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Sample records for fe ru os

  1. Thermodynamics and superconductivity of Th7(Fe, Ru, Os, Co, Rh, Ir)3 system

    SciTech Connect

    Smith, James L; Lashley, Jason C; Volz, Heather M; Fisher, Robert A

    2008-01-01

    Expanding the temperature range of previous specific-heat measurements on the Th7(Fe, Ru, Os, Co, Rh, Ir)3 system, we measure the effect of transition-metal substitution on total entropy (S{sub 298 k}), electronic specific heat ({gamma}), and Debye temperature ({Theta}D). In addition we measure the pressure dependence, up to 10 kbar, of the superconducting transition.

  2. Structural, electronic, elastic and magnetic properties of RuFe{sub 3}N and OsFe{sub 3}N: A first principle study

    SciTech Connect

    Puvaneswari, S.; Priyanga, G. Sudha; Rajeswarapalanichamy, R. Santhosh, M.

    2015-06-24

    The structural, electronic, elastic and magnetic properties of the perovskite structure of RuFe{sub 3}N, and OsFe{sub 3}N have been reported using the VASP within the gradient generalized approximation. Total energy calculations are performed using both spin and non-spin polarized calculations and it is found that, at ambient pressure both RuFe{sub 3}N and OsFe{sub 3}N are stable in ferromagnetic phase. The electronic structure reveals that both RuFe{sub 3}N and OsFe{sub 3}N are metallic in nature at ambient pressure.

  3. A comparative computationally study about the defined M(II) pincer hydrogenation catalysts (M = Fe, Ru, Os).

    PubMed

    Jiao, Haijun; Junge, Kathrin; Alberico, Elisabetta; Beller, Matthias

    2016-01-15

    The mechanism of acetonitrile and methyl benzoate catalytic hydrogenation using pincer catalysts M(H)2 (CO)[NH(C2 H4 PiPr2 )2 ] (1M) and M(H)(CO)[N(C2 H4 PiPr2 )2 ] (2M) (M = Fe, Ru, Os) has been computed at various levels of density functional theory. The computed equilibrium between 1Fe and 2Fe agrees perfectly with the experimental observations. On the basis of the activation barriers and reaction energies, the best catalysts for acetonitrile hydrogenation are 1Fe/2Fe and 1Ru/2Ru, and the best catalysts for methyl benzoate hydrogenation are 1Ru/2Ru. The best catalysts for the dehydrogenation of benzyl alcohol are 1Ru/2Ru. It is to note that the current polarizable continuum model is not sufficient in modeling the solvation effect in the energetic properties of these catalysts as well as their catalytic properties in hydrogenation reaction, as no equilibrium could be established between 1Fe and 2Fe. Comparison with other methods and procedures has been made. © 2015 Wiley Periodicals, Inc. © 2015 Wiley Periodicals, Inc.

  4. Comment on "comparison of the widely used HF pseudo-potentials: MH + (M = Fe, Ru, Os)"

    NASA Astrophysics Data System (ADS)

    Andrae, Dirk; Dolg, Michael; Stoll, Hermann; Ermler, Walter C.

    1994-04-01

    It is shown through calculations of the ionization energies of the Fe and Ru atoms that errors attributed to pseudo-potential defects in a recent paper by Leininger [Chem. Phys. Letters 205 (1993) 301] are due, instead, to shortcomings of their valence-interaction treatment.

  5. On the Highest Oxidation States of Metal Elements in MO4 Molecules (M = Fe, Ru, Os, Hs, Sm, and Pu).

    PubMed

    Huang, Wei; Xu, Wen-Hua; Schwarz, W H E; Li, Jun

    2016-05-02

    Metal tetraoxygen molecules (MO4, M = Fe, Ru, Os, Hs, Sm, Pu) of all metal atoms M with eight valence electrons are theoretically studied using density functional and correlated wave function approaches. The heavier d-block elements Ru, Os, Hs are confirmed to form stable tetraoxides of Td symmetry in (1)A1 electronic states with empty metal d(0) valence shell and closed-shell O(2-) ligands, while the 3d-, 4f-, and 5f-elements Fe, Sm, and Pu prefer partial occupation of their valence shells and peroxide or superoxide ligands at lower symmetry structures with various spin couplings. The different geometric and electronic structures and chemical bonding types of the six iso-stoichiometric species are explained in terms of atomic orbital energies and orbital radii. The variations found here contribute to our general understanding of the periodic trends of oxidation states across the periodic table.

  6. Structural and magnetic properties of U 2M 3Si 5 silicides (M = Fe, Ru, Os, Rh)

    NASA Astrophysics Data System (ADS)

    Hickey, E.; Chevalier, B.; Gravereau, P.; Etourneau, J.

    1990-12-01

    U 2Rh 3Si 5 orders antiferromagnetically below TN = 26 K. The magnetic susceptibility of U 2Fe 3Si 5 is practically independent of temperature between 4.2 and 300 K. The susceptibility of U 2Ru 3Si 5 and U 2Os 3Si 5 tends towards saturation below 20 and 60 K, respectively. All these magnetic behaviors are compared to those observed for the UM 2Si 2 suicides.

  7. Formation of Fe-Os, Fe-Ru, and Fe-Co bimetallic particles by thermal decomposition of heteropolynuclear clusters supported on a partially dehydroxylated magnesia

    SciTech Connect

    Choplin, A.; Huang, L.; Theolier, A.; Gallezot, P.; Basset, J.M.; Siriwardane, U.; Shore, S.G.; Mathieu, R.

    1986-07-09

    The authors wish to report here that with H/sub 2/FeOs/sub 3/(CO)/sub 13/, H/sub 2/FeRu/sub 3/(VO)/sub 13/, and HFeCo/sub 3/(CO)/sub 12/ supported on a partially hydroxylated magnesia, it is possible to obtain, after H/sub 2/ treatment at 400/sup 0/C, very small bimetallic particles, having the same bulk composition as that of the starting heteropolynuclear precursor cluster. This conclusion is based on high spatial resolution analytical microscopy.

  8. Metal Dependence of Signal Transmission through Molecular Quantum-Dot Cellular Automata (QCA): A Theoretical Study on Fe, Ru, and Os Mixed-Valence Complexes

    PubMed Central

    Tokunaga, Ken

    2010-01-01

    Dynamic behavior of signal transmission through metal complexes [L5M-BL-ML5]5+ (M=Fe, Ru, Os, BL=pyrazine (py), 4,4’-bipyridine (bpy), L=NH3), which are simplified models of the molecular quantum-dot cellular automata (molecular QCA), is discussed from the viewpoint of one-electron theory, density functional theory. It is found that for py complexes, the signal transmission time (tst) is Fe(0.6 fs) < Os(0.7 fs) < Ru(1.1 fs) and the signal amplitude (A) is Fe(0.05 e) < Os(0.06 e) < Ru(0.10 e). For bpy complexes, tst and A are Fe(1.4 fs) < Os(1.7 fs) < Ru(2.5 fs) and Os(0.11 e) < Ru(0.12 e) < Fe(0.13 e), respectively. Bpy complexes generally have stronger signal amplitude, but waste longer time for signal transmission than py complexes. Among all complexes, Fe complex with bpy BL shows the best result. These results are discussed from overlap integral and energy gap of molecular orbitals.

  9. Light harvesting and directional energy transfer in long-lived homo- and heterotrimetallic complexes of Fe(II), Ru(II), and Os(II).

    PubMed

    Maity, Dinesh; Bhaumik, Chanchal; Mardanya, Sourav; Karmakar, Srikanta; Baitalik, Sujoy

    2014-10-06

    A new family of trimetallic complexes of the form [(bpy)2 M(phen-Hbzim-tpy)M'(tpy-Hbzim-phen)M(bpy)2](6+) (M=Ru(II), Os; M'=Fe(II), Ru(II), Os; bpy=2,2'-bipyridine) derived from heteroditopic phenanthroline-terpyridine bridge 2-{4-[2,6-di(pyridin-2-yl) pyridine-4-yl]phenyl}-1H-imidazole[4,5-f][1,10]phenanthroline (phen-Hbzim-tpy) were prepared and fully characterized. Zn(2+) was used to prepare mixed-metal trimetallic complexes in situ by coordinating with the free tpy site of the monometallic precursors. The complexes show intense absorptions throughout the UV/Vis region and also exhibit luminescence at room temperature. The redox behavior of the compounds is characterized by several metal-centered reversible oxidation and ligand-centered reduction processes. Steady-state and time-resolved luminescence data show that the potentially luminescent Ru(II)- and Os(II)-based triplet metal-to-ligand charge-transfer ((3)MLCT) excited states in the triads are quantitatively quenched, most likely by intercomponent energy transfer to the lower lying (3)MLCT (for Ru and Os) or triplet metal-centered ((3)MC) excited states of the Fe(II) subunit (nonluminescent). Interestingly, iron did not adversely affect the photophysics of the respective systems. This suggests that the multicomponent molecular-wire-like complexes investigated here can behave as efficient light-harvesting antennas, because all the light absorbed by the various subunits is efficiently channeled to the subunit(s) in which the lowest-energy excited states are located.

  10. pH-Induced processes in wire-like multichromophoric homo- and heterotrimetallic complexes of Fe(II), Ru(II), and Os(II).

    PubMed

    Maity, Dinesh; Mardanya, Sourav; Karmakar, Srikanta; Baitalik, Sujoy

    2015-06-07

    In this work we studied the influence of pH on the absorption, steady state and time-resolved emission spectroscopic behaviors of recently reported multichromophoric trimetallic complexes of the forms [(bpy)2M(phen-Hbzim-tpy)M'(tpy-Hbzim-phen)M(bpy)2](6+) (M = Ru(II) or Os(II), and M' = Fe(II), Ru(II), and Os(II)) derived from a heteroditopic phenanthroline-terpyridine bridge, 2-(4-(2,6-di(pyridin-2-yl)pyridine-4-yl)phenyl)-1H-imidazole[4,5-f][1,10]phenanthroline (tpy-Hbzim-phen) and 2,2'-bipyridine (bpy) as the auxiliary ligand. For purposes of comparison, the UV-vis absorption and emission titrations of three monometallic model compounds [(bpy)2Ru(phen-Hbzim-tpy)](ClO4)2 (1), [(bpy)2Os(phen-Hbzim-tpy)] (ClO4)2 (2) and [(tpy-PhCH3)Ru(tpy-Hbzim-phen)](ClO4)2 (3), where tpy-PhCH3 = 4'-(4-methylphenyl)-2,2':6',2''-terpyridine) were studied under the same experimental conditions. The absorption titration data were used to determine the ground state pKa values, whereas the luminescence and lifetime data were utilized for the determination of excited state pKa* values of the complexes. The evolving factor analyses of the set of absorption spectra of the complexes obtained by varying the pH of the solution confirm that only three absorbing species exist in the pH window of 2-12. Moreover, the modulation of the rate of the intramolecular energy transfer among the components in the homo- and heterotrimetallic complexes as a function of pH of the solution was also demonstrated.

  11. Stereoselectivity in the formation of tris-diimine complexes of Fe(II), Ru(II), and Os(II) with a C2-symmetric chiral derivative of 2,2'-bipyridine.

    PubMed

    Drahonovský, Dusan; Knof, Ulrich; Jungo, Laurence; Belser, Thomas; Neels, Antonia; Labat, Gaël Charles; Stoeckli-Evans, Helen; von Zelewsky, Alex

    2006-03-21

    A C2-symmetric enantiopure 4,5-bis(pinene)-2,2'-bipyridine ligand (-)-L was used to investigate the diastereoselectivity in the formation of [ML3]2+ coordination species (M = Fe(II), Ru(II), Os(II), Zn(II), Cd(II), Cu(II), Ni(II)), and [ML2Cl2] (M = Ru(II), Os(II)). The X-ray structures of the [ML3]2+ complexes were determined for Delta-[FeL3](PF6)2, Delta-[RuL3](PF6)2, Lambda-[RuL3](PF6)2, Delta-[OsL3](PF6)2, and Lambda-[OsL3](TfO)2. All of these compounds were also characterized by NMR, CD and UV/VIS absorption spectroscopy. The [FeL3]2+ diastereoisomers were studied in equilibrated solutions at various temperatures and in several solvents. The [RuL3]2+ complexes, which are thermally stable up to 200 degrees C, were photochemically equilibrated.

  12. Structural, electronic, elastic, thermoelectric and thermodynamic properties of the NbMSb half heusler (M=Fe, Ru, Os) compounds with first principle calculations

    NASA Astrophysics Data System (ADS)

    Abid, O. Miloud; Menouer, S.; Yakoubi, A.; Khachai, H.; Omran, S. Bin; Murtaza, G.; Prakash, Deo; Khenata, R.; Verma, K. D.

    2016-05-01

    The structural, electronic, elastic, thermoelectric and thermodynamic properties of NbMSb (M = Fe, Ru, Os) half heusler compounds are reported. The full-potential linearized augmented plane wave (FP-LAPW) plus local orbital (lo) method, based on the density functional theory (DFT) was employed for the present study. The equilibrium lattice parameter results are in good compliance with the available experimental measurements. The electronic band structure and Boltzmann transport calculations indicated a narrow indirect energy band gap for the compound having electronic structure favorable for thermoelectric performance as well as with substantial thermopowers at temperature ranges from 300 K to 800 K. Furthermore, good potential for thermoelectric performance (thermopower S ≥ 500 μeV) was found at higher temperature. In addition, the analysis of the charge density, partial and total densities of states (DOS) of three compounds demonstrate their semiconducting, ionic and covalent characters. Conversely, the calculated values of the Poisson's ratio and the B/G ratio indicate their ductile makeup. The thermal properties of the compounds were calculated by quasi-harmonic Debye model as implemented in the GIBBS code.

  13. First principles static and dynamic calculations for the transition metal hydride series MH4L3 (M = Fe, Ru and Os; L = NH3, PH3 and PF3).

    PubMed

    Sieffert, Nicolas; Kendrick, Thomas; Tiana, Davide; Morrison, Carole A

    2015-03-07

    We present a first principles static and dynamical study of the transition metal hydride series MH4L3 (M = Fe, Ru and Os; L = NH3, PH3 and PF3), with a view to arriving at an understanding of how the variation in the electronic properties of the metal sites and ligands can influence the dynamics of the resulting complexes. A broad range of behaviour was observed, encompassing stable classical minima (M = Os, L = NH3 and M = Ru, L = PH3) to stable η(2)-H2 non-classical minima (M = Fe, L = PF3 and M = Ru, L = PH3 or PF3), with the other structures exhibiting dynamical behaviour that spontaneously converted between the classical and non-classical states during the molecular dynamics simulations. The importance of a small L(axial)-M-L(axial) angle in stabilising the non-classical state is highlighted, as is a short η(2)-H2···H(cis) distance in non-classical complexes that spontaneously convert to the classical form. We also investigated the changes in the electronic structure of the complex FeH4(PH3)3 during a η(2)-H2 bond breaking/bond making reaction and observed direct evidence of the 'cis effect', whereby a neighbouring hydride ligand acts to stabilise the intermediate classical state.

  14. Electronic, structural and magnetic studies of niobium borides of group 8 transition metals, Nb{sub 2}MB{sub 2} (M=Fe, Ru, Os) from first principles calculations

    SciTech Connect

    Touzani, Rachid St.; Fokwa, Boniface P.T.

    2014-03-15

    The Nb{sub 2}FeB{sub 2} phase (U{sub 3}Si{sub 2}-type, space group P4/mbm, no. 127) is known for almost 50 years, but until now its magnetic properties have not been investigated. While the synthesis of Nb{sub 2}OsB{sub 2} (space group P4/mnc, no. 128, a twofold superstructure of U{sub 3}Si{sub 2}-type) with distorted Nb-layers and Os{sub 2}-dumbbells was recently achieved, “Nb{sub 2}RuB{sub 2}” is still not synthesized and its crystal structure is yet to be revealed. Our first principles density functional theory (DFT) calculations have confirmed not only the experimental structures of Nb{sub 2}FeB{sub 2} and Nb{sub 2}OsB{sub 2}, but also predict “Nb{sub 2}RuB{sub 2}” to crystalize with the Nb{sub 2}OsB{sub 2} structure type. According to chemical bonding analysis, the homoatomic B–B interactions are optimized and very strong, but relatively strong heteroatomic M–B, B–Nb and M–Nb bonds (M=Fe, Ru, Os) are also found. These interactions, which together build a three-dimensional network, are mainly responsible for the structural stability of these ternary borides. The density-of-states at the Fermi level predicts metallic behavior, as expected, from metal-rich borides. Analysis of possible magnetic structures concluded preferred antiferromagnetic ordering for Nb{sub 2}FeB{sub 2}, originating from ferromagnetic interactions within iron chains and antiferromagnetic exchange interactions between them. -- Graphical abstract: Nb{sub 2}FeB{sub 2} (U{sub 3}Si{sub 2} structure type, space group P4/mbm, no. 127) is predicted to order antiferromagnetically, due to the presence of iron chains which show ferromagnetic interactions in the chains and antiferromagnetic interactions between them. “Nb{sub 2}RuB{sub 2}” is predicted to crystallize with the recently discovered Nb{sub 2}OsB{sub 2} twofold superstructure (space group P4/mnc, no. 128) of U{sub 3}Si{sub 2} structure type. The building of ruthenium dumbbells instead of chains along [001] is found to be

  15. The role of the [CpM(CO)2](-) chromophore in the optical properties of the [Cp2ThMCp(CO)2](+) complexes, where M = Fe, Ru and Os. A theoretical view.

    PubMed

    Cantero-López, Plinio; Le Bras, Laura; Páez-Hernández, Dayán; Arratia-Pérez, Ramiro

    2015-12-14

    The chemical bond between actinide and the transition metal unsupported by bridging ligands is not well characterized. In this paper we study the electronic properties, bonding nature and optical spectra in a family of [Cp2ThMCp(CO)2](+) complexes where M = Fe, Ru, Os, based on the relativistic two component density functional theory calculations. The Morokuma-Ziegler energy decomposition analysis shows an important ionic contribution in the Th-M interaction with around 25% of covalent character. Clearly, charge transfer occurs on Th-M bond formation, however the orbital term most likely represents a strong charge rearrangement in the fragments due to the interaction. Finally the spin-orbit-ZORA calculation shows the possible NIR emission induced by the [FeCp(CO)2](-) chromophore accomplishing the antenna effect that justifies the sensitization of the actinide complexes.

  16. Os-Ru-Ir and Os-(Ru)-Ir-Pt mineral phases from iron quartzites and weathered rocks of the Mikhailovka and Staryi Oskol KMA iron regions, central Russia

    NASA Astrophysics Data System (ADS)

    Chernyshov, N. M.; Ponamareva, M. M.

    2015-02-01

    Numerous natural Os-Ir-Ru and Os-Ir-Ru-Pt alloys have been found in iron quartzites and their weathered rocks. The Ir-Os alloys in the Mikhailovka and Staryi Oskol KMA iron regions are characterized by the densest hexagonal packing. Almost all of them contain a low amount of Fe and Ni at a relatively higher amount of Pt, Ru, and, locally, Rh. The highest Rh contents are typical of minerals with Ir dominant over Os or with a high Pt content.

  17. 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).

    PubMed

    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.

  18. What is the best bonding model of the (σ-H-BR) species bound to a transition metal? Bonding analysis in complexes [(H)2Cl(PMe3)2M(σ-H-BR)] (M = Fe, Ru, Os).

    PubMed

    Pandey, Krishna K

    2012-03-21

    Density Functional Theory calculations have been performed for the σ-hydroboryl complexes of iron, ruthenium and osmium [(H)(2)Cl(PMe(3))(2)M(σ-H-BR)] (M = Fe, Ru, Os; R = OMe, NMe(2), Ph) at the BP86/TZ2P/ZORA level of theory in order to understand the interactions between metal and HBR ligands. The calculated geometries of the complexes [(H)(2)Cl(PMe(3))(2)Ru(HBNMe(2))], [(H)(2)Cl(PMe(3))(2)Os(HBR)] (R = OMe, NMe(2)) are in excellent agreement with structurally characterized complexes [(H)(2)Cl(P(i)Pr(3))(2)Os(σ-H-BNMe(2))], [(H)(2)Cl(P(i)Pr(3))(2)Os{σ-H-BOCH(2)CH(2)OB(O(2)CH(2)CH(2))}] and [(H)(2)Cl(P(i)Pr(3))(2)Os(σ-H-BNMe(2))]. The longer calculated M-B bond distance in complex [(H)(2)Cl(PMe(3))(2)M(σ-H-BNMe(2))] are due to greater B-N π bonding and as a result, a weaker M-B π-back-bonding. The B-H2 bond distances reveal that (i) iron complexes contain bis(σ-borane) ligand, (ii) ruthenium complexes contain (σ-H-BR) ligands with a stretched B-H2 bond, and (iii) osmium complexes contain hydride (H2) and (σ-H-BR) ligands. The H-BR ligands in osmium complexes are a better trans-directing ligand than the Cl ligand. Values of interaction energy, electrostatic interaction, orbital interaction, and bond dissociation energy for interactions between ionic fragments are very large and may not be consistent with M-(σ-H-BR) bonding. The EDA as well as NBO and AIM analysis suggest that the best bonding model for the M-σ-H-BR interactions in the complexes [(H)(2)Cl(PMe(3))(2)M(σ-H-BR)] is the interaction between neutral fragments [(H)(2)Cl(PMe(3))(2)M] and [σ-H-BR]. This becomes evident from the calculated values for the orbital interactions. The electron configuration of the fragments which is shown for C in Fig. 1 experiences the smallest change upon the M-σ-H-BR bond formation. Since model C also requires the least amount of electronic excitation and geometry changes of all models given by the ΔE(prep) values, it is clearly the most appropriate choice of

  19. Spin-State Effects on the Thermal Dihydrogen Release from Solid-State [MH(η2-H2)dppe2]+ (M = Fe, Ru, Os) Organometallic Complexes for Hydrogen Storage Applications

    PubMed Central

    2015-01-01

    Mössbauer spectroscopy, experimental thermodynamic measurements, and computational studies were performed to investigate the properties of molecular hydrogen binding to the organometallic fragments [MHdppe2]+ (M = Fe, Ru, Os; dppe =1,2-bis(diphenylphosphino)ethane) to form the dihydrogen complex fragments [MH(η2-H2)dppe2]+. Mössbauer spectroscopy showed that the dehydrogenated complex [FeHdppe2]+ adopts a geometry consistent with the triplet spin state, transitioning to a singlet state complex upon addition of the dihydrogen molecule in a manner similar to the previously studied dinitrogen complexes. From simulations, this spin transition behavior was found to be responsible for the strong binding behavior experimentally observed in the iron complex. Spin-singlet to spin-singlet transitions were found to exhibit thermodynamics consistent with the 5d > 3d > 4d binding trend observed for other transition metal dihydrogen complexes. Finally, the method for distinguishing between dihydrogen and dihydride complexes based on partial quadrupole splittings observed in Mössbauer spectra was confirmed, providing a tool for further characterization of these unique species for Mössbauer active compounds. PMID:24803973

  20. Ru and Os film deposition from metal carbonyls

    SciTech Connect

    Berry, A.D.; Brown, D.J.; Kaplan, R.; Cukauskas, E.J.

    1986-03-01

    Adherent, highly reflective films of Ru and Os have been deposited in vacuum on heated Si substrates by thermal decomposition of the pentacarbonyls Ru(CO)/sub 5/ and Os(CO)/sub 5/, at 150 and 200 /sup 0/C, respectively. Auger analysis after ion bombardment cleaning revealed nearly O-free surfaces, with slight C contamination which grew with exposure to the primary electron beam, thus making accurate determination of C content difficult. X-ray diffraction showed the films to be polycrystalline with the expected hexagonal close-packed structure, while measured resistivities were about a factor of 3 greater than bulk values. This method of depositing Ru and Os offers the advantages of simplicity, modest temperature requirement, and metallization of heated surfaces only.

  1. Structural stability and phase transition in OsC and RuC.

    PubMed

    Zhao, Erjun; Wang, Jinping; Wu, Zhijian

    2010-12-01

    The structural stability and phase transition of osmium and ruthenium carbides (OsC and RuC) were investigated by first principles. Nine structures were considered for each carbide. Zinc blende structure has the lowest energy among the considered structures at ambient conditions for both carbides. For OsC at elevated pressures, the most stable phase is zinc blende structure from 0 to 10 GPa, FeSi from 10 to 32 GPa. In these two structures, Os atom is fourfold coordinated. From 32 to 40 GPa, tungsten carbide (WC) and NiAs are energetically competitive with Os atom sixfold coordinated. NiAs becomes energetically the most stable structure above 40 GPa. For RuC, zinc blende structure is the most stable from 0 to 20 GPa. From 20 to 100 GPa, WC structure is the most stable. © 2010 Wiley Periodicals, Inc.

  2. Ru, Re, Os, Pt and Au in iron meteorites

    NASA Technical Reports Server (NTRS)

    Pernicka, Ernst; Wasson, John T.

    1987-01-01

    Neutron activation analysis is used to ascertain the proportions of Ru, Re, Os, and Pt refractory siderophiles, and moderately volatile Au, in 41 iron meteorites. The Ni-element trends defined for groups IID and IIIF support a magmatic origin; in addition, the results obtained for groups IAB and IIICD contrast with trends observed in magmatic groups, where the Ru and Pt slopes are substantially less steep. In group IIIAB, at Ni concentrations above 90 mg/g, the steep decrease of Re, Os, and Ir with Ni levels off, and the interelement ratios exhibit considerable scatter. These observations may be explained in terms of the contamination of the residual molten core with small amounts of late primitive melts draining from the mantle.

  3. Determining the effect of Ru substitution on the thermal stability of CeFe[subscript 4-x]Ru[subscript x]Sb[subscript 12

    SciTech Connect

    Sigrist, Jessica A.; Walker, James D.S.; Hayes, John R.; Gaultois, Michael W.; Grosvenor, Andrew P.

