechanical, and medical device technologies. Metallic glasses with a fully amorphous structure are particularly suited for advanced soft-magnetic applications. However, fundamental scientific understanding is lacking for the spin-exchange interaction between metal and metalloid atoms, which typically constitute a metallic glass. Using an integrated experimental and molecular dynamics approach, we demonstrate the mechanism of electron interaction between transition metals and metalloids. Spin-exchange interactions were investigated for a Fe-Co metallic glass system of composition [(Co1-x Fe x )0.75B0.2Si0.05]96Cr4. The saturation magnetization increased with higher Fe concentration, but the trend significantly deviated from simple rule of mixtures. Ab initio molecular dynamics simulation was used to identify the ferromagnetic/anti-ferromagnetic interaction between the transition metals and metalloids. The overlapping band-structure and density of states represent ‘Stoner type’ magnetization for the amorphous alloys in contrast to ‘Heisenberg type’ in crystalline iron. The enhancement of magnetization by increasing iron was attributed to the interaction between Fe 3d and B 2p bands, which was further validated by valence-band study.

  5. Solvent Extraction of Alkaline Earth Metals with Alkylphosphorus Acids%有机磷(膦)酸对碱土金属的萃取

    Institute of Scientific and Technical Information of China (English)

    许新; 朱屯

    2002-01-01

    Solvent extraction equilibria of four main alkaline earth metals (magnesium, calcium, strontium and barium) with di(2-ethylhexyl) phosphoric acid (DEHPA), 2-ethylhexyl phosphonic acid mono-(2-ethylhexyl) ester,di(2,4,4-tri-methylpentyl) phosphinic acid and IR spectra of the extracts have been studied. The selectivity order is dependent on the e/r value and hydration energy of the metal ions. The minor shift of the P-O in IR absorption of the alkaline earth metal extracts indicates that the interaction between the metal ions and P-O is much weaker for alkaline earth metals than for transitional metals. The distribution of the four alkaline earth elements between aqueous solutions and solutions of DEHPA and neutral organophosphorus compounds, tri-n-butyl phosphate (TBP) or tri-octyl phosphine oxide (TOPO) in kerosene have been determined at varying ratio of TBP or TOPO to DEHPA and the positive synergism is observed. The synergic effect is explained by using IR spectra of the loaded organic phase.

  6. Metal-silicate partitioning during core formation on super-Earths

    Science.gov (United States)

    Schaefer, L. K.; Jacobsen, S. B.; Petaev, M. I.; Sasselov, D. D.; Remo, J. L.

    2015-12-01

    Separation of the Earth into a rocky mantle and metallic Fe core is a problem long studied in the planetary science community (e.g. [1]). The timing of core formation influences the abundances of the siderophile elements found in the Earth's mantle, and the mechanism of core formation influences the degree of chemical equilibration between the rocky mantle and the core at the time of metal separation. However, limited work has been done on formation of metallic cores and its effects on mantle chemistry in rocky planets larger than the Earth. Super-Earths, exoplanets with masses up to ~ 5 Earth masses and radii up to ~1.6-1.7 Earth radii, have significantly larger internal pressures and consequently higher internal temperatures than the Earth, therefore conclusions from Earth-centric studies of core formation may be erroneous. Partitioning coefficients for many of the relevant elements (e.g. Fe, Ni, Si, O, etc.) are available in the literature, but only to relatively low pressures. The relevant pressures for super-Earths are significantly larger. However, data on Fe-O-Ni-Si partitioning at pressures (200-500 GPa) and temperatures relevant to super-Earths have been measured by laser-induced shocks with the ZBL laser at Sandia National Laboratory with a method described in [2]. We will present a model which integrates this data with lower pressure partition coefficients from the literature (e.g. [3],[4],[5]), with special emphasis on Fe and O, to describe partitioning behavior at high pressures and discuss its implications for core size and composition on rocky super-Earths. [1] Ringwood, A.E. (1977) Geochem. J. 11, 111-135. [2] Remo, J.L., Petaev, M.I., Jacobsen, S. B. (2008) LPSC abstract, 1420. [3] Frost, D.J. et al. (2010) JGR, B02202. [4] Kombayashi, T. (2014) JGR, 4164-4177. [5] Rubie, D.C. et al. (2011) EPSL, 301, 31-42. [5

  7. MOST DETECTS TRANSITS OF HD 97658b, A WARM, LIKELY VOLATILE-RICH SUPER-EARTH

    Energy Technology Data Exchange (ETDEWEB)

    Dragomir, Diana; Eastman, Jason D. [Las Cumbres Observatory Global Telescope Network, 6740 Cortona Dr. suite 102, Goleta, CA 93117 (United States); Matthews, Jaymie M. [Department of Physics and Astronomy, University of British Columbia, Vancouver, BC V6T1Z1 (Canada); Cameron, Chris [Department of Mathematics, Physics and Geology, Cape Breton University, 1250 Grand Lake Road, Sydney, NS B1P 6L2 (Canada); Howard, Andrew W. [Institute for Astronomy, University of Hawaii, 2680 Woodlawn Drive, Honolulu, HI 96822 (United States); Guenther, David B. [Department of Astronomy and Physics, St. Mary' s University, Halifax, NS B3H 3C3 (Canada); Kuschnig, Rainer; Weiss, Werner W. [Universitaet Wien, Institut fuer Astronomie, Tuerkenschanzstrasse 17, A-1180 Wien (Austria); Moffat, Anthony F. J. [Dept de physique, Univ de Montreal C.P. 6128, Succ. Centre-Ville, Montreal, QC H3C 3J7 (Canada); Rowe, Jason F. [SETI Institute, 189 Bernardo Avenue, Mountain View, CA 94043 (United States); Rucinski, Slavek M. [Department of Astronomy and Astrophysics, University of Toronto, 50 St. George Street, Toronto, ON M5S 3H4 (Canada); Sasselov, Dimitar, E-mail: diana@lcogt.net [Harvard-Smithsonian Center for Astrophysics, 60 Garden Street, Cambridge, MA 02138 (United States)

    2013-07-20

    Through photometric monitoring of the extended transit window of HD 97658b with the MOST space telescope, we have found that this exoplanet transits with an ephemeris consistent with that predicted from radial velocity measurements. The mid-transit times are 5.6{sigma} earlier than those of the unverified transit-like signals reported in 2011, and we find no connection between the two sets of events. The transit depth together with our determined stellar radius (R{sub *} = 0.703{sub -0.034}{sup +0.039} R{sub Sun }) indicates a 2.34{sup +0.18}{sub -0.15} R{sub Circled-Plus} super-Earth. When combined with the radial velocity determined mass of 7.86 {+-} 0.73 M{sub Circled-Plus }, our radius measure allows us to derive a planet density of 3.44{sup +0.91}{sub -0.82} g cm{sup -3}. Models suggest that a planet with our measured density has a rocky core that is enveloped in an atmosphere composed of lighter elements. The star of the HD 97658 system is the second brightest known to host a transiting super-Earth, facilitating follow-up studies of this not easily daunted, warm and likely volatile-rich exoplanet.

  8. Two Transiting Earth-size Planets Near Resonance Orbiting a Nearby Cool Star

    CERN Document Server

    Petigura, Erik A; Crossfield, Ian J M; Howard, Andrew W; Deck, Katherine M; Ciardi, David R; Sinukoff, Evan; Allers, Katelyn N; Best, William M J; Liu, Michael C; Beichman, Charles A; Isaacson, Howard; Hansen, Brad M S; Lépine, Sébastien

    2015-01-01

    Discoveries from the prime Kepler mission demonstrated that small planets (< 3 Earth-radii) are common outcomes of planet formation. While Kepler detected many such planets, all but a handful orbit faint, distant stars and are not amenable to precise follow up measurements. Here, we report the discovery of two small planets transiting EPIC-206011691, a bright (K = 9.4) M0 dwarf located 65$\\pm$6 pc from Earth. We detected the transiting planets in photometry collected during Campaign 3 of NASA's K2 mission. Analysis of transit light curves reveals that the planets have small radii compared to their host star, 2.60 $\\pm$ 0.14% and 3.15 $\\pm$ 0.20%, respectively. We obtained follow up NIR spectroscopy of \\epic to constrain host star properties, which imply planet sizes of 1.59 $\\pm$ 0.43 Earth-radii and 1.92 $\\pm$ 0.53 Earth-radii, respectively, straddling the boundary between high-density, rocky planets and low-density planets with thick gaseous envelopes. The planets have orbital periods of 9.32414 days and...

  9. Holographic Metal-Insulator Transition in Higher Derivative Gravity

    CERN Document Server

    Ling, Yi; Wu, Jian-Pin; Zhou, Zhenhua

    2016-01-01

    We introduce a Weyl term into the Einstein-Maxwell-Axion theory in four dimensional spacetime. Up to the first order of the Weyl coupling parameter $\\gamma$, we construct charged black brane solutions without translational invariance in a perturbative manner. Among all the holographic frameworks involving higher derivative gravity, we are the first to obtain metal-insulator transitions (MIT) when varying the system parameters at zero temperature. Furthermore, we study the holographic entanglement entropy (HEE) of strip geometry in this model and find that the second order derivative of HEE with respect to the axion parameter exhibits maximization behavior near quantum critical points (QCPs) of MIT. It testifies the conjecture in 1502.03661 and 1604.04857 that HEE itself or its derivatives can be used to diagnose quantum phase transition (QPT).

  10. Holographic metal-insulator transition in higher derivative gravity

    Directory of Open Access Journals (Sweden)

    Yi Ling

    2017-03-01

    Full Text Available We introduce a Weyl term into the Einstein–Maxwell-Axion theory in four dimensional spacetime. Up to the first order of the Weyl coupling parameter γ, we construct charged black brane solutions without translational invariance in a perturbative manner. Among all the holographic frameworks involving higher derivative gravity, we are the first to obtain metal-insulator transitions (MIT when varying the system parameters at zero temperature. Furthermore, we study the holographic entanglement entropy (HEE of strip geometry in this model and find that the second order derivative of HEE with respect to the axion parameter exhibits maximization behavior near quantum critical points (QCPs of MIT. It testifies the conjecture in [1,2] that HEE itself or its derivatives can be used to diagnose quantum phase transition (QPT.

  11. Holographic metal-insulator transition in higher derivative gravity

    Science.gov (United States)

    Ling, Yi; Liu, Peng; Wu, Jian-Pin; Zhou, Zhenhua

    2017-03-01

    We introduce a Weyl term into the Einstein-Maxwell-Axion theory in four dimensional spacetime. Up to the first order of the Weyl coupling parameter γ, we construct charged black brane solutions without translational invariance in a perturbative manner. Among all the holographic frameworks involving higher derivative gravity, we are the first to obtain metal-insulator transitions (MIT) when varying the system parameters at zero temperature. Furthermore, we study the holographic entanglement entropy (HEE) of strip geometry in this model and find that the second order derivative of HEE with respect to the axion parameter exhibits maximization behavior near quantum critical points (QCPs) of MIT. It testifies the conjecture in [1,2] that HEE itself or its derivatives can be used to diagnose quantum phase transition (QPT).

  12. The Holographic Disorder-Driven Supeconductor-Metal Transition

    CERN Document Server

    Arean, Daniel; Landea, Ignacio Salazar; Scardicchio, Antonello

    2015-01-01

    We implement the effects of disorder on a holographic superconductor by introducing a random chemical potential on the boundary. We demonstrate explicitly that increasing disorder leads to the formation of islands where the superconducting order is enhanced and subsequently to the transition to a metal. We study the behavior of the superfluid density and of the conductivity as a function of the strength of disorder. We find explanations for various marked features in the conductivities in terms of hydrodynamic quasi-normal modes of the holographic superconductors. These identifications plus a particular disorder-dependent spectral weight shift in the conductivity point to a signature of the Higgs mode in the context of disordered holographic superconductors. We observe that the behavior of the order parameter close to the transition is not mean-field type as in the clean case, rather we find robust agreement with $\\exp(- A\\, |T-T_c|^{-\

  13. Transition metal catalysis in the mitochondria of living cells

    Science.gov (United States)

    Tomás-Gamasa, María; Martínez-Calvo, Miguel; Couceiro, José R.; Mascareñas, José L.

    2016-09-01

    The development of transition metal catalysts capable of promoting non-natural transformations within living cells can open significant new avenues in chemical and cell biology. Unfortunately, the complexity of the cell makes it extremely difficult to translate standard organometallic chemistry to living environments. Therefore, progress in this field has been very slow, and many challenges, including the possibility of localizing active metal catalysts into specific subcellular sites or organelles, remain to be addressed. Herein, we report a designed ruthenium complex that accumulates preferentially inside the mitochondria of mammalian cells, while keeping its ability to react with exogenous substrates in a bioorthogonal way. Importantly, we show that the subcellular catalytic activity can be used for the confined release of fluorophores, and even allows selective functional alterations in the mitochondria by the localized transformation of inert precursors into uncouplers of the membrane potential.

  14. Nanoparticle plasmonics: going practical with transition metal nitrides

    Directory of Open Access Journals (Sweden)

    Urcan Guler

    2015-05-01

    Full Text Available Promising designs and experimental realizations of devices with unusual properties in the field of plasmonics have attracted a great deal of attention over the past few decades. However, the high expectations for realized technology products have not been met so far. The main complication is the absence of robust, high performance, low cost plasmonic materials that can be easily integrated into already established technologies such as microelectronics. This review provides a brief discussion on alternative plasmonic materials for localized surface plasmon applications and focuses on transition metal nitrides, in particular, titanium nitride, which has recently been shown to be a high performance refractory plasmonic material that could replace and even outperform gold in various plasmonic devices. As a material compatible with biological environments and the semiconductor industry, titanium nitride possesses superior properties compared to noble metals such as high temperature durability, chemical stability, corrosion resistance, low cost and mechanical hardness.

  15. Efficient photocarrier injection in a transition metal oxide heterostructure

    CERN Document Server

    Muraoka, Y; Ueda, Y; Hiroi, Z

    2002-01-01

    An efficient method for doping a transition metal oxide (TMO) with hole carriers is presented: photocarrier injection (PCI) in an oxide heterostructure. It is shown that an insulating vanadium dioxide (VO sub 2) film is rendered metallic under light irradiation by PCI from an n-type titanium dioxide (TiO sub 2) substrate doped with Nb. Consequently, a large photoconductivity, which is exceptional for TMOs, is found in the VO sub 2 /TiO sub 2 :Nb heterostructure. We propose an electronic band structure where photoinduced holes created in TiO sub 2 :Nb can be transferred into the filled V 3d band via the low-lying O 2p band of VO sub 2. (letter to the editor)

  16. Topological Phase Transition in Metallic Single-Wall Carbon Nanotube

    Science.gov (United States)

    Okuyama, Rin; Izumida, Wataru; Eto, Mikio

    2017-01-01

    The topological phase transition is theoretically studied in a metallic single-wall carbon nanotube (SWNT) by applying a magnetic field B parallel to the tube. The Z topological invariant, winding number, is changed discontinuously when a small band gap is closed at a critical value of B, which can be observed as a change in the number of edge states owing to the bulk-edge correspondence. This is confirmed by numerical calculations for finite SWNTs of ˜1 µm length, using a one-dimensional lattice model to effectively describe the mixing between σ and π orbitals and spin-orbit interaction, which are relevant to the formation of the band gap in metallic SWNTs.

  17. Surface entropy of liquid transition and noble metals

    Science.gov (United States)

    Gosh, R. C.; Das, Ramprosad; Sen, Sumon C.; Bhuiyan, G. M.

    2015-07-01

    Surface entropy of liquid transition and noble metals has been investigated using an expression obtained from the hard-sphere (HS) theory of liquid. The expression is developed from the Mayer's extended surface tension formula [Journal of Non-Crystalline Solids 380 (2013) 42-47]. For interionic interaction in metals, Brettonet-Silbert (BS) pseudopotentials and embedded atom method (EAM) potentials have been used. The liquid structure is described by the variational modified hypernetted chain (VMHNC) theory. The essential ingredient of the expression is the temperature dependent effective HS diameter (or packing fraction), which is calculated from the aforementioned potentials together with the VMHNC theory. The obtained results for the surface entropy using the effective HS diameter are found to be good in agreement with the available experimental as well as other theoretical values.

  18. Transistor-like behavior of transition metal complexes

    DEFF Research Database (Denmark)

    Albrecht, Tim; Guckian, A; Ulstrup, Jens

    2005-01-01

    Electron transport through semiconductor and metallic nanoscale structures,(1) molecular monolayers,2-6 and single molecules(7-15) connected to external electrodes display rectification, switch, and staircase functionality of potential importance in future miniaturization of electronic devices....... Common to most reported systems is, however, ultrahigh vacuum and/or cryogenic working conditions. Here we introduce a single-molecule device concept based on a class of robust redox active transition metal (Os(II)/(III)) complexes inserted between the working electrode and tip in an electrochemical...... the redox level is brought into the energy window between the Fermi levels of the electrodes by the overpotential ("gate voltage"). The current-voltage characteristics for two Os(II)/(III) complexes have been characterized systematically and supported by theoretical frames based on molecular charge...

  19. Novel synthetic routes to nanocomposites of transition metal phosphides

    Energy Technology Data Exchange (ETDEWEB)

    Milne, S.B.; Lukehart, C.M.; Wittig, J.E. [Vanderbilt Univ., Nashville, TN (United States)] [and others

    1996-10-01

    Novel routes to nanocomposites of transition metal phosphides will be presented. Silica xerogels containing covalently attached organometallic or other coordination compounds were prepared using standard sol-gel methods. The doped xerogels were thermally treated in a reducing atmosphere to yield the desired nanocomposite. Using these techniques, Fe{sub 2}P, RuP, Co{sub 2}P, Rh{sub 2}P, Ni{sub 2}P, Pd{sub 5}P{sub 2}, and PtP{sub 2} nanocomposites have been prepared and characterized.

  20. First-principles study of transition metal carbides

    Science.gov (United States)

    Connétable, Damien

    2016-12-01

    This study investigates the physical properties of transition metal carbides compounds associated with the Nb-C, Ti-C, Mo-C and W-C alloys systems using first-principles calculations. The ground-state properties (lattice parameters, cohesive energies and magnetism) were analyzed and compared to the experimental and theoretical literature. The simulations are in excellent agreement with experimental findings concerning atomic positions and structures. Elastic properties, computed using a finite-differences approach, are then discussed in detail. To complete the work, their lattice dynamics properties (phonon spectra) were investigated. These results serve to establish that some structures, which are mechanically stable, are dynamically unstable.

  1. About Alloying of Aluminum Alloys with Transition Metals

    Science.gov (United States)

    Zakharov, V. V.

    2017-05-01

    An attempt is made to advance Elagin's principles of alloying of aluminum alloys with transition metals (TM) such as Mn, Cr, Zr, Ti, V with allowance for the ternary equilibrium and metastable Al - TM - TM phase diagrams. The key moments in the analysis of the phase diagrams are the curves (surfaces) of joint solubility of TM in aluminum, which bound the range of the aluminum solid solution. It is recommended to use combinations of such TM (two and more), the introduction of which into aluminum alloys widens the phase range of the aluminum solid solution.

  2. A Transiting Hot Jupiter Orbiting a Metal-Rich Star

    CERN Document Server

    Dunham, Edward W; Koch, David G; Batalha, Natalie M; Buchhave, Lars A; Brown, Timothy M; Caldwell, Douglas A; Cochran, William D; Endl, Michael; Fischer, Debra; Furesz, Gabor; Gautier, Thomas N; Geary, John C; Gilliland, Ronald L; Gould, Alan; Howell, Steve B; Jenkins, Jon M; Kjeldsen, Hans; Latham, David W; Lissauer, Jack J; Marcy, Geoffrey W; Meibom, Soren; Monet, David G; Rowe, Jason F; Sasselov, Dimitar D

    2010-01-01

    We announce the discovery of Kepler-6b, a transiting hot Jupiter orbiting a star with unusually high metallicity, [Fe/H] = +0.34 +/- 0.04. The planet's mass is about 2/3 that of Jupiter, Mp = 0.67 Mj, and the radius is thirty percent larger than that of Jupiter, Rp = 1.32 Rj, resulting in a density of 0.35 g/cc, a fairly typical value for such a planet. The orbital period is P = 3.235 days. The host star is both more massive than the Sun, Mstar = 1.21 Msun, and larger than the Sun, Rstar = 1.39 Rsun.

  3. Cross-plane thermal properties of transition metal dichalcogenides

    Energy Technology Data Exchange (ETDEWEB)

    Muratore, C. [Department of Chemical and Materials Engineering, University of Dayton, Dayton, Ohio 45469 (United States); Materials and Manufacturing Directorate, Air Force Research Laboratory, Wright-Patterson AFB, Ohio 45433 (United States); Varshney, V. [Materials and Manufacturing Directorate, Air Force Research Laboratory, Wright-Patterson AFB, Ohio 45433 (United States); Universal Technology Corporation, Dayton, Ohio 45432 (United States); Gengler, J. J. [Materials and Manufacturing Directorate, Air Force Research Laboratory, Wright-Patterson AFB, Ohio 45433 (United States); Spectral Energies LLC, Dayton, Ohio 45431 (United States); Hu, J. J.; Bultman, J. E. [Materials and Manufacturing Directorate, Air Force Research Laboratory, Wright-Patterson AFB, Ohio 45433 (United States); University of Dayton Research Institute, Dayton, Ohio 45469 (United States); Smith, T. M. [Department of Materials Science and Engineering, Ohio State University, Columbus, Ohio 43210 (United States); Shamberger, P. J.; Roy, A. K.; Voevodin, A. A. [Materials and Manufacturing Directorate, Air Force Research Laboratory, Wright-Patterson AFB, Ohio 45433 (United States); Qiu, B.; Ruan, X. [Department of Mechanical Engineering and Birck Nanotechnology Center, Purdue University, West Lafayette, Indiana 47907 (United States)

    2013-02-25

    In this work, we explore the thermal properties of hexagonal transition metal dichalcogenide compounds with different average atomic masses but equivalent microstructures. Thermal conductivity values of sputtered thin films were compared to bulk crystals. The comparison revealed a >10 fold reduction in thin film thermal conductivity. Structural analysis of the films revealed a turbostratic structure with domain sizes on the order of 5-10 nm. Estimates of phonon scattering lengths at domain boundaries based on computationally derived group velocities were consistent with the observed film microstructure, and accounted for the reduction in thermal conductivity compared to values for bulk crystals.

  4. Magnetism in 3d transition metal doped SnO

    KAUST Repository

    Albar, Arwa

    2016-09-12

    Using first principles calculations, we investigate the structural and electronic properties of 3d transition metal doped SnO. We examine the stability of different doping sites using formation energy calculations. The magnetic behavior of the dopant atoms is found to be complex because of interplay between strong structural relaxation, spin-lattice coupling, and crystal field splitting. The interaction between dopant atoms is analyzed as a function of their separation, showing that clustering typically counteracts spin polarization. An exception is found for V doping, which thus turns out to be a promising candidate for realizing a magnetic p-type oxide.

  5. CVD-graphene growth on different polycrystalline transition metals

    Directory of Open Access Journals (Sweden)

    M. P. Lavin-Lopez

    2017-01-01

    Full Text Available The chemical vapor deposition (CVD graphene growth on two polycrystalline transition metals (Ni and Cu was investigated in detail using Raman spectroscopy and optical microscopy as a way to synthesize graphene of the highest quality (i.e. uniform growth of monolayer graphene, which is considered a key issue for electronic devices. Key CVD process parameters (reaction temperature, CH4/H2flow rate ratio, total flow of gases (CH4+H2, reaction time were optimized for both metals in order to obtain the highest graphene uniformity and quality. The conclusions previously reported in literature about the performance of low and high carbon solubility metals in the synthesis of graphene and their associated reaction mechanisms, i.e. surface depositionand precipitation on cooling, respectively, was not corroborated by the results obtained in this work. Under the optimal reaction conditions, a large percentage of monolayer graphene was obtained over the Ni foil since the carbon saturation was not complete, allowing carbon atoms to be stored in the bulk metal, which could diffuse forming high quality monolayer graphene at the surface. However, under the optimal reaction conditions, the formation of a non-uniform mixture of few layers and multilayer graphene on the Cu foil was related to the presence of an excess of active carbon atoms on the Cu surface.

  6. Detection of a transit of the super-Earth 55 Cnc e with Warm Spitzer

    CERN Document Server

    Demory, B -O; Deming, D; Valencia, D; Seager, S; Benneke, B; Lovis, C; Cubillos, P; Harrington, J; Stevenson, K B; Mayor, M; Pepe, F; Queloz, D; Segransan, D; Udry, S

    2011-01-01

    We report on the detection of a transit of the super-Earth 55 Cnc e with Warm Spitzer in IRAC's 4.5-micron band. Our MCMC analysis includes an extensive modeling of the systematic effects affecting Warm Spitzer photometry, and yields a transit depth of 450 +- 50 ppm, which translates to a planetary radius of 2.13 +- 0.14 Earth Radii as measured in IRAC 4.5-micron channel. A planetary mass of 7.98 +- 0.69 Earth Masses is derived from an extensive set of radial-velocity data, yielding a planetary density of 0.83 +- 0.18 Earth density. Interestingly, the derived radius is 1.3 times larger than the one recently reported in the visible by Winn et al. Thanks to the brightness of its host star (V=6, K=4), 55 Cnc e is a unique target for the thorough characterization of a super-Earth orbiting around a solar-type star.

  7. Hubble Space Telescope search for the transit of the Earth-mass exoplanet Alpha Centauri Bb

    CERN Document Server

    Demory, Brice-Olivier; Queloz, Didier; Seager, Sara; Gilliland, Ronald; Chaplin, William J; Proffitt, Charles; Gillon, Michael; Guenther, Maximilian N; Benneke, Bjoern; Dumusque, Xavier; Lovis, Christophe; Pepe, Francesco; Segransan, Damien; Triaud, Amaury; Udry, Stephane

    2015-01-01

    Results from exoplanet surveys indicate that small planets (super-Earth size and below) are abundant in our Galaxy. However, little is known about their interiors and atmospheres. There is therefore a need to find small planets transiting bright stars, which would enable a detailed characterisation of this population of objects. We present the results of a search for the transit of the Earth-mass exoplanet Alpha Centauri Bb with the Hubble Space Telescope (HST). We observed Alpha Centauri B twice in 2013 and 2014 for a total of 40 hours. We achieve a precision of 115 ppm per 6-s exposure time in a highly-saturated regime, which is found to be consistent across HST orbits. We rule out the transiting nature of Alpha Centauri Bb with the orbital parameters published in the literature at 96.6% confidence. We find in our data a single transit-like event that could be associated to another Earth-size planet in the system, on a longer period orbit. Our program demonstrates the ability of HST to obtain consistent, hi...

  8. A Spitzer Search for Transits of Radial Velocity Detected Super-Earths

    CERN Document Server

    Kammer, J A; Howard, A W; Laughlin, G P; Deming, D; Todorov, K O; Desert, J -M; Agol, E; Burrows, A; Fortney, J J; Showman, A P; Lewis, N K

    2013-01-01

    Unlike hot Jupiters or other gas giants, super-Earths are expected to have a wide variety of compositions, ranging from terrestrial bodies like our own to more gaseous planets like Neptune. Observations of transiting systems, which allow us to directly measure planet masses and radii and constrain atmospheric properties, are key to understanding the compositional diversity of the planets in this mass range. Although Kepler has discovered hundreds of transiting super-Earth candidates over the past four years, the majority of these planets orbit stars that are too far away and too faint to allow for detailed atmospheric characterization and reliable mass estimates. Ground-based transit surveys focus on much brighter stars, but most lack the sensitivity to detect planets in this size range. One way to get around the difficulty of finding these smaller planets in transit is to start by choosing targets that are already known to contain super-Earth sized bodies detected using the radial velocity technique. Here we...