    2011-11-14

    The ternary, rare-earth filled (RE) Skutterudites (REM{sub 4}Pn{sub 12}; M = Fe-Os; Pn = P-Sb) have been proposed for use in high-temperature thermoelectric devices to convert waste heat to useful power. CeFe{sub 4}Sb{sub 12} has been one of the most popular materials proposed for this application; however, it oxidizes at relatively low temperatures. The thermal stability of Skutterudites can be enhanced by selective substitution of the constituent elements and Eu(Fe,Ru){sub 4}Sb{sub 12} variants have been found to oxidize at temperatures above that of CeFe{sub 4}Sb{sub 12}. Unfortunately, these materials have poor thermoelectric properties. In this study, the thermal stability of CeFe{sub 4-x}Ru{sub x}Sb{sub 12} was examined depending on the value of x. (These compounds have similar thermoelectric properties to those of CeFe{sub 4}Sb{sub 12}.) It has been found by use of TGA and XANES that the temperature at which point CeFe{sub 4-x}Ru{sub x}Sb{sub 12} oxidizes increases with greater Ru substitution. XANES was also used to confirm the general charge assignment of Ce{sup 3+}Fe{sub 4-x}{sup 2+}Ru{sub x}{sup 2+}Sb{sub 12}{sup 1-}.

  4. Ternary rare-earth aluminium intermetallics RE10TAl3 (RE = Y, Ho, Tm, Lu; T = Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt) with an ordered anti-Co2Al5 structure.

    PubMed

    Benndorf, Christopher; Eckert, Hellmut; Janka, Oliver

    2017-01-24

    Twenty new rare-earth metal rich intermetallic aluminium compounds, RE10TAl3 (RE = Y, Ho, Tm, Lu; T = Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt), were synthesized by arc melting the elements. The compounds crystallize, in analogy to e.g. the respective Cd representatives, with a ternary ordered structure as anti-type to the hexagonal Co2Al5 type, with the space group P63/mmc. The three crystallographically independent rare-earth metal sites occupy the aluminium positions of the aristotype, while the transition metal and aluminium atoms are ordered on the two cobalt sites. Like other rare-earth rich compounds the RE10TX3 members also exhibit transition-metal-centred T@RE6 trigonal prisms as striking structural building units. The prepared compounds have been investigated by susceptibility measurements and (27)Al solid-state MAS-NMR measurements conducted on the Pauli-paramagnetic Y and Lu compounds. Some compounds show a certain amount of disorder as seen from the single crystal structure analysis and from signal broadening in the NMR investigations. By separating Knight shifts from second-order quadrupolar shifts via field dependent measurements, monotonic trends can be discerned regarding the effect of the T atom valence electron concentration and period number, as well as the effect of the closed 4f shell contributed in the Lu compounds. The results confirm that a comparison of Knight shifts within a series of isotypic compounds can reveal important electronic structure information in intermetallic systems.

  5. Electronic structure of Fe- vs. Ru-based dye molecules

    SciTech Connect

    Johnson, Phillip S.; Himpsel, F. J.; Cook, Peter L.; Zegkinoglou, Ioannis; Garcia-Lastra, J. M.; Rubio, Angel; Ruther, Rose E.; Hamers, Robert J.

    2013-01-28

    In order to explore whether Ru can be replaced by inexpensive Fe in dye molecules for solar cells, the differences in the electronic structure of Fe- and Ru-based dyes are investigated by X-ray absorption spectroscopy and first-principles calculations. Molecules with the metal in a sixfold, octahedral N cage, such as tris(bipyridines) and tris(phenanthrolines), exhibit a systematic downward shift of the N 1s-to-{pi}* transition when Ru is replaced by Fe. This shift is explained by an extra transfer of negative charge from the metal to the N ligands in the case of Fe, which reduces the binding energy of the N 1s core level. The C 1s-to-{pi}* transitions show the opposite trend, with an increase in the transition energy when replacing Ru by Fe. Molecules with the metal in a fourfold, planar N cage (porphyrins) exhibit a more complex behavior due to a subtle competition between the crystal field, axial ligands, and the 2+ vs. 3+ oxidation states.

  6. Electronic structure of Fe- vs. Ru-based dye molecules.

    PubMed

    Johnson, Phillip S; Cook, Peter L; Zegkinoglou, Ioannis; García-Lastra, J M; Rubio, Angel; Ruther, Rose E; Hamers, Robert J; Himpsel, F J

    2013-01-28

    In order to explore whether Ru can be replaced by inexpensive Fe in dye molecules for solar cells, the differences in the electronic structure of Fe- and Ru-based dyes are investigated by X-ray absorption spectroscopy and first-principles calculations. Molecules with the metal in a sixfold, octahedral N cage, such as tris(bipyridines) and tris(phenanthrolines), exhibit a systematic downward shift of the N 1s-to-π* transition when Ru is replaced by Fe. This shift is explained by an extra transfer of negative charge from the metal to the N ligands in the case of Fe, which reduces the binding energy of the N 1s core level. The C 1s-to-π* transitions show the opposite trend, with an increase in the transition energy when replacing Ru by Fe. Molecules with the metal in a fourfold, planar N cage (porphyrins) exhibit a more complex behavior due to a subtle competition between the crystal field, axial ligands, and the 2+ vs. 3+ oxidation states.

  7. Crystal Structure and Anisotropic c--f Hybridization in CeT2Al10 (T=Ru, Fe)

    NASA Astrophysics Data System (ADS)

    Sera, Masafumi; Tanaka, Daiki; Tanida, Hiroshi; Moriyoshi, Chikako; Ogawa, Mayuko; Kuroiwa, Yoshihiro; Nishioka, Takashi; Matsumura, Masahiro; Kim, Jungeun; Tsuji, Naruki; Takata, Masaki

    2013-02-01

    We have performed the investigation of the charge density distribution of CeT2Al10 (T=Ru, Fe) and the crystal structure parameters of LnT2Al10. The lattice parameters of a-, b-, and c-axes exhibit the anisotropic contraction when Ru is replaced by Fe in LnT2Al10, different from the isotropic contraction simply expected from the smaller ionic radius of Fe than Ru. The contraction is larger in the a- and c-axes than in the b-axis. This anisotropic contraction of the YbFe2Al10-type crystal structure originates from the zigzag degree of the zigzag chain formed by T and Al bond along the a- and c-axes are larger than that along the b-axis. The lattice parameters of CeT2Al10 (T=Ru, Fe) exhibit the anisotropic deviation from the lanthanide contraction. The deviation is largest in the a-axis and is very small in the b-axis. Both the characteristic YbFe2Al10-type crystal structure and the anisotropic deviation towards the intermediate valence indicate that the largest c--f hybridization along the a-axis plays the important role and is associated with the unusual antiferromagnetic order in CeT2Al10 (T=Ru, Os).

  8. Characterization of Bimetallic Fe-Ru Oxide Nanoparticles Prepared by Liquid-Phase Plasma Method.

    PubMed

    Lee, Sung-Jin; Lee, Heon; Jeon, Ki-Joon; Park, Hyunwoong; Park, Young-Kwon; Jung, Sang-Chul

    2016-12-01

    The bimetallic Fe-Ru oxide nanoparticles were synthesized in the liquid-phase plasma (LPP) method which employed iron chloride and ruthenium chloride as precursors. The active species (OH·, Hα, Hβ, and O(I)) and the iron and ruthenium ions were observed in the plasma field created by the LPP process. The spherical-shaped bimetallic Fe-Ru oxide nanoparticles were synthesized by the LPP reaction, and the size of the particles was growing along with the progression of the LPP reaction. The synthesized bimetallic Fe-Ru oxide nanoparticles were comprised of Fe2O3, Fe3O4, RuO, and RuO2. Ruthenium had a higher reduction potential than iron and resulted in higher ruthenium composition in the synthesized bimetallic nanoparticles. The control of the molar ratio of the precursors in the reactant solution was found to be employed as a means to control the composition of the elements in bimetallic nanoparticles.

  9. Diffusion, phase equilibria and partitioning experiments in the Ni-Fe-Ru system

    NASA Astrophysics Data System (ADS)

    Blum, Joel D.; Wasserburg, G. J.; Hutcheon, I. D.; Beckett, J. R.; Stolper, E. M.

    1989-02-01

    Results are presented on thin-film diffusion experiments designed to investigate phase equilibria in systems containing high concentrations of Pt-group elements, such as Ni-Fe-Ru-rich systems containing Pt, at temperatures of 1273, 1073, and 873 K. The rate of Ru diffusion in Ni was determined as a function of temperature, and, in addition, the degree of Pt and Ir partitioning between phases in a Ni-Fe-Ru-rich system and of V between phases in a Ni-Fe-O-rich system at 873 were determined. It was found that Pt preferentially partitions into the (gamma)Ni-Fe phase, whereas Ir prefers the (epsilon)Ru-Fe phase. V partitions strongly into Fe oxides relative to (gamma)Ni-Fe. These results have direct application to the origin and thermal history of the alloys rich in Pt-group elements in meteorites.

  10. Diffusion, phase equilibria and partitioning experiments in the Ni-Fe-Ru system

    NASA Technical Reports Server (NTRS)

    Blum, Joel D.; Wasserburg, G. J.; Hutcheon, I. D.; Beckett, J. R.; Stolper, E. M.

    1989-01-01

    Results are presented on thin-film diffusion experiments designed to investigate phase equilibria in systems containing high concentrations of Pt-group elements, such as Ni-Fe-Ru-rich systems containing Pt, at temperatures of 1273, 1073, and 873 K. The rate of Ru diffusion in Ni was determined as a function of temperature, and, in addition, the degree of Pt and Ir partitioning between phases in a Ni-Fe-Ru-rich system and of V between phases in a Ni-Fe-O-rich system at 873 were determined. It was found that Pt preferentially partitions into the (gamma)Ni-Fe phase, whereas Ir prefers the (epsilon)Ru-Fe phase. V partitions strongly into Fe oxides relative to (gamma)Ni-Fe. These results have direct application to the origin and thermal history of the alloys rich in Pt-group elements in meteorites.

  11. Distance dependence of intrahelix Ru(II)* to Os(II) polypyridyl excited-state energy transfer in oligoproline assemblies.

    PubMed

    Brennaman, M Kyle; Fleming, Cavan N; Slate, Cheryl A; Serron, Scafford A; Bettis, Stephanie E; Erickson, Bruce W; Papanikolas, John M; Meyer, Thomas J

    2013-05-30

    Energy transfer between the metal-to-ligand charge transfer (MLCT) excited states of [Pra [M(II)(bpy)2(4-Me-4'(-N(H)CO)bpy)](PF6)2 units ([Pra(M(II)bpy2(mbpy)](2+): M(II) = Ru(II) or Os(II), bpy = 2,2'-bipyridine, mbpy = 4'-methyl-2,2'-bipyridine-4-carboxamido, Pra = 4-M(II)-L-proline) linked covalently to oligoproline assemblies in room temperature acetonitrile occurs on the picosecond-nanosecond time scale and has been time-resolved by transient emission measurements. Three derivatized oligoprolines, [CH3-CO-Pro6-Pra[Os(II)(bpy)2(mbpy)](2+)-Pro2-Pra[Ru(II)(bpy)2(mbpy)](2+)-Pro2-Pra[Ru(II)(bpy)2(mbpy)](2+)-Pro6-Glu-NH2](6+) (ORR-2, Pro = L-proline and Glu = glutamic acid); [CH3-CO-Pro6-Pra[Os(II)(bpy)2(mbpy)](2+)-Pro3-Pra[Ru(II)(bpy)2(mbpy)](2+)-Pro3-Pra[Ru(II)(bpy)2(mbpy)](2+)-Pro6-Glu-NH2](6+) (ORR-3); and CH3-CO-Pro6-Pra[Os(II)(bpy)2(mbpy)](2+)-Pro5-Pra[Ru(II)(bpy)2(mbpy)](2+)-Pro5-Pra[Ru(II)(bpy)2(mbpy)](2+)Pro6-Glu2-NH2](6+) (ORR-5), were prepared by using solid-phase peptide synthesis. Given the helical nature of the resulting assemblies and the nature of the synthesis, composition, length, and loading pattern are precisely controlled in the assemblies. In acetonitrile, they adopt a proline I helical secondary structure, confirmed by circular dichroism, in which the appended chromophores are ordered in well-defined orientations and internuclear separation distances although helix formation for ORR-2 is incomplete. Quantitative comparison of oligoproline ground-state absorption and steady-state emission spectra to those for the constituents, [Boc-Pra[M(II)(bpy)2(mbpy)](2+)-OH](PF6)2 (Boc = N(α)-(1,1-dimethylethoxycarbonyl), shows that following Ru(II) light absorption, Ru(II)* undergoes facile energy transfer resulting in sensitization of Os(II). Sensitization efficiencies are 93% for ORR-2, 77% for ORR-3, and 73% for ORR-5. Picosecond-resolved emission measurements reveal complex, coupled dynamics that arise from excited-state decay and kinetically

  12. Addition of Ru to L10-FePt thin film to lower Curie temperature

    NASA Astrophysics Data System (ADS)

    Ono, Takuya; Nakata, Hitoshi; Moriya, Tomohiro; Kikuchi, Nobuaki; Okamoto, Satoshi; Kitakami, Osamu; Shimatsu, Takehito

    2016-12-01

    The addition of Ru to L10 (fct)-FePt thin films was investigated to lower the Curie temperature (T c) of the films, which is beneficial for heat-assisted magnetic recording. The FePtRu films exhibited L10-ordering and perpendicular anisotropy for Ru contents up to at least 18 at. %, and T c was reduced by ∼100 °C/6 at. % Ru independent of the Fe/Pt ratio between 0.8 and 1.1. The T c versus uniaxial magnetic anisotropy diagrams exhibited a linear trend similar to that of FePtCu films but with a larger slope. Systematic analysis clarified that the Ru additive caused a slight decrease of the anisotropic field but greatly decreased the saturation magnetization, which was related to the observed reduction in T c.

  13. Enhancement of magnetoresistance using CoFe/Ru/CoFe synthetic ferrimagnetic pinned layer in BiFeO{sub 3} based spin-valves

    SciTech Connect

    Naganuma, Hiroshi; Kubota, Miho; Inami, Nobuhito; Kawada, Yuki; Oogane, Mikihiko; Ando, Yasuo; Bae, In-Tae; Miyazaki, Takamichi; Mizukami, Shigemi; Han, X. F.

    2012-08-13

    SrTiO{sub 3} (100) sub/BiFeO{sub 3}/CoFe/Ru/CoFe/Cu/CoFe/Ta structure was prepared by a combination of chemical solution deposition and sputtering method, and followed by a systematical investigation for the structural, magnetic and magnetoresistance properties at room temperature (RT) as a function of CoFe and Ru thicknesses. It was revealed that introduction of synthetic CoFe/Ru/CoFe as a pinning layer increased the giant magentoresistance (MR) ratio to 8.3% at RT. This enhancement of MR ratio might be attributed to (i) the increase of pinning field, and (ii) suppression of the influence of the surface roughness of BiFeO{sub 3} by inserting the synthetic CoFe/Ru/CoFe layer.

  14. Redox-responsive molecular switches based on azoterpyridine-bridged Ru/Os complexes.

    PubMed

    Akasaka, Tetsuo; Otsuki, Joe; Araki, Koji

    2002-01-04

    Three new terpyridine-based dinuclear complexes, [(tpy)Ru(azotpy)Ru(tpy)]4+ (tpy = 2,2':6',2''-terpyridine, azotpy = bis[2,6-bis(2-pyridyl)-4-pyridyl]diazene), [(tpy)Os(azotpy)Os(tpy)]4+, and [(tpy)Ru(azotpy)Os(tpy)]4+ were prepared and their electrochemical and photophysical properties investigated. The bridging ligand, azotpy, in these complexes is reduced at less negative potentials than the unsubstituted tpy ligand. These complexes exhibit absorption bands due to the metal-to-ligand charge-transfer transitions both to the unsubstituted tpy ligand and the bridging azotpy ligand, the latter absorption being observed at the lower energy side of the former. These observations are consistent with the lower lying pi* level of the azotpy ligand than that of the tpy ligand. These complexes are nonluminescent, since the excited electron is trapped in this lower lying pi* level of the azotpy ligand in the excited state. Reduction of this bridging ligand by constant potential electrolysis renders the shape of absorption spectra for these complexes nearly identical to those of the parent complexes, [M(tpy)2]2+ (M = Ru, Os). In this reduced state, the homodinuclear Os complex becomes luminescent at room temperature, whereas the homodinuclear Ru complex becomes luminescent at 77 K, thus establishing their photoswitching behavior. The reduced heterodinuclear complex exhibits luminescence from the Os center, which is sensitized by the Ru center in the same molecule as evidenced by the excitation spectra. Thus, the intramolecular energy transfer can be switched on and off by the redox reaction of the bridging component.

  15. Initial Os-isotopic composition of Os-Ir-Ru alloys from ultramafic massifs of the Polar Siberia

    NASA Astrophysics Data System (ADS)

    Malitch, K. N.; Badanina, I. Yu.; Kostoyanov, A. I.

    2011-09-01

    This study firstly presents chemical and initial Os-isotopic compositions of Os-Ir-Ru minerals of two ultramafic formations of Polar Siberia, which are exemplified by Guli clinopyroxene-dunite massif of the Maimecha-Kotui Province and the Kunar dunite-harzburgite massif from the Chelyuskin ultramafic belt of the Taimyr Peninsula. The study employed a range of methods, including electron microprobe analysis, negative thermal ionization mass spectrometry (N-TIMS) and laser ablation attached to an inductively coupled plasma mass spectrometry (LA MC-ICP-MS). The majority of platinum-group minerals (PGM) from the Guli massif are Os-(Ir-Ru) solid solutions or Os-rich minerals. At Kunar, minerals of Ru-Os-Ir system (i.e., osmium, ruthenium, iridium and rutheniridosmine) dominate the PGM assemblage. The ruthenium trend in the mineral compositions is due to the formation of these minerals under high pressures and temperatures at considerable depths. The 187Os/188Os values of Os-rich minerals from the Guli massif range from 0.12309 ± 0.00002 to 0.12606 ± 0.00003 ( n = 168). The initial Os-isotopic composition of PGM from the central block of the Guli massif is characterized by the 187Os/188Os values, varying in the range 0.12404-0.12606. Osmiumrich minerals from the southwestern block of the Guli massif are characterized by the least "radiogenic" 187Os/188Os values (i.e., 0.12309-0.12341). Low relative to the chondritic universal reservoir (CHUR) 187Os/188Os values are indicative of a near-to-chondritic source of platinum-group elements (PGE). The most "productive" stage of PGM formation at Guli ( n = 121) is recorded in the time interval of 545-615 Ma. The older model 187Os/188Os ages of osmium minerals are characteristic of the southwestern block of the Guli massif (e.g., 745-760 Ma). The results of the initial Os-isotopic composition for Os-rich alloys are consistent with a model, in which PGM were formed during multi-stage melt depletion events in the mantle. This

  16. Electronic, magnetic, and transport properties of the isotypic aluminides SmT2Al10 (T = Fe, Ru)

    NASA Astrophysics Data System (ADS)

    Peratheepan, P.; Strydom, A. M.

    2015-03-01

    We report the results of a comprehensive physical and magnetic property study of the new isotypic aluminides SmT2Al10 (T = Fe, Ru). These two compounds are members of a rare-earth based system which has become an exemplary case study of the interplay of magnetism and correlated electron phenomena. SmFe2Al10 and SmRu2Al10 are found to order in a putative antiferromagnetic spin arrangement at TN = 14.5 K and 12.5 K, respectively. Moreover, SmRu2Al10 shows a further phase transition at TSR = 5 K which is likely due to spin reorientation. The susceptibility of SmFe2Al10 points to a valence instability of the Sm ionic state at intermediate temperatures well above TN. Electronic and thermal transport confirm that SmFe2Al10 undergoes an antiferromagnetic superzone gap formation below TN, whereas SmRu2Al10 suffers a lattice anomaly driven magnetoelastic coupling at TN. Below TN, the physical properties of SmT2Al10 (T = Fe, Ru) are governed by magnons with an antiferromagnetic spin-wave spectrum that reveals spin-gap opening. Our findings in this work have exposed a new anomalous correlated compound in the RT2Al10 series. SmFe2Al10 has a magnetic ordered ground state in spite of an unstable valence at higher temperature. This is comparable with CeRu2Al10, which is a unique and controversial Kondo insulator that orders antiferromagnetic at TN = 27 K. Among the series of rare-earth RT2Al10 compounds, the presented Sm compounds are two new members with anomalously high magnetic ordering temperatures, and it is envisaged that together with the two very well studied compounds CeRu2Al10 and CeOs2Al10 our presented studies will enable a broader approach towards understanding the fascinating properties of this materials class.

  17. Directional alignment of FeCo crystallites in Si/NiFe/Ru/FeCoB multilayer with high anisotropy field above 500 Oe.

    PubMed

    Hirata, Ken-Ichiro; Gomi, Shunsuke; Nakagawa, Shigeki

    2011-03-01

    In-plane magnetic anisotropy and crystal structure of FeCoB layer on Si/NiFe/Ru underlayer were investigated by using X-Ray Diffraction (XRD) measurement. A pole-figure measurement of XRD showed directionally tilted alignment of FeCo crystallites in Si/NiFe/Ru/FeCoB multilayered film with high in-plane anisotropy field H(k) but no directional alignment was found in FeCoB single layered film. The higher H(k) appeared in the Si/NiFe/Ru/FeCoB multilayered configuration with the thicker FeCoB layer. Since Ru crystallites in a multiunderlayer configuration exhibited no directional alignment, the surface structure of underlayer should be no main reason for the directional alignment of FeCo crystallites deposited on it. The dependence of hickness of FeCoB layer in Si/NiFe/Ru/FeCoB film on H(k) indicated that the in-plane magnetic anisotropy is caused by not only the structure of Ru underlayer but also oblique incidence effect of sputtered particles, which is attained in configuration of Facing Targets Sputtering (FTS) system. From these experimental results, remarkably high H(k) of 540 Oe was obtained.

  18. Stoichiometric and catalytic homologation of olefins on the Fischer-Tropsch catalysts Fe/SiO/sub 2/, Ru/SiO/sub 2/, Os/SiO/sup 2/, and Rh/SiO/sub 2/. Mechanistic implication in the mode of C-C bond formation

    SciTech Connect

    Leconte, M.; Theolier, A.; Rojas, D.; Basset, J.M.

    1984-02-22

    The formation of C/sub 4/ olefinic hydrocarbons both in CO + H/sub 2/ and C/sub 3/H/sub 6/ + H/sub 2/ reactions has been studied to test the assumption that the same mechanism is involved in the C-C bond formation in syn gas conversion and olefin hydrogenation. The yields of linear and branched olefins were measured at various contact times, and initial selectivities were obtained by extrapolation to zero conversion. The catalyst systems studied for the reactions were Fe, Ru, Rh, and Os supported by SiO/sub 2/. The results indicated that the same mechanism was involved in the C-C bond formation starting from CO + H/sub 2/, CH/sub 2/N/sub 2/ + H/sub 2/, or C/sub n/ H/sub 2n/ + H/sub 2/, and the mode of the C-C bond formation was shown to involve the addition of a C/sub 1/ fragment to a C/sub n/ fragment.

  19. Excitation Power Modulates Energy-Transfer Dynamics in a Supramolecular Ru(II) -Fe(II) -Ru(II) Triad.

    PubMed

    Kübel, Joachim; Wächtler, Maria; Dietzek, Benjamin

    2017-08-11

    Multichromophoric arrays are key to light harvesting in natural and artificial photosynthesis. A trinuclear, symmetric Ru(II) -Fe(II) -Ru(II) triad may resemble a light-harvesting model system in which excitation energy from donor units (Ru-terpyridine fragments) is efficiently transferred to the acceptor (the Fe-terpyridine fragment). The photoinduced dynamics after simultaneous excitation of more than a single chromophoric unit (donor/acceptor) at varying excitation fluence is investigated in this contribution. Data suggests that energy transfer is decelerated if the acceptor states (on the Fe(II) unit) are not depopulated fast enough. As a consequence, the lifetime of a high-lying excited state (centered on either of the Ru(II) units) is prolonged. A kinetic model is suggested to account for this effect. Although the proposed model is specifically adopted to account for the experimental data reported here, it might be generalized to other situations in which multiple energy or electron donors are covalently linked to a single acceptor site, a situation of interest in contemporary artificial photosynthesis. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. A study of thermodynamic properties of dilute Fe-Ru alloys by 57Fe Mössbauer spectroscopy

    NASA Astrophysics Data System (ADS)

    Idczak, R.; Konieczny, R.; Chojcan, J.

    2016-12-01

    The room temperature Mössbauer spectra of 57Fe were measured for Fe1- x Ru x solid solutions with x in the range 0.01 ≤ x ≤ 0.08. The obtained data were analysed in terms of short-range order parameter (SRO) and the binding energy E b between two ruthenium atoms in the studied materials using the extended Hrynkiewicz-Królas idea. The extrapolated value of E b for x = 0 was used to compute the enthalpy of solution H FeRu of Ru in Fe matrix. The result was compared with corresponding values given in the literature which were derived from experimental calorimetric data as well as with the value resulting from the cellular atomic model of alloys by Miedema. It was found that all the H FeRu values are negative or Ru atoms interact repulsively. At the same time, the Mössbauer data were used to determine values of the short-range order parameter α 1. For the as-obtained samples in which atoms are frozen-in high temperature state, close to the melting point, the negative α 1 values were found. The findings indicates ordering tendencies in such specimens. On the other hand, in the case of the annealed samples where the observed distributions of atoms should be frozen-in state corresponding to the temperature 700 K, the Fe1- x Ru x alloys with x ≥ 0.05 exhibit clustering tendencies (a predominance of Fe-Fe and Ru-Ru bonds), which manifest themselves by positive values of the calculated SRO parameter. The clustering process leads to a local increase in ruthenium concentration and nucleation of a new ruthenium-rich phase with the hcp structure.

  1. Remarkable metal-rich ternary chalcogenides Sc14M3Te8 (M = Ru, Os).

    PubMed

    Chen, Ling; Corbett, John D

    2003-02-05

    In this novel motif, scandium atoms define infinite parallel chains of alternate trans-face-sharing cubes and pairs of square antiprisms in which each polyhedron is also centered by an M atom (M = Ru, Os). These chains are further linked into a three-dimensional structure by Sc(Te2Te4/2) octahedra. Physical property measurements show Sc14Ru3Te8 to be metallic and Pauli-paramagnetic, consistent with the results of extended Hückel band structure calculations. Matrix effects are evident in the dimensions within the chains. The major interactions are Sc-M and Sc-Te.

  2. Penta- and tetracarbonyls of Ru, Os, and Hs: Electronic structure, bonding, and volatility

    NASA Astrophysics Data System (ADS)

    Pershina, V.; Iliaš, M.