  9. Chemoselective single-site Earth-abundant metal catalysts at metal–organic framework nodes

    Energy Technology Data Exchange (ETDEWEB)

    Manna, Kuntal; Ji, Pengfei; Lin, Zekai; Greene, Francis X.; Urban, Ania; Thacker, Nathan C.; Lin, Wenbin (UC)

    2016-08-30

    Earth-abundant metal catalysts are critically needed for sustainable chemical synthesis. Here we report a simple, cheap and effective strategy of producing novel earth-abundant metal catalysts at metal–organic framework (MOF) nodes for broad-scope organic transformations. The straightforward metalation of MOF secondary building units (SBUs) with cobalt and iron salts affords highly active and reusable single-site solid catalysts for a range of organic reactions, including chemoselective borylation, silylation and amination of benzylic C–H bonds, as well as hydrogenation and hydroboration of alkenes and ketones. Our structural, spectroscopic and kinetic studies suggest that chemoselective organic transformations occur on site-isolated, electron-deficient and coordinatively unsaturated metal centres at the SBUs via σ-bond metathesis pathways and as a result of the steric environment around the catalytic site. MOFs thus provide a novel platform for the development of highly active and affordable base metal catalysts for the sustainable synthesis of fine chemicals.

  10. Shape transition and coexistence in neutron-deficient rare earth isotopes

    CERN Multimedia

    We propose to study spectroscopic quadrupole moments of excited states and electromagnetic transition rates between them in the neutron-deficient rare earth nuclei $^{140}$Sm and $^{142}$Gd using projectile Coulomb excitation at energies of 4.7 MeV per nucleon. The rare earth nuclei below the N=82 shell closure form one of the few regions of the nuclear chart where oblate shapes are expected to occur near the ground state. Nuclear shapes are expected to change rapidly in this region, with coexistence of oblate and prolate shapes in some nuclei. The measurement of electromagnetic matrix elements represents therefore a particularly sensitive test of theoretical nuclear structure models.

  11. Transition metal cations extraction by ester and ketone derivatives of chromogenic azocalix[4]arenes.

    Science.gov (United States)

    Ak, Metin; Taban, Deniz; Deligöz, Hasalettin

    2008-06-15

    The molecule of azocalix[n]arene is a macrocyclic used effectively in the complexation of the heavy metal pollutants (like silver and mercury). In this work, our main aim is to prepare new chromogenic azocalix[n]arene molecules to elaborate an extractant with high extractant selectivity for metal ions able to detect this type of pollutant. The solvent extraction properties of four acetyls, four methyl ketones and four benzoyls derivatives from azocalix[4]arenes which were prepared by linking 4-ethyl, 4-n-butyl, 4-acetamid anilin and 2-aminothiazol to calix[4]arene through a diazo-coupling reaction, the alkaline earth (Sr2+) and the transition (Ag+, Hg2+, Co2+, Ni2+, Cu2+, Zn2+, Cd2+, Cr3+) metal cations have been determined by extraction studies with metal picrates. Both ketones are better extractants than esters, and show a strong preference for Ag+, while Cu2+ and Cr3+ are the most extracted cation with the esters. Both acetyl and benzoyl esters are good carriers for Ag+ and Hg2+.

  12. Effect of transition metal dopants on mechanical properties and biocompatibility of zirconia ceramics.

    Science.gov (United States)

    Oh, Gye-Jeong; Park, Sang-Won; Yun, Kwi-Dug; Lim, Hyun-Pil; Son, Hye-Ju; Koh, Jeong-Tae; Lee, Kyung-Ku; Lee, Doh-Jae; Lee, Kwang-Min; Fisher, John G

    2013-06-01

    In this study, the effect of transition metal dopants, originally added as colouring agents, on the mechanical properties and biocompatibility of sintered zirconia was investigated. This study confirmed that transition metal dopants could have a slight detrimental effect on the mechanical properties of zirconia. The addition of metal dopants did not affect the adhesion and proliferation of gingival fibroblasts.

  13. Transition metal exchanged β zeolites: Characterization of the metal state and catalytic application in the methanol conversion to hydrocarbons

    NARCIS (Netherlands)

    Esquivel, D.; Cruz-Cabeza, A.J.; Jiménez-Sanchidrián, C.; Romero-Salguero, F.J.

    2013-01-01

    Various first-row transition metal cations (Cr3+, Mn2+, Fe3+, Co2+, Ni2+, Cu2+ and Zn2+) have been introduced to zeolite beta using ion exchange procedures. Both aluminum and transition metal sites were studied by UV-Vis spectroscopy, XPS and Al-27 NMR. Generally, ion exchange favored the incorporat

  14. Transition metal exchanged β zeolites: Characterization of the metal state and catalytic application in the methanol conversion to hydrocarbons

    NARCIS (Netherlands)

    Esquivel, D.; Cruz-Cabeza, A.J.; Jiménez-Sanchidrián, C.; Romero-Salguero, F.J.

    2013-01-01

    Various first-row transition metal cations (Cr3+, Mn2+, Fe3+, Co2+, Ni2+, Cu2+ and Zn2+) have been introduced to zeolite beta using ion exchange procedures. Both aluminum and transition metal sites were studied by UV-Vis spectroscopy, XPS and Al-27 NMR. Generally, ion exchange favored the

  15. Environmental Defects And Economic Impact On Global Market Of Rare Earth Metals

    Science.gov (United States)

    Charalampides, G.; Vatalis, K.; Karayannis, V.; Baklavaridis, A.

    2016-11-01

    Rare earth elements include the 14 lanthanides as well as lanthanium and often yttrium. Actually, most of them are not very rare and occur widely dispersed in a variety of rocks. Rare earth metals are vital to some of the world's faster growing industries: catalysts, Nd-magnets, ceramics, glass, metallurgy, battery alloys, electronics and phosphors. Worldwide, the main countries for distribution of rare earths deposits include China, USA, Russia, Brasil, India, Australia, Greenland and Malaysia. The mining and processing of rare earth metals usually result in significant environmental defects. Many deposits are associated with high concentrations of radioactive elements such as uranium and thorium, which requires separate treatment and disposal. The accumulation of rare earth elements in soils has occurred due to pollution caused by the exploitation of rare earth resources and the wide use of rare earths as fertilizers in agriculture. This accumulation has a toxic effect on the soil microfauna community. However, there are large differences in market prices due to the degree of purity determined by the specifications in the applications. The main focus of this article is to overview Rare Earth Metals’ overall impact on global economy and their environmental defects on soils during processing techniques and as they are used as fertilizers.

  16. Magnetism of Metals, Alloys and of Clusters of Transition Metal Atoms

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    A condition for local moment formation in metals derived by Stoddart and March (Ann. Phys.NY 1972 64, 174) is first used to discuss the ferromagnetism of body-centred-cubic Fe. A less detailed discussion is also added on Ni and Co. This leads into a treatment of the nonlinear response of such 3d ferromagnets to dilute substitutional impurities. Antiferromagnets responding to local changes in the exchange field caused by such impurities are also studied, Mn in Cr being one such system discussed. The paper concludes with a brief summary of clusters of transition metal atoms, with most attention devoted to Cr and to Mn.

  17. Nanostructured transition metal oxides for energy storage and conversion

    Science.gov (United States)

    Li, Qiang

    Lithium-ion batteries, supercapacitors and photovoltaic devices have been widely considered as the three major promising alternatives of fossil fuels facing upcoming depletion to power the 21th century. The conventional film configuration of electrochemical electrodes hardly fulfills the high energy and efficiency requirements because heavy electroactive material deposition restricts ion diffusion path, and lowers power density and fault tolerance. In this thesis, I demonstrate that novel nanoarchitectured transition metal oxides (TMOs), e.g. MnO2, V2O 5, and ZnO, and their relevant nanocomposites were designed, fabricated and assembled into devices to deliver superior electrochemical performances such as high energy and power densities, and rate capacity. These improvements could be attributed to the significant enhancement of surface area, shortened ion diffusion distances and facile penetration of electrolyte solution into open structures of networks as well as to the pseudocapacitance domination. The utilization of ForcespinningRTM, a newly developed nanofiber processing technology, for large-scale energy storage and conversion applications is emphasized. This process simplifies the tedious multi-step hybridization synthesis and facilitates the contradiction between the micro-batch production and the ease of large-scale manufacturing. Key Words: Transition metal oxides, energy storage and conversion, ForcespinningRTM, pseudocapacitance domination, high rate capacity

  18. Defects and ferromagnetism in transition metal doped zinc oxide

    Science.gov (United States)

    Thapa, Sunil

    Transition metal doped zinc oxide has been studied recently due to its potential application in spintronic devices. The magnetic semiconductor, often called Diluted Magnetic Semiconductors (DMS), has the ability to incorporate both charge and spin into a single formalism. Despite a large number of studies on ferromagnetism in ZnO based DMS and the realization of its room temperature ferromagnetism, there is still a debate about the origin of the ferromagnetism. In this work, the synthesis and characterization of transition metal doped zinc oxide have been carried out. The sol-gel method was used to synthesize thin films, and they were subsequently annealed in air. Characterization of doped zinc oxide films was carried out using the UV-visible range spectrometer, scanning electron microscopy, superconducting quantum interference device (SQUID), x-ray diffraction(XRD) and positron annihilation spectroscopy. Hysteresis loops were obtained for copper and manganese doped zinc oxide, but a reversed hysteresis loop was observed for 2% Al 3% Co doped zinc oxide. The reversed hysteresis loop has been explained using a two-layer model.

  19. Effects of interband transitions on Faraday rotation in metallic nanoparticles.

    Science.gov (United States)

    Wysin, G M; Chikan, Viktor; Young, Nathan; Dani, Raj Kumar

    2013-08-14

    The Faraday rotation in metallic nanoparticles is considered based on a quantum model for the dielectric function ϵ(ω) in the presence of a DC magnetic field B. We focus on effects in ϵ(ω) due to interband transitions (IBTs), which are important in the blue and ultraviolet for noble metals used in plasmonics. The dielectric function is found using the perturbation of the electron density matrix due to the optical field of the incident electromagnetic radiation. The calculation is applied to transitions between two bands (d and p, for example) separated by a gap, as one finds in gold at the L-point of the Fermi surface. The result of the DC magnetic field is a shift in the effective optical frequency causing IBTs by ±μBB/ħ, where opposite signs are associated with left/right circular polarizations. The Faraday rotation for a dilute solution of 17 nm diameter gold nanoparticles is measured and compared with both the IBT theory and a simpler Drude model for the bound electron response. Effects of the plasmon resonance mode on Faraday rotation in nanoparticles are also discussed.

  20. Recent Transits of the Super-Earth Exoplanet GJ 1214B

    Science.gov (United States)

    Sada, Pedro V.; Deming, Drake; Jackson, Brian; Jennings, Donald E.; Peterson, Steven W.; Haase, Flynn; Bays, Kevin; OGorman, Eamon; Lundsford, Alan

    2001-01-01

    We report recent ground-based photometry of the transiting super-Earth exoplanet GJ1214b at several wavelengths, including the infrared near 1.25 microns (J-band). We observed a J-band transit with the FLAMINGOS infrared imager and the 2.1-meter telescope on Kitt Peak, and we observed several optical transits using a 0.5-meter telescope on Kitt Peak and the 0.36-meter Universidad de Monterrey Observatory telescope. Our high-precision J-band observations exploit the brightness of the M-dwarf host star at this infrared wavelength as compared to the optical, as well as being significantly less affected by stellar activity and limb darkening. We fit the J-band transit to obtain an independent determination of the planetary and stellar radii. Our radius for the planet (2.61 +0.30 / -0.11 Earth radii) is in excellent agreement with the discovery value reported by Charbonneau et al. based on optical data. We demonstrate that the planetary radius is insensitive to degeneracies in the fitting process. We use all of our observations to improve the transit ephemeris, finding P=1.5804043 +/- 0.0000005 days, and T0=2454964.94390 +/- 0.00006 BJD.

  1. Electron-phonon coupling and structural phase transitions in early transition metal oxides and chalcogenides

    Science.gov (United States)

    Farley, Katie Elizabeth

    Pronounced nonlinear variation of electrical transport characteristics as a function of applied voltage, temperature, magnetic field, strain, or photo-excitation is usually underpinned by electronic instabilities that originate from the complex interplay of spin, orbital, and lattice degrees of freedom. This dissertation focuses on two canonical materials that show pronounced discontinuities in their temperature-dependent resistivity as a result of electron---phonon and electron---electron correlations: orthorhombic TaS3 and monoclinic VO2. Strong electron-phonon interactions in transition metal oxides and chalcogenides results in interesting structural and electronic phase transitions. The properties of the material can be changed drastically in response to external stimuli such as temperature, voltage, or light. Understanding the influence these interactions have on the electronic structure and ultimately transport characteristics is of utmost importance in order to take these materials from a fundamental aspect to prospective applications such as low-energy interconnects, steep-slope transistors, and synaptic neural networks. This dissertation describes synthetic routes to nanoscale TaS3 and VO2, develops mechanistic understanding of their electronic instabilities, and in the case of the latter system explores modulation of the electronic and structural phase transition via the incorporation of substitutional dopant atoms. We start in chapter 2 with a detailed study of the synthesis and electronic transport properties of TaS3, which undergoes a Peierls' distortion to form a charge density wave. Scaling this material down to the nanometer-sized regime allows for interrogation of single or discrete phase coherent domains. Using electrical transport and broad band noise measurements, the dynamics of pinning/depinning of the charge density wave is investigated. Chapter 3 provides a novel synthetic approach to produce high-edge-density MoS2 nanorods. MoS2 is a

  2. Polynuclear transition metal complexes with thiocarbohydrazide and dithiocarbamates

    Science.gov (United States)

    Siddiqi, K. S.; Khan, Sadaf; Nami, Shahab A. A.; El-ajaily, M. M.

    2007-07-01

    Sn(tch) 2{MCl 2} 2 was prepared from the precursor Sn(tch) 2 and MCl 2. It was subsequently allowed to react with diethyldithiocarbamate which yielded the trinuclear complexes of the type Sn(tch) 2{M 2(dtc) 4}, where tch = thiocarbohydrazide, M = Mn(II), Fe(II), Co(II), Ni(II), Cu(II) and dtc = diethyldithiocarbamate. They were characterized on the basis of microanalytical, thermal (TGA/DSC), spectral (IR, UV-vis, EPR, 1H NMR) studies, conductivity measurement and magnetic moment data. On the basis of spectral data a tetrahedral geometry has been proposed for the halide complexes, Sn(tch) 2{MCl 2} 2 except for Cu(II) which exhibits a square planar coordination although the transition metal ion in Sn(tch) 2{M 2(dtc) 4} achieves an octahedral geometry where the dithiocarbamato moiety acts as a symmetrical bidentate ligand. The bidentate nature has been established by the appearance of a sharp single ν(C-S) around 1000 cm -1. A downfield shift observed in NH a and NH b protons on moving from Sn(tch) 2 to Sn(tch) 2{MCl 2} 2 is due to the drift of electrons toward metal atoms. A two-step pyrolysis has been observed in the Sn(tch) 2{MCl 2} 2 complexes while their dithiocarbamato derivatives exhibit a three-stage degradation pattern. Finally, the in vitro antibacterial activity of Sn(tch) 2{M 2(dtc) 4} and the mononuclear Sn(tch) 2 has been carried out on bacterial strains Escherichia coli and Salmonella typhi. The compounds were found to be active against the test organisms. The activity of the complexes is enhanced with increasing concentration. The maximum activity in both the strains was achieved by cobalt(II) dithiocarbamate complex. Minimum activity was found for Sn(tch) 2 which generally increases with the introduction of transition metal ion in the complex.

  3. DNA nuclease activity of Rev-coupled transition metal chelates.

    Science.gov (United States)

    Joyner, Jeff C; Keuper, Kevin D; Cowan, J A

    2012-06-07

    Artificial nucleases containing Rev-coupled metal chelates based on combinations of the transition metals Fe(2+), Co(2+), Ni(2+), and Cu(2+) and the chelators DOTA, DTPA, EDTA, NTA, tripeptide GGH, and tetrapeptide KGHK have been tested for DNA nuclease activity. Originally designed to target reactive transition metal chelates (M-chelates) to the HIV-1 Rev response element mRNA, attachment to the arginine-rich Rev peptide also increases DNA-binding affinity for the attached M-chelates. Apparent K(D) values ranging from 1.7 to 3.6 µM base pairs for binding of supercoiled pUC19 plasmid DNA by Ni-chelate-Rev complexes were observed, as a result of electrostatic attraction between the positively-charged Rev peptide and negatively-charged DNA. Attachment of M-chelates to the Rev peptide resulted in enhancements of DNA nuclease activity ranging from 1-fold (no enhancement) to at least 13-fold (for Cu-DTPA-Rev), for the rate of DNA nicking, with second order rate constants for conversion of DNA(supercoiled) to DNA(nicked) up to 6 × 10(6) M(-1) min(-1), and for conversion of DNA(nicked) to DNA(linear) up to 1 × 10(5) M(-1) min(-1). Freifelder-Trumbo analysis and the ratios of linearization and nicking rate constants (k(lin)/k(nick)) revealed concerted mechanisms for nicking and subsequent linearization of plasmid DNA for all of the Rev-coupled M-chelates, consistent with higher DNA residency times for the Rev-coupled M-chelates. Observed rates for Rev-coupled M-chelates were less skewed by differing DNA-binding affinities than for M-chelates lacking Rev, as a result of the narrow range of DNA-binding affinities observed, and therefore relationships between DNA nuclease activity and other catalyst properties, such as coordination unsaturation, the ability to consume ascorbic acid and generate diffusible radicals, and the identity of the metal center, are now clearly illustrated in light of the similar DNA-binding affinities of all M-chelate-Rev complexes. This work

  4. Supported transition metal nanomaterials: Nanocomposites synthesized by ionizing radiation

    Science.gov (United States)

    Clifford, D. M.; Castano, C. E.; Rojas, J. V.

    2017-03-01

    Nanostructures decorated with transition metal nanoparticles using ionizing radiation as a synthesis method in aqueous solutions represents a clean alternative to existing physical, chemical and physicochemical methods. Gamma irradiation of aqueous solutions generates free radicals, both oxidizing and reducing species, all distributed homogeneously. The presence of oxidant scavengers in situ during irradiation generates a highly reductive environment favoring the reduction of the metal precursors promoting seed formation and nanoparticle growth. Particle growth is controlled by addition of surfactants, polymers or various substrates, otherwise referred to as supports, which enhance the formation of well dispersed nanoparticles. Furthermore, the combination of nanoparticles with supports can offer desirable synergisms not solely presented by the substrate or nanoparticles. Thus, supported nanoparticles offer a huge diversity of applications. Among the ionizing radiation methods to synthesize nanomaterials and modify their characteristics, gamma irradiation is of growing interest and it has shown tremendous potential in morphological control and distribution of particle size by judiciously varying parameters including absorbed dose, dose rate, concentration of metal precursor, and stabilizing agents. In this work, major advances on the synthesis of supported nanoparticles through gamma irradiation are reviewed as well as the opportunities to develop and exploit new composites using gamma-rays and other accessible ionizing radiation sources such as X-rays.

  5. Selective and low temperature transition metal intercalation in layered tellurides

    Science.gov (United States)

    Yajima, Takeshi; Koshiko, Masaki; Zhang, Yaoqing; Oguchi, Tamio; Yu, Wen; Kato, Daichi; Kobayashi, Yoji; Orikasa, Yuki; Yamamoto, Takafumi; Uchimoto, Yoshiharu; Green, Mark A.; Kageyama, Hiroshi

    2016-12-01

    Layered materials embrace rich intercalation reactions to accommodate high concentrations of foreign species within their structures, and find many applications spanning from energy storage, ion exchange to secondary batteries. Light alkali metals are generally most easily intercalated due to their light mass, high charge/volume ratio and in many cases strong reducing properties. An evolving area of materials chemistry, however, is to capture metals selectively, which is of technological and environmental significance but rather unexplored. Here we show that the layered telluride T2PTe2 (T=Ti, Zr) displays exclusive insertion of transition metals (for example, Cd, Zn) as opposed to alkali cations, with tetrahedral coordination preference to tellurium. Interestingly, the intercalation reactions proceed in solid state and at surprisingly low temperatures (for example, 80 °C for cadmium in Ti2PTe2). The current method of controlling selectivity provides opportunities in the search for new materials for various applications that used to be possible only in a liquid.

  6. Discovery of elusive structures of multifunctional transition-metal borides.

    Science.gov (United States)

    Liang, Yongcheng; Wu, Zhaobing; Yuan, Xun; Zhang, Wenqing; Zhang, Peihong

    2016-01-14

    A definitive determination of crystal structures is an important prerequisite for designing and exploiting new functional materials. Even though tungsten and molybdenum borides (TMBx) are the prototype for transition-metal light-element compounds with multiple functionalities, their elusive crystal structures have puzzled scientists for decades. Here, we discover that the long-assumed TMB2 phases with the simple hP3 structure (hP3-TMB2) are in fact a family of complex TMB3 polytypes with a nanoscale ordering along the axial direction. Compared with the energetically unfavorable and dynamically unstable hP3-TMB2 phase, the energetically more favorable and dynamically stable TMB3 polytypes explain the experimental structural parameters, mechanical properties, and X-ray diffraction (XRD) patterns better. We demonstrate that such a structural and compositional modification from the hP3-TMB2 phases to the TMB3 polytypes originates from the relief of the strong antibonding interaction between d electrons by removing one third of metal atoms systematically. These results resolve the longstanding structural mystery of this class of metal borides and uncover a hidden family of polytypic structures. Moreover, these polytypic structures provide an additional hardening mechanism by forming nanoscale interlocks that may strongly hinder the interlayer sliding movements, which promises to open a new avenue towards designing novel superhard nanocomposite materials by exploiting the coexistence of various polytypes.

  7. Metal enhanced fluorescence in rare earth doped plasmonic core-shell nanoparticles.

    Science.gov (United States)

    Derom, S; Berthelot, A; Pillonnet, A; Benamara, O; Jurdyc, A M; Girard, C; Colas des Francs, G

    2013-12-13

    We theoretically and numerically investigate metal enhanced fluorescence of plasmonic core-shell nanoparticles doped with rare earth (RE) ions. Particle shape and size are engineered to maximize the average enhancement factor (AEF) of the overall doped shell. We show that the highest enhancement (11 in the visible and 7 in the near-infrared) is achieved by tuning either the dipolar or the quadrupolar particle resonance to the rare earth ion's excitation wavelength. Additionally, the calculated AEFs are compared to experimental data reported in the literature, obtained in similar conditions (plasmon mediated enhancement) or when a metal-RE energy transfer mechanism is involved.

  8. Structure of Some 4f Rare Earth Liquid Metals - A Charged Hard Sphere Approach

    Institute of Scientific and Technical Information of China (English)

    P.B. Thakor; P.N. Gajjar; A.R. Jani

    2006-01-01

    A well-established pseodopotential is used to study the structure of some 4f rare earth liquid metals (Ce,Pr, Eu, Gd, Tb, and Yb). The structure factor S(q), pair distribution function g(r), interatomic distance r1, and coordination number n1 are calculated using Charged Hard Sphere (CHS) reference system. To introduce the exchange and correlation effects, the local field correction due to Sarkar et al. (S) is applied. The present investigation is successful in generating the structural information of Ce, Pr, Eu, Gd, Tb, and Yb 4f rare earth liquid metals.

  9. The Effects of Refraction on Transit Transmission Spectroscopy: Application to Earth-like Exoplanets

    CERN Document Server

    Misra, Amit; Crisp, Dave

    2014-01-01

    We quantify the effects of refraction in transit transmission spectroscopy on spectral absorption features and on temporal variations that could be used to obtain altitude-dependent spectra for planets orbiting stars of different stellar types. We validate our model against altitude-dependent transmission spectra of the Earth from ATMOS and against lunar eclipse spectra from Palle et al. (2009). We perform detectability studies to show the potential effects of refraction on hypothetical observations of Earth analogs with the James Webb Space Telescope (JWST) Near-Infrared Spectrograph (NIRSPEC). Due to refraction, there will be a maximum tangent pressure level that can be probed during transit for each given planet-star system. We show that because of refraction, for an Earth-analog planet orbiting in the habitable zone of a Sun-like star only the top 0.3 bars of the atmosphere can be probed, leading to a decrease in the signal to noise ratio (SNR) of absorption features by 60%, while for an Earth-analog plan...

  10. Inference on the Nature and the Mass of Earth's Late Veneer from Noble Metals and Gases

    CERN Document Server

    Dauphas, N

    2001-01-01

    Noble metals and gases are very sensitive to the late accretion to the Earth of asteroids and comets. We present mass balance arguments based on these elements that indicate that 0.7E22-2.7E22 kg of extraterrestrial bodies struck the Earth after core formation and that comets comprised less than 1E-5 by mass of the impacting population. These results imply that the dynamics of asteroids and comets changed drastically with time and that biogenic elements and prebiotic molecules were not delivered to the Earth by comets but rather by carbonaceous asteroids.

  11. Charge-transfer gap closure in transition-metal halides under pressure

    Energy Technology Data Exchange (ETDEWEB)

    Chen, A.L.; Yu, P.Y.

    1995-01-01

    Insulator-to-metal transition induced by pressure has been studied in three transition metal iodides: NiI{sub 2}, CoI{sub 2} and FeI{sub 2} using optical absorption and resistivity measurements at room temperature. Comparisons between the results obtained by these two techniques suggested that the closure of the charge-transfer gap is the principal mechanism responsible for the insulator-to-metal transition in these materials.

  12. Oxidation of Group 8 transition-Metal Hydrides and Ionic Hydrogenation of Ketones and Aldehydes

    Energy Technology Data Exchange (ETDEWEB)

    Smith, Kjell-Tore

    1996-08-01

    Transition-metal hydrides have received considerable attention during the last decades because of their unusual reactivity and their potential as homogeneous catalysts for hydrogenation and other reactions of organic substrates. An important class of catalytic processes where transition-metal hydrides are involved is the homogeneous hydrogenation of alkenes, alkynes, ketones, aldehydes, arenes and nitro compounds. This thesis studies the oxidation of Group 8 transition-metal hydrides and the ionic hydrogenation of ketones and aldehydes.

  13. Strain Induced Insulator-Metal Transition in Single Wall Carbon Nanotubes

    Institute of Scientific and Technical Information of China (English)

    丁建文; 颜晓红; 刘超平; 唐娜斯

    2004-01-01

    In terms of a single-π orbital model, an analytical expression of the lowest-lying conduction-band and the highestlying valence-band is derived for single wall carbon nanotubes under both the uniaxial and torsional strains. We observe not only semiconductor-metal transitions in primary metallic tubes, but also insulator-metal transitions in semiconducting tubes. Additionally, an indirect transition of electrons and a quantized electron-resonance have been expected in optical spectrum experiments of the nanotubes.

  14. Adlayer Core-Level Shifts of Random Metal Overlayers on Transition-Metal Substrates

    DEFF Research Database (Denmark)

    Ganduglia-Pirovano, M. V.; Kudrnovský, J.; Scheffler, M.

    1997-01-01

    We calculate the difference of the ionization energies of a core electron of a surface alloy, i.e., a B atom in a A(1-x)B(x) overlayer on a fee B(001) substrate, and a core electron of the clean fee B(001) surface using density-functional theory. We analyze the initial-state contributions and the...... the initial-state trends are explained in terms of the change of inter- and intra-atomic screening upon alloying. A possible role of alloying on the chemical reactivity of metal surfaces is discussed....... and the screening effects induced by the core hole, and study the influence of the alloy composition for a number of noble metal-transition metal systems. Our analysis clearly indicates the importance of final-state screening effects for the interpretation of measured core-level shifts. Calculated deviations from...

  15. Electronic Relaxation Processes of Transition Metal Atoms in Helium Nanodroplets

    Science.gov (United States)

    Kautsch, Andreas; Lindebner, Friedrich; Koch, Markus; Ernst, Wolfgang E.