    2017-05-01

    Calculations of the electronic structures and properties of M(CO)5 and M(CO)4, where M = Ru, Os, and Hs, have been performed using a variety of relativistic methods such as density functional theory and Dirac-Coulomb correlated ones implemented in program packages such as ADF, DIRAC, and ReSpect. The obtained results show that trends in spectroscopic properties of the M(CO)5 species in group 8 follow the same pattern as that of other compounds of group 4 through group 8 elements. The calculated first M-CO bond dissociation energy (FBDE) of Hs(CO)5 turned out to be significantly weaker than that of Os(CO)5. This was obtained both at the scalar relativistic and spin-orbit levels of theory. The reason for that is the relativistic destabilization and the expansion of the 6d AOs, responsible for weaker σ-forth and π-back donations in the Hs compound. Thus, the FBDEs of M(CO)5 have a Λ-shape behavior in the row Ru-Os-Hs. The non-relativistic FBDEs steadily increase in this row. Using the results of the molecular calculations and a molecule-slab dispersion interaction model, the volatility of the group-8 carbonyls was estimated as adsorption enthalpies, ΔHads, on surfaces of quartz and Teflon used in gas-phase chromatography experiments. It was found that Hs(CO)5 should be almost as volatile as the homologs; however, its interaction strength with these surfaces should be somewhat larger than that of both Ru(CO)5 and Os(CO)5, while the M(CO)4 (M = Ru, Os, and Hs) molecules should be non-volatile. It will, therefore, be difficult to distinguish between group-8 M(CO)5 species by measurements of their volatility as ΔHads on inert surfaces with error bars of ˜4 kJ/mol.

  3. Correlation between microstructure and thermionic electron emission from Os-Ru thin films on dispenser cathodes

    SciTech Connect

    Swartzentruber, Phillip D.; John Balk, Thomas; Effgen, Michael P.

    2014-07-01

    Osmium-ruthenium films with different microstructures were deposited onto dispenser cathodes and subjected to 1000 h of close-spaced diode testing. Tailored microstructures were achieved by applying substrate biasing during deposition, and these were evaluated with scanning electron microscopy, x-ray diffraction, and energy dispersive x-ray spectroscopy before and after close-spaced diode testing. Knee temperatures determined from the close-spaced diode test data were used to evaluate cathode performance. Cathodes with a large (10-11) Os-Ru film texture possessed comparatively low knee temperatures. Furthermore, a low knee temperature correlated with a low effective work function as calculated from the close-spaced diode data. It is proposed that the formation of strong (10-11) texture is responsible for the superior performance of the cathode with a multilayered Os-Ru coating.

  4. B11 NMR in the layered diborides OsB2 and RuB2

    NASA Astrophysics Data System (ADS)

    Suh, B. J.; Zong, X.; Singh, Y.; Niazi, A.; Johnston, D. C.

    2007-10-01

    B11 nuclear magnetic resonance (NMR) measurements have been performed on B11 enriched OsB2 and RuB2 polycrystalline powder samples in an external field of 4.7T and in the temperature range, 4.2KOsB2 and RuB2 , respectively. The experimental results indicate that a p character dominates the conduction electron wave function at the B site with a negligibly small s character in both compounds.

  5. Effect of Fe-Ru doping in the electronic and thermoelectric properties of new filled skutterudite Ba(Fe,Ru)4As12

    NASA Astrophysics Data System (ADS)

    Shankar, A.; Sandeep, Rai, D. P.; Thapa, R. K.; Mandal, P. K.

    2017-02-01

    We have performed the density functional theory based calculation to study the electronic and thermoelectric properties of BaFe4-xRuxAs12 (x = 0%, 25%, 50%, 75%, and 100%) within the framework of the full potential-linearized augmented plane wave method. The composite alloys are found to be stable in their optimized crystal structures and their lattice constants are in close agreement with the corresponding experimental reports. The structural stability and mechanical properties are also studied using their elastic constants. The hardness of these materials increases with increasing concentration of Ru, which also donates the covalent nature of inter-atomic bonding of BaRu4As12. The analysis of energy bands and density of states reflects the semi-metallic nature of BaFe4As12 and BaRu4As12, whereas other doped materials show metallic character. The electronic structure calculation suggests the high Seebeck coefficient with the efficient thermoelectric application of these materials. The thermal transport investigation also supports the result obtained from the electronic structure calculation. The thermoelectric efficiency defined by the figure of merit (ZT) of pure BaFe4As12 (ZT = 0.004) and BaRu4As12 (ZT = 0.005) has been enhanced to 0.357 with 75% Ru doping. The spin-polarized calculation shows a significant effect on their energy band structure, giving magnetic behavior of the sample materials. The analysis of their magnetic profile suggests the ferromagnetic nature of these materials, except BaRu4As12, which shows a paramagnetic ground state.

  6. Magnetoresistance behavior of Ni80Fe20/Ru/Ni80Fe20 nanostripes

    NASA Astrophysics Data System (ADS)

    Lupo, P.; Liu, X. M.; Adeyeye, A. O.

    2015-07-01

    We present a systematic investigation on the effects of interlayer coupling on the magnetoresistance (MR) behavior of Ni80Fe20/Ru(/Ni80Fe20 trilayer nanostripes (NSs) as a function of temperature T . By changing from 0.8 nm to 1.7 nm, either a ferromagnetic or an antiferromagnetic (AFM) type of interlayer coupling was achieved, leading to a markedly different MR behavior. We observed that the MR response is a superimposition of AMR and GMR effects, and it is significantly dependent on temperature. For AFM coupled NSs, there is a transition from a pure AFM state to a reversed spin-flop phase due to enhanced ferromagnetic pin-hole coupling at low T. Our experimental results are in good agreement with micromagnetic simulations.

  7. Characterization of Bimetallic Fe-Ru Oxide Nanoparticles Prepared by Liquid-Phase Plasma Method

    NASA Astrophysics Data System (ADS)

    Lee, Sung-Jin; Lee, Heon; Jeon, Ki-Joon; Park, Hyunwoong; Park, Young-Kwon; Jung, Sang-Chul

    2016-07-01

    The bimetallic Fe-Ru oxide nanoparticles were synthesized in the liquid-phase plasma (LPP) method which employed iron chloride and ruthenium chloride as precursors. The active species (OH·, Hα, Hβ, and OI) and the iron and ruthenium ions were observed in the plasma field created by the LPP process. The spherical-shaped bimetallic Fe-Ru oxide nanoparticles were synthesized by the LPP reaction, and the size of the particles was growing along with the progression of the LPP reaction. The synthesized bimetallic Fe-Ru oxide nanoparticles were comprised of Fe2O3, Fe3O4, RuO, and RuO2. Ruthenium had a higher reduction potential than iron and resulted in higher ruthenium composition in the synthesized bimetallic nanoparticles. The control of the molar ratio of the precursors in the reactant solution was found to be employed as a means to control the composition of the elements in bimetallic nanoparticles.

  8. Tuning of interlayer exchange coupling in Ni80Fe20/Ru/Ni80Fe20 nanowires

    NASA Astrophysics Data System (ADS)

    Liu, X. M.; Lupo, P.; Cottam, M. G.; Adeyeye, A. O.

    2015-09-01

    In this work, we demonstrate how the static and dynamic properties of Ni80Fe20/Ru/Ni80Fe20 nanowires can be tuned by varying the Ru spacer layer thickness. Specifically, changing the Ru thickness we have tuned the Ruderman-Kittel-Kasuya-Yosida exchange interaction, and thus the antiferromagnetic (AFM) strength between the Ni80Fe20 layers. We show that there is a strong correlation between the interlayer coupling and features in ferromagnetic resonance (FMR) modes. We found different mode-softening degree of the FMR curves as function of the strength of AFM coupling, together with a clear frequency gap at around zero field. These experimental results are in qualitative agreement with presented micromagnetic simulations that also include biquadratic interface exchange. Understanding these characteristics may offer insights for reconfigurable vertical magnetic logic devices and microwave filters.

  9. Fe Substitution Effect on the High-Field Magnetization in the Kondo Semiconductor CeRu2Al10

    NASA Astrophysics Data System (ADS)

    Kondo, Akihiro; Kindo, Koichi; Nohara, Hiroki; Nakamura, Michio; Tanida, Hiroshi; Sera, Masafumi; Nishioka, Takashi

    2017-02-01

    The magnetization of the Fe substitution system in the Kondo semiconductor CeRu2Al10 was measured in high magnetic fields of up to 72 T with the magnetic field (H) along the a-axis. The magnetization curve indicates that the critical field from the antiferromagnetic (AFM) phase to the paramagnetic one (Hcp) shows an increase from ˜51 (x = 0) to ˜60 T (x = 0.7) owing to the Fe substitution. The Fe concentration dependence of Hcp is similar to that of the magnitude of the energy of the spin gap. The degree of the concave H dependence of the magnetization curve, which is the characteristic feature for H ∥ a in CeT2Al10 (T = Ru, Os), is not strongly enhanced by the Fe substitution. This may be due to the suppression of the strong anisotropy of the hybridization between the conduction band and the localized 4f shell along the a-axis. These results reveal that the spin gap of the present system consists of at least two components, the gap due to the spin (Kondo) singlet formation and the anisotropy gap of the AF magnon.

  10. Magnetic properties of ultrathin Ni81Fe19 films with Ta and Ru capping layers.

    PubMed

    Kezilebieke, S; Ali, M; Shadeke, B; Gunnella, R

    2013-11-27

    Magnetic properties of Ni81Fe19 (permalloy) ultrathin films with Ru and Ta capping layers (CLs) were investigated for applications to magnetic random access memory units (MRAM). The sample structure, which simulated an MRAM free layer, is Si- sub./SiO2/Ni81Fe19/Ru(Ta). The Ni81Fe19 thin films less than 3 nm thick with Ru CL show low coercive fields compared with the Ta capping layer. Both systems showed loss of momentum equivalent to magnetically dead layers of thickness (δ) ~0.6 nm for Ru cap layer and ~1.4 nm for Ta cap layer, respectively. Moreover, after annealing the thicknesses are slightly increased to an equivalent magnetic dead layer thickness of δ ~0:84 nm and ~1.80 nm for Ru and Ta CL, respectively. Our calculations showed that the presence of only 11% Ta concentration at the interface reduced the Ni momentum to zero, with the Ni–Ta coupling being anti-ferromagnetic; while 50% Ru intermixing at the interface reduced the Ni momentum to zero with the coupling between Ru and Ni being ferromagnetic. To find out more about the intermixing at the interface, the composition and chemical states were characterized by the x-ray photoelectron spectroscopy and peak decomposition technique. The result showed that the peak positions were different from the pure metallic case at the interface region, mainly because of the intermixing between two layers. In conclusion, the Ru capping layer might be important for MRAM use in terms of low coercive field and small δ layer thickness if compared with the Ta capping layer.

  11. Reduction of critical current in magnetic tunnel junctions with CoFeB/Ru/CoFeB synthetic free layer

    NASA Astrophysics Data System (ADS)

    Zaleski, A.; Skowronski, W.; Czapkiewicz, M.; Kanak, J.; Stobiecki, T.; Macedo, R.; Cardoso, S.; Freitas, P. P.

    2010-01-01

    Reduction of the critical current density (Jc) in magnetic tunnel junctions (MTJs) can be achieved by replacing the standard Co40Fe40B20 free layer with a synthetic antiferromagnet. Patterned MTJs prepared by ion-beam assisted deposition (nanopillars, sizes down to 60 nm × 80 nm) with 2 nm CoFeB free layer and Co40Fe40B20/Ru (tRu)/ Co40Fe40B20 as a synthetic free layer (SyF) were studied. We have measured critical current density of CIMS in thermally activated switching regime (long current pulses). Values of switching current densities for standard MTJs with SyF were of the order 106 A/cm2, whilst MTJs with standard free layer demonstrated up to four times higher values of Jc.

  12. Multichromophoric hybrid species made of perylene bisimide derivatives and Ru(ii) and Os(ii) polypyridine subunits.

    PubMed

    Nastasi, Francesco; La Ganga, Giuseppina; Campagna, Sebastiano; Syrgiannis, Zois; Rigodanza, Francesco; Vitale, Stefania; Licciardello, Antonino; Prato, Maurizio

    2017-05-31

    Herein, the synthesis and the photophysical and redox properties of a new perylene bisimide (PBI) species (L), bearing two 1,10-phenanthroline (phen) ligands at the two imide positions of the PBI, and its dinuclear Ru(ii) and Os(ii) complexes, [(bpy)2Ru(μ-L)Ru(bpy)2](PF6)4 (Ru2; bpy = 2,2'-bipyridine) and [(Me2-bpy)2Os(μ-L)Os(Me2-bpy)2](PF6)4 (Os2; Me2-bpy = (4,4'-dimethyl)-2,2'-bipyridine), are reported. The absorption spectra of the compounds are dominated by the structured bands of the PBI subunit due to the lowest-energy spin-allowed π-π* transition. The spin-allowed MLCT transitions in Ru2 and Os2 are inferred by the absorption at 350-470 nm, where the PBI absorption is negligible. The absorption band extends towards the red region for Os2 due to the spin-forbidden MLCT transitions, intensified by the heavy osmium center. The reduction processes of the compounds are dominated by two successive mono-electronic PBI-based processes, which in the metal complexes are slightly shifted compared to the free ligand. On oxidation, both metal complexes undergo an apparent bi-electronic process (at 1.31 V vs. SCE for Ru2 and 0.77 V for Os2), attributed to the simultaneous one-electron oxidation of the two weakly-interacting metal centers. In Ru2 and Os2, the intense fluorescence of L subunit (λmax, 535 nm; τ, 4.3 ns; Φ, 0.91) is fully quenched, mainly by photoinduced electron transfer from the metal centers, on the ps timescale (time constant, 11 ps in Ru2 and 3 ps in Os2). Such photoinduced electron transfer leads to the formation of a charge-separated state, which directly decays to the ground state in about 70 ps in Os2, but produces the triplet π-π* state of the PBI subunit in 35 ps in Ru2. The results provide information on the excited-state processes of the hybrid species combining two dominant classes of chromophore/luminophore species, the PBI and the metal polypyridine complexes, and can be used for future design on new hybrid species with made

  13. Unusual sevenfold coordination of Ru in complex hydride Na3RuH7: Prospect for formation of [FeH7]3- anion

    NASA Astrophysics Data System (ADS)

    Takagi, Shigeyuki; Ikeshoji, Tamio; Matsuo, Motoaki; Sato, Toyoto; Saitoh, Hiroyuki; Aoki, Katsutoshi; Orimo, Shin-ichi

    2013-09-01

    We used density-functional calculations to clarify the origin of the unusual sevenfold coordination of Ru by H in Na3RuH7. We found that the D5h symmetry of the ligands enables the formation of strong covalent bonds of Ru and H through ligand-field effects, stabilizing the sevenfold coordination. We also examined the possible synthesis of the hypothetical 3d analog, Li3FeH7, which has a gravimetric hydrogen density of 8.4 mass%. The calculated enthalpy change of -16 kJ/mol H2 for the reaction, 3LiH+Fe+2H2→Li3FeH7, reveals a possible route to a stable complex hydride containing [FeH7]3-.

  14. Coupled Nd and B' spin ordering in the double perovskites Nd2NaB'O6 (B' = Ru, Os)

    SciTech Connect

    Aczel, Adam A; Bugaris, Dan; Yeon, Jeongho; Dela Cruz, Clarina R; Zur Loye, Hans-Conrad; Nagler, Stephen E

    2013-01-01

    We present a neutron powder diffraction study of the monoclinic double perovskite systems Nd$_2$NaB$'$O$_6$ (B$'$~$=$~Ru, Os), with magnetic atoms occupying both the A and B$'$ sites. Our measurements reveal coupled spin ordering between the Nd and B$'$ atoms with magnetic transition temperatures of 14~K for Nd$_2$NaRuO$_6$ and 16~K for Nd$_2$NaOsO$_6$. There is a Type I antiferromagnetic structure associated with the Ru and Os sublattices, with the ferromagnetic planes stacked along the c-axis and [110] direction respectively, while the Nd sublattices exhibit complex, canted antiferromagnetism with different spin arrangements in each system.

  15. Effects of hydrogen adsorption on the electronic and magnetic structures for variant terminations of NbRu (001) and M/NbRu (001) surfaces (M=Fe, Ni)

    NASA Astrophysics Data System (ADS)

    Mubarak, A. A.

    2013-06-01

    Density functional theory (DFT) calculations are performed using the full-potential linearized augmented plane wave (FP-LAPW) and generalized gradient approximation (GGA). The present study investigates the energetic, electronic and magnetic properties of the variant terminations of NbRu (001) with and without hydrogen atoms. The effects of Fe or Ni overlayer on the above properties are also investigated. Hydrogen atoms are found to prefer the octahedral sites in the bulk NbRu β-phase system. Absorbed H atoms act as a dilation center and cause a decrease of the cohesive energy of the NbRu β-phase system. Ru/NbRu (001) surface is found most stable and suitable for epitaxial growth deposition. The adsorption of H atoms on Ru/NbRu (001) surface is more energetic than that on Nb/NbRu (001) surface. Ferromagnetic order is found for Fe and Ni atoms in M/Ru/Nb/Ru (001) and M/Nb/Ru/Nb (001) surfaces (M=Fe, Ni). The adsorption of hydrogen is found to be preferable at the hollow fourfold sites on both H/Fe/Ru/Nb/Ru (001) and H/Fe/Nb/Ru/Nb (001) surfaces, while it prefers the bridge site on both H/Ni/Ru/Nb/Ru (001) and H/Ni/Nb/Ru/Nb (001) surfaces. A marked reduction of the local density of states at Fermi level and the magnetic moments of M surface layer is observed due to the presence of hydrogen.

  16. Pair distribution function analysis of La(Fe{sub 1−x}Ru{sub x})AsO compounds

    SciTech Connect

    Martinelli, A.; Palenzona, A.; Ferdeghini, C.; Mazzani, M.; Bonfa', P.; Allodi, G.

    2014-12-15

    The local structures of La(Fe{sub 1−x}Ru{sub x})AsO (0.00≤x≤0.80) compounds were investigated by means of pair distribution function analysis at room temperature; as a result, no phase separation or clustering takes place. Local distortions are no longer correlated beyond ∼15 Å for both pure and substituted samples, indicating that the presence of Ru atoms does not determine a notable variation in the length scale of the local distortion. Different types of short range correlation between Fe and Ru atoms do not produce significant changes in the pair distribution function. - Graphical abstract: Fe–As and Ru–As bond length distributions as obtained by pair distribution function analysis of La(Fe{sub 0.70}Ru{sub 0.30})AsO; As atoms (purple spheres) undergo a random shifting around their crystallographic positions (red spheres: Fe/Ru atoms). - Highlights: • No phase separation or clustering takes place in La(Fe{sub 1−x}Ru{sub x})AsO solid solutions. • Local distortions are no longer correlated beyond ∼15 Å. • Ru displays a tendency towards local enrichment in the transition metal sublattice.

  17. Disorder influenced magnetic phase transition in the Ce(Fe 0.9 Ru 0.1)2 alloy.

    PubMed

    Chattopadhyay, M K; Roy, S B

    2010-06-16

    We have studied a 10% Ru-doped CeFe(2) alloy, Ce(Fe(0.9)Ru(0.1))(2), through magnetization, magnetotransport, and heat capacity measurements. This study shows that, while this alloy is antiferromagnetic at low temperatures and paramagnetic at high temperatures, there exists evidence of ferromagnetic ordering in the intermediate temperature regime. We show here that with 10% Ru doping the first order magnetic transition observed in the Ce(Fe(1 - x)Ru(x))(2) alloys with x < 0.08 is reduced to a quasi-continuous phase transition. The characteristic thermomagnetic history effects associated with the ferromagnetic-antiferromagnetic phase transition in the Ce(Fe(1 - x)Ru(x))(2) alloys with x < 0.08 are not observed in the Ce(Fe(0.9)Ru(0.1))(2) alloy. This alloy continues to exhibit the large magnetoresistance and large magnetocaloric effect associated with this first order magnetic transition in the alloys with smaller Ru concentration, but it does not show any energy loss due to thermomagnetic hysteresis. The present work thus shows how the introduction of quenched disorder due to alloying effects may be used to tune the first order magnetic transition in a material for more efficient functional use.

  18. Spin density wave (SDW) transition in Ru doped BaFeAs{sub 2} investigated by AC steady state calorimetry

    SciTech Connect

    Vinod, K. Sharma, Shilpam; Sundar, C. S.; Bharathi, A.

    2015-06-24

    Heat capacity measurements were done on sub-micron sized BaFe{sub 2−x}Ru{sub x}As{sub 2} single crystals using thin film membrane based the AC steady state calorimetry technique. Noticeable thermal hysteresis is observed in the heat capacity of the BaFe{sub 2−x}Ru{sub x}As{sub 2} during cooling and warming cycles, indicating first order nature of the SDW transition.

  19. Study of anodic dissolution of Fe-Ru alloy with the aid of mossbauer spectroscopy

    SciTech Connect

    Khlystov, A.S.; Fasman, A.B.; Kil'dibekova, G.A.

    1986-01-10

    This paper uses Fe 57 Mossbauer spectroscopy, whereby iron compounds may be identified quantitatively and their composition and structure can be determined, for the study of the relationships of slime formation from Fe-Ru binary alloys. Both the products of dissolution and the composition and state of intermediate phases formed at various stages of anodic dissolution were studied simultaneously. It was found that the slimes formed both during chemical and during electrochemical destruction of ruthenium-iron alloys are finely dispersed systems of complex composition, analogous to those formed in the course of electrochemical dissolution of Ni-Ru alloys, which were found to contain oxide phases of ruthenium (by x-ray spectroscopy and ESCA) and of nickel (by x-ray phase analysis). The difference between the slime compositions is determined mainly by kinetic factors.

  20. Ferromagnetic quantum critical point in heavy-fermion iron oxypnictide Ce(Ru(1-x)Fe(x))PO.

    PubMed

    Kitagawa, S; Ishida, K; Nakamura, T; Matoba, M; Kamihara, Y

    2012-11-30

    We have performed (31)P-NMR measurements on Ce(Ru(1-x)Fe(x))PO in order to investigate ferromagnetic (FM) quantum criticality, since a heavy-fermion (HF) ferromagnet CeRuPO with a two-dimensional structure turns into a HF paramagnet by an isovalent Fe substitution for Ru. We found that Ce(Ru(0.15)Fe(0.85))PO shows critical fluctuations down to ~0.3 K, as well as the continuous suppression of Curie temperature and the ordered moments by the Fe substitution. These experimental results suggest the presence of a FM quantum critical point (QCP) at x~0.86, which is a rare example among itinerant ferromagnets. In addition, we point out that the critical behaviors in Ce(Ru(0.15)Fe(0.85))PO share a similarity with those in YbRh(2)Si(2), where the local criticality of f electrons has been discussed. We reveal that Ce(Ru(1-x)Fe(x))PO is a new system to study FM quantum criticality in HF compounds.

  1. Ferromagnetic resonance study of structure and relaxation of magnetization in NiFe/Ru superlattices

    NASA Astrophysics Data System (ADS)

    Alayo, W.; Landi, S., Jr.; Pelegrini, F.; Baggio-Saitovitch, E.

    2014-01-01

    The structural properties and relaxation processes of magnetization in [Ni81Fe19(t1)/Ru(t2)]N superlattices (N=number of bilayers) were analyzed by ferromagnetic resonance (FMR) with a fixed microwave frequency. One series of samples was deposited with constant NiFe layer thickness (t1) and variable Ru layer thickness (t2); the other series, with constant t2 and variable t1. A single FMR mode was observed for t2<15 Å and t1>75 Å and it has been attributed to the resonance of the exchange-coupled NiFe layers across the Ru interlayers. For the other values of t1 and t2, several FMR modes appeared and they were associated to non-coupled magnetic phases with different effective magnetization formed during the multilayer growth. The FMR linewidths were analyzed as a function of the magnetic layer thickness and a strong dependence on t1-2 was observed. It was attributed to the contribution of the two-magnon scattering mechanism for the linewidth.

  2. Modifying exchange-spring behavior of CoPt/NiFe bilayer by inserting a Pt or Ru spacer

    SciTech Connect

    Hsu, Jen-Hwa Tsai, C. L.; Lee, C.-M.; Saravanan, P.

    2015-05-07

    We herein explore the possibility of obtaining tunable tilted magnetic anisotropy in ordered-CoPt (5 nm)/NiFe(t{sub NiFe}) bilayers through modifying their exchange spring behavior by inserting Pt and Ru-spacers. The tuning process of tilt angle magnetization of NiFe-layer was systematically investigated by varying the Pt or Ru thickness (t{sub Pt} or t{sub Ru}) from 0 to 8 nm at different thicknesses of NiFe (t{sub NiFe} = 1.5, 4.0, and 6.0 nm). Polar magneto-optic Kerr effect (p-MOKE) studies reveal that the bilayers grown in absence of spacers exhibit almost a rectangular hysteresis loop. With the insertion of Pt-spacer, the loop becomes more and more tilted as t{sub Pt} increases; whereas, in the case of Ru-spacer, the nature of the loops is not simply changing in one direction. The estimated SQR{sub ⊥} (= θ{sub r}/θ{sub s}) values from the p-MOKE loops are found to monotonically decrease with increasing t{sub Pt} when t{sub Pt} ≦ 4 nm. In contrast, in the case of Ru-spacer, an oscillatory behavior for the SQR{sub ⊥} values is apparent when t{sub Ru} ≦ 4 nm. As a result, an oscillatory tilted angle of NiFe spin configuration was obtained in the case of Ru-spacer; while a decoupling effect was prominent for the Pt-spacer. The results of present study reveal that the insertion of Pt and Ru-spacers as an appropriate means for realizing tunable tilted magnetic anisotropy in the CoPt/NiFe exchange springs.

  3. Tuning the magnetic and structural phase transitions of PrFeAsO via Fe/Ru spin dilution

    SciTech Connect

    Yiu, Yuen; Bonfa, Pietro; Sanna, Samuele; De Renzi, Roberto; Caretta, Pietro; McGuire, Michael A; Huq, Ashfia; Nagler, Stephen E

    2014-01-01

    Neutron diffraction and muon spin relaxation measurements are used to obtain a detailed phase diagram of PrFe1{xRuxAsO. The isoelectronic substitution of Ru for Fe acts eectively as spin dilution, suppressing both the structural and magnetic phase transitions. The temperature, TS, of the tetragonal-orthorhombic structural phase transition decreases gradually as a function of x. Slightly below TS coherent precessions of the muon spin are observed corresponding to static magnetism, possibly re ecting a signicant magneto-elastic coupling in the FeAs layers. Short range order in both the Fe and Pr moments persists for higher levels of x. The static magnetic moments disappear at a concentration coincident with that expected for percolation of the J1 - J2 square lattice model.

  4. σ-Aromaticity in polyhydride complexes of Ru, Ir, Os, and Pt.

    PubMed

    Jimenez-Izal, Elisa; Alexandrova, Anastassia N

    2016-04-28

    Transition-metal hydrides represent a unique class of compounds, which are essential for catalysis, organic synthesis, and hydrogen storage. In this work we study IrH5(PPh3)2, (RuH5(P(i)Pr3)2)(-), (OsH5(P(i)Pr3)2)(-), and OsH4(PPhMe2)3 polyhydride complexes, inspired by the recent discovery of the σ-aromatic PtZnH5(-) cluster anion. The distinctive feature of these molecules is that, like in the PtZnH5(-) cluster, the metal is five-fold coordinated in-plane, and holds additional ligands at the axial positions. This work shows that the unusual coordination in these compounds indeed can be explained by σ-aromaticity in the pentagonal arrangement, stabilized by the atomic orbitals on the metal. Based on this newly elucidated bonding principle, we additionally propose a new family of polyhydrides that display a uniquely high coordination. We also report the first indications of how aromaticity may impact the reactivity of these molecules.

  5. Effects of Ru and Ag cap layers on microstructure and magnetic properties of FePt ultrathin films.

    PubMed

    Liu, Mingfeng; Jin, Tianli; Hao, Liang; Cao, Jiangwei; Wang, Ying; Wu, Dongping; Bai, Jianmin; Wei, Fulin

    2015-01-01

    The effects of Ru and Ag cap layers on the microstructure and magnetic properties of the FePt ultrathin films have been investigated. The results indicate that i) The Ag cap layer segregates from the FePt/Ag bilayer, lowers the FePt ordering temperature, promotes the FePt thin films to form island structure, and enhances the coercivity; ii) The Ru cap layer increases the FePt ordering temperature, helps to maintain smooth continuous structure film, and restrains the FePt (001) orientation and perpendicular magnetic anisotropy (PMA). The effects become more pronounced for the 3-nm-thick FePt thin films. The effects can be mainly attributed to the different melting point and thermal expansion stress between the cap layer and FePt thin films.

  6. Effects of Ru and Ag cap layers on microstructure and magnetic properties of FePt ultrathin films

    NASA Astrophysics Data System (ADS)

    Liu, Mingfeng; Jin, Tianli; Hao, Liang; Cao, Jiangwei; Wang, Ying; Wu, Dongping; Bai, Jianmin; Wei, Fulin

    2015-04-01

    The effects of Ru and Ag cap layers on the microstructure and magnetic properties of the FePt ultrathin films have been investigated. The results indicate that i) The Ag cap layer segregates from the FePt/Ag bilayer, lowers the FePt ordering temperature, promotes the FePt thin films to form island structure, and enhances the coercivity; ii) The Ru cap layer increases the FePt ordering temperature, helps to maintain smooth continuous structure film, and restrains the FePt (001) orientation and perpendicular magnetic anisotropy (PMA). The effects become more pronounced for the 3-nm-thick FePt thin films. The effects can be mainly attributed to the different melting point and thermal expansion stress between the cap layer and FePt thin films.

  7. Ru Catalyst-Induced Perpendicular Magnetic Anisotropy in MgO/CoFeB/Ta/MgO Multilayered Films.

    PubMed

    Liu, Yiwei; Zhang, Jingyan; Wang, Shouguo; Jiang, Shaolong; Liu, Qianqian; Li, Xujing; Wu, Zhenglong; Yu, Guanghua

    2015-12-09

    The high oxygen storage/release capability of the catalyst Ru is used to manipulate the interfacial electronic structure in spintronic materials to obtain perpendicular magnetic anisotropy (PMA). Insertion of an ultrathin Ru layer between the CoFeB and Ta layers in MgO/CoFeB/Ta/MgO films effectively induces PMA without annealing. Ru plays a catalytic role in Fe-O-Ta bonding and isolation at the metal-oxide interface to achieve moderate interface oxidation. In contrast, PMA cannot be obtained in the sample with a Mg insertion layer or without an insertion layer because of the lack of a catalyst. Our work would provide a new approach toward catalyst-induced PMA for future CoFeB-based spintronic device applications.

  8. Spin-orbit torque in Cr/CoFeAl/MgO and Ru/CoFeAl/MgO epitaxial magnetic heterostructures

    SciTech Connect

    Wen, Zhenchao; Kim, Junyeon; Sukegawa, Hiroaki; Hayashi, Masamitsu; Mitani, Seiji

    2016-05-15

    We study the spin-orbit torque (SOT) effective fields in Cr/CoFeAl/MgO and Ru/CoFeAl/MgO magnetic heterostructures using the adiabatic harmonic Hall measurement. High-quality perpendicular-magnetic-anisotropy CoFeAl layers were grown on Cr and Ru layers. The magnitudes of the SOT effective fields were found to significantly depend on the underlayer material (Cr or Ru) as well as their thicknesses. The damping-like longitudinal effective field (ΔH{sub L}) increases with increasing underlayer thickness for all heterostructures. In contrast, the field-like transverse effective field (ΔH{sub T}) increases with increasing Ru thickness while it is almost constant or slightly decreases with increasing Cr thickness. The sign of ΔH{sub L} observed in the Cr-underlayer devices is opposite from that in the Ru-underlayer devices while ΔH{sub T} shows the same sign with a small magnitude. The opposite directions of ΔH{sub L} indicate that the signs of spin Hall angle in Cr and Ru are opposite, which are in good agreement with theoretical predictions. These results show sizable contribution from SOT even for elements with small spin orbit coupling such as 3d Cr and 4d Ru.

  9. What Controls the Phase Diagram and Superconductivity in Ru-Substituted BaFe2As2?

    SciTech Connect

    Dhaka, R. S.; Liu, Chang; Fernandes, R.M.; Jiang, Riu; Strehlow, C.P.; Kondo, Takeshi; Thaler, A.; Schmalian, Joerg; Bud-ko, S.J.; Canfield, P.C.; Kaminski, A.

    2011-12-23

    We use high resolution angle-resolved photoemission to study the electronic structure of the iron based high-temperature superconductors Ba(Fe{sub 1-x}Ru{sub x}){sub 2}As{sub 2} as a function of Ru concentration. We find that substitution of Ru for Fe is isoelectronic, i.e., it does not change the value of the chemical potential. More interestingly, there are no measured, significant changes in the shape of the Fermi surface or in the Fermi velocity over a wide range of substitution levels (0 < x < 0.55). Given that the suppression of the antiferromagnetic and structural phase is associated with the emergence of the superconducting state, Ru substitution must achieve this via a mechanism that does not involve changes of the Fermi surface. We speculate that this mechanism relies on magnetic dilution which leads to the reduction of the effective Stoner enhancement.

  10. Enhanced nonvolatile holographic properties in Zn, Ru and Fe co-doped LiNbO3 crystals

    NASA Astrophysics Data System (ADS)

    Xu, Chao; Leng, Xuesong; Xu, Lei; Wen, Aihua; Xu, Yuheng

    2012-08-01

    A series of LiNbO3 crystals doped with various concentrations of ZnO and fixed concentrations of RuO2 and Fe2O3 have been grown by the Czochralski method from the congruent melts. The type of charge carriers was determined by Kr+ laser (476 nm) and He-Ne laser (633 nm). The results revealed that the holes were the dominant charge carriers at blue light irradiation. Dual-wavelength and two-color techniques were employed to investigate the nonvolatile holographic storage properties of Ru:Fe:LiNbO3 and Zn doped Ru:Fe:LiNbO3 crystals. The essential parameters of blue nonvolatile holographic storage in Zn:Ru:Fe:LiNbO3 crystals were enhanced greatly with the increase of Zn concentration. This indicates that the damage resistant dopants Zn2+ ions enhance the photorefractive properties at 476 nm wavelength instead of suppressing the photorefraction. The different mechanisms of blue photorefractive and nonvolatile holographic storage properties by dual wavelength recording in Zn:Ru:Fe:LiNbO3 crystals were discussed.

  11. Structural, electronic, and magnetic properties near the Fe(111) surface with a Mo, Ru, or Pd overlayer

    NASA Astrophysics Data System (ADS)

    Geng, W. T.; Freeman, A. J.; Wu, R.

    2000-03-01

    Structural, electronic, and magnetic properties near the Fe(111) surface, with and without a 4d transition metal overlayer of A (A= Mo, Ru, or Pd), are determined by means of the full-potential linearized augmented plane wave (FLAPW)(Wimmer, Krakauer, Weinert and Freeman, PRB) 24, 864 (1981). total energy/atomic force method with the generalized gradient approximation (GGA). Both the clean and A adsorbed surface are simulated by a 13-layer slab. When the surface Fe is replaced by A, multilayer relaxation is found to be extended to the fourth subsurface layer, indicating a long-distance perturbation. The calculated work function for the clean surface is 4.31 eV, in good agreement with the experiment (4.5 eV) and other first-principles results. It is increased by both Ru (to 4.62 eV) and Pd (to 4.89 eV), as expected from the fact that pure Ru and Pd metals have higher work functions than does Fe. Mo overlayer, however, lowers the work function to 3.98 eV, although the pure Mo metal also has a work function higher than Fe. We find that Mo couples anti-ferromagnetically and Ru and Pd couple ferromagnetically with the Fe(111) surface. The induced spin magnetic moment for Mo, Ru, and Pd is -0.79, 0.81, and 0.47 μ_B, respectively.

  12. Ferromagnetic resonance study of interface coupling for spin waves in narrow NiFe/Ru/NiFe multilayer nanowires

    NASA Astrophysics Data System (ADS)

    Lupo, P.; Haghshenasfard, Z.; Cottam, M. G.; Adeyeye, A. O.

    2016-12-01

    A systematic investigation is presented for the magnetization dynamics in trilayer nanowires, consisting of two permalloy (Ni80Fe20 ) layers separated by a nonmagnetic Ru spacer layer. The width of the wires ranges from 90 to 190 nm. By varying the Ru thickness between 0.7 and 2.0 nm, the interlayer coupling can be effectively controlled, modifying the corresponding magnetic ground state and the spin-wave dynamics. By contrast with previous work on coupled trilayer nanowires with larger widths (270 nm and more), the focus here is on nanowire arrays where the strong shape anisotropy competes with the Ruderman-Kittel-Kasuya-Yosida interactions and biquadratic exchange interactions across the Ru interface, as well as dipolar interactions and Zeeman energy. As a result, the spin-wave spectrum is found to be drastically modified. Ferromagnetic resonance and hysteresis loop measurements are reported over a wide range of applied magnetic fields, showing that the overall magnetization alignment between the permalloy layers may be parallel, antiparallel, or in a spin-flop state, depending on the overall interlayer coupling. The experimental results for different stripe widths are successfully analyzed using a microscopic dipole-dipole theory and micromagnetic simulations.

  13. Lattice dynamics and thermophysical properties of h.c.p. Os and Ru from the quasi-harmonic approximation

    NASA Astrophysics Data System (ADS)

    Palumbo, Mauro; Dal Corso, Andrea

    2017-10-01

    We report first-principles phonon frequencies and anharmonic thermodynamic properties of h.c.p. Os and Ru calculated within the quasi-harmonic approximation, including Grüneisen parameters, temperature-dependent lattice parameters, thermal expansion, and isobaric heat capacity. We discuss the differences between a full treatment of anisotropy and a simplified approach with a constant c/a ratio. The results are systematically compared with the available theoretical and experimental data and an overall satisfactory agreement is obtained.

  14. Lattice dynamics and thermophysical properties of h.c.p. Os and Ru from the quasi-harmonic approximation.

    PubMed

    Palumbo, Mauro; Dal Corso, Andrea

    2017-10-04

    We report first-principles phonon frequencies and anharmonic thermodynamic properties of h.c.p. Os and Ru calculated within the quasi-harmonic approximation, including Grüneisen parameters, temperature-dependent lattice parameters, thermal expansion, and isobaric heat capacity. We discuss the differences between a full treatment of anisotropy and a simplified approach with a constant [Formula: see text] ratio. The results are systematically compared with the available theoretical and experimental data and an overall satisfactory agreement is obtained.

  15. Strong uniaxial magnetic anisotropy in CoFe films on obliquely sputtered Ru underlayer

    SciTech Connect

    Fukuma, Y.; Lu, Z.; Fujiwara, H.; Mankey, G. J.; Butler, W. H.; Matsunuma, S.

    2009-10-01

    Co{sub 90}Fe{sub 10} films with an in-plane uniaxial magnetic anisotropy have been grown on an obliquely sputtered thin Ru underlayer. The anisotropy field can be increased up to 200 Oe. The hysteresis curves show a very high squareness in the easy axis direction and almost no hysteresis in the hard axis direction, suggesting that the induced uniaxial anisotropy is uniform throughout the films. The switching characteristics of the nanoelements fabricated from the films by e-beam lithography are also investigated. There is no degradation of the magnetic anisotropy after the annealing and lithographical process.

  16. Magnetic, magnetocaloric properties and phenomenological model in amorphous Fe60Ru20B20 alloy

    NASA Astrophysics Data System (ADS)

    Boutahar, A.; Lassri, H.; Hlil, E. K.

    2015-11-01

    Magnetic, magnetocaloric properties and phenomenological model of amorphous Fe60Ru20B20 alloy are investigated in detail. The amorphous alloy has been synthesized using melt spinning method. The magnetic transition nature undergoes a second-order magnetic phase transition from ferromagnetic to paramagnetic states with a Curie temperature of 254 K. Basis on the thermodynamic Maxwell's relation, magnetic entropy change (-ΔSM) is calculated. Further, we also report a theoretical investigation of the magnetocaloric effect using a phenomenological model. The best model parameters and their variation with temperature and the magnetic field were determined. The theoretical predictions are found to agree closely with experimental measurements.

  17. Isotopic studies of Mg, Fe, Mo, RU and W in Fremdlinge from Allende refractory inclusions

    NASA Astrophysics Data System (ADS)

    Hutcheon, I. D.; Armstrong, J. T.; Wasserburg, G. J.

    1987-12-01

    This paper presents the first isotopic measurements, made with an ion microprobe, of Mg, Fe, Mo, Ru, and W in Fremdlinge and refractory metal nuggets from Allende meteorite. No non-mass-dependent deviations exceeding 1 percent from normal solar isotopic abundances were found for any of the elements analyzed, despite the unusual mineralogy of Fremdlinge and the extreme enrichment in refractory siderophile elements. It is concluded that the chemical, petrologic, and isotopic data on Fremdlinge are most plausibly interpreted in terms of the origin of Fremdlinge within the solar nebula.

  18. Tracking antitumor metallodrugs: promising agents with the Ru(II)- and Fe(II)-cyclopentadienyl scaffolds.

    PubMed

    Morais, Tânia S; Valente, Andreia; Tomaz, Ana Isabel; Marques, Fernanda; Garcia, Maria Helena

    2016-04-01

    Research on the field of metal complexes for the treatment of cancer diseases has attracted increasing interest due to the urgency in finding more efficient and selective treatments. Owing to their wide structural diversity, organometallic complexes appear as potential alternatives to the design of new anticancer candidates. Herein, we review recent progress in our work toward the development of new drugs based on Ru(II)- and Fe(II)-cyclopentadienyl scaffolds. Their design and chemical properties are reviewed and correlated with their biological effects, in particular the key role that coligands play in the overall behavior of the complex.

  19. Isotopic studies of Mg, Fe, Mo, Ru and W in Fremdlinge from Allende refractory inclusions

    NASA Technical Reports Server (NTRS)

    Hutcheon, Ian D.; Armstrong, John T.; Wasserburg, G. J.

    1987-01-01

    This paper presents the first isotopic measurements, made with an ion microprobe, of Mg, Fe, Mo, Ru, and W in Fremdlinge and refractory metal nuggets from Allende meteorite. No non-mass-dependent deviations exceeding 1 percent from normal solar isotopic abundances were found for any of the elements analyzed, despite the unusual mineralogy of Fremdlinge and the extreme enrichment in refractory siderophile elements. It is concluded that the chemical, petrologic, and isotopic data on Fremdlinge are most plausibly interpreted in terms of the origin of Fremdlinge within the solar nebula.

  20. Non-Fermi surface nesting driven commensurate magnetic ordering in Fe-doped S r2Ru O4

    NASA Astrophysics Data System (ADS)

    Zhu, M.; Shanavas, K. V.; Wang, Y.; Zou, T.; Sun, W. F.; Tian, W.; Garlea, V. O.; Podlesnyak, A.; Matsuda, M.; Stone, M. B.; Keavney, D.; Mao, Z. Q.; Singh, D. J.; Ke, X.

    2017-02-01

    S r2Ru O4 , an unconventional superconductor, is known to possess an incommensurate spin-density wave instability driven by Fermi surface nesting. Here we report a static spin-density wave ordering with a commensurate propagation vector qc=(0.25 0.25 0 ) in Fe-doped S r2Ru O4 , despite the magnetic fluctuations persisting at the incommensurate wave vectors qic=(0.3 0.3 L ) as in the parent compound. The latter feature is corroborated by the first-principles calculations, which show that Fe substitution barely changes the nesting vector of the Fermi surface. These results suggest that in addition to the known incommensurate magnetic instability, S r2Ru O4 is also in proximity to a commensurate magnetic tendency that can be stabilized via Fe doping.

  1. Non-Fermi surface nesting driven commensurate magnetic ordering in Fe-doped Sr2RuO4

    DOE PAGES

    Zhu, M.; Shanavas, K. V.; Wang, Y.; ...

    2017-02-10

    Sr2RuO4, an unconventional superconductor, is known to possess an incommensurate spin-density wave instability driven by Fermi surface nesting. Here we report a static spin-density wave ordering with a commensurate propagation vector qc = (0.250.250) in Fe-doped Sr2RuO4, despite the magnetic fluctuations persisting at the incommensurate wave vectors qic = (0.30.3L) as in the parent compound. The latter feature is corroborated by the first-principles calculations, which show that Fe substitution barely changes the nesting vector of the Fermi surface. Finally, these results suggest that in addition to the known incommensurate magnetic instability, Sr2RuO4 is also in proximity to a commensurate magneticmore » tendency that can be stabilized via Fe doping.« less

  2. Interlayer Exchange Coupling in Asymmetric Co -Fe /Ru /Co -Fe Trilayers Investigated with Broadband Temperature-Dependent Ferromagnetic Resonance

    NASA Astrophysics Data System (ADS)

    Khodadadi, Behrouz; Mohammadi, Jamileh Beik; Jones, Joshua Michael; Srivastava, Abhishek; Mewes, Claudia; Mewes, Tim; Kaiser, Christian

    2017-07-01

    We report on a comprehensive study of the interlayer exchange coupling in Co -Fe (5 nm )/Ru (t )/Co -Fe (8 nm ) trilayers (t =0.8 ,…,2.8 nm ) using broadband ferromagnetic resonance. A systematic frequency dependence of the field separation between the acoustic and optic modes is found, which is caused by different effective magnetizations of the two ferromagnetic layers. Hence, it is shown that the broadband measurements are vital for reducing the systematic error margins in the determination of interlayer exchange coupling using ferromagnetic resonance. We also investigate the temperature dependence of the interlayer exchange coupling and compare our results with existing theories. It is shown that models which take into account the temperature dependence due to thermal excitations of spin waves within the ferromagnetic layers have a considerably better agreement with the experiment than models solely based on spacer and interface contributions to the temperature dependence.

  3. Quantum oscillations of the superconductor LaRu2P2: Comparable mass enhancement λ≈1 in Ru and Fe phosphides

    NASA Astrophysics Data System (ADS)

    Moll, Philip J. W.; Kanter, Jakob; McDonald, Ross D.; Balakirev, Fedor; Blaha, Peter; Schwarz, Karlheinz; Bukowski, Zbigniew; Zhigadlo, Nikolai D.; Katrych, Sergiy; Mattenberger, Kurt; Karpinski, Janusz; Batlogg, Bertram

    2011-12-01

    We have studied the angular-dependent de Haas-van Alphen oscillations of LaRu2P2 using magnetic torque in pulsed magnetic fields up to 60 T. The observed oscillation frequencies are in excellent agreement with the geometry of the calculated Fermi surface. The temperature dependence of the oscillation amplitudes reveals effective masses m*(α)=0.71 and m*(β)=0.99 me, which are enhanced over the calculated band mass by λcyc of 0.8. We find a similar enhancement of λγ≈1 in comparing the measured electronic specific heat (γ=11.5 mJ/mol K2) with the total density of states from band-structure calculations. Remarkably, very similar mass enhancements have been reported in other pnictides, LaFe2P2, LaFePO (Tc≈4K), and LaRuPO, independent of whether they are superconducting or not. This is contrary to the common perceptions that the normal-state quasiparticle renormalizations reflect the strength of the superconducting pairing mechanism and leads to new questions about pairing in isostructural and isoelectronic Ru- and Fe-pnictide superconductors.

  4. A cyanide-bridged trinuclear Fe(II)-Ru(II)-Fe(II) complex with three stable states: synthesis, crystal structures, electronic couplings and magnetic properties.

    PubMed

    Ma, Xiao; Hu, Sheng-Min; Tan, Chun-Hong; Wen, Yue-Hong; Zhu, Qi-Long; Shen, Chao-Jun; Sheng, Tian-Lu; Wu, Xin-Tao

    2012-10-21

    Treatment of trans-(Ph-tpy)Ru(PPh(3))(CN)(2) (Ph-tpy = 4'-phenyl-2,2':6',2''-terpyridine, PPh(3) = triphenylphosphine) with 2 equiv of Cp(dppe)Fe(NCCH(3))Br (dppe = bis(diphenylphosphino)ethane) in the presence of NH(4)PF(6) produced a trinuclear cyanide-bridged complex, trans-[Cp(dppe)Fe(CN)(Ph-tpy)Ru(PPh(3))(CN)Fe(dppe)Cp][PF(6)](2) (1[PF(6)](2)). Its one-electron oxidation product (1[PF(6)](3)) and two-electron-oxidation product (1[PF(6)](4)) were obtained by oxidation with (Cp)(2)FePF(6) and AgPF(6), respectively. Firstly, the crystal structures of the cyanide-bridged complexes with three stable states were fully characterized. The reversible electrochemistry measurement of 1(2)(+) shows the presence of a long range intervalence interaction between the external iron centres. Both 1(3)(+) and 1(4)(+) were considered to be Class II mixed valence complexes according to the classification of Robin and Day. Magnetic analysis indicated the presence of a moderately strong antiferromagnetic coupling between the two remote Fe(III) ions across the Fe-NC-Ru-CN-Fe array in 1(4)(+). This proves that the Ru(II)-dicyano complex is a bridging ligand that can transmit electro- and magneto-communication.

  5. Synthesis of Monomeric Fe(II) and Ru(II) Complexes of Tetradentate Phosphines

    SciTech Connect

    Jana, Barun; Ellern, Arkady; Pestovsky, Oleg; Sadow, Aaron; Bakac, Andreja

    2011-03-07

    rac-Bis[{l_brace}(diphenylphosphino)ethyl{r_brace}-phenylphosphino]methane (DPPEPM) reacts with iron(II) and ruthenium(II) halides to generate complexes with folded DPPEPM coordination. The paramagnetic, five-coordinate Fe(DPPEPM)Cl{sub 2} (1) in CD{sub 2}Cl{sub 2} features a tridentate binding mode as established by {sup 31}P{l_brace}{sup 1}H{r_brace} NMR spectroscopy. Crystal structure analysis of the analogous bromo complex, Fe(DPPEPM)Br{sub 2} (2) revealed a pseudo-octahedral, cis-{alpha} geometry at iron with DPPEPM coordinated in a tetradentate fashion. However, in CD{sub 2}Cl{sub 2} solution, the coordination of DPPEPM in 2 is similar to that of 1 in that one of the external phosphorus atoms is dissociated resulting in a mixture of three tridentate complexes. The chloro ruthenium complex cis-Ru({kappa}{sup 4}-DPPEPM)Cl{sub 2} (3) is obtained from rac-DPPEPM and either [RuCl{sub 2}(COD)]{sub 2} [COD = 1,5-cyclooctadiene] or RuCl{sub 2}(PPh{sub 3}){sub 4}. The structure of 3 in both the solid state and in CD{sub 2}Cl{sub 2} solution features a folded {kappa}{sup 4}-DPPEPM. This binding mode was also observed in cis-[Fe({kappa}{sup 4}-DPPEPM)(CH{sub 3}CN){sub 2}](CF{sub 3}SO{sub 3}){sub 2} (4). Addition of an excess of CO to a methanolic solution of 1 results in the replacement of one of the chloride ions by CO to yield cis-[Fe({kappa}{sup 4}-DPPEPM)Cl(CO)](Cl) (5). The same reaction in CH{sub 2}Cl{sub 2} produces a mixture of 5 and [Fe({kappa}{sup 3}-DPPEPM)Cl{sub 2}(CO)] (6) in which one of the internal phosphines has been substituted by CO. Complexes 2, 3, 4, and 5 appear to be the first structurally characterized monometallic complexes of {kappa}{sup 4}-DPPEPM.

  6. Packings of Os layers for the development of L10 order of FePt in nanoscale [Os-FePt]n multilayer systems

    NASA Astrophysics Data System (ADS)

    Su, T. T.; Hsiao, Ching-Hung; Lo, Shen-Chuan; Ouyang, Wen; Li, Tzu-Yuan; Ouyang, H.; Yao, Y. D.

    2013-05-01

    The element osmium (Os), with high melting and boiling points, plays a crucial role in the development of the L10 order for FePt in [Os(5 nm)/FePt(25 nm)]4 and [Os(1 nm)/FePt(5 nm)]20 systems. The large mismatches of lattice constants between Os and FePt, with specific epitaxial relations, induce a great strain in the [Os(5 nm) /FePt(25 nm)]4 system with fixed total thicknesses for the FePt and Os layers. Due to this large strain effect, the L10 order in a FePt structure can be enhanced through an application of stressing along the c axis for the face-centered cubic structure, which results in a higher coercivity. However, a smaller degree of average strain was observed in the 5 nm-thickness FePt system due to the existence of pinholes.