    2014-06-01

    Spectroscopy of doped superfluid helium nanodroplets (He_N) gives information about the influence of this cold, chemically inert, and least interacting matrix environment on the excitation and relaxation dynamics of dopant atoms and molecules. We present the results from laser induced fluorescence (LIF), photoionization (PI), and mass spectroscopy of Cr and Cu doped He_N. From these results, we can draw a comprehensive picture of the complex behavior of such transition metal atoms in He_N upon photo-excitation. The strong Cr and Cu ground state transitions show an excitation blueshift and broadening with respect to the bare atom transitions which can be taken as indication for the solvation inside the droplet. From the originally excited states the atoms relax to energetically lower states and are ejected from the He_N. The relaxation processes include bare atom spin-forbidden transitions, which clearly bears the signature of the He_N influence. Two-color resonant two-photon ionization (2CR2PI) also shows the formation of bare atoms and small Cr-He_n and Cu-He_n clusters in their ground and metastable states ^c. Currently, Cr dimer excitation studies are in progress and a brief outlook on the available results will be given. C. Callegari and W. E. Ernst, Helium Droplets as Nanocryostats for Molecular Spectroscopy - from the Vacuum Ultraviolet to the Microwave Regime, in Handbook of High-Resolution Spectroscopy, eds. M. Quack and F. Merkt, John Wiley & Sons, Chichester, 2011. A. Kautsch, M. Koch, and W. E. Ernst, J. Phys. Chem. A, 117 (2013) 9621-9625, DOI: 10.1021/jp312336m F. Lindebner, A. Kautsch, M. Koch, and W. E. Ernst, Int. J. Mass Spectrom. (2014) in press, DOI: 10.1016/j.ijms.2013.12.022 M. Koch, A. Kautsch, F. Lackner, and W. E. Ernst, submitted to J. Phys. Chem. A

  16. The metal-insulator transition of RNiO{sub 3} perovskites. What can we learn from neutron diffraction?

    Energy Technology Data Exchange (ETDEWEB)

    Medarde, M.L. [Paul Scherrer Inst. (PSI), Villigen (Switzerland)

    1996-11-01

    RNiO{sub 3} perovskites (R = rare earth) provide a remarkable opportunity to study the relationship between structural and physical properties since by moving along the 4f rare earth series, the evolution of several transport and magnetic properties can be nicely correlated to the steric effects associated with the lanthanide contraction. The most appealing example is probably the metal-insulator transition discovered for the compounds with R{ne}La, whose critical temperature T{sub M-I} increases with decreasing size of the rare earth ion. In this lecture, a summary of the most relevant neutron diffraction results on this system is presented. Moreover, the nickelates are used as an example to illustrate the performance of the diffractometers HRPT and DMCG to be installed at the SINQ. (author) 12 figs., 2 tabs., 17 refs.

  17. Transition metal chalcogenides: ultrathin inorganic materials with tunable electronic properties.

    Science.gov (United States)

    Heine, Thomas

    2015-01-20

    CONSPECTUS: After the discovery of graphene and the development of powerful exfoliation techniques, experimental preparation of two-dimensional (2D) crystals can be expected for any layered material that is known to chemistry. Besides graphene and hexagonal boron nitride (h-BN), transition metal chalcogenides (TMC) are among the most studied ultrathin materials. In particular, single-layer MoS2, a direct band gap semiconductor with ∼1.9 eV energy gap, is popular in physics and nanoelectronics, because it nicely complements semimetallic graphene and insulating h-BN monolayer as a construction component for flexible 2D electronics and because it was already successfully applied in the laboratory as basis material for transistors and other electronic and optoelectronic devices. Two-dimensional crystals are subject to significant quantum confinement: compared with their parent layered 3D material, they show different structural, electronic, and optical properties, such as spontaneous rippling as free-standing monolayer, significant changes of the electronic band structure, giant spin-orbit splitting, and enhanced photoluminescence. Most of those properties are intrinsic for the monolayer and already absent for two-layer stacks of the same 2D crystal. For example, single-layer MoS2 is a direct band gap semiconductor with spin-orbit splitting of 150 meV in the valence band, while the bilayer of the same material is an indirect band gap semiconductor without observable spin-orbit splitting. All these properties have been observed experimentally and are in excellent agreement with calculations based on density-functional theory. This Account reports theoretical studies of a subgroup of transition metal dichalcogenides with the composition MX2, with M = Mo, or W and X = Se or S, also referred to as "MoWSeS materials". Results on the electronic structure, quantum confinement, spin-orbit coupling, spontaneous monolayer rippling, and change of electronic properties in the

  18. New technology of extracting the amount of rare earth metals from the red mud

    Science.gov (United States)

    Martoyan, G. A.; Karamyan, G. G.; Vardan, G. A.

    2016-01-01

    The paper outlined the environmental and economic problems associated with red mud - the waste generated in processing of bauxite ore for aluminum production. The chemical analysis of red mud has identified a number of useful elements including rare earth metals. The electromembrane technology of red mud processing with extraction of valuable elements is described. A possible scheme of separation of these metals through electrolysis is also given.

  19. A nearby M star with three transiting super-Earths discovered by K2

    CERN Document Server

    Crossfield, Ian J M; Schlieder, Joshua; Howard, Andrew W; Fulton, B J; Aller, Kimberly M; Ciardi, David R; Lepine, Sebastien; Barclay, Thomas; de Pater, Imke; de Kleer, Katherine; Quintana, Elisa V; Christiansen, Jessie L; Schlafly, Eddie; Kaltenegger, Lisa; Crepp, Justin R; Henning, Thomas; Obermeier, Christian; Deacon, Niall; Hansen, Brad M S; Liu, Michael C; Greene, Tom; Howell, Steve B; Barman, Travis; Mordasini, Christoph

    2015-01-01

    Small, cool planets represent the typical end-products of planetary formation. Studying the archi- tectures of these systems, measuring planet masses and radii, and observing these planets' atmospheres during transit directly informs theories of planet assembly, migration, and evolution. Here we report the discovery of three small planets orbiting a bright (Ks = 8.6 mag) M0 dwarf using data collected as part of K2, the new transit survey using the re-purposed Kepler spacecraft. Stellar spectroscopy and K2 photometry indicate that the system hosts three transiting planets with radii 1.5-2.1 R_Earth, straddling the transition region between rocky and increasingly volatile-dominated compositions. With orbital periods of 10-45 days the planets receive just 1.5-10x the flux incident on Earth, making these some of the coolest small planets known orbiting a nearby star; planet d is located near the inner edge of the system's habitable zone. The bright, low-mass star makes this system an excellent laboratory to deter...

  20. GROUND-BASED TRANSIT OBSERVATIONS OF THE SUPER-EARTH 55 Cnc e

    Energy Technology Data Exchange (ETDEWEB)

    De Mooij, E. J. W. [Astronomy and Astrophysics, University of Toronto, Toronto (Canada); López-Morales, M. [Harvard-Smithsonian Center for Astrophysics, 60 Garden Street, Cambridge, MA (United States); Karjalainen, R.; Hrudkova, M. [Isaac Newton Group of Telescopes, La Palma (Spain); Jayawardhana, Ray, E-mail: demooij@astro.utoronto.ca [Physics and Astronomy, York University, Toronto (Canada)

    2014-12-20

    We report the first ground-based detections of the shallow transit of the super-Earth exoplanet 55 Cnc e using a 2 m class telescope. Using differential spectrophotometry, we observed one transit in 2013 and another in 2014, with average spectral resolutions of ∼700 and ∼250, spanning the Johnson BVR photometric bands. We find a white light planet-to-star radius ratio of 0.0190{sub −0.0027}{sup +0.0023} from the 2013 observations and 0.0200{sub −0.0018}{sup +0.0017} from the 2014 observations. The two data sets combined result in a radius ratio of 0.0198{sub −0.0014}{sup +0.0013}. These values are all in agreement with previous space-based results. Scintillation noise in the data prevents us from placing strong constraints on the presence of an extended hydrogen-rich atmosphere. Nevertheless, our detections of 55 Cnc e in transit demonstrate that moderate-sized telescopes on the ground will be capable of routine follow-up observations of super-Earth candidates discovered by the Transiting Exoplanet Survey Satellite around bright stars. We expect it also will be possible to place constraints on the atmospheric characteristics of those planets by devising observational strategies to minimize scintillation noise.

  1. Recent Transits of the Super-Earth Exoplanet GJ 1214b

    CERN Document Server

    Sada, Pedro V; Jackson, Brian; Jennings, Donald E; Peterson, Steven W; Haase, Flynn; Bays, Kevin; O'Gorman, Eamon; Lundsford, Alan

    2010-01-01

    We report recent ground-based photometry of the transiting super-Earth exoplanet GJ1214b at several wavelengths, including the infrared near 1.25 microns (J-band). We observed a J-band transit with the FLAMINGOS infrared imager and the 2.1-meter telescope on Kitt Peak, and we observed several optical transits using a 0.5-meter telescope on Kitt Peak and the 0.36-meter Universidad de Monterrey Observatory telescope. Our high-precision J-band observations exploit the brightness of the M-dwarf host star at this infrared wavelength as compared to the optical, as well as being significantly less affected by stellar activity and limb darkening. We fit the J-band transit to obtain an independent determination of the planetary and stellar radii. Our radius for the planet (2.61^+0.30_-0.11 Earth radii) is in excellent agreement with the discovery value reported by Charbonneau et al. based on optical data. We demonstrate that the planetary radius is insensitive to degeneracies in the fitting process. We use all of our ...

  2. Ground-Based Transit Observations of the Super-Earth 55 Cnc e

    CERN Document Server

    de Mooij, E J W; Karjalainen, R; Hrudkova, M; Jayawardhana, R

    2014-01-01

    We report the first ground-based detections of the shallow transit of the super-Earth exoplanet 55 Cnc e using a 2-meter-class telescope. Using differential spectrophotometry, we observed one transit in 2013 and another in 2014, with average spectral resolutions of ~700 and ~250, spanning the Johnson BVR photometric bands. We find a white-light planet-to-star radius ratio of 0.0190 -0.0027+0.0023 from the 2013 observations and 0.0200 -0.0018+0.0017 from the 2014 observations. The two datasets combined results in a radius ratio of 0.0198 -0.0014+0.0013. These values are all in agreement with previous space-based results. Scintillation noise in the data prevents us from placing strong constraints on the presence of an extended hydrogen-rich atmosphere. Nevertheless, our detections of 55 Cnc e in transit demonstrate that moderate-size telescopes on the ground will be capable of routine follow-up observations of super-Earth candidates discovered by the Transiting Exoplanet Survey Satellite (TESS) around bright st...

  3. Lifshitz and other transitions in alkaline-earth 122 pnictides under pressure

    Science.gov (United States)

    Quader, Khandker; Widom, Michael

    2014-10-01

    We carry out T =0 first-principles total energy calculations in the entire set of alkaline 122-pnictides (A Fe2As2 ; A = alkaline-earth element Ca, Sr, Ba, Ra) as a function of hydrostatic pressure. We find multiple distinct transitions to occur, namely an enthalpic transition in which the zero-pressure striped antiferromagnetic orthorhombic (OR-AFM) phase becomes thermodynamically less stable than a competing tetragonal (T) phase, a magnetic transition in which the OR-AFM phase loses its magnetism and orthorhombicity, and a lattice parameter anomaly in which the tetragonal c-axis collapses and a collapsed tetragonal (cT) phase becomes stable. Our results for energy band dispersions and spectra, lattice parameters, enthalpies, magnetism, and elastic constants over a wide range of hydrostatic pressure provide a coherent understanding of these experimentally observed transitions. In particular, the T-cT transition and anomalies in lattice parameters and elastic properties, observed at finite temperatures, are interpreted as arising from proximity to T =0 Lifshitz transitions, wherein pressure causes nontrivial changes in the Fermi surface topology in these materials.

  4. Optical limiting of layered transition metal dichalcogenide semiconductors

    CERN Document Server

    Dong, Ningning; Feng, Yanyan; Zhang, Saifeng; Zhang, Xiaoyan; Chang, Chunxia; Fan, Jintai; Zhang, Long; Wang, Jun

    2015-01-01

    Nonlinear optical property of transition metal dichalcogenide (TMDC) nanosheet dispersions, including MoS2, MoSe2, WS2, and WSe2, was performed by using Z-scan technique with ns pulsed laser at 1064 nm and 532 nm. The results demonstrate that the TMDC dispersions exhibit significant optical limiting response at 1064 nm due to nonlinear scattering, in contrast to the combined effect of both saturable absorption and nonlinear scattering at 532 nm. Selenium compounds show better optical limiting performance than that of the sulfides in the near infrared. A liquid dispersion system based theoretical modelling is proposed to estimate the number density of the nanosheet dispersions, the relationship between incident laser fluence and the size of the laser generated micro-bubbles, and hence the Mie scattering-induced broadband optical limiting behavior in the TMDC dispersions.

  5. Electronics and optoelectronics of two-dimensional transition metal dichalcogenides.

    Science.gov (United States)

    Wang, Qing Hua; Kalantar-Zadeh, Kourosh; Kis, Andras; Coleman, Jonathan N; Strano, Michael S

    2012-11-01

    The remarkable properties of graphene have renewed interest in inorganic, two-dimensional materials with unique electronic and optical attributes. Transition metal dichalcogenides (TMDCs) are layered materials with strong in-plane bonding and weak out-of-plane interactions enabling exfoliation into two-dimensional layers of single unit cell thickness. Although TMDCs have been studied for decades, recent advances in nanoscale materials characterization and device fabrication have opened up new opportunities for two-dimensional layers of thin TMDCs in nanoelectronics and optoelectronics. TMDCs such as MoS(2), MoSe(2), WS(2) and WSe(2) have sizable bandgaps that change from indirect to direct in single layers, allowing applications such as transistors, photodetectors and electroluminescent devices. We review the historical development of TMDCs, methods for preparing atomically thin layers, their electronic and optical properties, and prospects for future advances in electronics and optoelectronics.

  6. Ferromagnetic semiconductor-metal transition in europium monoxide

    Energy Technology Data Exchange (ETDEWEB)

    Arnold, M.

    2007-10-15

    We present a microscopical model to describe the simultaneous para-to-ferromagnetic and semiconductor-to-metal transition in electron-doped EuO. The physical properties of the model are systematically studied, whereas the main remark is on the interplay between magnetic order and the transport properties. The theory correctly describes detailed experimental features of the conductivity and of the magnetization, obtained for EuO{sub 1-x} or Gd-doped Gd{sub x}Eu{sub 1-x}0. In particular the doping dependence of the Curie temperature is reproduced The existence of correlation-induced local moments on the impurity sites is essential for this description. (orig.)

  7. Induced magnetism in transition metal intercalated graphitic systems

    KAUST Repository

    Kaloni, Thaneshwor P.

    2011-10-26

    We investigate the structure, chemical bonding, electronic properties, and magnetic behavior of a three-dimensional graphitic network in aba and aaa stacking with intercalated transition metal atoms (Mn, Fe, Co, Ni, and Cu). Using density functional theory, we find induced spin-polarization of the C atoms both when the graphene sheets are aba stacked (forming graphite) and aaa stacked (resembling bi-layer graphene). The magnetic moment induced by Mn, Fe, and Co turns out to vary from 1.38 μB to 4.10 μB, whereas intercalation of Ni and Cu does not lead to a magnetic state. The selective induction of spin-polarization can be utilized in spintronic and nanoelectronic applications.

  8. Transition Metal Carbides and Nitrides in Energy Storage and Conversion.

    Science.gov (United States)

    Zhong, Yu; Xia, Xinhui; Shi, Fan; Zhan, Jiye; Tu, Jiangping; Fan, Hong Jin

    2016-05-01

    High-performance electrode materials are the key to advances in the areas of energy conversion and storage (e.g., fuel cells and batteries). In this Review, recent progress in the synthesis and electrochemical application of transition metal carbides (TMCs) and nitrides (TMNs) for energy storage and conversion is summarized. Their electrochemical properties in Li-ion and Na-ion batteries as well as in supercapacitors, and electrocatalytic reactions (oxygen evolution and reduction reactions, and hydrogen evolution reaction) are discussed in association with their crystal structure/morphology/composition. Advantages and benefits of nanostructuring (e.g., 2D MXenes) are highlighted. Prospects of future research trends in rational design of high-performance TMCs and TMNs electrodes are provided at the end.

  9. Mechanism of Transition-Metal Nanoparticle Catalytic Graphene Cutting.

    Science.gov (United States)

    Ma, Liang; Wang, Jinlan; Yip, Joanne; Ding, Feng

    2014-04-03

    Catalytic cutting by transition-metal (TM) particles is a promising method for the synthesizing of high-quality graphene quantum dots and nanoribbons with smooth edges. Experimentally, it is observed that the cutting always results in channels with zigzag (ZZ) or armchair (AC) edges. However, the driving force that is responsible for such a cutting behavior remains a puzzle. Here, by calculating the interfacial formation energies of the TM-graphene edges with ab initio method, we show that the surface of a catalyst particle tends to be aligned along either AC or ZZ direction of the graphene lattice, and thus the cutting of graphene is guided as such. The different cutting behaviors of various catalysts are well-explained based on the competition between TM-passivated graphene edges and the etching-agent-terminated ones. Furthermore, the kinetics of graphene catalytic cutting along ZZ and AC directions, respectively, are explored at the atomic level.

  10. Chiral topological excitons in the monolayer transition metal dichalcogenides

    Science.gov (United States)

    Gong, Z. R.; Luo, W. Z.; Jiang, Z. F.; Fu, H. C.

    2017-02-01

    We theoretically investigate the chiral topological excitons emerging in the monolayer transition metal dichalcogenides, where a bulk energy gap of valley excitons is opened up by a position dependent external magnetic field. We find two emerging chiral topological nontrivial excitons states, which exactly connects to the bulk topological properties, i.e., Chern number = 2. The dependence of the spectrum of the chiral topological excitons on the width of the magnetic field domain wall as well as the magnetic filed strength is numerically revealed. The chiral topological valley excitons are not only important to the excitonic transport due to prevention of the backscattering, but also give rise to the quantum coherent control in the optoelectronic applications.

  11. Transition metal dichalcogenides based saturable absorbers for pulsed laser technology

    Science.gov (United States)

    Mohanraj, J.; Velmurugan, V.; Sivabalan, S.

    2016-10-01

    Ultrashort pulsed laser is an indispensable tool for the evolution of photonic technology in the present and future. This laser has been progressing tremendously with new pulse regimes and incorporating novel devices inside its cavity. Recently, a nanomaterial based saturable absorber (SA) was used in ultrafast laser that has improved the lasing performance and caused a reduction in the physical dimension when compared to conventional SAs. To date, the nanomaterials that are exploited for the development of SA devices are carbon nanotubes, graphene, topological insulators, transition metal dichalcogenides (TMDs) and black phosphorous. These materials have unique advantages such as high nonlinear optical response, fiber compatibility and ease of fabrication. In these, TMDs are prominent and an emerging two-dimensional nanomaterial for photonics and optoelectronics applications. Therefore, we review the reports of Q-switched and mode-locked pulsed lasers using TMDs (specifically MoS2, MoSe2, WS2 and WSe2) based SAs.

  12. Noncollinear exchange interaction in transition metal dichalcogenide edges

    Science.gov (United States)

    Ávalos-Ovando, Oscar; Mastrogiuseppe, Diego; Ulloa, Sergio E.

    2016-04-01

    We study the Ruderman-Kittel-Kasuya-Yosida effective exchange interaction between magnetic impurities embedded on the edges of transition metal dichalcogenide flakes, using a three-orbital tight-binding model. Electronic states lying midgap of the bulk structure have a strong one-dimensional (1D) character, localized on the edges of the crystallite. This results in exchange interactions with 1 /r (or slower) decay with distance r , similar to other 1D systems. Most interestingly, however, the strong spin-orbit interaction in these materials results in sizable noncollinear Dzyaloshinskii-Moriya interactions between impurities, comparable in size to the usual Ising and in-plane components. Varying the relevant Fermi energy by doping or gating may allow one to modulate the effective interactions, controlling the possible helical ground state configurations of multiple impurities.

  13. On holographic disorder-driven metal-insulator transitions

    CERN Document Server

    Baggioli, Matteo

    2016-01-01

    We give a minimal holographic model of a disorder-driven metal-insulator transition. It consists in a CFT with a charge sector and a translation-breaking sector that interact in the most generic way allowed by the symmetries and by dynamical consistency. In the gravity dual, it reduces to a Massive Gravity-Maxwell model with new direct couplings between the Maxwell and metric that are allowed when gravity is massive. We show that, generically, the effect of disorder is to decrease the DC electrical conductivity. This happens to such an extent that the conductivity does not obey any lower bound and can be very small in the insulating phase. In some cases, the large disorder limit produces gradient instabilities that hint at the formation of modulated phases.

  14. Ab initio study of the transition-metal carbene cations

    Institute of Scientific and Technical Information of China (English)

    李吉海; 冯大诚; 冯圣玉

    1999-01-01

    The geometries and bonding characteristics of the first-row transition-metal carbene cations MCH2+ were investigated by ab initio molecular orbital theory (HF/LANL2DZ). All of MCH2+ are coplanar. In the closed shell structures the C bonds to M with double bonds; while in the open shell structures the partial double bonds are formed, because one of the σ and π orbitals is singly occupied. It is mainly the π-type overlap between the 2px orbital of C and 4px, 3dxz, orbitals of M+ that forms the π orbitals. The dissociation energies of C—M bond appear in periodic trend from Sc to Cu. Most of the calculated bond dissociation energies are close to the experimental ones.

  15. Nonequilibrium carrier dynamics in transition metal dichalcogenide semiconductors

    Science.gov (United States)

    Steinhoff, A.; Florian, M.; Rösner, M.; Lorke, M.; Wehling, T. O.; Gies, C.; Jahnke, F.

    2016-09-01

    When exploring new materials for their potential in (opto)electronic device applications, it is important to understand the role of various carrier interaction and scattering processes. In atomically thin transition metal dichalcogenide semiconductors, the Coulomb interaction is known to be much stronger than in quantum wells of conventional semiconductors like GaAs, as witnessed by the 50 times larger exciton binding energy. The question arises, whether this directly translates into equivalently faster carrier-carrier Coulomb scattering of excited carriers. Here we show that a combination of ab initio band-structure and many-body theory predicts Coulomb-mediated carrier relaxation on a sub-100 fs time scale for a wide range of excitation densities, which is less than an order of magnitude faster than in quantum wells.

  16. Superconductor to Quantum Metal Transitions in Ultra Thin Films

    Science.gov (United States)

    Lin, Yen-Hsiang; Goldman, Allen M.

    2009-03-01

    Homogeneous films of amorphous bismuth have been continuously tuned from the superconducting state by increasing a perpendicular magnetic field. Electrical transport and Hall measurements show that the non-superconducting states of the films are quantum-corrected metals. In the vicinity of transition field, the resistance can be fit by an Arrhenius type of conduction at high temperatures but this form fails at lower temperatures where the resistance is a non-monotonic function of temperature. This suggests that a two-phase regime develops near criticality. Theories suggest that this is in the form of superconducting puddles embedded in a normal matrix^1,2. ^1B. Spivak, P. Oreto, and S. A. Kivelson, Phys. Rev. B 77, 214523 (2008) ^2Y. Dubi, Y. Meir, and Y. Avishai, Nature 449, 876-880 (2007)

  17. Liquid Exfoliation of Layered Transition Metal Dichalcogenides for Biological Applications.

    Science.gov (United States)

    Nguyen, Emily P; Daeneke, Torben; Zhuiykov, Serge; Kalantar-Zadeh, Kourosh

    2016-06-02

    Known to possess distinctive properties that differ greatly from their bulk form, layered two-dimensional materials have been extensively studied and incorporated into many versatile applications ranging from optoelectronics to sensors. For biomedical research, two-dimensional transition metal dichalcogenides (2D TMDs) have garnered much interest as they have been shown to exhibit relatively low toxicity, high stability in aqueous environments, and the ability to adhere to biological materials such as proteins. These materials are promising candidates, demonstrating potential applications in biosensing, cell imaging, diagnostics, and therapeutics. Preparation and exfoliation of 2D TMDs play an important part in these various applications as their properties are heavily dependent on the number of layers and lateral size. Described in this article are protocols for the liquid exfoliation of 2D TMDs from their bulk materials. Additional protocols are also provided for functionalizing or modifying the surface of the exfoliated 2D TMDs. © 2016 by John Wiley & Sons, Inc.

  18. Probing Magnetism in 2D Molecular Networks after in Situ Metalation by Transition Metal Atoms.

    Science.gov (United States)

    Schouteden, K; Ivanova, Ts; Li, Z; Iancu, V; Janssens, E; Van Haesendonck, C

    2015-03-19

    Metalated molecules are the ideal building blocks for the bottom-up fabrication of, e.g., two-dimensional arrays of magnetic particles for spintronics applications. Compared to chemical synthesis, metalation after network formation by an atom beam can yield a higher degree of control and flexibility and allows for mixing of different types of magnetic atoms. We report on successful metalation of tetrapyridyl-porphyrins (TPyP) by Co and Cr atoms, as demonstrated by scanning tunneling microscopy experiments. For the metalation, large periodic networks formed by the TPyP molecules on a Ag(111) substrate are exposed in situ to an atom beam. Voltage-induced dehydrogenation experiments support the conclusion that the porphyrin macrocycle of the TPyP molecule incorporates one transition metal atom. The newly synthesized Co-TPyP and Cr-TPyP complexes exhibit striking differences in their electronic behavior, leading to a magnetic character for Cr-TPyP only as evidenced by Kondo resonance measurements.

  19. Tracking environmental impacts in global product chains - Rare Earth Metals and other critical metals used in the cleantech industry

    Energy Technology Data Exchange (ETDEWEB)

    Pathan, A.; Schilli, A.; Johansson, J.; Vehvilaeinen, I.; Larsson, A.; Hutter, J.

    2013-03-15

    Metals form a central part of the global economy, but their extraction and supply are linked to several environmental and social concerns. This study aims to create a picture of the supply chain of Rare Earth Metals (REMs) and other critical metals used in the clean technology (cleantech) sectors of electric vehicles and solar panels. The study examines how Nordic cleantech companies are aware and acting on the challenges related to the lifecycle of these metals and what are the potentials to minimise environmental and social impacts. Recommendations of the study can be summarised as three initiatives: establishment of an awareness platform and roundtable initiative (short-term), research and information gathering (mid-term), and development of closed-loop solutions (long-term). (Author)

  20. Preparation and magnetic properties of phthalocyanine-based carbon materials containing transition metals

    Science.gov (United States)

    Honda, Z.; Sato, S.; Hagiwara, M.; Kida, T.; Sakai, M.; Fukuda, T.; Kamata, N.

    2016-07-01

    A simple method for the preparation of bulk quantities of magnetic carbon materials, which contain uniformly dispersed transition metals (M = Fe, Co, Ni, and Cu) as the magnetic components, is presented. By using highly chlorinated metal phthalocyanine as the building block and potassium as the coupling reagent, phthalocyanine-based carbon materials (PBCMs) containing transition metals were obtained. Our experiments demonstrate the structure of these PBCMs consists of transition metals embedded in graphitic carbon that includes a square planar MN4 magnetic core and the Fe and Co-PBCM possess spontaneous magnetization at room temperature. In addition, carbon-coated transition metal particles were obtained by the Wurtz-type reaction with excess amount of potassium coupling agent. The large transition metal surface area and magnetization of these M-PBCMs are useful for spintronic and catalytic applications.

  1. Improving the Transition of Earth Satellite Observations from Research to Operations

    Science.gov (United States)

    Goodman, Steven J.; Lapenta, William M.; Jedlovec, Gary J.

    2004-01-01

    There are significant gaps between the observations, models, and decision support tools that make use of new data. These challenges include: 1) Decreasing the time to incorporate new satellite data into operational forecast assimilation systems, 2) Blending in-situ and satellite observing systems to produce the most accurate and comprehensive data products and assessments, 3) Accelerating the transition from research to applications through national test beds, field campaigns, and pilot demonstrations, and 4) Developing the partnerships and organizational structures to effectively transition new technology into operations. At the Short-term Prediction Research and Transition (SPORT) Center in Huntsville, Alabama, a NASA-NOAA-University collaboration has been developed to accelerate the infusion of NASA Earth science observations, data assimilation and modeling research into NWS forecast operations and decision-making. The SPoRT Center research focus is to improve forecasts through new observation capability and the regional prediction objectives of the US Weather Research Program dealing with 0-1 day forecast issues such as convective initiation and 24-hr quantitative precipitation forecasting. The near real-time availability of high-resolution experimental products of the atmosphere, land, and ocean from the Moderate Resolution Imaging Spectroradiometer (MODIS), the Advanced Infrared Spectroradiometer (AIRS), and lightning mapping systems provide an opportunity for science and algorithm risk reduction, and for application assessment prior to planned observations from the next generation of operational low Earth orbiting and geostationary Earth orbiting satellites. This paper describes the process for the transition of experimental products into forecast operations, current products undergoing assessment by forecasters, and plans for the future. The SPoRT Web page is at (http://www.ghcc.msfc.nasa.gov/sport).

  2. Assaying the catalytic potential of transition metal sulfides for abiotic carbon fixation

    Science.gov (United States)

    Cody, G. D.; Boctor, N. Z.; Brandes, J. A.; Filley, T. R.; Hazen, R. M.; Yoder, H. S.

    2004-05-01

    A suite of nickel, cobalt, iron, copper, and zinc containing sulfides are assayed for the promotion of a model carbon fixation reaction with relevance to local reducing environments of the early Earth. The assay tests the promotion of hydrocarboxylation (the Koch reaction) wherein a carboxylic acid is synthesized via carbonyl insertion at a metal-sulfide-bound alkyl group. The experimental conditions are chosen for optimal assay, i.e., high reactant concentrations and pressures (200 MPa) to enhance chemisorption, and high temperature (250°C) to enhance reaction kinetics. All of the metal sulfides studied, with the exception CuS, promote hydrocarboxylation. Two other significant reactions involve the catalytic reduction of CO to form a surface-bound methyl group, detected after nucleophilic attack by nonane thiol to form methyl nonyl sulfide, and the formation of dinonyl sulfide via a similar reaction. Estimation of the catalytic turnover frequencies for each of the metal sulfides with respect to each of the primary reactions reveals that NiS, Ni 3S 2, and CoS perform comparably to commonly employed industrial catalysts. A positive correlation between the yield of primary product to NiS and Ni 3S 2 surface areas provides strong evidence that the reactions are surface catalytic in these cases. The sulfides FeS and Fe (1-x)S are unique in that they exhibit evidence of extensive dissolution, thus, complicating interpretation regarding heterogeneous vs. homogeneous catalysis. With the exception of CuS, each of the metal sulfides promotes reactions that mimic key intermediate steps manifest in the mechanistic details of an important autotrophic enzyme, acetyl-CoA synthase. The relatively high temperatures chosen for assaying purposes, however, are incompatible with the accumulation of thioesters. The results of this study support the hypothesis that transition metal sulfides may have provided useful catalytic functionality for geochemical carbon fixation in a prebiotic

  3. On the single-ion Magnetic Anisotropy of the Rare-Earth Metals

    DEFF Research Database (Denmark)

    Kolmakova, N.P.; Tishin, A.M.; Bohr, Jakob

    1996-01-01

    The temperature dependences of the single-ion magnetic anisotropy constants for Tb and Dy metals are calculated in terms of the multipole moments of the rare-earth ions utilizing the available crystal-field parameters. The results are compared with the existing experimental data....

  4. Doping of graphite by an alkaline-earth metal to reduce the work function

    NARCIS (Netherlands)

    Baturin, AS; Nikolski, KN; Knyazev, AI; Tchesov, RG; Sheshin, EP

    2004-01-01

    A technique for reducing the work function of a field-emission graphite cathode by doping it by an alkaline-earth metal (barium) is suggested. A model of formation of a barium monolayer on the cathode surface is proposed. Field-emission tests show that the operating voltage of the doped cathode is l

  5. Plasmonic percolation: Plasmon-manifested dielectric-to-metal transition

    KAUST Repository

    Chen, Huanjun

    2012-08-28

    Percolation generally refers to the phenomenon of abrupt variations in electrical, magnetic, or optical properties caused by gradual volume fraction changes of one component across a threshold in bicomponent systems. Percolation behaviors have usually been observed in macroscopic systems, with most studies devoted to electrical percolation. We report on our observation of plasmonic percolation in Au nanorod core-Pd shell nanostructures. When the Pd volume fraction in the shell consisting of palladium and water approaches the plasmonic percolation threshold, ∼70%, the plasmon of the nanostructure transits from red to blue shifts with respect to that of the unshelled Au nanorod. This plasmonic percolation behavior is also confirmed by the scattering measurements on the individual core-shell nanostructures. Quasistatic theory and numerical simulations show that the plasmonic percolation originates from a positive-to-negative transition in the real part of the dielectric function of the shell as the Pd volume fraction is increased. The observed plasmonic percolation is found to be independent of the metal type in the shell. Moreover, compared to the unshelled Au nanorods with similar plasmon wavelengths, the Au nanorod core-Pd shell nanostructures exhibit larger refractive index sensitivities, which is ascribed to the expulsion of the electric field intensity from the Au nanorod core by the adsorbed Pd nanoparticles. © 2012 American Chemical Society.

  6. Magnesium nanoparticles with transition metal decoration for hydrogen storage

    Science.gov (United States)

    Pasquini, Luca; Callini, Elsa; Brighi, Matteo; Boscherini, Federico; Montone, Amelia; Jensen, Torben R.; Maurizio, Chiara; Vittori Antisari, Marco; Bonetti, Ennio

    2011-11-01

    We report on the hydrogen storage behaviour of Mg nanoparticles (NPs) (size range 100 nm-1 μm) with metal-oxide core-shell morphology synthesized by inert gas condensation and decorated by transition metal (TM) (Pd or Ti) clusters via in situ vacuum deposition. The structure and morphology of the as-prepared and hydrogenated NPs is studied by electron microscopy, X-ray diffraction including in situ experiments and X-ray absorption spectroscopy, in order to investigate the relationships with the hydrogen storage kinetics measured by the volumetric Sieverts method. With both Pd and Ti, the decoration deeply improves the hydrogen sorption properties: previously inert NPs exhibit complete hydrogenation with fast transformation kinetics, good stability and reversible gravimetric capacity that can attain 6 wt%. In the case of Pd-decoration, the occurrence of Mg-Pd alloying is observed at high temperatures and in dependence of the hydrogen pressure conditions. These structural transformations modify both the kinetics and thermodynamics of hydride formation, while Ti-decoration has an effect only on the kinetics. The experimental results are discussed in relation with key issues such as the amount of decoration, the heat of mixing between TM and Mg and the binding energy between TM and hydrogen.

  7. Transistor-like behavior of transition metal complexes.

    Science.gov (United States)

    Albrecht, Tim; Guckian, Adrian; Ulstrup, Jens; Vos, Johannes G

    2005-07-01

    Electron transport through semiconductor and metallic nanoscale structures, molecular monolayers, and single molecules connected to external electrodes display rectification, switch, and staircase functionality of potential importance in future miniaturization of electronic devices. Common to most reported systems is, however, ultrahigh vacuum and/or cryogenic working conditions. Here we introduce a single-molecule device concept based on a class of robust redox active transition metal (Os(II)/(III)) complexes inserted between the working electrode and tip in an electrochemical scanning tunneling microscope (in situ STM). This configuration resembles a single-molecule transistor, where the reference electrode corresponds to the gate electrode. It operates at room temperature in a condensed matter (here aqueous) environment. Amplification on-off ratios up to 50 are found when the redox level is brought into the energy window between the Fermi levels of the electrodes by the overpotential ("gate voltage"). The current-voltage characteristics for two Os(II)/(III) complexes have been characterized systematically and supported by theoretical frames based on molecular charge transport theory.

  8. Formation enthalpies for transition metal alloys using machine learning

    Science.gov (United States)

    Ubaru, Shashanka; Miedlar, Agnieszka; Saad, Yousef; Chelikowsky, James R.

    2017-06-01

    The enthalpy of formation is an important thermodynamic property. Developing fast and accurate methods for its prediction is of practical interest in a variety of applications. Material informatics techniques based on machine learning have recently been introduced in the literature as an inexpensive means of exploiting materials data, and can be used to examine a variety of thermodynamics properties. We investigate the use of such machine learning tools for predicting the formation enthalpies of binary intermetallic compounds that contain at least one transition metal. We consider certain easily available properties of the constituting elements complemented by some basic properties of the compounds, to predict the formation enthalpies. We show how choosing these properties (input features) based on a literature study (using prior physics knowledge) seems to outperform machine learning based feature selection methods such as sensitivity analysis and LASSO (least absolute shrinkage and selection operator) based methods. A nonlinear kernel based support vector regression method is employed to perform the predictions. The predictive ability of our model is illustrated via several experiments on a dataset containing 648 binary alloys. We train and validate the model using the formation enthalpies calculated using a model by Miedema, which is a popular semiempirical model used for the prediction of formation enthalpies of metal alloys.

  9. Photoinduced energy transfer in transition metal complex oligomers

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1997-04-01

    The work we have done over the past three years has been directed toward the preparation, characterization and photophysical examination of mono- and bimetallic diimine complexes. The work is part of a broader project directed toward the development of stable, efficient, light harvesting arrays of transition metal complex chromophores. One focus has been the synthesis of rigid bis-bidentate and bis-tridentate bridging ligands. We have managed to make the ligand bphb in multigram quantities from inexpensive starting materials. The synthetic approach used has allowed us prepare a variety of other ligands which may have unique applications (vide infra). We have prepared, characterized and examined the photophysical behavior of Ru(II) and Re(I) complexes of the ligands. Energy donor/acceptor complexes of bphb have been prepared which exhibit nearly activationless energy transfer. Complexes of Ru(II) and Re(I) have also been prepared with other polyunsaturated ligands in which two different long lived ( > 50 ns) excited states exist; results of luminescence and transient absorbance measurements suggest the two states are metal-to-ligand charge transfer and ligand localized {pi}{r_arrow}{pi}* triplets. Finally, we have developed methods to prepare polymetallic complexes which are covalently bound to various surfaces. The long term objective of this work is to make light harvesting arrays for the sensitization of large band gap semiconductors. Details of this work are provided in the body of the report.

  10. Photoinduced energy transfer in transition metal complex oligomers

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1997-06-01

    The work done over the past three years has been directed toward the preparation, characterization and photophysical examination of mono- and bimetallic diimine complexes. The work is part of a broader project directed toward the development of stable, efficient, light harvesting arrays of transition metal complex chromophores. One focus has been the synthesis of rigid bis-bidentate and bis-tridentate bridging ligands. The authors have managed to make the ligand bphb in multigram quantities from inexpensive starting materials. The synthetic approach used has allowed them to prepare a variety of other ligands which may have unique applications (vide infra). They have prepared, characterized and examined the photophysical behavior of Ru(II) and Re(I) complexes of the ligands. Energy donor/acceptor complexes of bphb have been prepared which exhibit nearly activationless energy transfer. Complexes of Ru(II) and Re(I) have also been prepared with other polyunsaturated ligands in which two different long lived (> 50 ns) excited states exist; results of luminescence and transient absorbance measurements suggest the two states are metal-to-ligand charge transfer and ligand localized {pi}{r_arrow}{pi}* triplets. Finally, the authors have developed methods to prepare polymetallic complexes which are covalently bound to various surfaces. The long term objective of this work is to make light harvesting arrays for the sensitization of large band gap semiconductors. Details of this work are provided in the body of the report.

  11. The Transiting Exoplanet Survey Satellite (TESS): Discovering New Earths and Super-Earths in the Solar Neighborhood

    Science.gov (United States)

    Ricker, George R.

    2015-12-01

    The Transiting Exoplanet Survey Satellite (TESS) will discover thousands of exoplanets in orbit around the brightest stars in the sky. In its two-year prime survey mission, TESS will monitor more than 200,000 bright stars in the solar neighborhood for temporary drops in brightness caused by planetary transits. This first-ever spaceborne all-sky transit survey will identify planets ranging from Earth-sized to gas giants, around a wide range of stellar types and orbital distances.TESS stars will typically be 30-100 times brighter than those surveyed by the Kepler satellite; thus, TESS planets will be far easier to characterize with follow-up observations. For the first time it will be possible to study the masses, sizes, densities, orbits, and atmospheres of a large cohort of small planets, including a sample of rocky worlds in the habitable zones of their host stars.An additional data product from the TESS mission will be full frame images (FFI) with a cadence of 30 minutes or less. These FFI will provide precise photometric information for every object within the 2300 square degree instantaneous field of view of the TESS cameras. These objects will include more than 1 million stars and bright galaxies observed during sessions of several weeks. In total, more than 30 million objects brighter than I=16 will be precisely photometered during the two-year prime mission. In principle, the lunar-resonant TESS orbit could provide opportunities for an extended mission lasting more than a decade, with data rates in excess of 100 Mbits/s.An extended survey by TESS of regions surrounding the North and South Ecliptic Poles will provide prime exoplanet targets for characterization with the James Webb Space Telescope (JWST), as well as other large ground-based and space-based telescopes of the future.TESS will issue data releases every 4 months, inviting immediate community-wide efforts to study the new planets, as well as commensal survey candidates from the FFI. A NASA Guest

  12. Effect of Rare Earth Metals on the Microstructure of Al-Si Based Alloys

    Directory of Open Access Journals (Sweden)

    Saleh A. Alkahtani

    2016-01-01

    Full Text Available The present study was performed on A356 alloy [Al-7 wt %Si 0.0.35 wt %Mg]. To that La and Ce were added individually or combined up to 1.5 wt % each. The results show that these rare earth elements affect only the alloy melting temperature with no marked change in the temperature of Al-Si eutectic precipitation. Additionally, rare earth metals have no modification effect up to 1.5 wt %. In addition, La and Ce tend to react with Sr leading to modification degradation. In order to achieve noticeable modification of eutectic Si particles, the concentration of rare earth metals should exceed 1.5 wt %, which simultaneously results in the precipitation of a fairly large volume fraction of insoluble intermetallics. The precipitation of these complex intermetallics is expected to have a negative effect on the alloy performance.

  13. Effect of Rare Earth Metals on the Microstructure of Al-Si Based Alloys

    Science.gov (United States)

    Alkahtani, Saleh A.; Elgallad, Emad M.; Tash, Mahmoud M.; Samuel, Agnes M.; Samuel, Fawzy H.

    2016-01-01

    The present study was performed on A356 alloy [Al-7 wt %Si 0.0.35 wt %Mg]. To that La and Ce were added individually or combined up to 1.5 wt % each. The results show that these rare earth elements affect only the alloy melting temperature with no marked change in the temperature of Al-Si eutectic precipitation. Additionally, rare earth metals have no modification effect up to 1.5 wt %. In addition, La and Ce tend to react with Sr leading to modification degradation. In order to achieve noticeable modification of eutectic Si particles, the concentration of rare earth metals should exceed 1.5 wt %, which simultaneously results in the precipitation of a fairly large volume fraction of insoluble intermetallics. The precipitation of these complex intermetallics is expected to have a negative effect on the alloy performance. PMID:28787844

  14. Effect of Rare Earth Metals on the Microstructure of Al-Si Based Alloys.

    Science.gov (United States)

    Alkahtani, Saleh A; Elgallad, Emad M; Tash, Mahmoud M; Samuel, Agnes M; Samuel, Fawzy H

    2016-01-13

    The present study was performed on A356 alloy [Al-7 wt %Si 0.0.35 wt %Mg]. To that La and Ce were added individually or combined up to 1.5 wt % each. The results show that these rare earth elements affect only the alloy melting temperature with no marked change in the temperature of Al-Si eutectic precipitation. Additionally, rare earth metals have no modification effect up to 1.5 wt %. In addition, La and Ce tend to react with Sr leading to modification degradation. In order to achieve noticeable modification of eutectic Si particles, the concentration of rare earth metals should exceed 1.5 wt %, which simultaneously results in the precipitation of a fairly large volume fraction of insoluble intermetallics. The precipitation of these complex intermetallics is expected to have a negative effect on the alloy performance.

  15. PERVAPORATION SEPARATION OF WATER-ACETIC ACID MIXTURES THROUGH AN-co-AA MEMBRANES TREATED WITH RARE EARTH METAL IONS

    Institute of Scientific and Technical Information of China (English)

    SHEN Zhiquan; ZHANG Fuyao; ZHANG Yifeng

    1995-01-01

    Pervaporation separation of water-acetic acid mixtures through Poly (AN-co-AA)membranes and rare earth metal ions treated Poly(AN-co-AA)membranes was investigated for the first time. The results showed that the treatment with rare earth metal ions could greatly improve the characteristics of the separation of water-acetic acid mixtures.

  16. Discovery of Temperate Earth-Sized Planets Transiting a Nearby Ultracool Dwarf Star

    Science.gov (United States)

    Jehin, Emmanuel; Gillon, Michael; Lederer, Susan M.; Delrez, Laetitia; De Wit, Julien; Burdanov, Artem; Van Grootel, Valerie; Burgasser, Adam; Triaud, Amaury; Demory, Brice-Olivier; hide

    2016-01-01

    We report the discovery of three short-period Earth-sized planets transiting a nearby ultracool dwarf star using data collected by the Liège TRAPPIST telescope, located in la Silla (Chile). TRAPPIST-1 is an isolated M8.0+/-0.5-type dwarf star at a distance of 12.0+/-0.4 parsecs as measured by its trigonometric parallax, with an age constrained to be > 500 Myr, and with a luminosity, mass, and radius of 0.05%, 8% and 11.5% those of the Sun, respectively. The small size of the host star, only slightly larger than Jupiter, translates into Earth-like radii for the three discovered planets, as deduced from their transit depths. The inner two planets receive four and two times the irradiation of Earth, respectively, placing them close to the inner edge of the habitable zone of the star. Several orbits remain possible for the third planet based on our current data. The infrared brightness of the host star combined with its Jupiter-like size offer the possibility of thoroughly characterizing the components of this nearby planetary system.

  17. Discovery of temperate Earth-sized planets transiting a nearby ultracool dwarf star

    Science.gov (United States)

    Jehin, Emmanuel; Gillon, Michael; Lederer, Susan M.; Delrez, Laetitia; de Wit, Julien; Burdanov, Artem; Van Grootel, Valérie; Burgasser, Adam; Triaud, Amaury; Demory, Brice-Olivier; Queloz, Didier

    2016-10-01

    We report the discovery of three short-period Earth-sized planets transiting a nearby ultracool dwarf star using data collected by the Liège TRAPPIST telescope, located in la Silla (Chile). TRAPPIST-1 is an isolated M8.0±0.5-type dwarf star at a distance of 12.0±0.4 parsecs as measured by its trigonometric parallax, with an age constrained to be > 500 Myr, and with a luminosity, mass, and radius of 0.05%, 8% and 11.5% those of the Sun, respectively. The small size of the host star, only slightly larger than Jupiter, translates into Earth-like radii for the three discovered planets, as deduced from their transit depths. The inner two planets receive four and two times the irradiation of Earth, respectively, placing them close to the inner edge of the habitable zone of the star. Several orbits remain possible for the third planet based on our current data. The infrared brightness of the host star combined with its Jupiter-like size offer the possibility of thoroughly characterizing the components of this nearby planetary system.

  18. Ammonia and hydrazine. Transition-metal-catalyzed hydroamination and metal-free catalyzed functionalization

    Energy Technology Data Exchange (ETDEWEB)

    Bertrand, Guy [Univ. of California, San Diego, CA (United States)

    2012-06-29

    The efficient and selective preparation of organic molecules is critical for mankind. For the future, it is of paramount importance to find catalysts able to transform abundant and cheap feedstocks into useful compounds. Acyclic and heterocyclic nitrogen-containing derivatives are common components of naturally occurring compounds, agrochemicals, cosmetics, and pharmaceuticals; they are also useful intermediates in a number of industrial processes. One of the most widely used synthetic strategies, allowing the formation of an N-C bond, is the addition of an N-H bond across a carbon-carbon multiple bond, the so-called hydroamination reaction. This chemical transformation fulfills the principle of “green chemistry” since it ideally occurs with 100% atom economy. Various catalysts have been found to promote this reaction, although many limitations remain; one of the most prominent is the lack of methods that permit the use of NH3 and NH2NH2 as the amine partners. In fact, ammonia and hydrazine have rarely succumbed to homogeneous catalytic transformations. Considering the low cost and abundance of ammonia (136 million metric tons produced in 2011) and hydrazine, catalysts able to improve the reactivity and selectivity of the NH3- and NH2NH2-hydroamination reaction, and more broadly speaking the functionalization of these chemicals, are highly desirable. In the last funded period, we discovered the first homogeneous catalysts able to promote the hydroamination of alkynes and allenes with ammonia and the parent hydrazine. The key feature of our catalytic systems is that the formation of catalytically inactive Werner complexes is reversible, in marked contrast to most of the known ammonia and hydrazine transition metal complexes. This is due to the peculiar electronic properties of our neutral ancillary ligands, especially their strong donating capabilities. However, our catalysts currently require

  19. Strong electron correlations in biomimetic transition metal molecules

    Science.gov (United States)

    Labute, Montiago Xavier

    The first-row transition metals (Fe, Co, V,...) are key players in the active sites of proteins and enzymes responsible for diverse biological processes such as NO regulation and photosynthesis. Many small transition metal complexes possess chemical coordination environments in the vicinity of the metal atom that are reminiscent of these active sites. We have studied the electronic structure of these molecules and discussed the relevance for their biological analogues. The specific question on which we wish to focus is: Do strong correlations (resulting from the localized character of the TM 3d-orbitals) contribute significantly to the reaction energetics of these molecules and, if so, can these effects be observed by experiment? To accomplish these ends we focus on the cobalt valence tautomer molecules and the phenomenon of electron transfer in aqueous hexaammine cobalt ions. We utilize theoretical methods in order to study the cobalt valence tautomer molecules which undergo an interconversion with temperature that is reminiscent of the changes in structure and spin that the heme group experiences as the result of Fe-ligand interactions. We perform fully ab initio calculations using the GGA implementation of density functional theory with the computer code SIESTA. In addition, a simple Anderson Impurity Model has been employed that more properly accounts for the Coulomb interaction among the 3d electrons on the cobalt atom. The calculated Co K x-ray absorption near-edge spectra XANES agrees well with experimental data and a prediction for the Co L-edge XAS that could be tested in future experiments is also presented. We believe that there are structures in both spectra that may only be explained by a strong admixture of configurations. It is conjectured that strong electron correlations help explain the non-Arrhenius rate behavior observed in the high-spin to low-spin relaxation rate at low temperatures. Work on electron-transfer in CoNH32 +/3+6aq using these

  20. Review of magnetic properties and magnetocaloric effect in the intermetallic compounds of rare earth with low boiling point metals

    Science.gov (United States)

    Ling-Wei, Li

    2016-03-01

    The magnetocaloric effect (MCE) in many rare earth (RE) based intermetallic compounds has been extensively investigated during the last two decades, not only due to their potential applications for magnetic refrigeration but also for better understanding of the fundamental problems of the materials. This paper reviews our recent progress on studying the magnetic properties and MCE in some binary or ternary intermetallic compounds of RE with low boiling point metal(s) (Zn, Mg, and Cd). Some of them exhibit promising MCE properties, which make them attractive for low temperature magnetic refrigeration. Characteristics of the magnetic transition, origin of large MCE, as well as the potential application of these compounds are thoroughly discussed. Additionally, a brief review of the magnetic and magnetocaloric properties in the quaternary rare earth nickel boroncarbides RENi2B2C superconductors is also presented. Project supported by the National Natural Science Foundation of China (Grant Nos. 11374081 and 11004044), the Fundamental Research Funds for the Central Universities, China (Grant Nos. N150905001, L1509006, and N140901001), the Japan Society for the Promotion of Science Postdoctoral Fellowships for Foreign Researchers (Grant No. P10060), and the Alexander von Humboldt (AvH) Foundation (Research stipend to L. Li).

  1. Effect of rare earth metal on the spin-orbit torque in magnetic heterostructures

    Energy Technology Data Exchange (ETDEWEB)

    Ueda, Kohei; Pai, Chi-Feng; Tan, Aik Jun; Mann, Maxwell; Beach, Geoffrey S. D., E-mail: gbeach@mit.edu [Department of Materials Science and Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139 (United States)

    2016-06-06

    We report the effect of the rare earth metal Gd on current-induced spin-orbit torques (SOTs) in perpendicularly magnetized Pt/Co/Gd heterostructures, characterized using harmonic measurements and spin-torque ferromagnetic resonance (ST-FMR). By varying the Gd metal layer thickness from 0 nm to 8 nm, harmonic measurements reveal a significant enhancement of the effective fields generated from the Slonczewski-like and field-like torques. ST-FMR measurements confirm an enhanced effective spin Hall angle and show a corresponding increase in the magnetic damping constant with increasing Gd thickness. These results suggest that Gd plays an active role in generating SOTs in these heterostructures. Our finding may lead to spin-orbitronics device application such as non-volatile magnetic random access memory, based on rare earth metals.

  2. Solubility Behavior and Phase Stability of Transition Metal Oxides in Alkaline Hydrothermal Environments

    Energy Technology Data Exchange (ETDEWEB)

    S.E. Ziemniak

    2000-05-18

    The solubility behavior of transition metal oxides in high temperature water is interpreted by recognizing three types of chemical reaction equilibria: metal oxide hydration/dehydration, metal oxide dissolution and metal ion hydroxocomplex formation. The equilibria are quantified using thermodynamic concepts and the thermochemical properties of the metal oxides/ions representative of the most common constituents of construction metal alloys, i.e., element shaving atomic numbers between Z = 22 (Ti) and Z = 30 (Zn), are summarized on the basis of metal oxide solubility studies conducted in the laboratory. Particular attention is devoted to the uncharged metal ion hydrocomplex, M{sup Z}(OH){sub Z}(aq), since its thermochemical properties define minimum solubilities of the metal oxide at a given temperature. Experimentally-extracted values of standard partial molal entropy (S{sup 0}) for the transition metal ion neutral hydroxocomplex are shown to be influenced by ligand field stabilization energies and complex symmetry.

  3. Transit surveys for Earths in the habitable zones of white dwarfs

    CERN Document Server

    Agol, Eric

    2011-01-01

    To date the search for habitable Earth-like planets has primarily focused on nuclear burning stars. I propose that this search should be expanded to cool white dwarf stars that have expended their nuclear fuel. I define the continuously habitable zone of white dwarfs, and show that it extends from ~0.005 to 0.02 AU for white dwarfs with masses from 0.4-0.9 solar masses, temperatures less than 10,000 K, and habitable durations of at least 3 Gyr. As they are similar in size to Earth, white dwarfs may be completely eclipsed by terrestrial planets that orbit edge-on, which can easily be detected with ground-based telescopes. If planets can migrate inward or reform near white dwarfs, I show that a global robotic telescope network could carry out a transit survey of nearby white dwarfs placing interesting constraints on the presence of habitable Earths. If planets were detected, I show that the survey would favor detection of planets similar to Earth: similar size, temperature, rotation period, and host star temper...

  4. Magnetic-field-induced superconductor-metal-insulator transitions in bismuth metal graphite

    Science.gov (United States)

    Suzuki, Masatsugu; Suzuki, Itsuko S.; Lee, Robert; Walter, Jürgen

    2002-07-01

    Bismuth metal graphite (MG) has a unique layered structure where Bi nanoparticles are encapsulated between adjacent sheets of nanographites. The superconductivity below Tc (=2.48 K) is due to Bi nanoparticles. The Curie-like susceptibility below 30 K is due to conduction electrons localized near zigzag edges of nanographites. A magnetic-field-induced transition from metallic to semiconductorlike phase is observed in the in-plane resistivity ρa around Hc (~25 kOe) for both H⊥c and H||c (c: c axis). A negative magnetoresistance in ρa for H⊥c (040 kOe) suggest the occurrence of a two-dimensional weak-localization effect.