  7. The cleanup of CO in hydrogen for PEMFC applications using Pt, Ru, Co, and Fe in PROX reaction

    NASA Astrophysics Data System (ADS)

    Huang, Chih-Yung; Chen, Yan-Yi; Su, Chin-Chia; Hsu, Chuan-Fu

    An experimental investigation is performed into the cleanup of CO in hydrogen for proton exchange membrane fuel cell (PEMFC) using Pt/Al 2O 3 and Ru/Al 2O 3 catalysts. Additionally, the effects of adding the transition metals Co and Fe to a Ru/Al 2O 3 catalyst are examined. The results show that as the level of Pt addition is increased, the maximum CO conversion rate is achieved at a lower temperature. With Ru/Al 2O 3 catalysts, the CO conversion rate increases significantly with increasing Ru addition at temperatures lower than 80 °C For both catalysts, the methane yield increases with increasing temperature and increasing noble metal addition. At temperatures in the range of 100-140 °C, the CO conversion rate and methane yield of the Pt- and Ru-based preferential oxidation (PROX) reactions are both insensitive to the density of the honeycomb carrier. The CO conversion rate is significantly improved by the addition of Fe at temperatures lower than 160 °C and by the addition of Co at temperatures higher than 200 °C. Of the two metals, Fe results in a greater reduction of the methane yield at high temperatures. Finally, both catalysts achieve a stable cleanup performance over the course of a 12-h stability test and suppress the CO concentration to an acceptable level for PEMFC applications.

  8. High energy ball-milled Ti{sub 2}RuFe electrocatalyst for hydrogen evolution in the chlorate industry

    SciTech Connect

    Blouin, M.; Guay, D.; Huot, J.; Schulz, R.

    1997-06-01

    The high energy mechanical alloying of a Ti{endash}Ru{endash}Fe powder mixture (atomic ratio 2:1:1) has been performed by extensive ball-milling in a steel crucible. The structural evolution of the resulting materials has been studied by x-ray powder diffraction analysis. The identification of the various phases present in the materials, as well as the crystallite size and strain, has been performed by Rietveld refinement analysis. In the first stage of the material transformation, Ru or Fe atoms dissolved into Ti to yield to the formation of {beta}{minus}Ti. Upon further ball-milling, almost all the original constituents of the powder mixture have disappeared and a new simple cubic Ti{sub 2}RuFe phase is formed, with a crystallite size as small as 8 nm. The electrochemical properties of these materials have been tested in a typical chlorate electrolyte by cold-pressing the powders into disk electrodes. At 20 h of ball-milling, where the phase concentration of Ti{sub 2}RuFe reaches 96{percent}, a reduction of the activation overpotential at 250 mA cm{sup {minus}2} of nearly 250 mV is observed when compared to that of a pure iron electrode. {copyright} {ital 1997 Materials Research Society.}

  9. Order-disorder phase transition in Au2Fe on Ru(0001)

    NASA Astrophysics Data System (ADS)

    Marie, J.-B.; Bellec, A.; Chacon, C.; Girard, Y.; Lagoute, J.; Repain, V.; Rousset, S.; Garreau, Y.; Coati, A.

    2016-12-01

    Order-disorder transition of the epitaxial surface alloy of bulk immiscible elements Au1 -xFex on Ru(0001) is studied using complementary experiments of scanning tunneling microscopy and grazing incidence x-ray diffraction. For x ≃1 /3 , we evidence an apparent continuous transition towards disorder with increasing temperature from 550 to 700 K. An ordered Au2Fe two-dimensional alloy is found to be composed of nanometer size domains of the three variants that switch to a two-dimensional solid solution with temperature. A two-levels model is developed to analyze those results which conducts to interpret this phase transition as the result of an order-disorder transition within two dimensional uncorrelated grains, or domains, with nearly fixed size. This system is a good candidate in order to study two-dimensional phase transitions of surface alloy, a largely unexplored domain but crucial to understanding thermal stability of bimetallic nanoparticles.

  10. Theoretical study of the bonding in LaFe(2+), LaRu(2+) and YRu(2+)

    NASA Technical Reports Server (NTRS)

    Bauschlicher, Charles W., Jr.; Langhoff, Stephen R.

    1989-01-01

    The bonding in LaFe(2+) and LaRu(2+) involves nearly equal contributions from La(+) and La(2+). The second IP of Y is larger than that of La and this leads to predominantly Y(+) + Ru(+) character in the YRu(2+) wavefunction. The remarkable stability of these systems derives from multiple d-d bonds that lead to a bond-order of between two and three. Thus the ground states of these dications, which have relatively deep molecular wells and large barriers to dissociation, have essentially infinite lifetimes with respect to unimolecular decay.

  11. Low-temperature properties of Ce(Ru 1- xM x) 2Ge 2, M  Fe, Au

    NASA Astrophysics Data System (ADS)

    Fontes, M. B.; Elmassalami, M.; Aliaga-Guerra, D.; Giordanengo, B.; Bud'ko, S. L.; Guimaraes, A. P.; Gavilano, J. L.; Baggio-Saitovitch, E. M.

    1995-02-01

    We have performed measurements of electrical resistivity, AC susceptibility, magnetization, Mössbauer effect and NMR on the series of intermetallic compounds Ce(Ru 1- xM x) 2Ge 2, M  Fe, Au for 0 ⩽ x ⩽ 0.1. The parent compound CeRu 2Ge 2 orders ferromagnetically below 7.5 K, with f-electrons showing only a small mass-enhancement at low temperatures. However, its crystal structure and Fermi surface are closely related to the heavy-electron superconductor CeRu 2Si 2. Analysis of X-ray diffraction patterns confirmed the structure to be of thCr 2Si 2-type, with no foreign phases detected. The results of our Mössbauer studies indicate that Fe goes into the Ru sites with no magnetic moment. NMR signals were observed in the Fe-doped samples with quadrupolar interaction that can be related to 73Ge nucleus ( I = 9/2).

  12. Strain-induced topological transition in SrRu2O6 and CaOs2O6

    DOE PAGES

    Ochi, Masayuki; Arita, Ryotaro; Trivedi, Nandini; ...

    2016-05-24

    The topological property of SrRumore » $$_2$$O$$_6$$ and isostructural CaOs$$_2$$O$$_6$$ under various strain conditions is investigated using density functional theory. Based on an analysis of parity eigenvalues, we anticipate that a three-dimensional strong topological insulating state should be realized when band inversion is induced at the A point in the hexagonal Brillouin zone. For SrRu$$_2$$O$$_6$$, such a transition requires rather unrealistic tuning, where only the $c$ axis is reduced while other structural parameters are unchanged. However, given the larger spin-orbit coupling and smaller lattice constants in CaOs$$_2$$O$$_6$$, the desired topological transition does occur under uniform compressive strain. Our study paves a way to realize a topological insulating state in a complex oxide, which has not been experimentally demonstrated so far.« less

  13. Magnetoresistance Versus Oxygen Deficiency in Epi-stabilized SrRu1 - x Fe x O3 - δ Thin Films

    NASA Astrophysics Data System (ADS)

    Dash, Umasankar; Acharya, Susant Kumar; Lee, Bo Wha; Jung, Chang Uk

    2017-03-01

    Oxygen vacancies have a profound effect on the magnetic, electronic, and transport properties of transition metal oxide materials. Here, we studied the influence of oxygen vacancies on the magnetoresistance (MR) properties of SrRu1 - x Fe x O3 - δ epitaxial thin films ( x = 0.10, 0.20, and 0.30). For this purpose, we synthesized highly strained epitaxial SrRu1 - x Fe x O3 - δ thin films with atomically flat surfaces containing different amounts of oxygen vacancies using pulsed laser deposition. Without an applied magnetic field, the films with x = 0.10 and 0.20 showed a metal-insulator transition, while the x = 0.30 thin film showed insulating behavior over the entire temperature range of 2-300 K. Both Fe doping and the concentration of oxygen vacancies had large effects on the negative MR contributions. For the low Fe doping case of x = 0.10, in which both films exhibited metallic behavior, MR was more prominent in the film with fewer oxygen vacancies or equivalently a more metallic film. For semiconducting films, higher MR was observed for more semiconducting films having more oxygen vacancies. A relatively large negative MR ( 36.4%) was observed for the x = 0.30 thin film with a high concentration of oxygen vacancies ( δ = 0.12). The obtained results were compared with MR studies for a polycrystal of (Sr1 - x La x )(Ru1 - x Fe x )O3. These results highlight the crucial role of oxygen stoichiometry in determining the magneto-transport properties in SrRu1 - x Fe x O3 - δ thin films.

  14. Significance of β-dehydrogenation in ethanol electro-oxidation on platinum doped with Ru, Rh, Pd, Os and Ir.

    PubMed

    Sheng, Tian; Lin, Wen-Feng; Hardacre, Christopher; Hu, P

    2014-07-14

    In the exploration of highly efficient direct ethanol fuel cells (DEFCs), how to promote the CO2 selectivity is a key issue which remains to be solved. Some advances have been made, for example, using bimetallic electrocatalysts, Rh has been found to be an efficient additive to platinum to obtain high CO2 selectivity experimentally. In this work, the mechanism of ethanol electrooxidation is investigated using the first principles method. It is found that CH3CHOH* is the key intermediate during ethanol electrooxidation and the activity of β-dehydrogenation is the rate determining factor that affects the completeness of ethanol oxidation. In addition, a series of transition metals (Ru, Rh, Pd, Os and Ir) are alloyed on the top layer of Pt(111) in order to analyze their effects. The elementary steps, α-, β-C-H bond and C-C bond dissociations, are calculated on these bimetallic M/Pt(111) surfaces and the formation potential of OH* from water dissociation is also calculated. We find that the active metals increase the activity of β-dehydrogenation but lower the OH* formation potential resulting in the active site being blocked. By considering both β-dehydrogenation and OH* formation, Ru, Os and Ir are identified to be unsuitable for the promotion of CO2 selectivity and only Rh is able to increase the selectivity of CO2 in DEFCs.

  15. Tipping the magnetic instability in paramagnetic Sr3Ru2O7 by Fe impurities [Tipping the magnetic instability in paramagnetic Sr3Ru2O7 by modest Fe substitution

    DOE PAGES

    Zhu, M.; Wang, Y.; Li, P. G.; ...

    2017-05-19

    We report the magnetic and electronic properties of the bilayer ruthenate Sr3Ru2O7 upon Fe substitution for Ru. We find that Sr3(Ru1-xFex)2O7 shows spin-glass-like phase below 4 K for x = 0.01 and commensurate E-type antiferromagnetically ordered insulating ground state characterized by the propagation vector qc = (0.25 0.25 0) for x ≥ 0.03, in contrast to the paramagnetic metallic state in the parent compound with strong spin fluctuations occurring at wave vectors q = (0.09 0 0) and (0.25 0 0). The observed antiferromagnetic ordering is quasitwo-dimensional with very short correlation length along the c axis, a feature similar tomore » the Mndoped Sr3Ru2O7. Lastly, our results suggest that this ordered ground state is associated with the intrinsic magnetic instability in the pristine compound, which can be readily tipped by the local magnetic coupling between the 3d orbitals of the magnetic dopants and Ru 4d orbitals.« less

  16. Chemical pressure tuning of URu2Si2 via isoelectronic substitution of Ru with Fe

    DOE PAGES

    Das, Pinaki; Kanchanavatee, N.; Helton, J. S.; ...

    2015-02-26

    We have used specific heat and neutron diffraction measurements on single crystals of URu2–xFexSi₂ for Fe concentrations x ≤ 0.7 to establish that chemical substitution of Ru with Fe acts as “chemical pressure” Pch as previously proposed by Kanchanavatee et al. [Phys. Rev. B 84, 245122 (2011)] based on bulk measurements on polycrystalline samples. Neutron diffraction reveals a sharp increase of the uranium magnetic moment at x = 0.1, reminiscent of the behavior at the “hidden order” to large moment antiferromagnetic (LMAFM) phase transition observed at a pressure Px ≈ 0.5-0.7 GPa in URu₂Si₂. Using the unit cell volume determinedmore » from our measurements and an isothermal compressibility κT = 5.2×10⁻³ GPa⁻¹ for URu₂Si₂, we determine the chemical pressure Pch in URu2-xFexSi₂ as a function of x. The resulting temperature T-chemical pressure Pch phase diagram for URu2-xFexSi₂ is in agreement with the established temperature T-external pressure P phase diagram of URu₂Si₂.« less

  17. Engineering optical mode ferromagnetic resonance in FeCoB films with ultrathin Ru insertion

    PubMed Central

    Li, Shandong; Wang, Cuiling; Chu, Xian-Ming; Miao, Guo-Xing; Xue, Qian; Zou, Wenqin; Liu, Meimei; Xu, Jie; Li, Qiang; Dai, Youyong; Yan, Shishen; Kang, Shishou; Long, Yunze; Lü, Yueguang

    2016-01-01

    Ferromagnetic resonance (FMR) in soft magnetic films (SMFs) to a large extent determines the maximum working frequency of magnetic devices. The FMR frequency (fr) in an optical mode is usually much higher than that in the corresponding acoustic mode for exchange coupled ferromagnet/nonmagnet/ferromagnet (FM/NM/FM) trilayers. In this study, we prepared a 50 nm FeCoB film with uniaxial magnetic anisotropy (UMA), showing a high acoustic mode fr of 4.17 GHz. When an ultrathin Ru spacer was inserted in the very middle of the UMA-FeCoB film, the zero-field FMR was abruptly switched from an acoustic mode to an optical one with fr dramatically enhanced from 4.17 GHz to 11.32 GHz. Furthermore, the FMR mode can be readily tuned to optical mode only, acoustic mode only, or double mode by simply varying the applied filed, which provides a flexible way to design multi-band microwave devices. PMID:27628089

  18. Metal-insulator transition in Ba3Fe1 -xRu2 +xO9 : Interplay between site disorder, chemical percolation, and electronic structure

    NASA Astrophysics Data System (ADS)

    Middey, S.; Aich, Payel; Meneghini, C.; Mukherjee, K.; Sampathkumaran, E. V.; Siruguri, V.; Mahadevan, P.; Ray, Sugata

    2016-11-01

    Perovskites containing barium metal at the A site often take up unusual hexagonal structures having more than one type of possible sites for the B cation to occupy. This opens up various different B -B - or B -O-B -type connectivities and consequent physical properties which are naturally missing in cubic perovskites. BaRuO3 is one such system where doping of Ru (4 d4 ) by other transition metals (Mn +) creates similar conditions, giving rise to various M -Ru interactions. Interestingly, the 6 H hexagonal structure of doped barium ruthenate triple perovskite (Ba3M Ru2O9 ) seems to possess some internal checks because within the structure M ion always occupies the 2 a site and Ru goes to the 4 f site, allowing only M -O-Ru 180∘ and Ru-O-Ru 90∘ interactions to occur. The only exception is observed in the case of the Fe dopant, which allows us to study almost the full Ba3Fe1 -xRu2 +xO9 series of compounds with wide ranges of x because here Fe ions have the ability to freely go to the 4 f sites and Ru readily takes up the 2 a positions. Therefore, here one has the opportunity to probe the evolution of electronic and magnetic properties as a function of doping by going from BaRuO3 (paramagnetic metal) to BaFeO3 (ferromagnetic insulator). Our detailed experimental and theoretical results show that the series does exhibit a percolative metal-insulator transition with an accompanying but not coincidental magnetic transition as a function of x .

  19. Reactions of the tetrahedral clusters [MCo(3)(CO)(12)](-) (M = Ru, Fe) with functional mono- and diynes.

    PubMed

    Choualeb, Aldjia; Braunstein, Pierre; Rosé, Jacky; Welter, Richard

    2004-01-12

    The tetrahedral cluster [RuCo(3)(CO)(12)](-) reacts with various alkynes, including the new PhCtbd1;CC(O)NHCH(2)Ctbd1;CH (L(1)()), to afford the butterfly clusters [RuCo(3)(CO)(10)(micro(4)-eta(2)-RC(2)R')](-) (1, R = R' = C(O)OMe; 2, R = H, R' = Ph; 3, R = H, R' = MeC=CH(2); 4, R = H, R' = CH(2)OCH(2)Ctbd1;CH; 5, R = H, R' = CH(2)NHC(O)Ctbd1;CPh), in which the ruthenium atom occupies a hinge position and the alkyne is coordinated in a micro(4)-eta(2) fashion. Reaction of the anions 1-3 with [Cu(NCMe)(4)]BF(4) led to selective loss of the 12e fragment Co(CO)(-) to form [RuCo(2)(CO)(9)(micro(3)-eta(2)-RC(2)R')] (6, R = R' = C(O)OMe; 7, R = H, R' = Ph; 8, R = H, R' = MeC=CH(2)). To prepare functionalized RuCo(3) or FeCo(3) clusters that could be subsequently condensed with a silica matrix via the sol-gel method, we reacted [MCo(3)(CO)(12)](-) (M = Ru, Fe) with the alkyne PhCtbd1;CC(O)NH(CH(2))(3)Si(OMe)(3)(L(2)()) and obtained the butterfly clusters [MCo(3)(CO)(10)(micro(4)-eta(2)-PhC(2)C(O)NH(CH(2))(3)Si(OMe)(3))](-) 9 and 10, respectively. Air-stable [RuCo(3)(CO)(10)(micro(4)-eta(2)-Me(3)SiC(2)Ctbd1;CSiMe(3))](-) (11) was obtained from 1,4-bis(trimethylsilyl)butadiyne and reacted with [Cu(NCMe)(4)]BF(4) to give [RuCo(2)(CO)(9)(micro(3)-eta(2)-HC(2)Ctbd1;CSiMe(3))] (12), owing to partial ligand proto-desilylation, and not the expected [RuCo(2)(CO)(9)(micro(3)-eta(2)-Me(3)SiC(2)Ctbd1;CSiMe(3))]. Reaction of 11 with [NO]BF(4) afforded, in addition to 12, [RuCo(3)(CO)(9)(NO)(micro(4)-eta(2)-Me(3)SiC(2)Ctbd1;CSiMe(3))] (13) owing to selective CO substitution on a wing-tip cobalt atom with NO. The thermal reaction of 11 with [AuCl(PPh(3))] led to replacement of a CO on Ru by the PPh(3) originating from [AuCl(PPh(3))] and afforded [RuCo(3)(CO)(9)(PPh(3))(micro(4)-eta(2)-Me(3)SiC(2)Ctbd1;CSiMe(3))](-) (14), also obtained directly by reaction of 11 with one equivalent of PPh(3). Proto-desilylation of 11 using TBAF/THF-H(2)O afforded [RuCo(3)(CO)(10)(micro(4)-eta(2)-Me(3)Si

  20. Analysis of the weak coupling of the IrMn/Co/Ru/NiFe structures by ferromagnetic resonance

    SciTech Connect

    Alayo, W.; Baggio-Saitovitch, E.; Sousa, M. A.; Pelegrini, F.

    2011-04-15

    The Ir{sub 20}Mn{sub 80}/Co/Ru/Ni{sub 81}Fe{sub 19} spin valve structures have been produced by sputtering deposition and analyzed by ferromagnetic resonance. Two well resolved modes are identified in the FMR spectra as the resonance of the Co and NiFe layers. The in-plane angular dependence of the resonance peaks for the NiFe layer present a small asymmetry, which is attributed to the interlayer exchange interaction between ferromagnetic layers across the nonmagnetic spacer. The data were analyzed considering the exchange bias at the IrMn/Co interface and the indirect coupling between Co and NiFe. The in-plane angular dependence of the resonance fields of both Co and NiFe layers present an upward (downward) shift for antiferromagnetic (ferromagnetic) coupling with respect to a system with no interlayer coupling.

  1. Analysis of the weak coupling of the IrMn/Co/Ru/NiFe structures by ferromagnetic resonance

    NASA Astrophysics Data System (ADS)

    Alayo, W.; Sousa, M. A.; Pelegrini, F.; Baggio-Saitovitch, E.

    2011-04-01

    The Ir20Mn80/Co/Ru/Ni81Fe19 spin valve structures have been produced by sputtering deposition and analyzed by ferromagnetic resonance. Two well resolved modes are identified in the FMR spectra as the resonance of the Co and NiFe layers. The in-plane angular dependence of the resonance peaks for the NiFe layer present a small asymmetry, which is attributed to the interlayer exchange interaction between ferromagnetic layers across the nonmagnetic spacer. The data were analyzed considering the exchange bias at the IrMn/Co interface and the indirect coupling between Co and NiFe. The in-plane angular dependence of the resonance fields of both Co and NiFe layers present an upward (downward) shift for antiferromagnetic (ferromagnetic) coupling with respect to a system with no interlayer coupling.

  2. In situ epitaxial growth of ordered FePt (001) films with ultra small and uniform grain size using a RuAl underlayer

    SciTech Connect

    Shen, W.K.; Judy, J. H.; Wang Jianping

    2005-05-15

    In situ epitaxial growth of ordered FePt thin films with small and uniform grain size using RuAl underlayer is reported. A transmission electron microscopy image of a 20-nm RuAl layer deposited on a glass substrate revealed small (D{approx}5.0 nm) and uniform ({delta}D/D{approx}15%) grains. The (001) texture was formed in RuAl films at a substrate temperature higher than 100 deg. C. The FePt L1{sub 0} (001) texture with mean grain size of 6.63 nm and narrow size distribution (17%) has been successfully induced using a RuAl underlayer at a substrate temperature of 400 deg. C. The influences of the RuAl composition ratio and Pt interlayer were studied.

  3. Theory of the metal-insulator transition in Pr Ru4 P12 and Pr Fe4 P12

    NASA Astrophysics Data System (ADS)

    Curnoe, S. H.; Harima, H.; Takegahara, K.; Ueda, K.

    2004-12-01

    All symmetry-allowed couplings between the 4f2 -electron ground state doublet of trivalent praseodymium in PrRu4P12 and PrFe4P12 and displacements of the phosphorus, iron, or ruthenium ions are considered. Two types of displacements can change the crystal lattice from body-centred cubic to simple orthorhombic or to simple cubic. The first type lowers the point group symmetry from tetrahedral to orthorhombic, while the second type leaves it unchanged, with corresponding space group reductions Im3¯→Pmmm and Im3¯→Pm3¯ , respectively. In former case, the lower point group symmetry splits the degeneracy of the 4f2 doublet into states with opposite quadrupole moment, which then leads to antiquadrupolar ordering, as in PrFe4P12 . Either kind of displacement may conspire with nesting of the Fermi surface to cause the metal-insulator or partial metal-insulator transition observed in PrFe4P12 and PrRu4P12 . We investigate this scenario using band-structure calculations, and it is found that displacements of the phosphorus ions in PrRu4P12 (with space-group reduction Im3¯→Pm3¯ ) open a gap everywhere on the Fermi surface.

  4. Combinatorial PtSnM (M = Fe, Ni, Ru and Pd) nanoparticle catalyst library toward ethanol electrooxidation

    NASA Astrophysics Data System (ADS)

    Almeida, T. S.; Van Wassen, A. R.; VanDover, R. B.; de Andrade, A. R.; Abruña, H. D.

    2015-06-01

    Electrode arrays containing 91 combinations of Pt-Sn-M (M = Fe, Ni, Pd, and Ru) were prepared by borohydride reduction of aqueous metal salts on carbon paper, and screened by fluorescence assay for activity as ethanol electrooxidation catalysts. Catalysts that showed high activity for this reaction were identified as being Pt(80)Sn(10)Fe(10), Pt(80)Sn(10)Ni(10), Pt(70)Sn(20)Pd(10), and Pt(70)Sn(10)Ru(20) (numbers in parenthesis indicate atomic percent). These were significantly more active than Pt or PtSn catalysts, also present in the electrode arrays. These 4 compositions were synthesized as nanoparticles and characterized physically and electrochemically. X-ray diffraction showed a Pt face-centered cubic (fcc) structure with an average crystallite size of about 2.0 nm for all catalysts. The electrochemical tests for the oxidation of ethanol revealed excellent electrocatalytic activity and single cell (fuel cell) power density for all four catalyst formulations. Fe-containing catalysts exhibited the highest activity (13 A gPt-1) and single-cell performance (50 mW cm-2) followed by Ni- and Pd-containing materials with similar results; electrocatalytic activity around 10 A gPt-1 and power densities of 43 mW cm-2. The lowest performance was observed for the Ru-containing catalyst. However, its single-cell performance (30 mW cm-2) was still comparable to that of the commercial PtSn-Etek electrocatalyst.

  5. Structural and mechanical properties of transition metal borides Nb2MB2 (M=Tc, Ru, and Os) under pressure

    NASA Astrophysics Data System (ADS)

    Li, Xiaofeng; Yan, Haiyan; Wei, Qun

    2016-10-01

    First-principle total energy calculations are employed to provide a fundamental understanding of the structural, mechanical, and electronic properties of transition metal borides Nb2MB2 (M=Tc, Ru, and Os) within the tetragonal superstructure P4/mnc structure. The mechanically and dynamically stabilities of three borides have been demonstrated by the elastic constants and phonons calculations under pressure. Among these three compounds, Nb2TcB2 exhibits the biggest bulk and Young's modulus, smallest Poission's ratio, and highest harness. Density of states of them revealed that the strong B-B, Nb-B and M-B covalent bonds are major driving forces for their high bulk and shear moduli as well as small Poisson's ratio.

  6. Studies on the reactivity of organometallic Ru-, Rh- and Os-pta complexes with DNA model compounds.

    PubMed

    Dorcier, Antoine; Hartinger, Christian G; Scopelliti, Rosario; Fish, Richard H; Keppler, Bernhard K; Dyson, Paul J

    2008-01-01

    The reactions of arene-metal complexes (arene=p-cymene, benzene or pentamethylcyclopentadienyl, metal=Ru, Rh or Os), including 1,3,5-triaza-7-phosphatricyclo-[3.3.1.1]decanephosphine (pta) and chloro co-ligands, with 9-methylguanine, adenine, and a series of nucleosides were studied in water to ascertain the binding modes. The products were characterized by NMR spectroscopy and electrospray ionization mass spectrometry (ESI-MS). Tandem mass spectrometry was found to provide excellent information on preferential binding sites. In general, the N7 position on guanine (the most basic site) was found to be the preferred donor atom for coordination to the metal complexes. The X-ray structures of the precursor complexes, [(eta5-C10H15)RhCl(pta-Me)2]Cl2, [(eta6-C10H14)OsCl(pta)2]Cl, and [(eta6-C6H6)OsCl2(CH3CN)], are also reported.