  5. Ternary Amides Containing Transition Metals for Hydrogen Storage: A Case Study with Alkali Metal Amidozincates.

    Science.gov (United States)

    Cao, Hujun; Richter, Theresia M M; Pistidda, Claudio; Chaudhary, Anna-Lisa; Santoru, Antonio; Gizer, Gökhan; Niewa, Rainer; Chen, Ping; Klassen, Thomas; Dornheim, Martin

    2015-11-01

    The alkali metal amidozincates Li4 [Zn(NH2)4](NH2)2 and K2[Zn(NH2)4] were, to the best of our knowledge, studied for the first time as hydrogen storage media. Compared with the LiNH2-2 LiH system, both Li4 [Zn(NH2)4](NH2)2-12 LiH and K2[Zn(NH2)4]-8 LiH systems showed improved rehydrogenation performance, especially K2[Zn(NH2)4]-8 LiH, which can be fully hydrogenated within 30 s at approximately 230 °C. The absorption properties are stable upon cycling. This work shows that ternary amides containing transition metals have great potential as hydrogen storage materials.

  6. Mott metal-insulator transition in a metallic liquid - Gutzwiller molecular dynamics simulations

    Science.gov (United States)

    Barros, Kipton; Chern, Gia-Wei; Batista, Cristian D.; Kress, Joel D.; Kotliar, Gabriel

    2015-03-01

    Molecular dynamics (MD) simulations are crucial to modern computational physics, chemistry, and materials science, especially when combined with potentials derived from density-functional theory. However, even in state of the art MD codes, the on-site Coulomb repulsion is only treated at the self-consistent Hartree-Fock level. This standard approximation may miss important effects due to electron correlations. The Gutzwiller variational method captures essential correlated-electron physics yet is much faster than, e.g., the dynamical-mean field theory approach. We present our efficient Gutzwiller-MD implementation. With it, we investigate the Mott metal-insulator transition in a metallic fluid and uncover several surprising static and dynamic properties of this system.

  7. Effect of transition metal ions on the conductivity and stability of stabilized zirconia

    DEFF Research Database (Denmark)

    Lybye, D.; Mogensen, Mogens Bjerg

    2007-01-01

    the effect of co-doping with smaller transition metal ions such as Ti-, Fe- and Mn-ions. Many of the ionic radii of the transition metal ions are too small compared to the host lattice ionic radius of zirconium. Here we explore the effect of a) the small ionic radii compared to the large ionic radii...

  8. The control of magnetism near metal-to-insulator transitions of VO2 nano-belts

    CSIR Research Space (South Africa)

    Nkosi, SS

    2016-12-01

    Full Text Available changes near the metal-insulator phase transition of VO(sub2) produces magnetoelastic anisotropy. We observe intrinsic paramagnetic centres (PM-C) both at the near film surface and bulk/deep PM-C that are affected by the metal-insulator phase transition...

  9. Synthetic Fabrication of Nanoscale MoS2-Based Transition Metal Sulfides

    Directory of Open Access Journals (Sweden)

    Jikang Yuan

    2010-01-01

    Full Text Available Transition metal sulfides are scientifically and technologically important materials. This review summarizes recent progress on the synthetic fabrication of transition metal sulfides nanocrystals with controlled shape, size, and surface functionality. Special attention is paid to the case of MoS2 nanoparticles, where organic (surfactant, polymer, inorganic (support, promoter, doping compounds and intercalation chemistry are applied.

  10. Metal-insulator transition and local moment formation: A spin-density functional approach

    Science.gov (United States)

    Ghazali, A.; Leroux-Hugon, P.

    1980-01-01

    A more thorough description of the metal-insulator transition in correlated systems including local moment formation may be achieved through the spin-density functional method when compared to the Hubbard model. We have applied this method to doped semiconductors and found a transition between an insulating phase with local moments and a metallic one without moments.

  11. Late transition metal m-or chemistry and D6 metal complex photoeliminations

    Energy Technology Data Exchange (ETDEWEB)

    Sharp, Paul [Univ. of Missouri, Columbia, MO (United States)

    2015-07-31

    With the goal of understanding and controlling photoreductive elimination reactions from d6 transition metal complexes as part of a solar energy storage cycle we have investigated the photochemistry of Pt(IV) bromo, chloro, hydroxo, and hydroperoxo complexes. Photoreductive elimination reactions occur for all of these complexes and appear to involve initial Pt-Br, Pt-Cl, or Pt-O bond fission. In the case of Pt-OH bond fission, the subsequent chemistry can be controlled through hydrogen bonding to the hydroxo group.

  12. Ligational behavior of Schiff bases towards transition metal ion and metalation effect on their antibacterial activity.

    Science.gov (United States)

    Devi, Jai; Batra, Nisha; Malhotra, Rajesh

    2012-11-01

    New Schiff bases pyrazine-2-carboxylicacid (phenyl-pyridin-2-yl-methylene)-hydrazide (Hpch-bp) HL(1) and pyrazine-2-carboxylicacid (pyridin-2-ylmethylene)-hydrazide (Hpch-pc) HL(2) derived from condensation of pyrazine carboxylic hydrazide (Hpch) with 2-benzoyl pyridine (bp) or pyridine 2-carbaldehyde (pc) and their transition metal complexes of type ML((1-2)2) have been synthesized, where M=Mn(II), Co(II), Ni(II), Cu(II) and Zn(II). Characterization of ligands and their metal complexes was carried out by elemental analysis, conductimetric studies, magnetic susceptibility, spectroscopic techniques (IR, UV-VIS, NMR, ESR, Mass) and thermogravimetric analysis. The physico-chemical studies revealed octahedral geometry or distorted octahedral geometry around metal ion. These azomethine Schiff base ligands acted as tridentate coordinating through carbonyl, azomethine and pyridine nitrogen present in the ligand. The thermodynamic and thermal properties of the complexes have been investigated and it was observed on the basis of these studies that thermal stability of complexes follows the order Mnantibacterial activity at different concentrations against bacteria viz. Gram positive Bacillus subtilis, Micrococcus luteus and Gram negative Pseudomonas aeruginosa, Pseudomonas mendocina. A marked enhancement in biocidal activity of the ligands under similar experimental conditions was observed as a consequence of coordination with metal ions. The trend of growth inhibition in the complexes was found to be in the order: Cu>Mn>Ni>Co>Zn.

  13. Ligational behavior of Schiff bases towards transition metal ion and metalation effect on their antibacterial activity

    Science.gov (United States)

    Devi, Jai; Batra, Nisha; Malhotra, Rajesh

    2012-11-01

    New Schiff bases pyrazine-2-carboxylicacid (phenyl-pyridin-2-yl-methylene)-hydrazide (Hpch-bp) HL1 and pyrazine-2-carboxylicacid (pyridin-2-ylmethylene)-hydrazide (Hpch-pc) HL2 derived from condensation of pyrazine carboxylic hydrazide (Hpch) with 2-benzoyl pyridine (bp) or pyridine 2-carbaldehyde (pc) and their transition metal complexes of type ML(1-2)2 have been synthesized, where M = Mn(II), Co(II), Ni(II), Cu(II) and Zn(II). Characterization of ligands and their metal complexes was carried out by elemental analysis, conductimetric studies, magnetic susceptibility, spectroscopic techniques (IR, UV-VIS, NMR, ESR, Mass) and thermogravimetric analysis. The physico-chemical studies revealed octahedral geometry or distorted octahedral geometry around metal ion. These azomethine Schiff base ligands acted as tridentate ? coordinating through carbonyl, azomethine and pyridine nitrogen present in the ligand. The thermodynamic and thermal properties of the complexes have been investigated and it was observed on the basis of these studies that thermal stability of complexes follows the order Mn complexes were tested for in vitro antibacterial activity at different concentrations against bacteria viz. Gram positive Bacillus subtilis, Micrococcus luteus and Gram negative Pseudomonas aeruginosa, Pseudomonas mendocina. A marked enhancement in biocidal activity of the ligands under similar experimental conditions was observed as a consequence of coordination with metal ions. The trend of growth inhibition in the complexes was found to be in the order: Cu > Mn > Ni > Co > Zn.

  14. Red-emitting alkaline-earth rare-earth pentaoxometallates powders prepared by metal carboxylates solution

    Indian Academy of Sciences (India)

    Kyu-Seog Hwang; Sung-Dae Kim; Seung Hwangbo; Jin-Tae Kim

    2013-06-01

    Moisture-insensitive metal carboxylates that are mostly liquids at room temperature have been first applied to the preparation of strontium europium aluminate (Sr2EuAlO5) powders for red-emitting phosphor under near ultraviolet radiation. Strontium naphthenate, aluminium-2-ethylhexanoate and europium-2-ethylhexanoate were dissolved with toluene to prepare starting solution. Precursor pyrolyzed at 500 °C for 240 min was finally annealed at 900–1200 °C for 240 min in Ar. X-ray diffraction analysis, field emission–scanning electron microscope and fluorescent spectrophotometer were used to evaluate structural and optical properties. For the 1000 °C-annealed powders with regular shape and narrow size distribution confirmed by FE–SEM observation, strong red emission at 615nm under the excitation of 395nm maximum was reached, then the higher annealed samples at above 1100 °C gave the lower emission intensities.

  15. Tuning the metal-insulator transition in NdNiO3 thin films

    Science.gov (United States)

    Shiyani, T.; Shekhada, K. G.; Savaliya, C. R.; Markna, J. H.

    2017-05-01

    The RNiO3 (R is rare earth) perovskites are famous for their metal to insulator transition (MIT). The temperature can be transformed and depends on the nature of the rare earth. The MIT in thin films and heterostructures of RNiO3 propose the chance to control the MIT as a function of thickness via strain using different substrates. We have reported the electrical transport properties of NdNiO3/NdGaO3, and NNO/NGO/STO structures. These structures were fabricated by pulsed laser deposition (PLD) method. The temperature of the MIT changes from 155K to 195 K. The electrical resistivity of the heterostructures undergoes MIT, depending on the thickness and deposition conditions. Thickness and deposition temperature were found to have a great impact on the electrical transport properties. The shift in TMI changes with thickness and it larger for thinner NdNiO3. The MIT of NNO thin films is responsive to strain and its partial relaxation creates an inhomogeneous strain field that broadens the MIT. This study may be potentially applicable to Mott transistor devices.

  16. The highly synergistic, broad spectrum, antibacterial activity of organic acids and transition metals

    Science.gov (United States)

    Zhitnitsky, Daniel; Rose, Jessica; Lewinson, Oded

    2017-01-01

    For millennia, transition metals have been exploited to inhibit bacterial growth. We report here the potentiation of the anti-bacterial activity of transition metals by organic acids. Strong synergy between low, non-toxic concentrations of transition metals and organic acids was observed with up to ~1000-fold higher inhibitory effect on bacterial growth. We show that organic acids shuttle transition metals through the permeability barrier of the bacterial membrane, leading to increased influx of transition metals into bacterial cells. We demonstrate that this synergy can be effectively used to inhibit the growth of a broad range of plant and human bacterial pathogens, and suggest that a revision of food preservation and crop protection strategies may be in order. These findings bear significant biomedical, agricultural, financial and environmental opportunities. PMID:28294164

  17. BREEDING SUPER-EARTHS AND BIRTHING SUPER-PUFFS IN TRANSITIONAL DISKS

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Eve J.; Chiang, Eugene, E-mail: evelee@berkeley.edu, E-mail: echiang@astro.berkeley.edu [Department of Astronomy, University of California Berkeley, Berkeley, CA 94720-3411 (United States)

    2016-02-01

    The riddle posed by super-Earths (1–4R{sub ⊕}, 2–20M{sub ⊕}) is that they are not Jupiters: their core masses are large enough to trigger runaway gas accretion, yet somehow super-Earths accreted atmospheres that weigh only a few percent of their total mass. We show that this puzzle is solved if super-Earths formed late, as the last vestiges of their parent gas disks were about to clear. This scenario would seem to present fine-tuning problems, but we show that there are none. Ambient gas densities can span many (in one case up to 9) orders of magnitude, and super-Earths can still robustly emerge after ∼0.1–1 Myr with percent-by-weight atmospheres. Super-Earth cores are naturally bred in gas-poor environments where gas dynamical friction has weakened sufficiently to allow constituent protocores to gravitationally stir one another and merge. So little gas is present at the time of core assembly that cores hardly migrate by disk torques: formation of super-Earths can be in situ. The basic picture—that close-in super-Earths form in a gas-poor (but not gas-empty) inner disk, fed continuously by gas that bleeds inward from a more massive outer disk—recalls the largely evacuated but still accreting inner cavities of transitional protoplanetary disks. We also address the inverse problem presented by super-puffs: an uncommon class of short-period planets seemingly too voluminous for their small masses (4–10R{sub ⊕}, 2–6M{sub ⊕}). Super-puffs most easily acquire their thick atmospheres as dust-free, rapidly cooling worlds outside ∼1 AU where nebular gas is colder, less dense, and therefore less opaque. Unlike super-Earths, which can form in situ, super-puffs probably migrated in to their current orbits; they are expected to form the outer links of mean-motion resonant chains, and to exhibit greater water content. We close by confronting observations and itemizing remaining questions.

  18. Selective extraction and recovery of rare earth metals from phosphor powders in waste fluorescent lamps using an ionic liquid system.

    Science.gov (United States)

    Yang, Fan; Kubota, Fukiko; Baba, Yuzo; Kamiya, Noriho; Goto, Masahiro

    2013-06-15

    The recycling of rare earth metals from phosphor powders in waste fluorescent lamps by solvent extraction using ionic liquids was studied. Acid leaching of rare earth metals from the waste phosphor powder was examined first. Yttrium (Y) and europium (Eu) dissolved readily in the acid solution; however, the leaching of other rare earth metals required substantial energy input. Ionization of target rare earth metals from the waste phosphor powders into the leach solution was critical for their successful recovery. As a high temperature was required for the complete leaching of all rare earth metals, ionic liquids, for which vapor pressure is negligible, were used as an alternative extracting phase to the conventional organic diluent. An extractant, N, N-dioctyldiglycol amic acid (DODGAA), which was recently developed, showed a high affinity for rare earth metal ions in liquid-liquid extraction although a conventional commercial phosphonic extractant did not. An effective recovery of the rare earth metals, Y, Eu, La and Ce, from the metal impurities, Fe, Al and Zn, was achieved from the acidic leach solution of phosphor powders using an ionic liquid containing DODGAA as novel extractant system.

  19. Transition-metal embedded carbon nitride monolayers: high-temperature ferromagnetism and half-metallicity

    Science.gov (United States)

    Choudhuri, Indrani; Kumar, Sourabh; Mahata, Arup; Rawat, Kuber Singh; Pathak, Biswarup

    2016-07-01

    High-temperature ferromagnetic materials with planar surfaces are promising candidates for spintronics applications. Using state-of-the-art density functional theory (DFT) calculations, transition metal (TM = Cr, Mn, and Fe) incorporated graphitic carbon nitride (TM@gt-C3N4) systems are investigated as possible spintronics devices. Interestingly, ferromagnetism and half-metallicity were observed in all of the TM@gt-C3N4 systems. We find that Cr@gt-C3N4 is a nearly half-metallic ferromagnetic material with a Curie temperature of ~450 K. The calculated Curie temperature is noticeably higher than other planar 2D materials studied to date. Furthermore, it has a steel-like mechanical stability and also possesses remarkable dynamic and thermal (500 K) stability. The calculated magnetic anisotropy energy (MAE) in Cr@gt-C3N4 is as high as 137.26 μeV per Cr. Thereby, such material with a high Curie temperature can be operated at high temperatures for spintronics devices.High-temperature ferromagnetic materials with planar surfaces are promising candidates for spintronics applications. Using state-of-the-art density functional theory (DFT) calculations, transition metal (TM = Cr, Mn, and Fe) incorporated graphitic carbon nitride (TM@gt-C3N4) systems are investigated as possible spintronics devices. Interestingly, ferromagnetism and half-metallicity were observed in all of the TM@gt-C3N4 systems. We find that Cr@gt-C3N4 is a nearly half-metallic ferromagnetic material with a Curie temperature of ~450 K. The calculated Curie temperature is noticeably higher than other planar 2D materials studied to date. Furthermore, it has a steel-like mechanical stability and also possesses remarkable dynamic and thermal (500 K) stability. The calculated magnetic anisotropy energy (MAE) in Cr@gt-C3N4 is as high as 137.26 μeV per Cr. Thereby, such material with a high Curie temperature can be operated at high temperatures for spintronics devices. Electronic supplementary information (ESI

  20. Electronic self-organization in layered transition metal dichalcogenides

    Energy Technology Data Exchange (ETDEWEB)

    Ritschel, Tobias

    2015-10-30

    The interplay between different self-organized electronically ordered states and their relation to unconventional electronic properties like superconductivity constitutes one of the most exciting challenges of modern condensed matter physics. In the present thesis this issue is thoroughly investigated for the prototypical layered material 1T-TaS{sub 2} both experimentally and theoretically. At first the static charge density wave order in 1T-TaS{sub 2} is investigated as a function of pressure and temperature by means of X-ray diffraction. These data indeed reveal that the superconductivity in this material coexists with an inhomogeneous charge density wave on a macroscopic scale in real space. This result is fundamentally different from a previously proposed separation of superconducting and insulating regions in real space. Furthermore, the X-ray diffraction data uncover the important role of interlayer correlations in 1T-TaS{sub 2}. Based on the detailed insights into the charge density wave structure obtained by the X-ray diffraction experiments, density functional theory models are deduced in order to describe the electronic structure of 1T-TaS{sub 2} in the second part of this thesis. As opposed to most previous studies, these calculations take the three-dimensional character of the charge density wave into account. Indeed the electronic structure calculations uncover complex orbital textures, which are interwoven with the charge density wave order and cause dramatic differences in the electronic structure depending on the alignment of the orbitals between neighboring layers. Furthermore, it is demonstrated that these orbital-mediated effects provide a route to drive semiconductor-to-metal transitions with technologically pertinent gaps and on ultrafast timescales. These results are particularly relevant for the ongoing development of novel, miniaturized and ultrafast devices based on layered transition metal dichalcogenides. The discovery of orbital textures

  1. Electron Scattering at Surfaces and Interfaces of Transition Metals

    Science.gov (United States)

    Zheng, Pengyuan

    The effect of surfaces on the electron transport at reduced scales is attracting continuous interest due to its broad impact on both the understanding of materials properties and their application for nanoelectronics. The size dependence of for conductor's electrical resistivity rho due to electron surface scattering is most commonly described within the framework of Fuchs and Sondheimer (FS) and their various extensions, which uses a phenomenological scattering parameter p to define the probability of electrons being elastically (i.e. specularly) scattered by the surface without causing an increase of rho at reduced size. However, a basic understanding of what surface chemistry and structure parameters determine the specularity p is still lacking. In addition, the assumption of a spherical Fermi surface in the FS model is too simple for transition metals to give accurate account of the actual surface scattering effect. The goal of this study is to develop an understanding of the physics governing electron surface/interface scattering in transition metals and to study the significance of their Fermi surface shape on surface scattering. The advancement of the scientific knowledge in electron surface and interface scattering of transition metals can provide insights into how to design high-conductivity nanowires that will facilitate the viable development of advanced integrated circuits, thermoelectric power generation and spintronics. Sequential in situ and ex situ transport measurements as a function of surface chemistry demonstrate that electron surface/interface scattering can be engineered by surface doping, causing a decrease in the rho. For instance, the rho of 9.3-nm-thick epitaxial and polycrystalline Cu is reduced by 11--13% when coated with 0.75 nm Ni. This is due to electron surface scattering which exhibits a specularity p = 0.7 for the Cu-vacuum interface that transitions to completely diffuse (p = 0) when exposed to air. In contrast, Ni-coated surfaces

  2. Deoxygenation of Palmitic Acid on Unsupported Transition-Metal Phosphides

    Energy Technology Data Exchange (ETDEWEB)

    Peroni, Marco [Technische Universität München, Department; Lee, Insu [Technische Universität München, Department; Huang, Xiaoyang [Technische Universität München, Department; Baráth, Eszter [Technische Universität München, Department; Gutiérrez, Oliver Y. [Technische Universität München, Department; Lercher, Johannes A. [Technische Universität München, Department; Institute

    2017-08-18

    Abstract Highly active bulk transition metal phosphides (WP, MoP, and Ni2P) were synthesized for the catalytic hydrodeoxygenation of palmitic acid, hexadecanol, hexadecanal, and microalgae oil. The specific activities positively correlated with the concentration of exposed metal sites, although the relative rates changed with temperature due to activation energies varying from 57 kJ·mol-1 for MoP to 142 kJ·mol-1 for WP. The reduction of the fatty acid to the aldehyde occurs through a Langmuir-Hinshelwood mechanism, where the rate-determining step is the addition of the second H to the hydrocarbon. On WP, the conversion of palmitic acid proceeds via R-CH2COOH R-CH2CHO R-CH2CH2OH R-CHCH2 R-CH2CH3 (hydrodeoxygenation). Decarbonylation of the intermittently formed aldehyde (R-CH2COOH R-CH2CHO R-CH3) was an important pathway on MoP and Ni2P. Conversion via dehydration to a ketene, followed by its decarbonylation occurred only on Ni2P. The rates of alcohol dehydration (R-CH2CH2OH R-CHCH2) correlate with the concentration of Lewis acid sites of the phosphides. Acknowledgements The authors would like to thank Roel Prins for the critical discussion of the results. We are also grateful to Xaver Hecht for technical support. Funding by the German Federal Ministry of Food and Agriculture in the framework of the Advanced Biomass Value project (03SF0446A) is gratefully acknowledged. J.A.L. acknowledges support for his contribution by the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences for exploring non-oxidic supports for deoxygenation reactions.

  3. Voltage controlled magnetism in 3d transitional metals

    Science.gov (United States)

    Wang, Weigang

    2015-03-01

    Despite having attracted much attention in multiferroic materials and diluted magnetic semiconductors, the impact of an electric field on the magnetic properties remains largely unknown in 3d transitional ferromagnets (FMs) until recent years. A great deal of effort has been focused on the voltage-controlled magnetic anisotropy (VCMA) effect where the modulation of anisotropy field is understood by the change of electron density among different d orbitals of FMs in the presence of an electric field. Here we demonstrate another approach to alter the magnetism by electrically controlling the oxidation state of the 3d FM at the FM/oxide interface. The thin FM film sandwiched between a heavy metal layer and a gate oxide can be reversibly changed from an optimally-oxidized state with a strong perpendicular magnetic anisotropy to a metallic state with an in-plane magnetic anisotropy, or to a fully-oxidized state with nearly zero magnetization, depending on the polarity and time duration of the applied electric fields. This is a voltage controlled magnetism (VCM) effect, where both the saturation magnetization and anisotropy field of the 3d FM layer can be simultaneously controlled by voltage in a non-volatile fashion. We will also discuss the impact of this VCM effect on magnetic tunnel junctions and spin Hall switching experiments. This work, in collaboration with C. Bi, Y.H. Liu, T. Newhouse-Illige, M. Xu, M. Rosales, J.W. Freeland, O. Mryasov, S. Zhang, and S.G.E. te Velthuis, was supported in part by NSF (ECCS-1310338) and by C-SPIN, one of six centers of STARnet, a Semiconductor Research Corporation program, sponsored by MARCO and DARPA.

  4. Spin Transition of Iron in the Earth's Lower Mantle

    Energy Technology Data Exchange (ETDEWEB)

    Lin, J; Tsuchiya, T

    2007-05-23

    Electronic spin-pairing transitions of iron and associated effects on the physical properties of host phases have been reported in lower-mantle minerals including ferropericlase, silicate perovskite, and possibly in post-perovskite at lower-mantle pressures. Here we evaluate current understanding of the spin and valence states of iron in the lower-mantle phases, emphasizing the effects of the spin transitions on the density, sound velocities, chemical behavior, and transport properties of the lower-mantle phases. The spin transition of iron in ferropericlase occurs at approximately 50 GPa but likely turns into a wide spin crossover under lower-mantle temperatures. Current experimental results indicate a continuous nature of the spin crossover in silicate perovskite at high pressures, but which valence state of iron undergoes the spin crossover and what is its associated crystallographic site remain uncertain. The spin transition of iron results in enhanced density, incompressibility, and sound velocities, and reduced radiative thermal conductivity in the low-spin ferropericlase, which should be considered in future geophysical and geodynamic modeling of the Earth's lower mantle. Our evaluation of the experimental and theoretical pressure-volume results shows that the spin crossover of iron results in a density increase of 3-4% in ferropericlase containing 17-19% FeO. Here we have modeled the density and bulk modulus profiles of ferropericlase across the spin crossover under lower-mantle pressure-temperature conditions and showed how the ratio of the spin states of iron affects our understanding of the state of the Earth's lower mantle.

  5. Liquid-Liquid Structure Transition in Metallic Melts: Experimental Evidence by Viscosity Measurement

    Institute of Scientific and Technical Information of China (English)

    WANG Yu-Qing; WU Yu-Qin; BIAN Xiu-Fang

    2007-01-01

    Temperature dependence of viscosity for more than ten kinds of metallic melts is analysed based on viscosity measurements. An obvious turning point is observed on the Arrhenius curves. Since viscosity is one of the physical properties sensitive to structure, its discontinuous change with temperature reveals the possible liquidliquid structure transition in the metallic melts. Furthermore, an integrated liquid structure transition diagram of the Sn-Bi system is presented. The universality of liquid-liquid structure transition is also discussed simply.

  6. Insulator/metal phase transition and colossal magnetoresistance in holographic model

    CERN Document Server

    Cai, Rong-Gen

    2015-01-01

    We construct a gravity dual for insulator/metal phase transition and colossal magnetoresistance (CMR) effect found in some manganese oxides materials. The computations shows a remarkable magnetic-field-sensitive DC resistivity peak appearing at the Curie temperature, where an insulator/metal phase transition happens and the magnetoresistance is scaled with the square of field-induced magnetization. We find that metallic and insulating phases coexist below the Curie point and the relation with the electronic phase separation is discussed.

  7. Influence of alkaline earth metals on molecular structure of 3-nitrobenzoic acid in comparison with alkali metals effect.

    Science.gov (United States)

    Samsonowicz, M; Regulska, E; Lewandowski, W

    2011-11-01

    The influence of beryllium, magnesium, calcium, strontium and barium cations on the electronic system of 3-nitrobenzoic acid was studied in comparison with studied earlier alkali metal ions. The vibrational FT-IR (in KBr and ATR techniques) and (1)H and (13)C NMR spectra were recorded for 3-nitrobenzoic acid and its salts. Characteristic shifts in IR and NMR spectra along 3-nitrobenzoates of divalent metal series Mg→Ba were compared with series of univalent metal Li→Cs salts. Good correlations between the wavenumbers of the vibrational bands in the IR spectra for 3-nitrobenzoates and ionic potential, electronegativity, inverse of atomic mass, atomic radius and ionization energy of metals were found for alkaline earth metals as well as for alkali metals. The density functional (DFT) hybrid method B3LYP with two basis sets: 6-311++G** and LANL2DZ were used to calculate optimized geometrical structures of studied compounds. The theoretical wavenumbers and intensities of IR spectra as well as chemical shifts in NMR spectra were obtained. Geometric aromaticity indices, atomic charges, dipole moments and energies were also calculated. The calculated parameters were compared to experimental characteristic of studied compounds.