  7. Synthesis of higher alcohols from CO2 hydrogenation over a PtRu/Fe2O3 catalyst under supercritical condition.

    PubMed

    He, Zhenhong; Qian, Qingli; Zhang, Zhaofu; Meng, Qinglei; Zhou, Huacong; Jiang, Zhiwei; Han, Buxing

    2015-12-28

    Hydrogenation of CO(2) to alcohols is of great importance, especially when producing higher alcohols. In this work, we synthesized heterogeneous PtRu/Fe(2)O(3), in which the Pt and Ru bimetallic catalysts were supported on Fe(2)O(3). The catalyst was used to catalyse CO(2) hydrogenation to alcohols. It was demonstrated that the activity and selectivity could be tuned by the bimetallic composition, and the catalyst with a Pt to Ru molar ratio of 1:2 (Pt(1)Ru(2)/Fe(2)O(3)) had high activity and selectivity at 200°C, which is very low for heterogeneous hydrogenation of CO(2) to produce higher alcohols. The conversion and the selectivity increased with increasing pressures of CO(2) and/or H(2). The catalyst could be reused at least five times without any obvious change in activity or selectivity.

  8. Complex transition metal hydrides incorporating ionic hydrogen: thermal decomposition pathway of Na2Mg2FeH8 and Na2Mg2RuH8.

    PubMed

    Humphries, Terry D; Matsuo, Motoaki; Li, Guanqiao; Orimo, Shin-Ichi

    2015-03-28

    Complex transition metal hydrides have potential technological application as hydrogen storage materials, smart windows and sensors. Recent exploration of these materials has revealed that the incorporation of anionic hydrogen into these systems expands the potential number of viable complexes, while varying the countercation allows for optimisation of their thermodynamic stability. In this study, the optimised synthesis of Na2Mg2TH8 (T = Fe, Ru) has been achieved and their thermal decomposition properties studied by ex situ Powder X-ray Diffraction, Gas Chromatography and Pressure-Composition Isotherm measurements. The temperature and pathway of decomposition of these isostructural compounds differs considerably, with Na2Mg2FeH8 proceeding via NaMgH3 in a three-step process, while Na2Mg2RuH8 decomposes via Mg2RuH4 in a two-step process. The first desorption maxima of Na2Mg2FeH8 occurs at ca. 400 °C, while Na2Mg2RuH8 has its first maxima at 420 °C. The enthalpy and entropy of desorption for Na2Mg2TH8 (T = Fe, Ru) has been established by PCI measurements, with the ΔHdes for Na2Mg2FeH8 being 94.5 kJ mol(-1) H2 and 125 kJ mol(-1) H2 for Na2Mg2RuH8.

  9. Voltage control of magnetic anisotropy in epitaxial Ru/Co2FeAl/MgO heterostructures

    NASA Astrophysics Data System (ADS)

    Wen, Zhenchao; Sukegawa, Hiroaki; Seki, Takeshi; Kubota, Takahide; Takanashi, Koki; Mitani, Seiji

    2017-03-01

    Voltage control of magnetic anisotropy (VCMA) in magnetic heterostructures is a key technology for achieving energy-efficiency electronic devices with ultralow power consumption. Here, we report the first demonstration of the VCMA effect in novel epitaxial Ru/Co2FeAl(CFA)/MgO heterostructures with interfacial perpendicular magnetic anisotropy (PMA). Perpendicularly magnetized tunnel junctions with the structure of Ru/CFA/MgO were fabricated and exhibited an effective voltage control on switching fields for the CFA free layer. Large VCMA coefficients of 108 and 139 fJ/Vm for the CFA film were achieved at room temperature and 4 K, respectively. The interfacial stability in the heterostructure was confirmed by repeating measurements. Temperature dependences of both the interfacial PMA and the VCMA effect were also investigated. It is found that the temperature dependences follow power laws of the saturation magnetization with an exponent of ~2, where the latter is definitely weaker than that of conventional Ta/CoFeB/MgO. The significant VCMA effect observed in this work indicates that the Ru/CFA/MgO heterostructure could be one of the promising candidates for spintronic devices with voltage control.

  10. Voltage control of magnetic anisotropy in epitaxial Ru/Co2FeAl/MgO heterostructures.

    PubMed

    Wen, Zhenchao; Sukegawa, Hiroaki; Seki, Takeshi; Kubota, Takahide; Takanashi, Koki; Mitani, Seiji

    2017-03-23

    Voltage control of magnetic anisotropy (VCMA) in magnetic heterostructures is a key technology for achieving energy-efficiency electronic devices with ultralow power consumption. Here, we report the first demonstration of the VCMA effect in novel epitaxial Ru/Co2FeAl(CFA)/MgO heterostructures with interfacial perpendicular magnetic anisotropy (PMA). Perpendicularly magnetized tunnel junctions with the structure of Ru/CFA/MgO were fabricated and exhibited an effective voltage control on switching fields for the CFA free layer. Large VCMA coefficients of 108 and 139 fJ/Vm for the CFA film were achieved at room temperature and 4 K, respectively. The interfacial stability in the heterostructure was confirmed by repeating measurements. Temperature dependences of both the interfacial PMA and the VCMA effect were also investigated. It is found that the temperature dependences follow power laws of the saturation magnetization with an exponent of ~2, where the latter is definitely weaker than that of conventional Ta/CoFeB/MgO. The significant VCMA effect observed in this work indicates that the Ru/CFA/MgO heterostructure could be one of the promising candidates for spintronic devices with voltage control.

  11. Voltage control of magnetic anisotropy in epitaxial Ru/Co2FeAl/MgO heterostructures

    PubMed Central

    Wen, Zhenchao; Sukegawa, Hiroaki; Seki, Takeshi; Kubota, Takahide; Takanashi, Koki; Mitani, Seiji

    2017-01-01

    Voltage control of magnetic anisotropy (VCMA) in magnetic heterostructures is a key technology for achieving energy-efficiency electronic devices with ultralow power consumption. Here, we report the first demonstration of the VCMA effect in novel epitaxial Ru/Co2FeAl(CFA)/MgO heterostructures with interfacial perpendicular magnetic anisotropy (PMA). Perpendicularly magnetized tunnel junctions with the structure of Ru/CFA/MgO were fabricated and exhibited an effective voltage control on switching fields for the CFA free layer. Large VCMA coefficients of 108 and 139 fJ/Vm for the CFA film were achieved at room temperature and 4 K, respectively. The interfacial stability in the heterostructure was confirmed by repeating measurements. Temperature dependences of both the interfacial PMA and the VCMA effect were also investigated. It is found that the temperature dependences follow power laws of the saturation magnetization with an exponent of ~2, where the latter is definitely weaker than that of conventional Ta/CoFeB/MgO. The significant VCMA effect observed in this work indicates that the Ru/CFA/MgO heterostructure could be one of the promising candidates for spintronic devices with voltage control. PMID:28332569

  12. From antiferromagnetic to ferromagnetic interaction in cyanido-bridged Fe(III)-Ru(II)-Fe(III) complexes by change of the central diamagnetic cyanido-metal geometry.

    PubMed

    Ma, Xiao; Hu, Sheng-Min; Tan, Chun-Hong; Zhang, Yong-Fan; Zhang, Xu-Dong; Sheng, Tian-Lu; Wu, Xin-Tao

    2013-10-07

    Cis- and trans-isomeric heterotrinuclear-metallic complexes and their two-electron-oxidation products, cis-/trans-[Cp(dppe)Fe(μ-CN)Ru(bpy)2(μ-CN)Fe(dppe)Cp][PF6]2 (cis-/trans-1[PF6]2) and cis-/trans-[Cp(dppe)Fe(μ-CN)Ru(bpy)2(μ-CN)Fe(dppe)Cp][PF6]4 (cis-/trans-1[PF6]4), have been synthesized and structurally characterized. To the best of our knowledge, the complexes are the first example of a cis-/trans-isomer with multistates. Although separated by the diamagnetic cyanido-metal bridge, the two distant paramagnetic metal centers in both the oxidized complexes exhibit quite strong magnetic couplings. As a unique example, cis-1[PF6]4 is antiferromagnetic, and trans-1[PF6]4 is ferromagnetic. Density functional theory (DFT) calculations suggest that the spin-delocalization mechanism should be responsible for the magnetic interactions between the two distant paramagnetic Fe(III) centers across the diamagnetic cyanido-metal in both cis- and trans-1(4+). Most importantly, the DFT calculations revealed that the type (antiferromagnetic or ferromagnetic) and strength (J) of the magnetic interactions in such compounds can be controlled by the variation (cis or trans) of the diamagnetic central metal configurations.

  13. Robust paramagnetism in Bi2- xMxRu2O7 (M=Mn,Fe,Co,Ni,Cu) pyrochlore

    NASA Astrophysics Data System (ADS)

    Haas, M. K.; Cava, R. J.; Avdeev, M.; Jorgensen, J. D.

    2002-09-01

    We report magnetic susceptibility, resistivity, and Seebeck coefficients for Bi2-xMxRu2O7 pyrochlore. The solid solution exists up to x=0.5 for M=Cu,Ni,Co and up to x=0.1 for M=Fe,Mn. The doped materials do not exhibit ferromagnetism or any localized ruthenium moment behavior. Instead we find the Ru-O and Bi-O sublattices to be essentially independent, with any magnetism resulting from the unpaired first-row transition metal dopant spins. Cobalt substitution for bismuth results in localized Co2+ and low-temperature spin-glass transitions in several cases. Nickel moments on the pyrochlore lattice display properties intermediate to localized and itinerant. Finally, copper doping results in an enhancement of the Pauli metallic density of states.

  14. Composition dependence of the electronic properties of Al-Cu-Fe and Al-Cu-Ru-Si semimetallic quasicrystals

    NASA Astrophysics Data System (ADS)

    Pierce, F. S.; Bancel, P. A.; Biggs, B. D.; Guo, Q.; Poon, S. J.

    1993-03-01

    Electronic transport properties and specific heats of ordered icosahedral phase alloys in the Al-Cu-Ru-Si and Al-Cu-Fe systems are examined, and comparison with high-quality rhombohedral (3/2) approximant phase samples of Al-Cu-Fe is made. Strong temperature dependence and sensitivity to composition changes of these properties are observed. The similarity of transport properties between the icosahedral (i) and rhombohedral (r) phases of Al62.5Cu26.5Fe11 is noted. The results can be qualitatively interpreted in terms of band structure. There appears to be sufficient evidence for a rapidly varying conductivity spectrum σ(E) in the ordered i phases. However, important questions concerning the physics of these semimetallic quasicrystals remain to be answered.

  15. Exotic magnetism on the quasi-fcc lattices of the d3 double Perovskites La2NaB'O6 (B'=Ru, Os).

    PubMed

    Aczel, A A; Baker, P J; Bugaris, D E; Yeon, J; Zur Loye, H-C; Guidi, T; Adroja, D T

    2014-03-21

    We find evidence for long-range and short-range (ζ=70 Å at 4 K) incommensurate magnetic order on the quasi-face-centered-cubic (fcc) lattices of the monoclinic double perovskites La2NaRuO6 and La2NaOsO6, respectively. Incommensurate magnetic order on the fcc lattice has not been predicted by mean field theory, but may arise via a delicate balance of inequivalent nearest neighbor and next nearest neighbor exchange interactions. In the Ru system with long-range order, inelastic neutron scattering also reveals a spin gap Δ ∼ 2.75 meV. Magnetic anisotropy is generally minimized in the more familiar octahedrally coordinated 3d3 systems, so the large gap observed for La2NaRuO6 may result from the significantly enhanced value of spin-orbit coupling in this 4d(3) material.

  16. Exotic magnetism on the quasi-FCC lattices of the d3 double perovskites La2NaB'O6 (B' = Ru, Os)

    SciTech Connect

    Aczel, Adam A; Baker, Peter J.; Bugaris, Dan; Yeon, Jeongho; Zur Loye, Hans-Conrad; Guidi, T.; Adroja, D. T.

    2014-01-01

    We find evidence for long-range and short-range ($\\zeta$~$=$~70~\\AA~at 4~K) incommensurate magnetic order on the quasi-face-centered-cubic (FCC) lattices of the monoclinic double perovskites La$_2$NaRuO$_6$ and La$_2$NaOsO$_6$ respectively. Incommensurate magnetic order on the FCC lattice has not been predicted by mean field theory, but may arise via a delicate balance of inequivalent nearest neighbour and next nearest neighbour exchange interactions. In the Ru system with long-range order, inelastic neutron scattering also reveals a spin gap $\\Delta$~$\\sim$~2.75~meV. Magnetic anisotropy is generally minimized in the more familiar octahedrally-coordinated $3d^3$ systems, so the large gap observed for La$_2$NaRuO$_6$ may result from the significantly enhanced value of spin-orbit coupling in this $4d^3$ material.

  17. Effects of isoelectronic Ru substitution at the Fe site on the energy gaps of optimally F-doped SmFeAsO

    NASA Astrophysics Data System (ADS)

    Daghero, D.; Tortello, M.; Ummarino, G. A.; Stepanov, V. A.; Bernardini, F.; Tropeano, M.; Putti, M.; Gonnelli, R. S.

    2012-08-01

    We studied the effects of isoelectronic Ru substitution at the Fe site on the energy gaps of optimally F-doped SmFeAsO by means of point-contact Andreev-reflection spectroscopy. The results show that the SmFe1-xRuxAsO0.85F0.15 system keeps a multigap character at least up to x = 0.50, and that the gap amplitudes Δ1 and Δ2 scale almost linearly with the local critical temperature {T}_{{c}}^{A}. The gap ratios 2Δi/kBTc remain approximately constant only as long as Tc ≥ 30 K, and increase dramatically when Tc decreases further. This trend seems to be common to many Fe-based superconductors, irrespective of their family. Based on first-principle calculations of the bandstructure and of the density of states projected on the different bands, we show that this trend, as well as the Tc dependence of the gaps and the reduction of Tc upon Ru doping, can be explained within an effective three-band Eliashberg model as being due to a suppression of the superfluid density at finite temperature that, in turn, modifies the temperature dependence of the characteristic spin-fluctuation energy.

  18. Magnetic and electric properties of Ru-substituted CoFe2O4 thin films fabricated by pulsed laser deposition

    NASA Astrophysics Data System (ADS)

    Iwamoto, Fujiyuki; Seki, Munetoshi; Tabata, Hitoshi

    2012-11-01

    Epitaxial thin films of Ru-substituted CoFe2O4 with a cubic spinel structure were fabricated on α-Al2O3 (001) substrates using pulsed laser deposition, and their magnetic and electric properties were investigated. The films showed room temperature ferrimagnetic behavior with hard magnetic features similar to those of non-Ru-substituted cobalt ferrite films. The electrical conductivity of the films was dramatically enhanced by the substitution of Ru. The anomalous Hall effect was observed in all films even at 300 K suggesting that carriers in the films are highly spin-polarized at room temperature as expected from a first-principles calculation.

  19. The Disposition of Pt, Pd, Ir, Os, and Ru in Marine Sediments and the K/T Boundary

    NASA Technical Reports Server (NTRS)

    Lee, Cin-Ty; Wasserburg, Gerald; Kyte, Frank

    2003-01-01

    The marine record of platinum group elements (PGEs) and Os isotopic compositions provides information on different inputs of PGEs into the oceans. Some studies based on a smaller subset of the PGEs suggest that the PGEs may suffer post-depositional mobility during diagenesis. In some K/T boundary clays, Kyte and others showed that the relative abundances of Pt, Pd, Ir, and Os can differ significantly from chondritic, which is the signature expected from fallout of the meteorite impact. In some K/T boundary sections, elevated Ir concentrations are observed as far as 1 meter from the cm-thick boundary clay containing the meteoritic ejecta. The purpose of this study was to characterize Pt, Pd, Ir, Os, and Ru abundances in zones including the K/T boundary. We determined PGE abundances of boundary clays at two hemipelagic sites (Stevns Klint, Denmark and Caravaca, Spain) in which previous studies by Kyte and others showed that the Ir anomaly is confined to within a few cm. We also analyzed two pelagic Pacific sites: a boundary clay from the north Pacific (Hole 465A) characterized by a 0.5 m thick Ir anomaly and a transect across the K/T boundary from the south Pacific (Hole 596) where the Ir anomaly spans 2 m. The Stevns Klint, Caravaca, and north Pacific sites are characterized by abundant marls and limestones in the section, whereas the south Pacific site is dominated by clays. Samples were spiked with isotopic tracers, mixed with a flux, S and Ni, and equilibrated by fusion. PGEs were extracted from the Ni and analyzed on a Finnigan Element ICP-MS. We find that the narrow Caravaca and Stevns Klint boundary clays have relative PGE abundance patterns indistinguishable from chondritic values. The two Pacific sites were found to have nearly identical PGE patterns but have ratios at the peak, which differ from chondritic values as found earlier by Evans et al. The Pacific sites were found to have nearly identical PGE patterns but are extremely depleted in OS (Os/Ir = 0

  20. The Disposition of Pt, Pd, Ir, Os, and Ru in Marine Sediments and the K/T Boundary

    NASA Technical Reports Server (NTRS)

    Lee, Cin-Ty; Wasserburg, Gerald; Kyte, Frank

    2003-01-01

    The marine record of platinum group elements (PGEs) and Os isotopic compositions provides information on different inputs of PGEs into the oceans. Some studies based on a smaller subset of the PGEs suggest that the PGEs may suffer post-depositional mobility during diagenesis. In some K/T boundary clays, Kyte and others showed that the relative abundances of Pt, Pd, Ir, and Os can differ significantly from chondritic, which is the signature expected from fallout of the meteorite impact. In some K/T boundary sections, elevated Ir concentrations are observed as far as 1 meter from the cm-thick boundary clay containing the meteoritic ejecta. The purpose of this study was to characterize Pt, Pd, Ir, Os, and Ru abundances in zones including the K/T boundary. We determined PGE abundances of boundary clays at two hemipelagic sites (Stevns Klint, Denmark and Caravaca, Spain) in which previous studies by Kyte and others showed that the Ir anomaly is confined to within a few cm. We also analyzed two pelagic Pacific sites: a boundary clay from the north Pacific (Hole 465A) characterized by a 0.5 m thick Ir anomaly and a transect across the K/T boundary from the south Pacific (Hole 596) where the Ir anomaly spans 2 m. The Stevns Klint, Caravaca, and north Pacific sites are characterized by abundant marls and limestones in the section, whereas the south Pacific site is dominated by clays. Samples were spiked with isotopic tracers, mixed with a flux, S and Ni, and equilibrated by fusion. PGEs were extracted from the Ni and analyzed on a Finnigan Element ICP-MS. We find that the narrow Caravaca and Stevns Klint boundary clays have relative PGE abundance patterns indistinguishable from chondritic values. The two Pacific sites were found to have nearly identical PGE patterns but have ratios at the peak, which differ from chondritic values as found earlier by Evans et al. The Pacific sites were found to have nearly identical PGE patterns but are extremely depleted in OS (Os/Ir = 0

  1. New ternary tantalum borides containing boron dumbbells: Experimental and theoretical studies of Ta2OsB2 and TaRuB

    NASA Astrophysics Data System (ADS)

    Mbarki, Mohammed; Touzani, Rachid St.; Rehorn, Christian W. G.; Gladisch, Fabian C.; Fokwa, Boniface P. T.

    2016-10-01

    The new ternary transition metal-rich borides Ta2OsB2 and TaRuB have been successfully synthesized by arc-melting the elements in a water-cooled crucible under an argon atmosphere. The crystal structures of both compounds were solved by single-crystal X-ray diffraction and their metal compositions were confirmed by EDX analysis. It was found that Ta2OsB2 and TaRuB crystallize in the tetragonal Nb2OsB2 (space group P4/mnc, no. 128) and the orthorhombic NbRuB (space group Pmma, no. 51) structure types with lattice parameters a=5.878(2) Å, c=6.857(2) Å and a=10.806(2) Å, b=3.196(1) Å, c=6.312(2) Å, respectively. Furthermore, crystallographic, electronic and bonding characteristics have been studied by density functional theory (DFT). Electronic structure relaxation has confirmed the crystallographic parameters while COHP bonding analysis indicates that B2-dummbells are the strongest bonds in both compounds. Moreover, the formation of osmium dumbbells in Ta2OsB2 through a Peierls distortion along the c-axis, is found to be the origin of superstructure formation. Magnetic susceptibility measurements reveal that the two phases are Pauli paramagnets, thus confirming the theoretical DOS prediction of metallic character. Also hints of superconductivity are found in the two phases, however lack of single phase samples has prevented confirmation. Furthermore, the thermodynamic stability of the two modifications of AMB (A=Nb, Ta; M =Ru, Os) are studied using DFT, as new possible phases containing either B4- or B2-units are predicted, the former being the most thermodynamically stable modification.

  2. Probing the links between structure and magnetism in Sr(2-x)Ca(x)FeOsO₆ double perovskites.

    PubMed

    Morrow, Ryan; Freeland, John W; Woodward, Patrick M

    2014-08-04

    The synthesis, structure, and properties of the ordered double perovskites Sr2FeOsO6, Ca2FeOsO6, and SrCaFeOsO6 are reported. The latter two compounds have monoclinic P2₁/n symmetry and a(-)a(-)b(+) tilting of the octahedra, while Sr2FeOsO6 is tetragonal with I4/m symmetry and a(0)a(0)c(-) tilting. Magnetic measurements indicate and neutron powder diffraction studies confirm that Ca2FeOsO6 is a ferrimagnet with a Curie temperature of 350 K. The ferrimagnetism is retained if half of the Ca(2+) ions are replaced with larger Sr(2+) ions to form SrCaFeOsO6 (T(C) = 210 K). This substitution reduces the degree of octahedral tilting, but unlike most perovskites, the magnetic ordering temperature decreases as the Fe-O-Os bond angles approach a linear geometry. In contrast, Sr2FeOsO6 orders antiferromagnetically, as previously reported. X-ray absorption spectroscopy confirms the assignment of Fe(III) and Os(V) oxidation states for all three compounds. In these insulating double perovskites, the magnetic ground state is governed by a competition between the four-bond Fe-O-Os-O-Fe antiferromagnetic superexchange coupling of Fe(III) ions and the two-bond Fe-O-Os antiferromagnetic superexchange coupling between neighboring Fe(III) and Os(V) ions. When the Fe-O-Os bonds are linear, as they are in the c direction in Sr2FeOsO6, the four-bond coupling between Fe(III) ions prevails. The competition shifts in favor of antiferromagnetic coupling of Fe(III) and Os(V) as the Fe-O-Os bond angles bend in response to chemical pressure.

  3. Current-Induced Magnetization Switching in MgO Barrier Based Magnetic Tunnel Junctions with CoFeB/Ru/CoFeB Synthetic Ferrimagnetic Free Layer

    NASA Astrophysics Data System (ADS)

    Hayakawa, Jun; Ikeda, Shoji; Lee, Young Min; Sasaki, Ryutaro; Meguro, Toshiyasu; Matsukura, Fumihiro; Takahashi, Hiromasa; Ohno, Hideo

    2006-10-01

    We report the intrinsic critical current density (Jc0) in current-induced magnetization switching and the thermal stability factor (E/kBT, where E, kB, and T are the energy potential, the Boltzmann constant, and temperature, respectively) in MgO based magnetic tunnel junctions with a Co40Fe40B20(2 nm)/Ru(0.7-2.4 nm)/Co40Fe40B20(2 nm) synthetic ferrimagnetic (SyF) free layer. We show that Jc0 and E/kBT can be determined by analyzing the average critical current density as a function of coercivity using the Slonczewski’s model taking into account thermal fluctuation. We find that high antiferromagnetic coupling between the two CoFeB layers in a SyF free layer results in reduced Jc0 without reducing high E/kBT.

  4. Ru, Os, Rh mixed-metal complexes are a potential novel class of oxygen independent photosensitizers for photodynamic therapy (PDT)

    NASA Astrophysics Data System (ADS)

    Storrie, Brian; Holder, Alvin; Brewer, Karen J.

    2006-02-01

    Mixed-metal supramolecular complexes coupling Ru and Os light absorber units to a central, reactive Rh site have been designed of the type [{(bpy)2M(dpp)}2RhCl2]5+. These complexes possess intense metal-to-ligand charge transfer transitions when excited at 500-700 nm making them good light absorbers. The presence of the Rh site introduces low lying metal-to-metal charge transfer states that are capable of visible light induced photocleavage of DNA via an oxygen independent pathway.1 We report here a study of the photodynamic action of supramolecular mixed-metal complexes showing that these systems inhibit cell replication after exposure to light while displaying no impact on cell replication in the dark. This photodynamic action has been studied using cultured Vero cells with a pre-incubation with the complexes, rinsing to remove complex from the media, followed by photo-activation and cell growth assay. The photodynamic action of this new series of complexes can be tuned as a function of components of the supramolecular assembly and complexes capable of coupling to targeting proteins and fluorescent reporter groups have been synthesized.

  5. Ferrimagnetism in the double perovskite Ca2FeOsO6: A density functional study

    NASA Astrophysics Data System (ADS)

    Wang, Hongbo; Zhu, Shasha; Ou, Xuedong; Wu, Hua

    2014-08-01

    Using density functional calculations, we find that the newly synthesized Ca2FeOsO6 has the high-spin Fe3+ (3d5)-Os5+ (5d3) state. The octahedral Os5+ ion has a large intrinsic exchange splitting, and its t2g↑3 configuration makes the spin-orbit coupling ineffective. Moreover, there is a strong antiferromagnetic (AF) coupling between the neighboring Fe3+ (S=5/2) and Os5+ (S=-3/2), but the AF couplings within both the fcc Fe3+ and Os5+ sublattices are one order of magnitude weaker. Therefore a magnetic frustration is suppressed and a stable ferrimagnetic ground state appears. This ferrimagnetic order is due to the virtual hopping of the t2g electrons from Os5+ (t2g↓3) to Fe3+ (t2g↑3eg↑2). However, if the experimental bended Fe3+-O2--Os5+ exchange path gets straight, the eg hopping from Fe3+ (t2g↑3eg↑2) to Os5+ (t2g↑3) would be facilitated and then a ferromagnetic (FM) coupling would occur.

  6. First-Principles Study of Effects of Boron on Magnetic Anisotropy in MgO/CoFe(B)/X (X = Ru, Ta) Systems

    NASA Astrophysics Data System (ADS)

    Suzuki, Shugo; Shiota, Masashi; Fukuchi, Yasushi

    2016-09-01

    We study the effects of boron on the magnetic anisotropy in the MgO/CoFe(B)/X (X = Ru, Ta) systems using relativistic first-principles calculations. It is found that the B atoms tend to be rejected from the CoFeB layer into the X underlayer. The system with no B atoms shows perpendicular magnetic anisotropy when the Fe atoms are adjacent to the MgO layer.

  7. Frustration by competing interactions in the highly-distorted double perovskites La2NaB'O6 (B' = Ru, Os)

    SciTech Connect

    Aczel, Adam A; Bugaris, Dan; Li, Ling; Yan, Jiaqiang; Dela Cruz, Clarina R; Zur Loye, Hans-Conrad; Nagler, Stephen E

    2013-01-01

    The usual classical behaviour of S = 3/2, B-site ordered double perovskites generally results in simple, commensurate magnetic ground states. In contrast, heat capacity and neutron powder diffraction measurements for the S = 3/2 systems La2NaB'O6 (B = Ru, Os) reveal an incommensurate magnetic ground state for La2NaRuO6 and a drastically suppressed ordered moment for La2NaOsO6. This behaviour is attributed to the large monoclinic structural distortions of these double perovskites. The distortions have the effect of weakening the nearest neighbour superexchange interactions, presumably to an energy scale that is comparable to the next nearest neighbour superexchange. The exotic ground states in these materials can then arise from a competition between these two types of antiferromagnetic interactions, providing a novel mechanism for achieving frustration in the double perovskite family.

  8. Reduced magnetic coercivity and switching field in NiFeCuMo/Ru/NiFeCuMo synthetic-ferrimagnetic nanodots

    NASA Astrophysics Data System (ADS)

    Li, X.; Leung, C. W.; Chiu, C.-C.; Lin, K.-W.; Chan, Mansun; Zhou, Y.; Pong, Philip W. T.

    2017-07-01

    The coercivity (Hc) and switching field (Hsw) of free layers increase remarkably with shrinking structural dimensions, reducing the sensitivity of nanosized magnetoresistive sensors. In this work, conetic-alloy (NiFeCuMo) synthetic ferrimagnetic (SyF) trilayers are proposed to reduce Hc and Hsw in magnetic nanostructures. SyF stacks of NiFeCuMo/Ru/NiFeCuMo were patterned into nanodot arrays with diameter of 60 nm by nanosphere lithography. The thickness of Ru layer was chosen so that high interlayer coupling energy existed in the continuous film. The linear dependence of Hc and Hsw of SyF nanodot on the amplification factor was revealed. Magnetic field annealing was conducted at various temperatures (Tan) ranging from 373 K to 673 K. Annealing at low temperature (Tan ≤ 473 K) relaxed the structural disorders, resulting in reduced surface roughness and decreased Hc and Hsw. Higher Tan changed the preferred orientations in the crystalline structures, leading to increased roughness and higher Hc and Hsw. This work shows that the Hc and Hsw of nanostructures can be reduced through engaging Conetic alloy in SyF stack. The Conetic-alloy-based SyF structures are a promising candidate as free layers in nanosized spintronic devices.

  9. Rigid rod-like dinuclear Ru(II)/Os(II) terpyridine-type complexes. Electrochemical behavior, absorption spectra, luminescence properties, and electronic energy transfer through phenylene bridges

    SciTech Connect

    Barigelletti, F.; Flamigni, L.; Balzani, V. ||

    1994-08-24

    The absorption spectra, the luminescence properties (at 293 and 77 K), and the electrochemical behavior of six dinuclear heterometallic compounds have been investigated. The compounds are made of Ru(tpy){sub 2}{sup 2+}- and Os(tpy){sub 2}{sup 2+}-type components (tpy = 2,2{prime}:6{prime},2 inches-terpyridine, which in some cases carries p-tolyl (Meph) or methylsulphone (MeO{sub 2}S) substituents in the 4{prime} position), connected by n phenylene (ph) spacers (n=0,1, and 2). In the resulting rigid rod-like structures of general formula (X{sub 1}tpy)Ru(tpy(ph){sub n}tpy)Os(tpyX{sub 2}){sup 4+} the metal-to-metal distance varies form 11 to 20 {Angstrom}. The absorption spectra of the two components are slightly perturbed in the dinuclear compounds, and metal-metal and ligand-ligand interactions are evidenced by the trends of the oxidation and reduction potentials. The luminescence of the Ru-based unit is quenched by the connected Os-based unit with practically unitary efficiency, regardless of the number of interposed phenylene spacers. Quenching is accompanied by quantitative sensitization of the Os-based luminescence. The rate of energy transfer at 293 K is larger than 10{sup 10} s{sup -1} in all cases. The Foerster (Coulombic) mechanism does not satisfactorily account for such a fast rate, particularly for the species with n=2. It is concluded that the observed energy-transfer processes take place most likely via a Dexter (electron exchange) mechanism. This is consistent with the strong electronic coupling of the Ru-based units in the compound with n=0, and with the relatively small insulating effect expected for the phenylene spacers. 37 refs., 7 figs., 3 tabs.

  10. Limits on superconductivity-related magnetization in Sr 2RuO 4 and PrOs 4Sb 12 from scanning SQUID microscopy

    SciTech Connect

    Moler, Kathryn

    2010-08-26

    We present scanning SQUID microscopy data on the superconductors Sr{sub 2}RuO{sub 4} (T{sub c} = 1.5 K) and PrOs{sub 4}Sb{sub 12} (T{sub c} = 1.8 K). In both of these materials, superconductivity-related time-reversal symmetry-breaking fields have been observed by muon spin rotation; our aim was to visualize the structure of these fields. However in neither Sr{sub 2}RuO{sub 4} nor PrOs{sub 4}Sb{sub 12} do we observe spontaneous superconductivity-related magnetization. In Sr{sub 2}RuO{sub 4}, many experimental results have been interpreted on the basis of a p{sub x} {+-} ip{sub y} superconducting order parameter. This order parameter is expected to give spontaneous magnetic induction at sample edges and order parameter domain walls. Supposing large domains, our data restrict domain wall and edge fields to no more than {approx}0.1% and {approx}0.2% of the expected magnitude, respectively. Alternatively, if the magnetization is of the expected order, the typical domain size is limited to {approx}30 nm for random domains, or {approx} 500 nm for periodic domains.

  11. Ionization and photofragmentation of Ru{sub 3}(CO){sub 12} and Os{sub 3}(CO){sub 12}

    SciTech Connect

    Schalk, Oliver E-mail: melanie.mucke@physics.uu.se; Josefsson, Ida; Odelius, Michael; Richter, Robert; Prince, Kevin C.; Mucke, Melanie E-mail: melanie.mucke@physics.uu.se

    2015-10-21

    In this paper, we use a combination of photoelectron spectroscopy, mass spectrometry, and density functional theory calculations to get a detailed understanding of valence single and double ionization and the subsequent dissociation processes. This is exemplified on benchmark systems, trimetallo-dodecacarbonyls M{sub 3}(CO){sub 12} with M = Ru, Os, where the energy remaining in the molecule after photoionization can be retrieved by measuring the degree of fragmentation of the molecular ion. The intensity of different mass peaks can thus be directly related to ionization cross sections obtained by photoelectron spectroscopy. We find that the M—CO dissociation energy rises as the number of CO ligands decreases due to dissociation. Moreover, ionization of the CO ligands has a higher cross section than that of the metal center for both single and double ionization. After advanced fragmentation, a CO bond can break and the carbon atom remains bonded to the metal core. In addition, we found that the valence ionization cross sections of M{sub 3}(CO){sub 12} are maximal at about 40 eV photon energy thus showing a more pronounced shape resonance than Ru and Os-complexes with a single metal atom center. Finally, an np → nd giant resonance absorption causes a significant increase of the ionization cross section above 50 eV for Ru{sub 3}(CO){sub 12}.

  12. Substitution effects on superconducting and normal state properties in (Mo1-xTx)3Sb7, where T = Ru and Fe

    NASA Astrophysics Data System (ADS)

    Tran, V. H.

    2016-12-01

    The effects of Ru- and Fe-doping on the physical properties of Mo3Sb7 were studied by measuring ac-susceptibility, dc-magnetization, electrical resistivity and specific heat. It is found that single-phased (Mo{}1-xRu x )3Sb7 and (Mo{}1-xFe x )3Sb7 samples are obtained for the concentrations x ≤slant 0.1. In this concentration range, the lattice parameter shrinks with increasing dopant content. The substitution effects on the superconducting and normal state properties are completely different between two investigated systems. In the Ru-based solid solution alloys, the substitution enhances the superconducting parameters T c and H c2 and also benefits the spin-gap opening at {T}* ˜ 50 K. In contrast, in the Fe-substituted samples, there is a depression of both T c and H c2, accompanied by vanishing spin-gap and low-dimensional magnetic correlation. The substitution of the Mo atoms by Ru and Fe atoms suppresses the cubic-tetragonal distortion, but presumably favours the magnetic field to induce a magnetic order below T *.

  13. On the inter-layer magneto-electric coupling in BiFeO3/SrRuO3 heterostructure

    NASA Astrophysics Data System (ADS)

    Sil, Anomitra; Wagh, Aditya A.; Sharma, Deepak; Ranjan, Rajeev; Anil Kumar, P. S.

    2017-09-01

    Interlayer magneto-electric coupling in BiFeO3/SrRuO3 heterostructures was investigated by impedance spectroscopy over a temperature range of 80 K-260 K. In-plane impedance measurements were performed using interdigitated gold electrodes fabricated on the BiFeO3 layer. The Nyquist plots at different temperatures were fitted with an equivalent circuit model of the heterostructure. A pronounced dip in the temperature coefficient of equivalent-capacitance and a distinct increase in the temperature coefficient of equivalent-resistance of the BiFeO3 layer were observed on cooling across ferromagnetic TC of the bottom SrRuO3 layer. Temperature dependent capacitance (at 0 T magnetic fields) and magneto-capacitance (at 5 T magnetic fields) plots showed anomalies near 160 K. A shift of the hysteresis loop along the magnetization axis in field cooled M-H measurements was also found, which indicates the presence of pinned SrRuO3 moments due to the magnetic interaction at the interface. These observations suggest a strong magneto-electric coupling between the BiFeO3 and SrRuO3 layers of this heterostructure.

  14. Tailoring the composition of ultrathin, ternary alloy PtRuFe nanowires for the methanol oxidation reaction and formic acid oxidation reaction

    DOE PAGES

    Scofield, Megan E.; Koenigsmann, Christopher; Wang, Lei; ...

    2014-11-25

    In the search for alternatives to conventional Pt electrocatalysts, we have synthesized ultrathin, ternary PtRuFe nanowires (NW), possessing different chemical compositions in order to probe their CO tolerance as well as electrochemical activity as a function of composition for both (i) the methanol oxidation reaction (MOR) and (ii) the formic acid oxidation reaction (FAOR). As-prepared ‘multifunctional’ ternary NW catalysts exhibited both higher MOR and FAOR activity as compared with binary Pt₇Ru₃ NW, monometallic Pt NW, and commercial catalyst control samples. In terms of synthetic novelty, we utilized a sustainably mild, ambient wet-synthesis method never previously applied to the fabrication ofmore » crystalline, pure ternary systems in order to fabricate ultrathin, homogeneous alloy PtRuFe NWs with a range of controlled compositions. Thus, these NWs were subsequently characterized using a suite of techniques including XRD, TEM, SAED, and EDAX in order to verify not only the incorporation of Ru and Fe into the Pt lattice but also their chemical homogeneity, morphology, as well as physical structure and integrity. Lastly, these NWs were electrochemically tested in order to deduce the appropriateness of conventional explanations such as (i) the bi-functional mechanism as well as (ii) the ligand effect to account for our MOR and FAOR reaction data. Specifically, methanol oxidation appears to be predominantly influenced by the Ru content, whereas formic acid oxidation is primarily impacted by the corresponding Fe content within the ternary metal alloy catalyst itself.« less

  15. Tailoring the composition of ultrathin, ternary alloy PtRuFe nanowires for the methanol oxidation reaction and formic acid oxidation reaction

    SciTech Connect

    Scofield, Megan E.; Koenigsmann, Christopher; Wang, Lei; Liu, Haiqing; Wong, Stanislaus S.

    2014-11-25

    In the search for alternatives to conventional Pt electrocatalysts, we have synthesized ultrathin, ternary PtRuFe nanowires (NW), possessing different chemical compositions in order to probe their CO tolerance as well as electrochemical activity as a function of composition for both (i) the methanol oxidation reaction (MOR) and (ii) the formic acid oxidation reaction (FAOR). As-prepared ‘multifunctional’ ternary NW catalysts exhibited both higher MOR and FAOR activity as compared with binary Pt₇Ru₃ NW, monometallic Pt NW, and commercial catalyst control samples. In terms of synthetic novelty, we utilized a sustainably mild, ambient wet-synthesis method never previously applied to the fabrication of crystalline, pure ternary systems in order to fabricate ultrathin, homogeneous alloy PtRuFe NWs with a range of controlled compositions. Thus, these NWs were subsequently characterized using a suite of techniques including XRD, TEM, SAED, and EDAX in order to verify not only the incorporation of Ru and Fe into the Pt lattice but also their chemical homogeneity, morphology, as well as physical structure and integrity. Lastly, these NWs were electrochemically tested in order to deduce the appropriateness of conventional explanations such as (i) the bi-functional mechanism as well as (ii) the ligand effect to account for our MOR and FAOR reaction data. Specifically, methanol oxidation appears to be predominantly influenced by the Ru content, whereas formic acid oxidation is primarily impacted by the corresponding Fe content within the ternary metal alloy catalyst itself.

  16. Simplified method for the determination of Ru, Pd, Re, Os, Ir and Pt in chromitites and other geological materials by isotope dilution ICP-MS and acid digestion.

    PubMed

    Meisel, T; Moser, J; Fellner, N; Wegscheider, W; Schoenberg, R

    2001-03-01

    A method for the determination of low Ru, Pd, Re, Os, Ir and Pt abundances in geological reference materials by isotope dilution inductively coupled plasma mass spectrometry (ICP-MS) after acid digestion in a high pressure asher (HPA-S) is presented. The digestion technique is similar to that using Carius tubes but easier to handle and reaches higher temperatures. Osmium can be determined as OsO4 with ICP-MS directly after digestion through a sparging technique. The remaining elements are preconcentrated by means of anion column chromatography. The resin is digested directly without elution leading to high yields but this causes problems if Zr is present at higher levels in the silicate rich materials. The analytical results for international platinum group element (PGE) reference materials, chromitite CHR-Bkg, basalt TDB-1 and gabbro WGB-1, are presented and compared with literature data, demonstrating the validity of the described method. Although higher in concentration, PGEs determined for reference material WGB-1 were worse than for TDB-1 indicating a more inhomogeneous distribution of the platinum group mineral phases. The low PGE abundance chromitite standard, CHR-Bkg, is likely to be homogeneous for Ru, Re, Os and Ir and is recommended as a reference material for the study of chromitites. Detection limits (3s x total procedure blank) range from 0.012 ng (Re and Os) to 0.77 ng (Pt), which could be further improved by applying higher quality acids.

  17. Structure and magnetic properties of L1{sub 0}-FePt thin films on TiN/RuAl underlayers

    SciTech Connect

    Yang En; Ratanaphan, Sutatch; Zhu Jiangang; Laughlin, David E.

    2011-04-01

    Highly ordered L1{sub 0} FePt-oxide thin films with small grains were prepared by using a RuAl layer as a grain size defining seed layer along with a TiN barrier layer. Different HAMR (Heat Assisted Magnetic Recording) favorable underlayers were studied to encourage perpendicular texture and preferred microstructure. It was found that the epitaxial and small grain growth from the RuAl/TiN underlayer results in small and uniform grains in the FePt layer with perpendicular texture. By introducing the grain size defining underlayers, the FePt grain size can be reduced from 30 to 6 nm with the same volume fraction (9%) of SiO{sub 2} in the film, excellent perpendicular texture, and very high order parameter at 520 deg. C.

  18. First-principles study on the structure, elastic properties, hardness and electronic structure of TMB{sub 4} (TM=Cr, Re, Ru and Os) compounds

    SciTech Connect

    Pan, Y.; Zheng, W.T.; Guan, W.M.; Zhang, K.H.; Fan, X.F.

    2013-11-15

    The structural formation, elastic properties, hardness and electronic structure of TMB{sub 4} (TM=Cr, Re, Ru and Os) compounds are investigated using first-principles approach. The value of C{sub 22} for these compounds is almost two times bigger than the C{sub 11} and C{sub 33}. The intrinsic hardness, shear modulus and Young's modulus are calculated to be in a sequence of CrB{sub 4}>ReB{sub 4}>RuB{sub 4}>OsB{sub 4}, and the Poisson's ratio and B/G ratio of TMB{sub 4} follow the order of CrB{sub 4}RuB{sub 4}<OsB{sub 4}. The intrinsic hardness of CrB{sub 4} and ReB{sub 4} by LDA is bigger than 40 GPa. The high hardness of TMB{sub 4} compounds is derived from the feature of B–B bonds cage and higher C{sub 22} value. The B–B covalent bonds as bonds cage enhances the resistance to shear deformation and improve the hardness. We predict that the TMB{sub 4} compounds with CrB{sub 4}-type are the potential superhard materials. - Graphical abstract: The first-principles calculations show that the intrinsic hardness of CrB{sub 4} and ReB{sub 4} are bigger than 40 GPa, which are the potential superhard materials due to the B–B bonds cage structure. Display Omitted - Highlights: • The intrinsic hardness of CrB{sub 4} and ReB{sub 4} is bigger than 40 GPa. • The hardness of TMB{sub 4} is calculated to be in a sequence of CrB{sub 4}>ReB{sub 4}>RuB{sub 4}>OsB{sub 4}. • The trend of hardness for TMB{sub 4} is consistent with the variation of elastic modulus. • The C{sub 22} value of TMB{sub 4} is bigger than that of C{sub 11} and C{sub 33}. • The high hardness of TMB{sub 4} is originated from the B–B bonds cage.

  19. Magnetoresistance Versus Oxygen Deficiency in Epi-stabilized SrRu1 - x Fe x O3 - δ Thin Films.

    PubMed

    Dash, Umasankar; Acharya, Susant Kumar; Lee, Bo Wha; Jung, Chang Uk

    2017-12-01

    Oxygen vacancies have a profound effect on the magnetic, electronic, and transport properties of transition metal oxide materials. Here, we studied the influence of oxygen vacancies on the magnetoresistance (MR) properties of SrRu1 - x Fe x O3 - δ epitaxial thin films (x = 0.10, 0.20, and 0.30). For this purpose, we synthesized highly strained epitaxial SrRu1 - x Fe x O3 - δ thin films with atomically flat surfaces containing different amounts of oxygen vacancies using pulsed laser deposition. Without an applied magnetic field, the films with x = 0.10 and 0.20 showed a metal-insulator transition, while the x = 0.30 thin film showed insulating behavior over the entire temperature range of 2-300 K. Both Fe doping and the concentration of oxygen vacancies had large effects on the negative MR contributions. For the low Fe doping case of x = 0.10, in which both films exhibited metallic behavior, MR was more prominent in the film with fewer oxygen vacancies or equivalently a more metallic film. For semiconducting films, higher MR was observed for more semiconducting films having more oxygen vacancies. A relatively large negative MR (~36.4%) was observed for the x = 0.30 thin film with a high concentration of oxygen vacancies (δ = 0.12). The obtained results were compared with MR studies for a polycrystal of (Sr1 - x La x )(Ru1 - x Fe x )O3. These results highlight the crucial role of oxygen stoichiometry in determining the magneto-transport properties in SrRu1 - x Fe x O3 - δ thin films.

  20. Observation of spin-wave Doppler shift in Co90Fe10/Ru micro-strips for evaluating spin polarization

    NASA Astrophysics Data System (ADS)

    Sugimoto, Satoshi; Rosamond, Mark C.; Linfield, Edmund H.; Marrows, Christopher H.

    2016-09-01

    The current-induced spin-wave Doppler shift has been investigated for Co90Fe10 films, with and without under- and overlayers of Ru, aiming to obtain quantitative insights into the value of spin polarization of the diffusive electrical currents flowing in this material. This extends the use of spin-wave Doppler shift spectroscopy beyond the study of permalloy to other soft magnetic materials suitable for use in spintronic applications such as racetrack memories. The Damon-Eshbach spin-wave mode was employed, and a control experiment of permalloy yielded a value of spin polarization of P = 0.44 ± 0.03 for that material. An extended method to properly evaluate spin-wave Doppler shifts is developed that takes account of the non-negligible Oersted fields that are generated by the current density asymmetry caused by conducting under- or overlayers. The values of spin polarization for various Co90Fe10-based structures are found to lie in the range of 0.3-0.35, only slightly less than in permalloy.

  1. Noncollinear ferromagnetic easy axes in Py/Ru/FeCo/IrMn spin valves induced by oblique deposition

    SciTech Connect

    Bueno, T. E. P.; Parreiras, D. E.; Gomes, G. F. M.; Krambrock, K.; Paniago, R.; Michea, S.; Rodríguez-Suárez, R. L.; Filho, M. S. Araújo; Macedo, W. A. A.

    2014-06-16

    We present an investigation on the magnetic properties of Py/Ru/FeCo/IrMn spin valves grown by dc magnetron sputtering. The sample fabrication setup has two important features, (i) the five magnetron sputtering sources are placed in a cluster flange 72° from each other, and (ii) each source is tilted with respect to the sample normal. In-plane angular dependence of the ferromagnetic resonance (FMR) was used to obtain the relevant magnetic anisotropies, such as uniaxial and exchange bias fields. The oblique deposition geometry employed has induced non-collinear easy axes of the two ferromagnetic (FM) layers, with high uniaxial field strengths. The symmetry shift of the angular dependence of the FMR resonances of the two FM layers gives us directly the angle between the easy axes of FM{sub 1} (Py) and FM{sub 2} (FeCo), which turned out to be the angle between two adjacent sputtering sources. The observations of the present study suggest that, by combining oblique deposition and appropriate angles of incidence of the deposition flux, the uniaxial (and unidirectional) axes of individual FM layers can be precisely engineered in spin valve fabrication.

  2. Chemical Tuning of Magnetic Properties through Ru/Rh Substitution in Th7Fe3-type FeRh6-nRunB3 (n = 1-5) Series.

    PubMed

    Shankhari, Pritam; Misse, Patrick R N; Mbarki, Mohammed; Park, Hyounmyung; Fokwa, Boniface P T

    2017-01-03

    The new quaternary boride series FeRh6-nRunB3 (n = 1-5) was synthesized by arc melting and characterized by powder and single-crystal X-ray diffraction (XRD), energy-dispersive X-ray analysis, and superconducting quantum interference device magnetometry. Single-crystal structure refinement showed the distribution of the iron atoms in two of three possible crystallographic 4d metal sites in the structure (Th7Fe3-type, space group P63mc). Rietveld refinements of the powder XRD data indicated single-phase synthesis of all the members. A linear decrease of the lattice parameters and the unit cell volume with increasing Ru content was found, indicating Vegard's behavior. Susceptibility measurements show decreasing Curie temperature and magnetic moment (μa(5T)) recorded at 5 T with increasing Ru content from TC = 295 K and μa(5T) = 3.35 μB (FeRh5RuB3) to TC = 205 K and μa(5T) = 0.70 μB (FeRhRu5B3). The measured coercivities lie between 1.0 and 2.2 kA/m indicating soft to semihard magnetic materials.

  3. Synthesis, crystal structure, and electronic properties of high-pressure PdF2-type oxides MO2 (M = Ru, Rh, Os, Ir, Pt).

    PubMed

    Shirako, Yuichi; Wang, Xia; Tsujimoto, Yoshihiro; Tanaka, Kie; Guo, Yanfeng; Matsushita, Yoshitaka; Nemoto, Yoshihiro; Katsuya, Yoshio; Shi, Youguo; Mori, Daisuke; Kojitani, Hiroshi; Yamaura, Kazunari; Inaguma, Yoshiyuki; Akaogi, Masaki

    2014-11-03

    The polycrystalline MO2's (HP-PdF2-type MO2, M = Rh, Os, Pt) with high-pressure PdF2 compounds were successfully synthesized under high-pressure conditions for the first time, to the best of our knowledge. The crystal structures and electromagnetic properties were studied. Previously unreported electronic properties of the polycrystalline HP-PdF2-type RuO2 and IrO2 were also studied. The refined structures clearly indicated that all compounds crystallized into the HP-PdF2-type structure, M(4+)O(2-)2, rather than the pyrite-type structure, M(n+)(O2)(n-) (n < 4). The MO2 compounds (M = Ru, Rh, Os, Ir) exhibited metallic conduction, while PtO2 was highly insulating, probably because of the fully occupied t2g band. Neither superconductivity nor a magnetic transition was detected down to a temperature of 2 K, unlike the case of 3d transition metal chalcogenide pyrites.

  4. Synthesis of, characterization of, and photoinduced processes in polymetallic triad complexes containing Fe(II), Ru(II), and Rh(III) metal centers

    SciTech Connect

    Ronco, S.E. |; Thompson, D.W.; Gahan, S.L.; Petersen, J.D. |

    1998-04-20

    A series of new trimetallic mixed complexes containing Fe(II), Ru(II), and Rh(III) metal centers have been prepared and characterized, and their excited-state properties in a nanosecond time domain have been investigated. These new compounds were synthesized by following a building block strategy from monomeric Rh(III) and Ru(II) polyazines and tetracyanoferrate(II) ions. The products generated in each synthetic step were fully characterized and their excited-state properties investigated. These new trimetallic complexes, [(CN){sub 4}Fe{sup II}(BL(1))Ru{sup II}(bpy)-(BL(2))Rh{sup III}(tpy)(MQ{sup +})](PF{sub 6}){sub 4} (tpy = 2,2{prime}:6{prime}:2{double_prime}-terpyridine; BL(1) = 2,3-bis(2-pyridyl)pyrazine (dpp) or 2,2{prime}-bipyrimidine (bpm); BL(2) = dpp or bpm; MQ{sup +} = N-methyl-4,4{prime}-bipyridinium (monoquat)), consist of three fundamental parts linked by bridging ligands (1) an electron donor group, the tetracyanoferrate(II) unit; (2) an antenna fragment, the Ru(II) polypyridyl moiety; and (3) an electron acceptor group. The electron acceptor group is a Rh(III) polypyridyl that contains the ligands tpy and MQ{sup +}. No emission was observed in any of the reported complexes either in fluid solutions at room temperature or in glassy solutions at 77 K. Time-resolved experiments conducted on these triads showed formation of a transient intermediate within the laser pulse. Redox properties and transient absorption observations helped the authors to identify the nature of this intermediate as an Fe(III)/Ru(II) mixed-valence species that decays exponentially by following a first-order law with a lifetime of {tau} {le} 70 ns in fluid solution at room temperature.

  5. Investigation of magnetic order in SmTr2Zn20 (Tr=Fe ,Co,Ru) and SmTr2Cd20 (Tr=Ni ,Pd)

    NASA Astrophysics Data System (ADS)

    Yazici, D.; White, B. D.; Ho, P.-C.; Kanchanavatee, N.; Huang, K.; Friedman, A. J.; Wong, A. S.; Burnett, V. W.; Dilley, N. R.; Maple, M. B.