  8. Ground-based transit observations of the super-Earth GJ 1214b

    CERN Document Server

    Caceres, Claudio; Hoyer, Sergio; Ivanov, Valentin D; Rojo, Patricio; Girard, Julien H; Kempton, Eliza Miller-Ricci; Fortney, Jonathan J; Minniti, Dante

    2014-01-01

    GJ 1214b is one of the few known transiting super-Earth-sized exoplanets with a measured mass and radius. It orbits an M-dwarf, only 14.55 pc away, making it a favorable candidate for follow-up studies. However, the composition of GJ 1214b's mysterious atmosphere has yet to be fully unveiled. Our goal is to distinguish between the various proposed atmospheric models to explain the properties of GJ 1214b: hydrogen-rich or hydrogen-He mix, or a heavy molecular weight atmosphere with reflecting high clouds, as latest studies have suggested. Wavelength-dependent planetary radii measurements from the transit depths in the optical/NIR are the best tool to investigate the atmosphere of GJ 1214b. We present here (i) photometric transit observations with a narrow-band filter centered on 2.14 microns and a broad-band I-Bessel filter centered on 0.8665 microns, and (ii) transmission spectroscopy in the H and K atmospheric windows that cover three transits. The obtained photometric and spectrophotometric time series were...

  9. Magnetic-field-induced valence transition in rare-earth systems

    Indian Academy of Sciences (India)

    G Gangadhar Reddy; A Ramakanth; S K Ghatak

    2002-05-01

    The magnetic-field-induced valence transition in rare-earth systems has been investigated using the periodic Anderson model supplemented by the Falicov–Kimball term. This model has been solved by first decoupling the Falicov–Kimball term as proposed by Khomskii and Koharjan and then taking the limit of infinite intra-site Coulomb repulsion. The valence transition both in the absence and in the presence of magnetic field as a function of temperature is studied. It has been found that the system makes transition from non-magnetic to magnetic state when the magnetic field increases beyond a critical value c. The phase boundary defined in terms of reduced field c()/c(0) and reduced temperature /v (v being the valence transition temperature in the absence of field) is almost independent of the position of the localized level. The results are in qualitative agreement with experimental observations in Yb- and Eu-compounds.

  10. Metamagnetism of η-carbide-type transition-metal carbides and nitrides

    Science.gov (United States)

    Waki, T.; Terazawa, S.; Umemoto, Y.; Tabata, Y.; Sato, K.; Kondo, A.; Kindo, K.; Nakamura, H.

    2011-09-01

    η-carbide-type transition-metal compounds include the frustrated stella quadran-gula lattice. Due to characteristics of the lattice, we expect subtle transitions between frustrated and non-frustrated states. Here, we report metamagnetic transitions newly found in η-carbide-type compounds Fe3W3C, Fe6W6C and Co6W6C.

  11. Dissociation of N2, NO, and CO on transition metal surfaces

    DEFF Research Database (Denmark)

    Mavrikakis, Manos; Hansen, Lars Bruno; Mortensen, Jens Jørgen;

    1999-01-01

    Using density functional theory we study the dissociation of N2, NO, and CO on transition metal surfaces. We discuss an efficient method to locate the minimum energy path and the transition state, and review recent calculations using this method to determine the transition state for dissociation...

  12. Synthesis and characterization of anhydrous rare earth metal nitrates, rare earth acetates and rare earth oxyacetates; Synthese und Charakterisierung wasserfreier Seltenerdmetall-Nitrate, -Acetate und -Oxyacetate

    Energy Technology Data Exchange (ETDEWEB)

    Heinrichs, Christina

    2013-10-29

    Anhydrous rare-earth metal (RE) nitrates, RE nitrate monohydrates and RE acetates were synthesized by thermal dehydration of RE nitrate hydrates and RE acetate hydrates in an argon flow or vacuum. RE oxyacetates were synthesized by thermal decomposition of RE acetates. Furthermore praseodymium carbonate hydroxide was synthesized by heating Pr carbonate hydrate. The compounds were analyzed by X-ray powder diffraction and, for selected examples, measurements with high-resolution synchrotron radiation were performed. Three new crystal structure types were found for RE nitrates: RE(NO{sub 3}){sub 3} with RE = La - Sm (type I) crystallize monoclinically in space group C2/c with Z = 16 (CN = 12, 11). RE(NO{sub 3}){sub 3} with RE = Y, Eu - Yb (type II) crystallize monoclinically in space group P2{sub 1}/c with Z = 4 (CN = 10) and Lu(NO{sub 3}){sub 3} (type III) monoclinically in space group I2/a with Z = 16 (CN = 8, 7). With decreasing CN (coordination number) a structural trend within the RE nitrates is observed: The RE nitrates of type I with the largest RE{sup 3+} cations build a three-dimensional network, the RE nitrates of type II form close packed layers and the preliminary structural model of Lu(NO{sub 3}){sub 3} (type III) with the smallest RE{sup 3+} cation shows layers and chains. The product of the dehydration of Sc(NO{sub 3}){sub 3} . n H{sub 2}O was indexed monoclinically in space group P2{sub 1}/c. Monohydrates RE(NO{sub 3}){sub 3} . H{sub 2}O with RE = Dy - Yb crystallize isotypically with Y(NO{sub 3}){sub 3} . H{sub 2}O in the triclinic space group P anti 1 with Z = 2 (CN = 9). Pr(CH{sub 3}CO{sub 2}){sub 3} does not crystallize in the known Pr acetate type but in the trigonal space group R anti 3 with Z = 18 (CN = 10) isotypically with the La acetate type which was only known for La(CH{sub 3}CO{sub 2}){sub 3} and Ce(CH{sub 3}CO{sub 2}){sub 3} up to now. In addition to the known Ho acetate type a new crystal structure type (Ho acetate type II) was found for

  13. Nature of the Metallization Transition in Solid Hydrogen

    CERN Document Server

    Azadi, Sam; Foulkes, W M C

    2016-01-01

    We present an accurate study of the static-nucleus electronic energy band gap of solid molecular hydrogen at high pressure. The excitonic and quasiparticle gaps of the $C2/c$, $Pc$, $Pbcn$, and $P6_3/m$ structures at pressures of 250, 300, and 350~GPa are calculated using the fixed-node diffusion quantum Monte Carlo (DMC) method. The difference between the mean-field and many-body band gaps at the same density is found to be almost independent of system size and can therefore be applied as a scissor correction to the mean-field gap of an infinite system to obtain an estimate of the many-body gap in the thermodynamic limit. By comparing our static-nucleus DMC energy gaps with available experimental results, we demonstrate the important role played by nuclear quantum effects in the electronic structure of solid hydrogen. Our DMC results suggest that the metallization of high-pressure solid hydrogen occurs via a structural phase transition rather than band gap closure.

  14. Defect engineering of two-dimensional transition metal dichalcogenides

    Science.gov (United States)

    Lin, Zhong; Carvalho, Bruno R.; Kahn, Ethan; Lv, Ruitao; Rao, Rahul; Terrones, Humberto; Pimenta, Marcos A.; Terrones, Mauricio

    2016-06-01

    Two-dimensional transition metal dichalcogenides (TMDs), an emerging family of layered materials, have provided researchers a fertile ground for harvesting fundamental science and emergent applications. TMDs can contain a number of different structural defects in their crystal lattices which significantly alter their physico-chemical properties. Having structural defects can be either detrimental or beneficial, depending on the targeted application. Therefore, a comprehensive understanding of structural defects is required. Here we review different defects in semiconducting TMDs by summarizing: (i) the dimensionalities and atomic structures of defects; (ii) the pathways to generating structural defects during and after synthesis and, (iii) the effects of having defects on the physico-chemical properties and applications of TMDs. Thus far, significant progress has been made, although we are probably still witnessing the tip of the iceberg. A better understanding and control of defects is important in order to move forward the field of Defect Engineering in TMDs. Finally, we also provide our perspective on the challenges and opportunities in this emerging field.

  15. Optoelectronics of Transition Metal Dichalcogenide Monolayers and Heterostructures

    Science.gov (United States)

    Schaibley, John

    2015-03-01

    Monolayer transition metal dichalcogenides (TMDs) contain 2D valley excitons which reside in two degenerate momentum space valleys at the edges of the Brillouin zone. It is crucially important to understand fundamental 2D exciton properties in TMD monolayers and van der Waals heterostructures. By performing coherent nonlinear optical spectroscopy with high spectral resolution, we observe nanosecond decay dynamics in single monolayers of MoSe2, implying the presence of a previously unreported long-lived state that appears to trap the exciton population. In MoSe2-WSe2 vertical heterostructures, we observe intralayer excitons, where the electron and hole are confined to different monolayers, and show evidence of strong exciton-exciton interaction effects and long lifetimes. Based on TMD monolayer excitons, we have also investigated a variety of fundamental quantum devices, including a nano-cavity laser and a second-harmonic generation transistor. Finally, we report a new type of single quantum emitter, based on single localized excitons spatially confined to defects in monolayers of WSe2. The photoluminescence from these localized excitons is spectrally narrow and shows strong anti-bunching, demonstrating the single photon nature of the emission.

  16. Robust quantum anomalous Hall effect in ferromagnetic transition metal halides

    CERN Document Server

    Huang, Chengxi; Wu, Haiping; Deng, Kaiming; Jena, Puru; Kan, Erjun

    2016-01-01

    The quantum anomalous Hall (QAH) effect is a novel topological spintronic phenomenon arising from inherent magnetization and spin-orbit coupling. Various theoretical and experimental efforts have been devoted in search of robust intrinsic QAH insulators. However, up to now, it has only been observed in Cr or V doped (Bi,Sb)2Te3 film in experiments with very low working temperature. Based on the successful synthesis of transition metal halides, we use first-principles calculations to predict that RuI3 monolayer is an intrinsic ferromagnetic QAH insulator with a topologically nontrivial global band gap of 11 meV. This topologically nontrivial band gap at the Fermi level is due to its crystal symmetry, thus the QAH effect is robust. Its Curie temperature, estimated to be ~360 K using Monte-Carlo simulation, is above room temperature and higher than most of two-dimensional ferromagnetic thin films. We also discuss the manipulation of its exchange energy and nontrivial band gap by applying in-plane strain. Our wor...

  17. Odd-parity superconductivity in bilayer transition metal dichalcogenides

    Science.gov (United States)

    Nakamura, Yasuharu; Yanase, Youichi

    2017-08-01

    Spin-orbit coupling in transition metal dichalcogenides (TMDCs) causes spin-valley locking, giving rise to unconventional optical, transport, and superconducting properties. In this paper, we propose exotic superconductivity in bilayer group-IV TMDCs by symmetry control. The sublattice-dependent "hidden" spin-orbit coupling arising from local inversion symmetry breaking in the crystal structure may stabilize the odd-parity superconductivity by purely s -wave local pairing interaction. The stability of the odd-parity superconducting state depends on the bilayer stacking. The 2 Hb stacking in MoX2 and WX2 (X =S ,Se) favors the odd-parity superconductivity due to interlayer quantum interference. On the other hand, the odd-parity superconductivity is suppressed by the 2 Ha stacking of NbSe2. Calculating the phase diagram of the tight-binding model derived from first-principles band calculations, we conclude that the intercalated bilayer MoS2 and WS2 are candidates for a new class of odd-parity superconductors by spin-orbit coupling.

  18. PNP-Pincer-Type Phosphaalkene Complexes of Late Transition Metals.

    Science.gov (United States)

    Ozawa, Fumiyuki; Nakajima, Yumiko

    2016-10-01

    This account summarizes our recent studies on PNP-pincer-type phosphaalkene complexes. Phosphaalkenes with a P=C bond possess an extremely low-lying π* orbital and have a marked tendency to engage in strong π back-bonding with transition metals. This particular ligand property provides PNP-pincer complexes with unique structures and reactivities. 2,6-Bis(phosphaethenyl)pyridine leads to the isolation of coordinatively unsaturated complexes of Fe(I) and Cu(I); the former adopts a trigonal monopyramidal configuration, whereas the latter has a strong affinity for PF6- and SbF6- as non-coordinating anions. Unsymmetrical PNP-pincer-type phosphaalkene complexes of Ir(I) bearing a dearomatized pyridine unit instantly cleave the N-H bond of NH3 and the C-H bond of MeCN at room temperature. The dearomatized iridium complexes catalyze the dehydrative coupling of amines with alcohols to afford N-alkylated amines and imines in high yields.

  19. Band Alignment of 2D Transition Metal Dichalcogenide Heterojunctions

    KAUST Repository

    Chiu, Ming Hui

    2016-09-20

    It is critically important to characterize the band alignment in semiconductor heterojunctions (HJs) because it controls the electronic and optical properties. However, the well-known Anderson\\'s model usually fails to predict the band alignment in bulk HJ systems due to the presence of charge transfer at the interfacial bonding. Atomically thin 2D transition metal dichalcogenide materials have attracted much attention recently since the ultrathin HJs and devices can be easily built and they are promising for future electronics. The vertical HJs based on 2D materials can be constructed via van der Waals stacking regardless of the lattice mismatch between two materials. Despite the defect-free characteristics of the junction interface, experimental evidence is still lacking on whether the simple Anderson rule can predict the band alignment of HJs. Here, the validity of Anderson\\'s model is verified for the 2D heterojunction systems and the success of Anderson\\'s model is attributed to the absence of dangling bonds (i.e., interface dipoles) at the van der Waal interface. The results from the work set a foundation allowing the use of powerful Anderson\\'s rule to determine the band alignments of 2D HJs, which is beneficial to future electronic, photonic, and optoelectronic devices. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Interactions between lasers and two-dimensional transition metal dichalcogenides.

    Science.gov (United States)

    Lu, Junpeng; Liu, Hongwei; Tok, Eng Soon; Sow, Chorng-Haur

    2016-05-03

    The recent increasing research interest in two-dimensional (2D) layered materials has led to an explosion of in the discovery of novel physical and chemical phenomena in these materials. Among the 2D family, group-VI transition metal dichalcogenides (TMDs), such as represented by MoS2 and WSe2, are remarkable semiconductors with sizable energy band gaps, which make the TMDs promising building blocks for new generation optoelectronics. On the other hand, the specificity and tunability of the band gaps can generate particularly strong light-matter interactions between TMD crystals and specific photons, which can trigger complex and interesting phenomena such as photo-scattering, photo-excitation, photo-destruction, photo-physical modification, photochemical reaction and photo-oxidation. Herein, we provide an overview of the phenomena explained by various interactions between lasers and the 2D TMDs. Characterizations of the optical fundamentals of the TMDs via laser spectroscopies are reviewed. Subsequently, photoelectric conversion devices enabled by laser excitation and the functionality extension and performance improvement of the TMDs materials via laser modification are comprehensively summarized. Finally, we conclude the review by discussing the prospects for further development in this research area.

  1. Quantum dot behavior in transition metal dichalcogenides nanostructures

    Science.gov (United States)

    Luo, Gang; Zhang, Zhuo-Zhi; Li, Hai-Ou; Song, Xiang-Xiang; Deng, Guang-Wei; Cao, Gang; Xiao, Ming; Guo, Guo-Ping

    2017-08-01

    Recently, transition metal dichalcogenides (TMDCs) semiconductors have been utilized for investigating quantum phenomena because of their unique band structures and novel electronic properties. In a quantum dot (QD), electrons are confined in all lateral dimensions, offering the possibility for detailed investigation and controlled manipulation of individual quantum systems. Beyond the definition of graphene QDs by opening an energy gap in nanoconstrictions, with the presence of a bandgap, gate-defined QDs can be achieved on TMDCs semiconductors. In this paper, we review the confinement and transport of QDs in TMDCs nanostructures. The fabrication techniques for demonstrating two-dimensional (2D) materials nanostructures such as field-effect transistors and QDs, mainly based on e-beam lithography and transfer assembly techniques are discussed. Subsequently, we focus on electron transport through TMDCs nanostructures and QDs. With steady improvement in nanoscale materials characterization and using graphene as a springboard, 2D materials offer a platform that allows creation of heterostructure QDs integrated with a variety of crystals, each of which has entirely unique physical properties.

  2. Unconventional superconductivity from magnetism in transition-metal dichalcogenides

    Science.gov (United States)

    Rahimi, M. A.; Moghaddam, A. G.; Dykstra, C.; Governale, M.; Zülicke, U.

    2017-03-01

    We investigate proximity-induced superconductivity in monolayers of transition-metal dichalcogenides (TMDs) in the presence of an externally generated exchange field. A variety of superconducting order parameters is found to emerge from the interplay of magnetism and superconductivity, covering the entire spectrum of possibilities to be symmetric or antisymmetric with respect to the valley and spin degrees of freedom, as well as even or odd in frequency. More specifically, when a conventional s -wave superconductor with singlet Cooper pairs is tunnel-coupled to the TMD layer, both spin-singlet and triplet pairings between electrons from the same and opposite valleys arise due to the combined effects of intrinsic spin-orbit coupling and a magnetic-substrate-induced exchange field. As a key finding, we reveal the existence of an exotic even-frequency triplet pairing between equal-spin electrons from different valleys, which arises whenever the spin orientations in the two valleys are noncollinear. All types of superconducting order turn out to be highly tunable via straightforward manipulation of the external exchange field.

  3. Optical fingerprint of non-covalently functionalized transition metal dichalcogenides

    Science.gov (United States)

    Feierabend, Maja; Malic, Ermin; Knorr, Andreas; Berghäuser, Gunnar

    2017-09-01

    Atomically thin transition metal dichalcogenides (TMDs) hold promising potential for applications in optoelectronics. Due to their direct band gap and the extraordinarily strong Coulomb interaction, TMDs exhibit efficient light-matter coupling and tightly bound excitons. Moreover, large spin orbit coupling in combination with circular dichroism allows for spin and valley selective optical excitation. As atomically thin materials, they are very sensitive to changes in the surrounding environment. This motivates a functionalization approach, where external molecules are adsorbed to the materials surface to tailor its optical properties. Here, we apply the density matrix theory to investigate the potential of non-covalently functionalized monolayer TMDs. Considering exemplary molecules with a strong dipole moment, we predict spectral redshifts and the appearance of an additional side peak in the absorption spectrum of functionalized TMDs. We show that the molecular characteristics, e.g. coverage, orientation and dipole moment, crucially influence the optical properties of TMDs, leaving a unique optical fingerprint in the absorption spectrum. Furthermore, we find that the molecular dipole moments open a channel for coherent intervalley coupling between the high-symmetry K and K\\prime points which may create new possibilities for spin-valleytronics application.

  4. Quantum anomalous Hall effect in ferromagnetic transition metal halides

    Science.gov (United States)

    Huang, Chengxi; Zhou, Jian; Wu, Haiping; Deng, Kaiming; Jena, Puru; Kan, Erjun

    2017-01-01

    The quantum anomalous Hall (QAH) effect is a novel topological spintronic phenomenon arising from inherent magnetization and spin-orbit coupling. Various theoretical and experimental efforts have been devoted in search of intrinsic QAH insulators. However, up to now, it has only been observed in Cr or V doped (Bi,Sb ) 2T e3 film in experiments with very low working temperature. Based on the successful synthesis of transition metal halides, we use first-principles calculations to predict that the Ru I3 monolayer is an intrinsic ferromagnetic QAH insulator with a topologically nontrivial global band gap of 11 meV. This topologically nontrivial band gap at the Fermi level is due to its crystal symmetry, thus the QAH effect is robust. Its Curie temperature, estimated to be ˜360 K using Monte Carlo simulation, is above room temperature and higher than most two-dimensional ferromagnetic thin films. The inclusion of Hubbard U in the Ru-d electrons does not affect this result. We also discuss the manipulation of its exchange energy and nontrivial band gap by applying in-plane strain. Our work adds an experimentally feasible member to the QAH insulator family, which is expected to have broad applications in nanoelectronics and spintronics.

  5. Application of transition metal isotope tracers in global change research

    Institute of Scientific and Technical Information of China (English)

    SONG Jinming; Thomas F. Pedersen

    2005-01-01

    High-precision isotope composition determinations using multicollector, magnetic-sector inductively coupled plasma mass spectrometry (MC-ICPMS) have recently revealed that some transition metal isotopes such as those of Mo, Fe, Cu, Zn etc. can be used as biogeochemical tracers in global change research.The Mo isotope system may be useful in paleoredox investigations indicating that δ 97/95Mo in seawater may co-vary with changes in the relative proportions of anoxic and oxic sedimentation in the ocean, and that this variation may be recorded in δ 97/95Mo of anoxic sediments. The Mo continental flux into the oceans and the global Mo isotope budget can be estimated fromδ 97/95MO values. The Fe isotope composition in seawater is an important issue because Fe plays a controlling role in biological productivity in the oceans and its abundance in seawater may have substantial effect on climate changes. Iron isotope fractionations could result from bio- and abio-processes and have about 0.1% variation (δ 56/54Fe), so Fe isotopes considered alone cannot be used to distinguish the products of abiotic and biotic Fe processing in geological records. Cu and Zn isotopes are also used as biogeochemical tracers, but the researches are relatively less. This review mainly focuses on the methods for preparation, purification and determination of new isotope tracer samples, and on isotope applications in marine environmental changes.

  6. Coherent quantum dynamics of excitons in monolayer transition metal dichalcogenides

    KAUST Repository

    Moody, Galan

    2016-03-14

    Transition metal dichalcogenides (TMDs) have garnered considerable interest in recent years owing to their layer thickness-dependent optoelectronic properties. In monolayer TMDs, the large carrier effective masses, strong quantum confinement, and reduced dielectric screening lead to pronounced exciton resonances with remarkably large binding energies and coupled spin and valley degrees of freedom (valley excitons). Coherent control of valley excitons for atomically thin optoelectronics and valleytronics requires understanding and quantifying sources of exciton decoherence. In this work, we reveal how exciton-exciton and exciton-phonon scattering influence the coherent quantum dynamics of valley excitons in monolayer TMDs, specifically tungsten diselenide (WSe2), using two-dimensional coherent spectroscopy. Excitation-density and temperature dependent measurements of the homogeneous linewidth (inversely proportional to the optical coherence time) reveal that exciton-exciton and exciton-phonon interactions are significantly stronger compared to quasi-2D quantum wells and 3D bulk materials. The residual homogeneous linewidth extrapolated to zero excitation density and temperature is ~1:6 meV (equivalent to a coherence time of 0.4 ps), which is limited only by the population recombination lifetime in this sample. © (2016) COPYRIGHT Society of Photo-Optical Instrumentation Engineers (SPIE). Downloading of the abstract is permitted for personal use only.

  7. Fluorine substituent effects on dihydrogen bonding of transition metal hydrides.

    Science.gov (United States)

    Jacobsen, Heiko

    2009-09-07

    Hydrogen and dihydrogen bonding of the fluorinated alcohol (CF(3))(2)CHOH with the transition metal complex WH(CO)(2)(NO)(PMe(3))(2) has been explored by a set of four exemplary density functional theory methods that comprises the BP86, PBE, B3LYP and TPSS functionals. The hydride, nitrosyl and carbonyl ligands of the tungsten complex have been considered as sites of protonation. The main effect of fluorination is an increased dihydrogen bond strength by about 15 kJ mol(-1). The [see equation in text] dihydrogen bond is about 10 kJ mol(-1) stronger than the [W]-NOH-OR hydrogen bond. Of the four DFT methods investigated, the BP86 functional provides the most satisfying quantitative as well as qualitative agreement with experiment. The geometry of the [see equation in text] linkage is significantly influenced by secondary dispersive intermolecular bonding. Linear and bent dihydrogen bonds are separated in energy only by about 1 kJ mol(-1), and represent local minima on the corresponding energy hypersurface.

  8. Superconductivity Series in Transition Metal Dichalcogenides by Ionic Gating.

    Science.gov (United States)

    Shi, Wu; Ye, Jianting; Zhang, Yijin; Suzuki, Ryuji; Yoshida, Masaro; Miyazaki, Jun; Inoue, Naoko; Saito, Yu; Iwasa, Yoshihiro

    2015-08-03

    Functionalities of two-dimensional (2D) crystals based on semiconducting transition metal dichalcogenides (TMDs) have now stemmed from simple field effect transistors (FETs) to a variety of electronic and opto-valleytronic devices, and even to superconductivity. Among them, superconductivity is the least studied property in TMDs due to methodological difficulty accessing it in different TMD species. Here, we report the systematic study of superconductivity in MoSe2, MoTe2 and WS2 by ionic gating in different regimes. Electrostatic gating using ionic liquid was able to induce superconductivity in MoSe2 but not in MoTe2 because of inefficient electron accumulation limited by electronic band alignment. Alternative gating using KClO4/polyethylene glycol enabled a crossover from surface doping to bulk doping, which induced superconductivities in MoTe2 and WS2 electrochemically. These new varieties greatly enriched the TMD superconductor families and unveiled critical methodology to expand the capability of ionic gating to other materials.

  9. Transition metal dichalcogenide heterojunction PN diode toward ultimate photovoltaic benefits

    Science.gov (United States)

    Ahn, Jongtae; Jeon, Pyo Jin; Raza, Syed Raza Ali; Pezeshki, Atiye; Min, Sung-Wook; Hwang, Do Kyung; Im, Seongil

    2016-12-01

    Recently, two-dimensional (2D) transition metal dichalcogenide (TMDC) semiconductors as van der Waals (vdW) materials have attracted much attention from researchers. Among many 2D TMDC materials, a few layer-thin molybdenum disulfide (MoS2) and tungsten diselenide (WSe2) have been most intensively studied respectively as 2D n- and p-type semiconductors. Here, we have fabricated vertical vdW heterojunction n-MoS2/p-WSe2 diode with a few tens nm-thick layers by using vertically-sandwiched ohmic terminals, so that no quasi neutral region may exist between two terminals. As a result, we obtained high photo responsivity at zero volt without any electric power, and it appears comparable to those of commercially-optimized Si PN diode. Photo-voltage output of 0.3 V was easily obtained from our vdW PN diode as open circuit voltage, and can be doubled up to 0.6 V by using two PN diodes. These beneficial photovoltaic results from vdW PN diode were directly applied to PV switching dynamics and transistor photo gating, for the first time. We regard that our vdW n-MoS2/p-WSe2 heterojunction diode could maximize its photovoltaic energy benefits with optimized TMDC thicknesses.

  10. THE ELECTROCONDUCTIVITY OF THE LIQUID ALLOYS OF TRANSITION METALS

    Directory of Open Access Journals (Sweden)

    V.T.Shvets

    2004-01-01

    Full Text Available The concentration dependance of electroresistivity of the liquid binary alloys of transition metals Fe, Co and Ni is calculated. We considered the contribution to conductivity from the s-electrons, described within the model of nearly free electrons. The role of the partially occupied d-bands is reduced to resonance scattering of the s-electrons on d-states. The interaction of the s- and d-electrons is described by the hybridization potential of s- and d-states. The interaction with the ions, not including the partially occupied d-states, is described using the pseudopotential of the electron-ion interaction. The electroresistivity of the alloys is calculated in the second order of the perturbation theory in pseudopotential and hybridization potential. The concentration dependance of electroresistivity of the binary alloys approaches the linear regime as the resonance scattering of the s-electrons on d-states prevails over the scattering on the ions. The calculations exhibit good agreement with the experimental data.

  11. Rare earth element recycling from waste nickel-metal hydride batteries.

    Science.gov (United States)

    Yang, Xiuli; Zhang, Junwei; Fang, Xihui

    2014-08-30

    With an increase in number of waste nickel-metal hydride batteries, and because of the importance of rare earth elements, the recycling of rare earth elements is becoming increasingly important. In this paper, we investigate the effects of temperature, hydrochloric acid concentration, and leaching time to optimize leaching conditions and determine leach kinetics. The results indicate that an increase in temperature, hydrochloric acid concentration, and leaching time enhance the leaching rate of rare earth elements. A maximum rare earth elements recovery of 95.16% was achieved at optimal leaching conditions of 70°C, solid/liquid ratio of 1:10, 20% hydrochloric acid concentration, -74μm particle size, and 100min leaching time. The experimental data were best fitted by a chemical reaction-controlled model. The activation energy was 43.98kJ/mol and the reaction order for hydrochloric acid concentration was 0.64. The kinetic equation for the leaching process was found to be: 1-(1-x)(1/3)=A/ρr0[HCl](0.64)exp-439,8008.314Tt. After leaching and filtration, by adding saturated oxalic solution to the filtrate, rare earth element oxalates were obtained. After removing impurities by adding ammonia, filtering, washing with dilute hydrochloric acid, and calcining at 810°C, a final product of 99% pure rare earth oxides was obtained.

  12. Revisiting rho 1 Cancri e: A New Mass Determination Of The Transiting super-Earth

    CERN Document Server

    Endl, Michael; Cochran, William D; MacQueen, Phillip J; Brugamyer, Erik J; Caldwell, Caroline; Wittenmyer, Robert A; Barnes, Stuart I; Gullikson, Kevin

    2012-01-01

    We present a mass determination for the transiting super-Earth rho 1 Cancri e based on nearly 700 precise radial velocity (RV) measurements. This extensive RV data set consists of data collected by the McDonald Observatory planet search and published data from Lick and Keck observatories (Fischer et al. 2008). We obtained 212 RV measurements with the Tull Coude Spectrograph at the Harlan J. Smith 2.7 m Telescope and combined them with a new Doppler reduction of the 131 spectra that we have taken in 2003-2004 with the High-Resolution-Spectrograph (HRS) at the Hobby-Eberly Telescope (HET) for the original discovery of rho 1 Cancri e. Using this large data set we obtain a 5-planet Keplerian orbital solution for the system and measure an RV semi-amplitude of K = 6.29 +/- 0.21 m/s for rho 1 Cnc e and determine a mass of 8.37 +/- 0.38 M_Earth. The uncertainty in mass is thus less than 5%. This planet was previously found to transit its parent star (Winn et al. 2011, Demory et al. 2011), which allowed them to estima...

  13. Dephasing mechanisms of optical transitions in rare-earth-doped transparent ceramics

    Science.gov (United States)

    Kunkel, Nathalie; Bartholomew, John; Welinski, Sacha; Ferrier, Alban; Ikesue, Akio; Goldner, Philippe

    2016-11-01

    We identify and analyze dephasing mechanisms that broaden the optical transitions of rare-earth ions in randomly oriented transparent ceramics. The study examines the narrow F70↔D50 transition of Eu3 + dopants in a series of Y2O3 ceramic samples prepared under varying conditions. We characterize the temperature and magnetic field dependence of the homogeneous linewidth, as well as long-term spectral diffusion on time scales up to 1 s. The results highlight significant differences between samples with differing thermal treatments and Zr4 + additive concentrations. In particular, several distinct magnetic interactions from defect centers are observed, which are clearly distinguished from the broadening due to interactions with two-level systems and phonons. By minimizing the broadening due to the different defect centers, linewidths of the order of 4 kHz are achieved for all samples. The linewidths are limited by temperature-dependent interactions and by an interaction that is yet to be identified. Although the homogeneous linewidth can be narrowed further in these ceramic samples, the broadening is now comparable to the linewidths achieved in rare-earth-ion-doped single crystals. Thus, this work emphasizes the usefulness of studying ceramics to gain insights into dephasing mechanisms relevant to single crystals and suggests that ceramics may be an interesting alternative for applications in classical and quantum information processing.

  14. Theoretical Transit Spectra for GJ 1214b and Other "Super-Earths"

    CERN Document Server

    Howe, Alex R

    2012-01-01

    We present new calculations of transit spectra of super-Earths that allow for atmospheres with arbitrary proportions of common molecular species and haze. We test this method with generic spectra, reproducing the expected systematics and absorption features, then apply it to the nearby super-Earth GJ 1214b, which has produced conflicting observational data, leaving the questions of a hydrogen-rich versus hydrogen-poor atmosphere and the water content of the atmosphere ambiguous. We present representative transit spectra for a range of classes of atmosphere models for GJ 1214b. Our analysis supports a hydrogen-rich atmosphere with a cloud or haze layer, although a hydrogen-poor model with less than 10% water is not ruled out. Several classes of models are ruled out, however, including hydrogen-rich atmospheres with no haze, hydrogen-rich atmospheres with a haze of about 0.01-micron tholin particles, and hydrogen-poor atmospheres with major sources of absorption other than water. We propose an observational tes...

  15. Transition metal catalysis in the generation of petroleum and natural gas. Final report, September 1, 1992--October 31, 1995

    Energy Technology Data Exchange (ETDEWEB)

    Mango, F.D.

    1997-01-21

    This project originated on the premise that natural gas could be formed catalytically in the earth rather than thermally as commonly believed. The intention was to test this hypothetical view and to explore generally the role of sedimentary metals in the generation of light hydrocarbons (C1 - C9). We showed the metalliferous source rocks are indeed catalytic in the generation of natural gas. Various metal compounds in the pure state show the same levels of catalytic activity as sedimentary rocks and the products are identical. Nickel is particularly active among the early transition metals and is projected to remain catalytically robust at all stages of catagenesis. Nickel oxide promotes the formation of n-alkanes in addition to natural gas (NG), demonstrating the full scope of the hypothetical catalytic process. The composition of catalytic gas duplicates the entire range of natural gas, from so-called wet gas to dry gas (60 to 95+ wt % methane), while gas generated thermally is consistently depleted in methane (10 to 60 wt % methane). These results support the view that metal catalysis is a major pathway through which natural gas is formed in the earth.

  16. Electrocatalytic reduction of carbon dioxide on post-transition metal and metal oxide nanoparticles

    Science.gov (United States)

    White, James L.

    The electroreduction of carbon dioxide to liquid products is an important component in the utilization of CO2 and in the high-density storage of intermittent renewable energy in the form of chemical bonds. Materials based on indium and tin, which yield predominantly formic acid, have been investigated in order to gain a greater understanding of the electrochemically active species and the mechanism of CO2 reduction on these heavy post-transition metals, since prior studies on the bulk metals did not provide thermodynamically sensible reaction pathways. Nanoparticles of the oxides and hydroxides of tin and indium have been prepared and characterized by transmission electron microscopy, X-ray diffractometry, X-ray photoelectron spectroscopy, and various electrochemical methods in order to obtain structural information and analyze the role of various surface species on the CO2 reduction pathway. On both indium and tin, metastable surface-bound hydroxides bound CO2 and formed metal carbonates, which can then be reduced electrochemically. The relevant oxidation state of tin was suggested to be SnII rather than SnIV, necessitating a pre reduction to generate the CO2-binding species. Metallic indium nanoparticles partially oxidized in air and became highly efficient CO2 reduction electrocatalysts. Unit Faradaic efficiencies for formate, much higher than on bulk indium, were achieved with only 300 mV of overpotential on these particles, which possessed an oxyhydroxide shell surrounding a conductive metallic core. Alloys and mixed-metal oxide and hydroxide particles of tin and indium have also been studied for their carbon dioxide electrocatalytic capabilities, especially in comparison to the pure metal species. Additionally, a solar-driven indium-based CO2 electrolyzer was developed to investigate the overall efficiency for intermittent energy storage. The three flow cells were powered by a commercial photovoltaic array and had a maximum conversion efficiency of incident

  17. Magnetic-field induced superconductor-metal-insulator transitions in bismuth metal-graphite

    Science.gov (United States)

    Suzuki, Masatsugu; Suzuki, Itsuko S.; Lee, Robert; Walter, Jürgen

    2002-03-01

    Bismuth-metal graphite (MG) has a unique layered structure where Bi nanoparticles are encapsulated in nanographites. The size of nanographite is on the same order as that of Bi nanographite. The observed superconductivity below Tc (= 2.48 K) and the Curie-like Pauli paramagnetic susceptibility below 30 K are related to the high density of states at the Fermi energy arising from edge states of nanographites.^1 A magnetic-field induced transition from metallic to semiconductor-like phase is observed in the in-plane resistivity ρa around Hc (≈ 25 kOe) for both H⊥c and H‖c (c: c axis). The suppression of the metallic phase by H is independent of the directions of H (H‖c and H⊥c) for Bi-MG, suggesting that the spin related effect is significant compared to the orbital effect. The Zeemann energy gSμ_BH at 25 kOe corresponds to a thermal energy k_BTH with TH = 1.7 K, where g = 2 and S = 1/2. The temperature TH is slightly lower than T_c. A negative magnetoresistance in ρa for H⊥c (040 kOe) suggest the occurrence of two-dimensional weak localization effect. ^1K. Wakabayashi, M. Fujita, H. Ajiki, and M. Sigrist, Phys. Rev. 59, 8271 (1999).

  18. Transmission spectrum of Earth as a transiting exoplanet - from the ultraviolet to the near-infrared

    CERN Document Server

    Betremieux, Y

    2013-01-01

    Transmission spectroscopy of exoplanets is a tool to characterize rocky planets and explore their habitability. Using the Earth itself as a proxy, we model the atmospheric cross section as a function of wavelength, and show the effect of each atmospheric species, Rayleigh scattering and refraction from 115 to 1000nm. Clouds do not significantly affect this picture because refraction prevents the lowest 12.75km of the atmosphere, in a transiting geometry for an Earth-Sun analog, to be sampled by a distant observer. We calculate the effective planetary radius for the primary eclipse spectrum of an Earth-like exoplanet around a Sun-like star. Below 200nm, ultraviolet(UV) O_2 absorption increases the effective planetary radius by about 180km, versus 27km at 760.3nm, and 14km in the near-infrared (NIR) due predominantly to refraction. This translates into a 2.6% change in effective planetary radius over the UV-NIR wavelength range, showing that the ultraviolet is an interesting wavelength range for future space mi...

  19. TRANSMISSION SPECTRUM OF EARTH AS A TRANSITING EXOPLANET FROM THE ULTRAVIOLET TO THE NEAR-INFRARED

    Energy Technology Data Exchange (ETDEWEB)

    Betremieux, Y. [Max-Planck-Institut fuer Astronomie, Koenigstuhl 17, D-69117 Heidelberg (Germany); Kaltenegger, L., E-mail: betremieux@mpia.de, E-mail: kaltenegger@mpia.de [Harvard-Smithsonian Center for Astrophysics, 60 Garden street, Cambridge MA 02138 (United States)

    2013-08-01

    Transmission spectroscopy of exoplanets is a tool to characterize rocky planets and explore their habitability. Using the Earth itself as a proxy, we model the atmospheric cross section as a function of wavelength, and show the effect of each atmospheric species, Rayleigh scattering, and refraction from 115 to 1000 nm. Clouds do not significantly affect this picture because refraction prevents the lowest 12.75 km of the atmosphere, in a transiting geometry for an Earth-Sun analog, to be sampled by a distant observer. We calculate the effective planetary radius for the primary eclipse spectrum of an Earth-like exoplanet around a Sun-like star. Below 200 nm, ultraviolet (UV) O{sub 2} absorption increases the effective planetary radius by about 180 km, versus 27 km at 760.3 nm, and 14 km in the near-infrared (NIR) due predominantly to refraction. This translates into a 2.6% change in effective planetary radius over the UV-NIR wavelength range, showing that the UV is an interesting wavelength range for future space missions.

  20. Transitioning Earth Remote Sensing Data to Benefit Society: A Paradigm for a Center of Excellence

    Science.gov (United States)

    Jedlovec, Gary; Bjorgo, Einar; Burn, Anthony

    2015-01-01

    Over the past decade there has been a substantial increase in the number of Earth remote sensing satellites launched for research and operational usage and numerous others planned by the international community. These satellites have been used to varying degrees by their supporting agencies for weather and environmental monitoring, climate studies, disaster monitoring and response, and other humanitarian activities. While there are success stories on useful applications of remote sensing data, the broader use of these satellite assets by other organizations and entities has been limited for a number of reasons including lack of data services, data dissemination issues, and a general failure to engage the broader end user community with useful data access and knowledge of how to use the data and products. This paper describes some of these current limitations on the broader use of Earth remote sensing data by the international community and describes the concept of a general "Center of Excellence" to facilitate the development, transition, and utilization of these Earth remote sensing observations by the broader international community.

  1. Chemoselective single-site Earth-abundant metal catalysts at metal–organic framework nodes

    Science.gov (United States)

    Manna, Kuntal; Ji, Pengfei; Lin, Zekai; Greene, Francis X.; Urban, Ania; Thacker, Nathan C.; Lin, Wenbin

    2016-01-01

    Earth-abundant metal catalysts are critically needed for sustainable chemical synthesis. Here we report a simple, cheap and effective strategy of producing novel earth-abundant metal catalysts at metal–organic framework (MOF) nodes for broad-scope organic transformations. The straightforward metalation of MOF secondary building units (SBUs) with cobalt and iron salts affords highly active and reusable single-site solid catalysts for a range of organic reactions, including chemoselective borylation, silylation and amination of benzylic C–H bonds, as well as hydrogenation and hydroboration of alkenes and ketones. Our structural, spectroscopic and kinetic studies suggest that chemoselective organic transformations occur on site-isolated, electron-deficient and coordinatively unsaturated metal centres at the SBUs via σ-bond metathesis pathways and as a result of the steric environment around the catalytic site. MOFs thus provide a novel platform for the development of highly active and affordable base metal catalysts for the sustainable synthesis of fine chemicals. PMID:27574182

  2. Distribution of Rare Earth Metals in Technogenic Wastes of Energy Enterprises (Results of the Laboratory Studies)

    OpenAIRE

    Alexandr Ivanovich Khanchuk; Aleksandr Alekseevich Yudakov; Mikhail Azaryevich Medkov; Leonid Nikolayevich Alekseyko; Andrey Vasilyevich Taskin; Sergey Igorevich Ivannikov

    2016-01-01

    The results of the research interaction between ash and slag samples from Vladivostok TPP’s landfills saturated with underburning and ammonium hydrodifluoride were given. It was found out that the reactions of the main components of a concentrate with NH4HF2 are flowing with creation of complex ammonium fluoro-metalate. It is shown that the distribution of REM (rare earth metals) between foam and heavier products is going during the flotation process of carbon-containing ash and slag samples ...

  3. Modification of Non-Metallic Inclusions by Rare-Earth Elements in Microalloyed Steels

    OpenAIRE

    Opiela M.; Grajcar A.

    2012-01-01

    The modification of the chemical composition of non-metallic inclusions by rare-earth elements in the new-developed microalloyed steels was discussed in the paper. The investigated steels are assigned to production of forged elements by thermo- mechanical treatment. The steels were melted in a vaccum induction furnace and modification of non-metallic inclusions was carried out by the michmetal in the amount of 2.0 g per 1 kg of steel. It was found that using material charge of high purity and...

  4. Counterion influence on the vibrational wavenumbers in ternary and quaternary metal hydride salts, A2MH6 (A = alkali metal, alkaline earth, and lanthanides; M = Ir, Fe, Ru, Os, Pt, Mn).

    Science.gov (United States)

    Gilson, Denis F R; Moyer, Ralph O

    2012-02-06

    The wavenumbers of the ν(3) metal-hydrogen stretching mode (T(1u)) in the IR spectra of both ternary and quaternary hexahydrido salts of transition metals from groups 7 to 10 ([Mn(I)H(6)](5-), [Fe(II)H(6)](4-), [Ru(II)H(6)](4-), [Os(II)H(6)](4-), [Ir(III)H(6)](3-), and [Pt(IV)H(6)](2-)) depend linearly upon the ionization energies of the counterions (alkali metal, alkaline earth, and lanthanide) with a separate line for each metal. This relationship provides quantitative support for the charge-transfer mechanism for explaining the stabilities of these compounds.

  5. Thermal oxidation of the surface of binary aluminum alloys with rare-earth metals

    Science.gov (United States)

    Akashev, L. A.; Popov, N. A.; Kuznetsov, M. V.; Shevchenko, V. G.

    2015-05-01

    The kinetics of oxidation of the surface of Al alloys with 1-2.5 at % rare-earth metals (REMs) at 400-500°C in air was studied by ellipsometry and X-ray photoelectron spectroscopy (XPS). The addition (1-2.5 at % REM) of all rare-earth metals to aluminum was shown to increase the thickness of the oxide layer. The addition of surfactant and chemically active REMs (Yb, Sm, La, and Ce) increased the rate of oxidation of solid aluminum most effectively. The oxidation can be accelerated by the polymorphic transformations of the individual REM oxides in the film. The surface activity of Sm with respect to solid Al was confirmed by XRS.

  6. Distribution of Rare Earth Metals in Technogenic Wastes of Energy Enterprises (Results of the Laboratory Studies

    Directory of Open Access Journals (Sweden)

    Alexandr Ivanovich Khanchuk

    2016-12-01

    Full Text Available The results of the research interaction between ash and slag samples from Vladivostok TPP’s landfills saturated with underburning and ammonium hydrodifluoride were given. It was found out that the reactions of the main components of a concentrate with NH4HF2 are flowing with creation of complex ammonium fluoro-metalate. It is shown that the distribution of REM (rare earth metals between foam and heavier products is going during the flotation process of carbon-containing ash and slag samples without significant concentrating. It is shown that the water leaching of fluoridated product lets transfer silicone, aluminum and iron salts into solution and concentrate rare earth elements in insoluble residue in the form of complex salts of NaLnF4 general formula. We propose a schematic diagram of hydrodifluoride recycling of carbon-containing sample, which provides concentrating of REM with incomplete separation of macro-components.

  7. Molecular dynamics of liquid alkaline-earth metals near the melting point

    Indian Academy of Sciences (India)

    J K Baria; A R Jani

    2010-10-01

    Results of the studies of the properties like binding energy, the pair distribution function (), the structure factor (), specific heat at constant volume, velocity autocorrelation function (VACF), radial distribution function, self-diffusion coefficient and coordination number of alkaline-earth metals (Be, Mg, Ca, Sr and Ba) near melting point using molecular dynamics (MD) simulation technique using a pseudopotential proposed by us are presented in this article. Good agreement with the experiment is achieved for the binding energy, pair distribution function and structure factor, and these results compare favourably with the results obtained by other such calculations, showing the transferability of the pseudopotential used from solid to liquid environment in the case of alkaline-earth metals.

  8. Solvation structures and dynamics of alkaline earth metal halides in supercritical water: A molecular dynamics study

    Science.gov (United States)

    Keshri, Sonanki; Mandal, Ratnamala; Tembe, B. L.

    2016-09-01

    Constrained molecular dynamics simulations of alkaline earth metal halides have been carried out to investigate their structural and dynamical properties in supercritical water. Potentials of mean force (PMFs) for all the alkaline earth metal halides in supercritical water have been computed. Contact ion pairs (CIPs) are found to be more stable than all other configurations of the ion pairs except for MgI2 where solvent shared ion pair (SShIP) is more stable than the CIP. There is hardly any difference in the PMFs between the M2+ (M = Mg, Ca, Sr, Ba) and the X- (X = F, Cl, Br, I) ions whether the second X- ion is present in the first coordination shell of the M2+ ion or not. The solvent molecules in the solvation shells diffuse at a much slower rate compared to the bulk. Orientational distribution functions of solvent molecules are sharper for smaller ions.

  9. Magnetoelectric coupling effect in transition metal modified polycrystalline BiFeO{sub 3} thin films

    Energy Technology Data Exchange (ETDEWEB)

    Sreenivas Puli, Venkata, E-mail: pvsri123@gmail.com [Department of Physics and Engineering Physics, Tulane University, New Orleans, LA 70118 (United States); Department of Physics and Institute of Functional Nanomaterials, University of Puerto Rico, San Juan, PR 00936 (United States); Kumar Pradhan, Dhiren [Department of Physics and Institute of Functional Nanomaterials, University of Puerto Rico, San Juan, PR 00936 (United States); Gollapudi, Sreenivasulu [Department of Physics, Oakland University, Rochester, MI 48309-4401 (United States); Coondoo, Indrani [Department of Materials and Ceramic and CICECO, University of Aveiro, 3810-193 Aveiro (Portugal); Panwar, Neeraj [Department of Physics, Central University of Rajasthan, Bandar Sindri, Kishangarh 305801, Rajasthan (India); Adireddy, Shiva; Chrisey, Douglas B. [Department of Physics and Engineering Physics, Tulane University, New Orleans, LA 70118 (United States); Katiyar, Ram S. [Department of Physics and Institute of Functional Nanomaterials, University of Puerto Rico, San Juan, PR 00936 (United States)

    2014-11-15

    Rare-earth (Sm) and transition metal (Co) modified polycrystalline BiFeO{sub 3} (BFO) thin films have been deposited on Pt/TiO{sub 2}/SiO{sub 2}/Si substrate successfully through pulsed laser deposition (PLD) technique. Piezoelectric, leakage current and temperature dependent dielectric and magnetic behaviour were investigated for the films. Typical “butterfly-shaped” loop were observed in BSFCO films with an effective piezoelectric constant (d{sub 33}) ∼94 pm/V at 0.6 MV/cm. High dielectric constant ∼900 and low dielectric loss ∼0.25 were observed at room temperature. M–H loops have shown relatively high saturation magnetization ∼35 emu/cm{sup 3} at a maximum field of H ∼20 kOe. Enhanced magnetoelectric coupling response is observed under applied magnetic field. The multiferroic, piezoelectric, leakage current behaviours were explored. Such studies should be helpful in designing multiferroic materials based on BSFCO films. - Highlights: • Transition metal modified polycrystalline BiFeO{sub 3} thin films prepared using PLD. • High ME-coupling response was observed in co-substituted BiFeO{sub 3} thin films. • High magnetization ∼35 emu/cm{sup 3} at a maximum field of H ∼20 kOe. • Low leakage current might be due to co-substitution in BiFeO{sub 3} thin films. • A notable piezoelectric constant d{sub 33} ∼94 pm/V was found in BiFeO{sub 3} thin films.

  10. Atomic structure of the adsorption of transition metals on silicon surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Cocoletzi, G.H. [IF-BUAP, 72000 Puebla (Mexico); Takeuchi, N. [CCMC-UNAM, Ensenada, BCN (Mexico)

    2007-07-01

    Full text: Solid state devices are useful for their high sensitivity in a small volume. Applications of such devices as dose materials include semi-conducting dose-rate, and dose-reading measuring devices. Transition metals (TM) have electronic and atomic properties similar to those of rare earth elements when they are adsorbed on silicon surfaces. The interfaces of transition metals silicides with Si (111) have very small lattice mismatches, sharp interfaces, and low Schottky barrier, making them ideal in electronic devices, such as infrared detectors and rectifying contacts. In this work we shall describe our first principles total energy calculations to investigate structural properties of bulk ScSi and YSi, the two dimensional arrangement of ScSi{sub 2} and YSi{sub 2} on the Si(111) surface, and the growth of a few layers of ScSi{sub 1.7} and YSi{sub 1.7} on the Si(111) surface. Our calculated bulk structural parameters are in excellent agreement with experimental values. It will be shown that one monolayer of a TM on Si( l l 1) yields a two dimensional phase with (lxl) periodicity consisting of a layer of TM atoms on T4 sites and a Si bilayer on top. This double layer of Si atoms is very close to ideal Si(111)-(1x1) surface, but rotated 180 with respect to the rest of the crystal. More layers of TM silicide epitaxially grown on Si(l 11) result in a hexagonal structure similar to bulk ScSi2 and YSi2: graphite-like Si planes (with vacancies) intercalated with TM planes, and forming a ({radical}3x{radical}3) arrangement with a ScSi{sub 1.7} and YSi{sub 1.7} stoichiometry. The top Si layer does not contain vacancies and it does not present a graphite-like structure, but forms a bilayer arrangement as in bulk Si. (Author)

  11. Studies on the Transition Metal Ion Induced Fluorescence Enhancement of 1,8-Naphthalimide Derivatives

    Institute of Scientific and Technical Information of China (English)

    WEN,Guo-Tao; ZHU,Man-Zhou; WANG,Zhuo; MENG,Xiang-Ming; HU,Hui-Yuan; GUO,Qing-Xiang

    2006-01-01

    Two fluorosensor systems have been designed and synthesized with their photophysical properties and fluorescence responses toward the transition metal ions studied. The fluorosensor was composed of 1,8-naphthalimide and 4-chloro-1,8-naphthalimide as fluorophore respectively, an amino moiety as the receptor and a hydrocarbon chain as the spacer to link the fluorophore and receptor. Fluorescence intensity of these systems is very weak due to the process of the efficient intramolecular photoinduced electron transfer (PET) in the absence of metal ions. Titration of the transition metal ions can switch on the fluorescence immediately. The intensity of released fluorescence is even higher than the expected from the consideration of the PET in these systems. It may be rationalized that the receptor bound to transition metal ions and the solvation of the fluorophore by the water molecules from the hydrated transition metal salts, may significantly cause fluorescence enhancement.

  12. Recent advances in transition metal-catalyzed Csp2-monofluoro-, difluoro-, perfluoromethylation and trifluoromethylthiolation

    Directory of Open Access Journals (Sweden)

    Grégory Landelle

    2013-11-01

    Full Text Available In the last few years, transition metal-mediated reactions have joined the toolbox of chemists working in the field of fluorination for Life-Science oriented research. The successful execution of transition metal-catalyzed carbon–fluorine bond formation has become a landmark achievement in fluorine chemistry. This rapidly growing research field has been the subject of some excellent reviews. Our approach focuses exclusively on transition metal-catalyzed reactions that allow the introduction of –CFH2, –CF2H, –CnF2n+1 and –SCF3 groups onto sp² carbon atoms. Transformations are discussed according to the reaction-type and the metal employed. The review will not extend to conventional non-transition metal methods to these fluorinated groups.

  13. Formation of an integrated holding company to produce rare-earth metal articles

    Science.gov (United States)

    Bogdanov, S. V.; Grishaev, S. I.

    2013-12-01

    The possibility of formation of a Russian holding company for the production of rare-earth metal articles under conditions of its increasing demand on the world market is considered. It is reasonable to ensure stable business operation on the market under conditions of state-private partnership after the fraction of soled products is determined and supported by the competitive advantages of Russian products.

  14. No Giant Two-Ion Anisotropy in the Heavy-Rare-Earth Metals

    DEFF Research Database (Denmark)

    Lindgård, Per-Anker

    1976-01-01

    A new Bose-operator expansion of tensor operators is applied to the heavy-rare-earth metals. The Er data for the cone phase have been analyzed successfully with single-ion anisotropy and isotropic exchange interaction. The Tb data can be understood on the same basis. The previously found large two......-ion anisotropy was due to an inadequate treatment of the large single-ion anisotropy leading to an incorrect expression for the spin-wave energy....

  15. Neutral binuclear rare-earth metal complexes with four μ₂-bridging hydrides.

    Science.gov (United States)

    Rong, Weifeng; He, Dongliang; Wang, Meiyan; Mou, Zehuai; Cheng, Jianhua; Yao, Changguang; Li, Shihui; Trifonov, Alexander A; Lyubov, Dmitrii M; Cui, Dongmei

    2015-03-25

    The first neutral rare-earth metal dinuclear dihydrido complexes [(NPNPN)LnH2]2 (2-Ln; Ln = Y, Lu; NPNPN: N[Ph2PNC6H3((i)Pr)2]2) bearing μ2-bridging hydride ligands have been synthesized. In the presence of THF, 2-Y undergoes intramolecular activation of the sp(2) C-H bond to form dinuclear aryl-hydride complex 3-Y containing three μ2-bridging hydride ligands.

  16. Porous nanoarchitectures of spinel-type transition metal oxides for electrochemical energy storage systems.

    Science.gov (United States)

    Park, Min-Sik; Kim, Jeonghun; Kim, Ki Jae; Lee, Jong-Won; Kim, Jung Ho; Yamauchi, Yusuke

    2015-12-14

    Transition metal oxides possessing two kinds of metals (denoted as AxB3-xO4, which is generally defined as a spinel structure; A, B = Co, Ni, Zn, Mn, Fe, etc.), with stoichiometric or even non-stoichiometric compositions, have recently attracted great interest in electrochemical energy storage systems (ESSs). The spinel-type transition metal oxides exhibit outstanding electrochemical activity and stability, and thus, they can play a key role in realising cost-effective and environmentally friendly ESSs. Moreover, porous nanoarchitectures can offer a large number of electrochemically active sites and, at the same time, facilitate transport of charge carriers (electrons and ions) during energy storage reactions. In the design of spinel-type transition metal oxides for energy storage applications, therefore, nanostructural engineering is one of the most essential approaches to achieving high electrochemical performance in ESSs. In this perspective, we introduce spinel-type transition metal oxides with various transition metals and present recent research advances in material design of spinel-type transition metal oxides with tunable architectures (shape, porosity, and size) and compositions on the micro- and nano-scale. Furthermore, their technological applications as electrode materials for next-generation ESSs, including metal-air batteries, lithium-ion batteries, and supercapacitors, are discussed.

  17. Ground-state properties of rare-earth metals: an evaluation of density-functional theory.

    Science.gov (United States)

    Söderlind, Per; Turchi, P E A; Landa, A; Lordi, V

    2014-10-15

    The rare-earth metals have important technological applications due to their magnetic properties, but are scarce and expensive. Development of high-performance magnetic materials with less rare-earth content is desired, but theoretical modeling is hampered by complexities of the rare earths electronic structure. The existence of correlated (atomic-like) 4f electrons in the vicinity of the valence band makes any first-principles theory challenging. Here, we apply and evaluate the efficacy of density-functional theory for the series of lanthanides (rare earths), investigating the influence of the electron exchange and correlation functional, spin-orbit interaction, and orbital polarization. As a reference, the results are compared with those of the so-called 'standard model' of the lanthanides in which electrons are constrained to occupy 4f core states with no hybridization with the valence electrons. Some comparisons are also made with models designed for strong electron correlations. Our results suggest that spin-orbit coupling and orbital polarization are important, particularly for the magnitude of the magnetic moments, and that calculated equilibrium volumes, bulk moduli, and magnetic moments show correct trends overall. However, the precision of the calculated properties is not at the level of that found for simpler metals in the Periodic Table of Elements, and the electronic structures do not accurately reproduce x-ray photoemission spectra.

  18. Alkaline earth metal doped tin oxide as a novel oxygen storage material

    Energy Technology Data Exchange (ETDEWEB)

    Dong, Qiang, E-mail: dong@tagen.tohoku.ac.jp [Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, 2-1-1 Katahira, Aoba-ku Sendai 980-8577 (Japan); Yin, Shu; Yoshida, Mizuki; Wu, Xiaoyong; Liu, Bin [Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, 2-1-1 Katahira, Aoba-ku Sendai 980-8577 (Japan); Miura, Akira; Takei, Takahiro; Kumada, Nobuhiro [Department of Research Interdisciplinary Graduate School of Medicine and Engineering, University of Yamanashi, Miyamae cho-7, Kofu 400-8511 (Japan); Sato, Tsugio [Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, 2-1-1 Katahira, Aoba-ku Sendai 980-8577 (Japan)

    2015-09-15

    Alkaline earth metal doped tin oxide (SnO{sub 2}) hollow nanospheres with a diameter of 50 nm have been synthesized successfully via a facial solvothermal route in a very simple system composed of only ethanol, acetic acid, SnCl{sub 4}·5H{sub 2}O and A(NO{sub 3}){sub 2}·xH{sub 2}O (A = Mg, Ca, Sr, Ba). The synthesized undoped SnO{sub 2} and A-doped SnO{sub 2} hollow nanospheres were characterized by the oxygen storage capacity (OSC), X-ray diffraction, transmission electron microscopy and the Brunauer–Emmet–Teller (BET) technique. The OSC values of all samples were measured using thermogravimetric-differential thermal analysis. The incorporation of alkaline earth metal ion into tin oxide greatly enhanced the thermal stability and OSC. Especially, Ba-doped SnO{sub 2} hollow nanospheres calcined at 1000 °C for 20 h with a BET surface area of 61 m{sup 2} g{sup −1} exhibited the considerably high OSC of 457 μmol-O g{sup −1} and good thermal stability. Alkaline earth metal doped tin oxide has the potential to be a novel oxygen storage material.

  19. Effect of Rare Earth Metals on Structure and Properties of Electroless Co-B Alloy Coating

    Institute of Scientific and Technical Information of China (English)

    宣天鹏; 张雷; 黄秋华

    2002-01-01

    The effect of rare earth metals cerium, lanthanum and yttrium on chemical composition, structure and properties of electroless Co-B alloy coating was studied. By plasma transmitting spectrograph, electron energy spectrometer, X-ray diffractometter, micro-hardometer and vibratory sample magnetometer the chemical constitution, structure and properties of the alloy coatings were analyzed and inspected. The results show that with a tiny quantity of rare earth metal added into Co-B alloy coating, the content of boron is decreased in the alloy coatings, and the kinds of rare earth metal have enormous effect on the structure and properties of electroless Co-B alloy coating. At the same time electroless Co-B alloy with amorphous structure is transformed to electroless Co-B-RE alloy with microcrystalline or crystalline structure. In this way microhardness of the coatings is increased remarkably. Cerium and lanthanum would also increase the saturated magnetic intensity and decrease coercitive force of the coating. So soft magnetization of the coatings would be improved.

  20. Rules for maximum solid solubility of transition metals in Ti, Zr and Hf solvents

    Institute of Scientific and Technical Information of China (English)

    周自强; 方守狮; 冯锋

    2003-01-01

    Based on the principle of energy change of alloy formation, the rules for the maximum solid solubility (Cmax) of various transition metals in the metals Ti, Zr and Hf were studied. It is deduced that the Cmax of transition metals in the metals Ti, Zr and Hf can be described as a semi-empirical equation using three atomic parameters, i.e., electronegativity difference, atomic diameter and electron concentration. From the equation analysis by using experimental data, it shows that atomic size parameter and electronegativity difference are the main factors that affect the Cmax of the transition metals in the metals Ti, Zr and Hf while electron concentration parameter has the smallest effect on Cmax.

  1. Laser surface alloying of aluminium-transition metal alloys

    Directory of Open Access Journals (Sweden)

    Almeida, A.

    1998-04-01

    Full Text Available Laser surface alloying has been used as a tool to produce hard and corrosion resistant Al-transition metal (TM alloys. Cr and Mo are particularly interesting alloying elements to produce stable highstrength alloys because they present low diffusion coefficients and solid solubility in Al. To produce Al-TM surface alloys a two-step laser process was developed: firstly, the material is alloyed using low scanning speed and secondly, the microstructure is modified by a refinement step. This process was used in the production of Al-Cr, Al-Mo and Al-Nb surface alloys by alloying Cr, Mo or Nb powder into an Al and 7175 Al alloy substrate using a CO2 laser. This paper presents a review of the work that has been developed at Instituto Superior Tecnico on laser alloying of Al-TM alloys, over the last years.

    En el presente trabajo se estudia la aleación superficial mediante láser de aluminio con metales de transición. El cromo y el molibdeno son particularmente interesantes porque producen aleaciones de alta resistencia y por el bajo coeficiente de difusión y solución sólida en aluminio. Para producir estas aleaciones se ha seguido un procedimiento desarrollado en dos partes. En primer lugar, el material se alea usando una baja velocidad de procesado y en segundo lugar la estructura se modifica mediante un refinamiento posterior. Este procedimiento se ha empleado en la producción de aleaciones Al-Cr, Al-Mo y Al-Nb mediante aleación con láser de CO2 de polvos de Cr, Mo o Nb en aluminio y la aleación 7175. Este trabajo es una revisión del desarrollado en el Instituto Superior Técnico de Lisboa en los últimos años.

  2. Scaling Relationships for Adsorption Energies of C2 Hydrocarbons on Transition Metal Surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Jones, G

    2011-08-18

    Using density functional theory calculations we show that the adsorption energies for C{sub 2}H{sub x}-type adsorbates on transition metal surfaces scale with each other according to a simple bond order conservation model. This observation generalizes some recently recognized adsorption energy scaling laws for AH{sub x}-type adsorbates to unsaturated hydrocarbons and establishes a coherent simplified description of saturated as well as unsaturated hydrocarbons adsorbed on transition metal surfaces. A number of potential applications are discussed. We apply the model to the dehydrogenation of ethane over pure transition metal catalysts. Comparison with the corresponding full density functional theory calculations shows excellent agreement.

  3. Microalloying of transition metal silicides by mechanical activation and field-activated reaction

    Energy Technology Data Exchange (ETDEWEB)

    Munir, Zuhair A. (Davis, CA); Woolman, Joseph N. (Davis, CA); Petrovic, John J. (Los Alamos, NM)

    2003-09-02

    Alloys of transition metal suicides that contain one or more alloying elements are fabricated by a two-stage process involving mechanical activation as the first stage and densification and field-activated reaction as the second stage. Mechanical activation, preferably performed by high-energy planetary milling, results in the incorporation of atoms of the alloying element(s) into the crystal lattice of the transition metal, while the densification and field-activated reaction, preferably performed by spark plasma sintering, result in the formation of the alloyed transition metal silicide. Among the many advantages of the process are its ability to accommodate materials that are incompatible in other alloying methods.

  4. Density functional theory optimized basis sets for gradient corrected functionals: 3d transition metal systems.

    Science.gov (United States)

    Calaminici, Patrizia; Janetzko, Florian; Köster, Andreas M; Mejia-Olvera, Roberto; Zuniga-Gutierrez, Bernardo

    2007-01-28

    Density functional theory optimized basis sets for gradient corrected functionals for 3d transition metal atoms are presented. Double zeta valence polarization and triple zeta valence polarization basis sets are optimized with the PW86 functional. The performance of the newly optimized basis sets is tested in atomic and molecular calculations. Excitation energies of 3d transition metal atoms, as well as electronic configurations, structural parameters, dissociation energies, and harmonic vibrational frequencies of a large number of molecules containing 3d transition metal elements, are presented. The obtained results are compared with available experimental data as well as with other theoretical data from the literature.

  5. Effect of transition-metal additives on hydrogen desorption kinetics of MgH2

    Science.gov (United States)

    Roy, Anindya; Janotti, Anderson; Van de Walle, Chris G.

    2013-01-01

    Using first-principles calculations, we study the effect of transition-metal additives (Ti, Fe, Co, and Ni) on the rate of hydrogen desorption in MgH2. The presence of large concentrations of transition-metal impurities causes the Fermi level to shift according to the position of the transition-metal acceptor/donor levels in the band gap. This shift can lower the formation energy of native defects and increase their concentration. The resulting higher rates of hydrogen desorption enhance the prospect of MgH2 as a solid-state hydrogen-storage material.

  6. Evaluating transition-metal catalysis in gas generation from the Permian Kupferschiefer by hydrous pyrolysis

    Science.gov (United States)

    Lewan, M.D.; Kotarba, M.J.; Wieclaw, D.; Piestrzynski, A.

    2008-01-01

    Transition metals in source rocks have been advocated as catalysts in determining extent, composition, and timing of natural gas generation (Mango, F. D. (1996) Transition metal catalysis in the generation of natural gas. Org. Geochem.24, 977–984). This controversial hypothesis may have important implications concerning gas generation in unconventional shale-gas accumulations. Although experiments have been conducted to test the metal-catalysis hypothesis, their approach and results remain equivocal in evaluating natural assemblages of transition metals and organic matter in shale. The Permian Kupferschiefer of Poland offers an excellent opportunity to test the hypothesis with immature to marginally mature shale rich in both transition metals and organic matter. Twelve subsurface samples containing similar Type-II kerogen with different amounts and types of transition metals were subjected to hydrous pyrolysis at 330° and 355 °C for 72 h. The gases generated in these experiments were quantitatively collected and analyzed for molecular composition and stable isotopes. Expelled immiscible oils, reacted waters, and spent rock were also quantitatively collected. The results show that transition metals have no effect on methane yields or enrichment. δ13C values of generated methane, ethane, propane and butanes show no systematic changes with increasing transition metals. The potential for transition metals to enhance gas generation and oil cracking was examined by looking at the ratio of the generated hydrocarbon gases to generated expelled immiscible oil (i.e., GOR), which showed no systematic change with increasing transition metals. Assuming maximum yields at 355 °C for 72 h and first-order reaction rates, pseudo-rate constants for methane generation at 330 °C were calculated. These rate constants showed no increase with increasing transition metals. The lack of a significant catalytic effect of transition metals on the extent, composition, and timing of

  7. Rare earth elements and critical metal content of extracted landfilled material and potential recovery opportunities

    Energy Technology Data Exchange (ETDEWEB)

    Gutiérrez-Gutiérrez, Silvia C.; Coulon, Frédéric; Jiang, Ying; Wagland, Stuart, E-mail: s.t.wagland@cranfield.ac.uk

    2015-08-15

    Highlights: • Samples from multiple core drills were obtained from 4× landfill sites in the UK. • Each sample analysed for rare earth elements, critical metals and valuable metals. • Two stage microwave digestion method ensuring high yield. • High quantities of copper and aluminium were observed in the soil layers of landfill. • Across 4× landfills aluminium and copper present has a value of around $400 million. - Abstract: Rare earth elements (REEs), Platinum group metals (PGMs) and other critical metals currently attract significant interest due to the high risks of supply shortage and substantial impact on the economy. Their uses in many applications have made them present in municipal solid waste (MSW) and in commercial and industrial waste (C&I), since several industrial processes produce by-products with high content of these metals. With over 4000 landfills in the UK alone, the aim of this study was to assess the existence of these critical metals within landfills. Samples collected from four closed landfills in UK were subjected to a two-step acid digestion to extract 27 metals of interest. Concentrations across the four landfill sites were 58 ± 6 mg kg{sup −1} for REEs comprising 44 ± 8 mg kg{sup −1} for light REEs, 11 ± 2 mg kg{sup −1} for heavy REEs and 3 ± 1 mg kg{sup −1} for Scandium (Sc) and 3 ± 1.0 mg kg{sup −1} of PGMs. Compared to the typical concentration in ores, these concentrations are too low to achieve a commercially viable extraction. However, content of other highly valuable metals (Al and Cu) was found in concentrations equating to a combined value across the four landfills of around $400 million, which increases the economic viability of landfill mining. Presence of critical metals will mainly depend on the type of waste that was buried but the recovery of these metals through landfill mining is possible and is economically feasible only if additional materials (plastics, paper, metallic items and other) are

  8. Lanthanide Single-Molecule Magnets Framed by Alkali Metals & Magnetic and Spectroscopic Studies of 3d Transition Metal Complexes

    DEFF Research Database (Denmark)

    Konstantatos, Andreas

    )imino)- methyl)benzene-1,2-diol]. Using this ligand, we were able to synthesize four different families of lanthanide complexes framed by alkali metals. Throughout the chapter we demonstrate how we can exploit the presence of the coordinated alkali metal ions in order to induce changes to the structure....... In Chapter 3 we present the results of our work with third row (3d) transition metal ions and their complexes. Specifically, in section 2.1 we report a series of complexes synthesized using a tripodal hexadentate Schiff-base ligand. The ligand demonstrates the ability to form mononuclear or trinuclear...... complexes of M3+ or M2+ metal ions (M: 3d transition metal) with the preference to either approximate octahedral or trigonal prismatic coordination geometry. A detailed magnetic characterization for most of the complexes is presented where a trinuclear Co2+ cluster stands out for its pronounced SMM...

  9. Structural and Electrochemical Characterization of Lithium Transition Metal Phosphates

    Science.gov (United States)

    Hashambhoy, Ayesha Maria

    The lithium ion battery has emerged as one of the most promising hybrid vehicle energy storage systems of the future. Of the potential cathode chemistries explored, lithium transition metal phosphates have generated a significant amount of interest due to their low-cost precursors, potential ease of synthesis, stability, and their environmentally friendly nature. This is in contrast to layered oxide systems such as LiCoO2, which have long been considered state of the art, but are now being reevaluated due to their structural instability at elevated temperatures, and higher cost. In particular, LiFePO4 has an operating potential comparable to those batteries available on the market (˜3.5V vs. Li/Li+), and higher theoretical specific capacity (170mAh/g vs. that of LiCoO2 which is 140mAh/g). The manganese analog to LiFePO4, LiMnPO4, exhibits a higher operating potential (˜4.1V v Li/Li+), and the same theoretical capacity, however Li-ion diffusion through this structure is much more rate limited and its theoretical capacity cannot be realized at rates suitable for commercial applications. The purpose of this work was threefold: 1) To explore the impact of Fe substitution on Mn sites in LiMnPO 4. 2) To examine the effects of alterations to the particle/electrolyte interface on rate capability. 3) To explore a novel fabrication route for LiMnPO4 using microwaves, and determine an optimal power and time combination for best performance. The coexistence of Fe and Mn on the transition metal site M, of LiMPO 4 resulted in an improved apparent Li-ion diffusivity in both Fe and Mn regimes as compared to that observed for LiFePO4 and LiMnPO 4 respectively. Calculations made from two different analysis methods, cyclic voltammetry (CV) and galvanostatic intermittent titration (GITT) drew this same conclusion. The signature characteristics observed from the CVs pertaining to single and dual phase reactions led to a delithiation model of LiFe0.5Mn0.5PO4 proposing the localization

  10. A warm, likely volatile-rich super-Earth: HD 97658b transits, but not quite when expected

    CERN Document Server

    Dragomir, Diana; Eastman, Jason D; Cameron, Chris; Howard, Andrew W; Guenther, David B; Kuschnig, Rainer; Moffat, Anthony F J; Rowe, Jason F; Rucinski, Slavek M; Sasselov, Dimitar; Weiss, Werner W

    2013-01-01

    Through photometric monitoring of the extended transit window of HD 97658b with the MOST space telescope, we have found that this exoplanet transits with an ephemeris consistent with that predicted from radial velocity measurements. The mid-transit times are 6$\\sigma$ earlier than those of the unverified transit-like signals reported in 2011, and we find no connection between the two sets of events. The transit depth indicates a 2.34$^{+0.18}_{-0.15}$ $R_\\earth$ super-Earth. When combined with the radial velocity determined mass of 7.86 $\\pm 0.73$ $M_\\earth$, our radius measure allows us to derive a planet density of 3.44$^{+0.91}_{-0.82}$ g cm$^{-3}$. Models suggest that a planet with our measured density has a rocky core that is enveloped in an atmosphere composed of lighter elements. The star of the HD 97658 system is the second brightest known to host a transiting super-Earth, facilitating folllow-up studies of this not easily daunted, warm and likely volatile-rich exoplanet.

  11. Infrared Spectroscopy of Transition Metal-Molecular interactions in the Gas Phase

    Energy Technology Data Exchange (ETDEWEB)

    Duncan, Michael A. [Univ. of Georgia, Athens, GA (United States)

    2008-11-14

    Transition metal-molecular complexes produced in a molecular beam are mass-selected and studied with infrared laser photodissociation spectroscopy. Metal complexes with carbon monoxide, carbon dioxide, nitrogen, water, acetylene or benzene are studied for a variety of metals. The number and intensity of infrared active bands are compared to the predictions of density functional theory calculations to derive structures, spin states and coordination numbers in these systems. These studied provide new insights into subtle details of metal-molecular interactions important in heterogeneous catalysis, metal-ligand bonding and metal ion solvation.

  12. Metal-insulator transition in 3d transition-metal oxides with ABO 3 and A 2BO 4 type structures

    Science.gov (United States)

    Eisaki, H.; Ido, T.; Magoshi, K.; Mochizuki, M.; Yamatsu, H.; Ito, T.; Uchida, S.

    1991-12-01

    3d transition-metal oxides with perovskite and K 2NiF 4 crystal structures, (La,Sr)VO 3, (La,Sr)FeO 3, (La,Sr)CoO 3, LaNiO 3 and (La,Sr) 2NiO 4 systems are investigated focusing on the effect of carrier doping performed by the A-site ion substitution. Both (La,Sr)VO 3 and (La,Sr)CoO 3 systems show an insulator to metal transition by Sr substitution, however, the magnetic behavior differs drastically. The mid-infrared structure induced by Sr substitution is observed in the optical spectra of (La,Sr) 2NiO 4 system. Relation between the behavior of metal-insulator transition and the variation of the electronic and/or spin structure in these systems is discussed in comparison with the high-T c copper oxides.

  13. Noncollinear magnetism in surfaces and interfaces of transition metals

    Energy Technology Data Exchange (ETDEWEB)

    Tan, Huahai

    2009-09-15

    Noncollinear (NC) magnetism is common in nature, especially when there exist geometrical frustration and chemical imparity in the system. In this work we studied the NC magnetism and the response to external magnetic fields in surfaces and interfaces of transition metals by using an semi-empirical tight-binding (TB) method that parameterized to the ab initio TB-LMTO calculations. We implemented this method to study two systems. The first one is the system of 6 Mn monolayers on Fe(001) substrate. Due to the complex structure and magnetic properties of Mn, we found 23 collinear magnetic configurations but only one NC configuration. The collinear ground state has a layered antiferromagnetic (AFM) coupling which agrees with previous experiments and calculations. In the NC configuration the local AFM coupling in the Mn layers is preserved, but the surface is 90 degree coupled to the substrate. Similar to the experiment in CdCr{sub 2}O{sub 4}, we obtained a collinear plateau in the NC evolution of the average magnetic moment in Mn slab under external magnetic fields. Another is the system of a Cr monolayer on a stepped Fe(001) substrate. As expected, the local AFM coupling in the interface of Cr and Fe are preserved. However, the edge Cr atoms is about 90 coupled to their nearest Fe neighbors. We also simulated the procedure of adding more Cr coverages gradually to a Cr bilayer coverage. As coverages increase, the magnetic moments in the Cr interface reduce, and the collinear plateau becomes wider as coverages increase. However, the saturation fields in both the two systems are extremely high, around 10 kT.We expect that when the effect of temperature is taken into account, and in some proper systems, the saturation fields could be largely reduced to the scale that can be implemented in experiment, and our study may shed light on information storage devices with ultrahigh storage density. (orig.)

  14. k-asymmetric spin splitting at the interface between transition metal ferromagnets and heavy metals

    KAUST Repository

    Grytsyuk, Sergiy

    2016-05-23

    We systematically investigate the spin-orbit coupling-induced band splitting originating from inversion symmetry breaking at the interface between a Co monolayer and 4d (Tc, Ru, Rh, Pd, and Ag) or 5d (Re, Os, Ir, Pt, and Au) transition metals. In spite of the complex band structure of these systems, the odd-in-k spin splitting of the bands displays striking similarities with the much simpler Rashba spin-orbit coupling picture. We establish a clear connection between the overall strength of the odd-in-k spin splitting of the bands and the charge transfer between the d orbitals at the interface. Furthermore, we show that the spin splitting of the Fermi surface scales with the induced orbital moment, weighted by the spin-orbit coupling.

  15. CO adsorption on metal-oxide surfaces doped with transition-metal adatoms

    Energy Technology Data Exchange (ETDEWEB)

    Blomqvist, Janne; Lehman, Lauri; Salo, Petri [Department of Applied Physics, Aalto University, FI-00076 Aalto (Finland)

    2012-05-15

    Using first principles density functional theory calculations, we have studied the adsorption of carbon monoxide (CO) on clean, Ag and Pd doped MgO(001), TiO{sub 2}(110), and {alpha}-Al{sub 2}O{sub 3}(0001) surfaces. Our results show that adsorption of CO on the clean surfaces is generally weak. Ag doping improves the adsorption only weakly, except on the TiO{sub 2} surface. The presence of Pd, however, significantly improves adsorption on all the surfaces studied. On the doped surfaces, the best adsorption sites are always the sites on top of the transition metal adatom, and the interaction range is 3-4 Aa around an isolated adatom. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  16. Metal-silicate Partitioning and Its Role in Core Formation and Composition on Super-Earths

    Science.gov (United States)

    Schaefer, Laura; Jacobsen, Stein B.; Remo, John L.; Petaev, M. I.; Sasselov, Dimitar D.

    2017-02-01

    We use a thermodynamic framework for silicate-metal partitioning to determine the possible compositions of metallic cores on super-Earths. We compare results using literature values of the partition coefficients of Si and Ni, as well as new partition coefficients calculated using results from laser shock-induced melting of powdered metal-dunite targets at pressures up to 276 GPa, which approaches those found within the deep mantles of super-Earths. We find that larger planets may have little to no light elements in their cores because the Si partition coefficient decreases at high pressures. The planet mass at which this occurs will depend on the metal-silicate equilibration depth. We also extrapolate the equations of state (EOS) of FeO and FeSi alloys to high pressures, and present mass–radius diagrams using self-consistent planet compositions assuming equilibrated mantles and cores. We confirm the results of previous studies that the distribution of elements between mantle and core will not be detectable from mass and radius measurements alone. While observations may be insensitive to interior structure, further modeling is sensitive to compositionally dependent properties, such as mantle viscosity and core freeze-out properties. We therefore emphasize the need for additional high pressure measurements of partitioning as well as EOSs, and highlight the utility of the Sandia Z-facilities for this type of work.

  17. Prediction of spin-dependent electronic structure in 3d-transition-metal doped antimonene

    Science.gov (United States)

    Yang, L. F.; Song, Y.; Mi, W. B.; Wang, X. C.

    2016-07-01

    We investigate the geometric structure and electronic and magnetic properties of 3d-transition-metal atom doped antimonene using spin-polarized first-principles calculations. Strong orbital hybridization exhibits between 3d-transition-metal and Sb atoms, where covalent bonds form in antimonene. A spin-polarized semiconducting state appears in Cr-doped antimonene, while half-metallic states appear by doping Ti, V, and Mn. These findings indicate that once combined with doping states, the bands of antimonene systems offer a variety of features. Specific dopants lead to half-metallic characters with high spin polarization that has potential application in spintronics.

  18. Theory of the magnetic and metal-insulator transitions in RNiO3 bulk and layered structures.

    Science.gov (United States)

    Lau, Bayo; Millis, Andrew J

    2013-03-22

    A slave rotor--Hartree-Fock formalism is presented for studying the properties of the p-d model describing perovskite transition metal oxides, and a flexible and efficient numerical formalism is developed for its solution. The methodology is shown to yield, within a unified formulation, the significant aspects of the rare-earth nickelate phase diagram, including the paramagnetic metal state observed for the LaNiO3 and the correct ground-state magnetic order of insulating compounds. It is then used to elucidate ground state changes occurring as morphology is varied from bulk to strained and unstrained thin-film form. For ultrathin films, epitaxial strain and charge transfer to the apical out-of-plane oxygen sites are shown to have significant impact on the phase diagram.

  19. Theory of the magnetic and metal-insulator transitions in RNiO3 bulk and layered

    Science.gov (United States)

    Lau, Bayo; Millis, Andrew J.

    2013-03-01

    A slave rotor-Hartree Fock formalism is presented for studying the properties of the p-d model describing perovskite transition metal oxides, and a flexible and efficient numerical formalism is developed for its solution. The methodology is shown to yield, within an unified formulation, the significant aspects of the rare earth nickelate phase diagram, including the paramagnetic metal state observed for the LaNiO3 and the correct ground-state magnetic order of insulating compounds. It is then used to elucidate ground state changes occurring as morphology is varied from bulk to strained and un-strained thin-film form. For ultrathin films, epitaxial strain and charge-transfer to the apical out-of-plane oxygen sites are shown to have significant impact on the phase diagram. This effort is supported by US National Science Foundation under grant NSF-DMR-1006282

  20. Theory of the Magnetic and Metal-Insulator Transitions in RNiO3 Bulk and Layered Structures

    Science.gov (United States)

    Lau, Bayo; Millis, Andrew J.

    2013-03-01

    A slave rotor—Hartree-Fock formalism is presented for studying the properties of the p-d model describing perovskite transition metal oxides, and a flexible and efficient numerical formalism is developed for its solution. The methodology is shown to yield, within a unified formulation, the significant aspects of the rare-earth nickelate phase diagram, including the paramagnetic metal state observed for the LaNiO3 and the correct ground-state magnetic order of insulating compounds. It is then used to elucidate ground state changes occurring as morphology is varied from bulk to strained and unstrained thin-film form. For ultrathin films, epitaxial strain and charge transfer to the apical out-of-plane oxygen sites are shown to have significant impact on the phase diagram.