    2014-10-01

    Single crystals of the "cage compounds" SmTr2Zn20 (Tr=Fe, Co, Ru) and SmTr2Cd20 (Tr=Ni, Pd) have been investigated by means of electrical resistivity, magnetization, and specific-heat measurements. The compounds SmFe2Zn20,SmRu2Zn20, and SmNi2Cd20 exhibit ferromagnetic order with Curie temperatures of TC=47.4, 7.6, and 7.5 K, respectively, whereas SmPd2Cd20 is an antiferromagnet with a Néel temperature of TN=3.4 K. No evidence for magnetic order is observed in SmCo2Zn20 down to 110 mK. The Sommerfeld coefficients γ are found to be 57 mJ /molK2 for SmFe2Zn20,79.5 mJ /molK2 for SmCo2Zn20,258 mJ /molK2 for SmRu2Zn20,165 mJ /molK2 for SmNi2Cd20, and 208 mJ /molK2 for SmPd2Cd20. Enhanced values of γ and a quadratic temperature dependence of the electrical resistivity at low temperature for SmRu2Zn20 and SmPd2Cd20 suggest an enhancement of the quasiparticle masses due to hybridization between localized 4f and conduction electron states.

  6. Investigation of magnetic order in SmTr2Zn20 (Tr = Fe, Co, Ru) and SmTr2Cd20 (Tr = Ni, Pd)

    NASA Astrophysics Data System (ADS)

    Yazici, Duygu; White, B. D.; Ho, P.-C.; Kanchanavatee, N.; Huang, K.; Dilley, N. R.; Maple, M. B.

    2015-03-01

    Single crystals of the cage compounds Sm Tr 2Zn20 (Tr = Fe, Co, Ru) and Sm Tr 2Cd20 (Tr = Ni, Pd) have been investigated by means of electrical resistivity, magnetization, and specific heat measurements. The compounds SmFe2Zn20, SmRu2Zn20,andSmNi2Cd20 exhibit ferromagnetic order with Curie temperatures of TC = 47.4 K, 7.6 K, and 7.5 K, respectively, whereas SmPd2Cd20 is an antiferromagnet with a Néel temperature of TN = 3.4 K. No evidence for magnetic order is observed in SmCo2Zn20 down to 110 mK. The Sommerfeld coefficients γ are found to be 57 mJ/mol-K2 for SmFe2Zn20, 79.5 mJ/mol-K2 for SmCo2Zn20, 258 mJ/mol-K2 for SmRu2Zn20, 165 mJ/mol-K2 for SmNi2Cd20, and 208 mJ/mol-K2 for SmPd2Cd20. Enhanced values of Sommerfeld coefficients γ and a quadratic temperature dependence of the electrical resistivity at low temperature for SmRu2Zn20andSmPd2Cd20 suggest an enhancement of the quasiparticle masses due to hybridization between localized 4 f and conduction electron states. Research at UCSD was supported by the U.S. DOE under Grant No. DE-FG02-04-ER46105 and the U.S. NSF under Award Grant No. DMR 1206553. Research at California State University, Fresno was supported by the U.S. NSF under Grant No. DMR 1104544.

  7. Rational synthetic tuning between itinerant antiferromagnetism and ferromagnetism in the complex boride series Sc2FeRu(5-n)RhnB2 (0

    PubMed

    Fokwa, Boniface P T; Lueken, Heiko; Dronskowski, Richard

    2007-01-01

    Single crystals of the complex boride series Sc(2)FeRu(5-n)Rh(n)B(2) (n=1, 3, 4) were synthesized by arc-melting the elements in water-cooled copper crucibles under argon atmospheres and were chemically characterized by single-crystal XRD and EDX analyses. The new compounds are isotypic and crystallize in the tetragonal space group P4/mbm with Z=2, adopting a substitutional variant of the Ti(3)Co(5)B(2)-type structure. The magnetically active iron atoms are arranged in chains with intra- and interchain distances of about 3.02 and 6.60 A, respectively. Strong ferromagnetic interactions are observed for both Sc(2)FeRuRh(4)B(2) (64 valence electrons (VE), TC approximately 350 K, mu(a)=3.1 mu(B)) and Sc(2)FeRu(2)Rh(3)B(2) (63 VE, T(C) approximately 300 K, mu(a)=3.0 mu(B)), whereas antiferromagnetic interactions are found in the case of Sc(2)FeRu(4)RhB(2) (61 VE, T(N) approximately 10 K, mu(eff)=3.2): The magnetism of the entire Sc(2)FeRu(5-n)Rh(n)B(2) (0Fe-Fe bonding character, and it is also compared with other isoelectronic systems.

  8. Direct observation of an anisotropic in-plane residual stress induced by B addition as an origin of high magnetic anisotropy field of Ru/FeCoB film

    SciTech Connect

    Hirata, Ken-ichiro; Gomi, Shunsuke; Mashiko, Yasuhiro; Nakagawa, Shigeki

    2010-05-15

    Although boron-free FeCo films prepared on a Ru underlayer exhibits isotropic in-plane magnetic property, boron added FeCoB films prepared on Ru underlayer revealed large in-plane magnetic anisotropy with a high anisotropy field of 500 Oe. The effect of boron addition on the in-plane anisotropic residual stress in FeCoB film was investigated using sin{sup 2} {psi} method of x-ray diffraction analysis. Large isotropic compressive stress was observed in Ru/FeCo film. In contrast, anisotropic in-plane residual stress was observed in Ru/FeCoB film. The compressive stress along the easy axis of Ru/FeCoB film is released more than that along the hard axis. Such anisotropic residual stress is regarded as an origin of the in-plane magnetic anisotropy through inverse magnetostriction effect. Owing to the configuration of the facing targets sputtering system, boron atoms are sputtered and deposited anisotropically, and so they penetrate FeCo crystals and release the compressive stress along the incidence direction.

  9. RuO2 nanoparticle-modified (Ce,Mn,Fe)O2/(La,Sr) (Fe,Mn)O3 composite oxide as an active anode for direct hydrocarbon type solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Shin, Tae Ho; Hagiwara, Hidehisa; Ida, Shintaro; Ishihara, Tatsumi

    2015-09-01

    Composite oxide anodes have recently attracted great attention as alternative materials for solid oxide fuel cell anodes because of their potential to overcome the serious performance deterioration associated with the traditional Ni-based cermet. In particular, oxide anodes show a greater tolerance to coke and reoxidation than existing Ni-based cermets. In this study, the anodic performance of a (Ce,Mn,Fe)O2/(La,Sr) (Fe,Mn)O3 composite oxide modified with additional amounts of catalytically active RuO2 nanoparticles was investigated. Heat treatment resulted in highly dispersed RuO2 particles (ca. 10 nm). Anodes containing 10 wt% added RuO2 exhibited fairly high maximum power densities of 0.3 and 1.5 W cm-2 in H2 and C3H8, respectively, at 800 °C. The cells showed stable power density and negligible carbon formation even after 50 h of operation at 1 A cm-2. The increased power density was assigned to decreased anodic overpotential and internal resistance losses because RuO2 nanoparticles contribute to the increase in electrical conductivity.

  10. Predicting a Ferrimagnetic Phase of Zn2FeOsO6 with Strong Magnetoelectric Coupling

    NASA Astrophysics Data System (ADS)

    Wang, P. S.; Ren, W.; Bellaiche, L.; Xiang, H. J.

    2015-04-01

    Multiferroic materials, in which ferroelectric and magnetic ordering coexist, are of practical interest for the development of novel memory devices that allow for electrical writing and nondestructive magnetic readout operation. The great challenge is to create room temperature multiferroic materials with strongly coupled ferroelectric and ferromagnetic (or ferrimagnetic) orderings. BiFeO3 is the most heavily investigated single-phase multiferroic to date due to the coexistence of its magnetic order and ferroelectric order at room temperature. However, there is no net magnetic moment in the cycloidal (antiferromagneticlike) magnetic state of bulk BiFeO3 , which severely limits its realistic applications in electric field controlled memory devices. Here, we predict that LiNbO3 -type Zn2FeOsO6 is a new multiferroic with properties superior to BiFeO3 . First, there are strong ferroelectricity and strong ferrimagnetism at room temperature in Zn2FeOsO6 . Second, the easy plane of the spontaneous magnetization can be switched by an external electric field, evidencing the strong magnetoelectric coupling existing in this system. Our results suggest that ferrimagnetic 3 d -5 d LiNbO3 -type material may therefore be used to achieve voltage control of magnetism in future memory devices.

  11. Predicting a ferrimagnetic phase of Zn(2)FeOsO(6) with strong magnetoelectric coupling.

    PubMed

    Wang, P S; Ren, W; Bellaiche, L; Xiang, H J

    2015-04-10

    Multiferroic materials, in which ferroelectric and magnetic ordering coexist, are of practical interest for the development of novel memory devices that allow for electrical writing and nondestructive magnetic readout operation. The great challenge is to create room temperature multiferroic materials with strongly coupled ferroelectric and ferromagnetic (or ferrimagnetic) orderings. BiFeO_{3} is the most heavily investigated single-phase multiferroic to date due to the coexistence of its magnetic order and ferroelectric order at room temperature. However, there is no net magnetic moment in the cycloidal (antiferromagneticlike) magnetic state of bulk BiFeO_{3}, which severely limits its realistic applications in electric field controlled memory devices. Here, we predict that LiNbO_{3}-type Zn_{2}FeOsO_{6} is a new multiferroic with properties superior to BiFeO_{3}. First, there are strong ferroelectricity and strong ferrimagnetism at room temperature in Zn_{2}FeOsO_{6}. Second, the easy plane of the spontaneous magnetization can be switched by an external electric field, evidencing the strong magnetoelectric coupling existing in this system. Our results suggest that ferrimagnetic 3d-5d LiNbO_{3}-type material may therefore be used to achieve voltage control of magnetism in future memory devices.

  12. Tunneling magnetoresistance of perpendicular magnetic tunnel junction using L10 FePt electrodes on MgO/CrRu/TiN under-layers

    NASA Astrophysics Data System (ADS)

    Soo Kim, Chang; Jung, Jin-Won; Choi, Dooho; Sahashi, Masashi; Kryder, Mark H.

    2014-05-01

    A perpendicular magnetic tunnel junction (pMTJ) device was fabricated using L10 ordered FePt electrodes, which were deposited on MgO(8 nm)/CrRu(10 nm)/TiN(4 nm) under-layers. It was found that the MgO/CrRu/TiN under-layer helps lower the required FePt deposition temperature to below 400 °C, and provides a well-ordered bottom L10 FePt electrode with root-mean-square (RMS) surface roughness close to 0.4 nm. Magnetoresistance (MR) ratio and resistance-area (RA) were measured at room temperature by the current-in-plane tunneling (CIPT) method from a lithographically unpatterned PMTJ sample and 138% and 6.4 kΩ μm2 were obtained, respectively. A PMTJ test pattern, with a junction size of 80 × 40 μm2, was also fabricated and showed a MR ratio and RA product of 108% and 4 ˜ 6 kΩ μm2, respectively, in good agreement with the CIPT measurements.

  13. Pressure-induced superconductivity and structural transitions in Ba(Fe0.9Ru0.1)2As2

    NASA Astrophysics Data System (ADS)

    Uhoya, Walter O.; Tsoi, Georgiy M.; Vohra, Yogesh K.; Sefat, Athena S.; Weir, Samuel T.

    2014-03-01

    Electrical transport and structural characterizations of isoelectronically substituted Ba(Fe0.9Ru0.1)2As2 have been performed as a function of pressure up to ~30 GPa and temperature down to ~10 K using designer diamond anvil cell. Similar to undoped members of the AFe2As2 (A = Ca, Sr, Ba) family, Ba(Fe0.9Ru0.1)2As2 shows anomalous a-lattice parameter expansion with increasing pressure and a concurrent ThCr2Si2 type isostructural (I4/mmm) phase transition from tetragonal (T) phase to a collapsed tetragonal (cT) phase occurring between 12 and 17 GPa where the a is maximum. Above 17 GPa, the material remains in the cT phase up to 30 GPa at 200 K. The resistance measurements show evidence of pressure-induced zero resistance that may be indicative of high-temperature superconductivity for pressures above 3.9 GPa. The onset of the resistive transition temperature decreases gradually with increasing pressure before completely disappearing for pressures above ~10.6 GPa near the T-cT transition. We have determined the crystal structure of the high-Tc phase of Ru-doped BaFe2As2 to remain as tetragonal (I4/mmm) by analyzing the X-ray diffraction pattern obtained at 10 K and 9.7 ± 0.7 GPa, as opposed to inferring the structural transition from electrical resistance measurement, as in a previous report [S.K. Kim, M.S. Torikachvili, E. Colombier, A. Thaler, S.L. Bud'ko, P.C. Canfield, Phys. Rev. B 84, 134525 (2011)].

  14. Distribution of nonequivalent aluminum sites revealed in Al-Cu-Ru and Al-Cu-Fe quasicrystals by [sup 27]Al NQR

    SciTech Connect

    Shastri, A.; Borsa, F.; Torgeson, D.R.; Goldman, A.I. )

    1994-08-01

    The distribution of nonequivalent aluminum sites was studied in Al-Cu-Fe and Al-Cu-Ru stable icosahedral quasicrystalline phases using [sup 27]Al NQR spectra taken at 4.2 K. The observed spectra---which give directly the distribution of nonequivalent aluminum sites---were broad, asymmetric, and structureless. A simple electric-field-gradient model calculation accounted for the spectral width in terms of a wide distribution of local atomic environments, and an estimate for the lower limit on the number of nonequivalent aluminum sites was found.

  15. Rigid MIIL2Gd2III (M = Fe, Ru) complexes of a terpyridine-based heteroditopic chelate: a class of candidates for MRI contrast agents.

    PubMed

    Costa, Jérôme; Ruloff, Robert; Burai, László; Helm, Lothar; Merbach, André E

    2005-04-13

    Rigid chelates of high-molecular weight, [M(tpy-DTTA)2]6- (M = Fe, Ru), are obtained upon self-assembly around one M(II) ion of two terpyridine-based molecules substituted in the 4'-position with the polyaminocarboxylate diethylenetriamine-N,N,N'',N''-tetraacetate, tpy-DTTA4-. The protonation constants of tpy-DTTA4- (log K1 = 8.65(4), log K2 = 7.63(4), log K3 = 5.25(6), log K4 = 3.30(7)) and [Fe(tpy-DTTA)2]6- (log K1 = 8.40(4), log K2 = 7.26(4)) have been determined by potentiometry, 1H NMR and UV-vis titrations. The thermodynamic stability constant log K(GdL) of [Fe(tpy-DTTA)2Gd2(H2O)4] measured at 25 degrees C by potentiometry is 10.87. This relatively low value is due to the direct linkage of the polyaminocarboxylate part to the electron-withdrawing terpyridine. UV-vis absorbance spectra of [M(tpy-DTTA)2Gd2(H2O)4] and 1H NMR spectra of [M(tpy-DTTA)2Eu2(H2O)4] revealed similar solution behavior of the Fe and Ru complexes. An I(d) water-exchange mechanism (DeltaV++ = +6.8 +/- 1 cm3 mol(-1)) with a rate constant of k(ex)298 = (5.1 +/- 0.3) x 10(6) s(-1) has been found for [Fe(tpy-DTTA)2Gd2(H2O)4] by 17O NMR. A slow rotational correlation time (tau(RO) = 410 +/- 10 ps) and the presence of two water molecules (q = 2) in the coordination inner-sphere of each Gd(III) ion have also been determined for this complex. A remarkably high relaxivity has been observed for both [M(tpy-DTTA)2Gd2(H2O)4] complexes (at 20 MHz and 37 degrees C, r(1) = 15.7 mM(-1) s(-1) for the Fe complex, and r(1) = 15.6 mM(-1) s(-1) for the Ru complex).

  16. [Phlebotominae: vectors of leishmaniasis in the provinces of Santa Fe and Entre Ríos, Argentina].

    PubMed

    Salomón, Oscar D; Mocarbel, Nicolás J; Pedroni, Elena; Colombo, Javier; Sandillú, Mónica

    2006-01-01

    The transmission of tegumentary leishmaniasis (TL) has increased in 9 provinces of Argentina since 1985. Santa Fe and Entre Ríos did not record in this period autochtonous probed cases: however, an epidemic outbreak took place in 2003 in Bella Vista, Corrientes, located in an area with ecological continuity and contiguous to both provinces. In order to evaluate the potential risk of transmission of LT, Phlebotominae were captured at locations close to and southern from Bella Vista during February 2004. The traps located on the shores of Parana river in Santa Fe (El Rabón, Villa Ocampo, Cayastá), and Entre Ríos (La Paz. La Celina-Villa Urquiza) captured 860 individuals of Lutzomyia neivai (99.5%) and Lu. migonei (0.5 %), both species with vectorial capacity for Leishmania (V.) braziliensis. In Tartagal, Santa Fe, the captures were consistent with the residual "chaco" landscape, 7 individuals of Lu. nerivai, Lu. migonei and Lu. cortelezzii. The risk of LT epidemic transmission in these provinces is highlighted, mainly due to the progressive southern tropicalization of the paranaense gallery forest. Clinical and entomological surveillance is recommended.

  17. Ru-Os dyads based on a mixed bipyridine-terpyridine bridging ligand: modulation of the rate of energy transfer and pH-induced luminescence switching in the infrared domain.

    PubMed

    Bar, Manoranjan; Maity, Dinesh; Deb, Sourav; Das, Shyamal; Baitalik, Sujoy

    2017-10-03

    A series of heterobimetallic complexes of compositions [(bpy/phen)2Ru(dipy-Hbzim-tpy)Os (tpy-PhCH3/H2pbbzim)](4+) (bpy = 2,2'-bipyridine, phen = 1,10-phenanthroline, tpy-PhCH3 = 4'-(4-methylphenyl)-2,2':6',2''-terpyridine and H2pbbzim = 2,6-bis(benzimidazole-2-yl)pyridine)), derived from a heteroditopic bpy-tpy bridging ligand, were synthesized and thoroughly characterized in this work. The heterometallic complexes exhibit two successive one-electron reversible metal-centered oxidations corresponding to Os(II)/Os(III) at lower potential and Ru(II)/Ru(III) at higher potential. All the four dyads exhibit very intense, ligand centered absorption bands in the UV region and moderately intense MLCT bands in the visible region. The dyads also show intense infrared emission with the emission maximum spanning between 734 nm and 775 nm with reasonably long room temperature lifetimes varying between 30 ns and 104 ns. Both steady state and time resolved luminescence spectroscopic investigations indicate that efficient and fast intramolecular energy transfer from the (3)MLCT state of the Ru(ii) center to the Os-center takes place in all the four dyads. In addition, the rate of energy transfer was found to depend on the terminal ligand on the Os-site. Due to the presence of a number of imidazole NH protons in the dyads, significant modulation of both the ground and excited state properties of the complexes was made possible by varying the pH of the solution. By varying the terminal ligand, pH-induced "on-off", "off-off-on" and "on-off-on" emission switching of the complexes was nicely demonstrated in the infrared region.

  18. First-principles study of the Hume-Rothery electron concentration rule in Al-Cu-(Fe,Ru)-Si 1/1-cubic approximants

    NASA Astrophysics Data System (ADS)

    Asahi, Ryoji; Kontsevoi, O. Y.; Mizutani, U.; Takeuchi, T.; Freeman, A. J.

    2006-03-01

    To elucidate the Hume-Rothery electron concentration rule, we determined the self-consistent electronic structures of the Al108Ru24Cu6Si6 and Al108Fe24Cu6Si6 1/1-1/1-1/1 approximants containing 144 atoms in each Pm-3 cubic unit cell using the full-potential linearized augmented plane wave (FLAPW) method [1], now running on massively parallel computer platforms. A significant pseudogap was found around the Fermi level for both alloys in the calculated densities of states, which should contribute to stabilization of the system. The FLAPW wave functions provide a direct observation of the Brillouin zone resonance in the Fermi surface [2]: a Fourier analysis of the wave functions confirms the Hume-Rothery matching rule 2kF=K where the reciprocal lattice vectors K consist of 543, 550, and 710 planes highly degenerate at the N point. Consequently, an effective electron concentration per atom (e/a) was evaluated to be 0.8 for both Ru and Fe in these structures making a sharp contrast with the previously assumed empirical value of -2.7 proposed by Raynor [3]. [1] Wimmer et al., Phys. Rev. B 24, 864 (1981). [2] Asahi et al., Phys. Rev. B 72, 125102 (2005). [3] Raynor, Prog. Metal Phys. 1, 1 (1949).

  19. Room-temperature polarization switching and antiferromagnetic coupling in epitaxial (Ga,Fe){sub 2}O{sub 3}/SrRuO{sub 3} heterostructures

    SciTech Connect

    Oh, Seol Hee; Lee, Ji Hye; Shin, Ran Hee; Jo, William; Shin, Yooleemi; Meny, Christian

    2015-04-06

    Room-temperature reversible remnant polarization of gallium ferrite thin-films is reported as a multiferroic material with non-zero order parameters of polarization and magnetization. With the addition of Fe ions in Ga sites, Ga{sub 0.6}Fe{sub 1.4}O{sub 3} (GFO) thin films have been considered as potentially promising of multiferroicity. The b-axis oriented epitaxial GFO films were grown on SrRuO{sub 3}(111)/SrTiO{sub 3}(111). The six-fold symmetric in-plane epitaxy of the GFO films was confirmed using X-ray diffraction. The magnetic moment of the films was measured as a function of temperature and external magnetic field, which shows a room-temperature non-zero magnetization. Macroscopic and microscopic methods have been applied to demonstrate the polarization switching of the films. The remnant polarization is measured as 0.05 μC/cm{sup 2}. Reduction of leaky behaviors of the GFO films owing to the conducting oxide of SrRuO{sub 3} will pave a way to take advantage of the room-temperature non-zero multi-orders for future non-volatile memory device applications.

  20. New Ru(II)/Os(II)-polypyridyl complexes for coupling to TiO2 surfaces through acetylacetone functionality and studies on interfacial electron-transfer dynamics.

    PubMed

    Banerjee, Tanmay; Biswas, Abul Kalam; Sahu, Tuhin Subhra; Ganguly, Bishwajit; Das, Amitava; Ghosh, Hirendra Nath

    2014-09-28

    New Ru(ii)- and Os(ii)-polypyridyl complexes have been synthesized with pendant acetylacetone (acac) functionality for anchoring on nanoparticulate TiO2 surfaces with a goal of developing an alternate sensitizer that could be utilized for designing an efficient dye-sensitized solar cell (DSSC). Time-resolved transient absorption spectroscopic studies in the femtosecond time domain have been carried out. The charge recombination rates are observed to be very slow, compared with those for strongly coupled dye molecules having catechol as the anchoring functionality. The results of such studies reveal that electron-injection rates from the metal complex-based LUMO to the conduction band of TiO2 are faster than one would expect for an analogous complex in which the chromophoric core and the anchoring moiety are separated with multiple saturated C-C linkages. Such an observation is rationalized based on computational studies, and a relatively smaller spatial distance between the dye LUMO and the TiO2 surface accounted for this. Results of this study are compared with those for analogous complexes having a gem-dicarboxy group as the anchoring functionality for covalent binding to the TiO2 surface to compare the role of binding functionalities on electron-transfer dynamics.

  1. Materials discovery by crystal growth: Lanthanide metal containing oxides of the platinum group metals (Ru, Os, Ir, Rh, Pd, Pt) from molten alkali metal hydroxides

    SciTech Connect

    Mugavero, Samuel J.; Gemmill, William R.; Roof, Irina P.; Loye, Hans-Conrad zur

    2009-07-15

    This review addresses the process of materials discovery via crystal growth, specifically of lanthanide metal containing oxides of the platinum group metals (Ru, Os, Ir, Rh, Pd, Pt). It provides a detailed overview of the use of hydroxide fluxes for crystal growth. The melt chemistry of hydroxide fluxes, specifically, the extensive acid base chemistry, the metal cation solubility, and the ability of hydroxide melts to oxidize metals are described. Furthermore, a general methodology for the successful crystal growth of oxides is provided, including a discussion of experimental considerations, suitable reaction vessels, reaction profiles and temperature ranges. Finally, a compilation of complex platinum group metal oxides recently synthesized using hydroxide melts, focusing on their crystal growth and crystal structures, is included. - Graphical abstract: A review that addresses the process of materials discovery via crystal growth using hydroxide fluxes. It provides a detailed overview of the use of hydroxide fluxes for crystal growth and describes the melt chemistry of hydroxide fluxes, specifically, the extensive acid base chemistry, the metal cation solubility, and the ability of hydroxide melts to oxidize metals. In addition, a compilation of complex platinum group metal oxides recently synthesized using hydroxide melts is included.

  2. Conducting polymers containing in-chain metal centers: electropolymerization of oligothienyl-substituted {M(tpy)2} complexes and in situ conductivity studies, M = Os(II), Ru(II).

    PubMed

    Hjelm, Johan; Handel, Robyn W; Hagfeldt, Anders; Constable, Edwin C; Housecroft, Catherine E; Forster, Robert J

    2005-02-21

    The electropolymerization of a series of Ru and Os bis-terpyridine complexes that form rodlike polymers with bithienyl, quaterthienyl, or hexathienyl bridges has been studied. Absorption spectroscopy, scanning electron microscopy, and cyclic voltammetry have been used to characterize the monomers and resulting polymer films. The absolute dc conductivity of the quaterthienyl-bridged {Ru(tpy)2} and {Os(tpy)2} polymers is unusually large and independent of the identity of the metal center at 1.6 x 10(-3) S cm(-1). The maximum conductivity occurs at the formal potential of each redox process, which typically is observed for systems where redox conduction is the dominant charge transport mechanism. Significantly, the dc conductivity of the metal-based redox couple observed in these polymers is 2 orders of magnitude higher thanthat of a comparable nonconjugated system.

  3. Strain-induced topological transition in SrRu2O6 and CaOs2O6

    SciTech Connect

    Ochi, Masayuki; Arita, Ryotaro; Trivedi, Nandini; Okamoto, Satoshi

    2016-05-24

    The topological property of SrRu$_2$O$_6$ and isostructural CaOs$_2$O$_6$ under various strain conditions is investigated using density functional theory. Based on an analysis of parity eigenvalues, we anticipate that a three-dimensional strong topological insulating state should be realized when band inversion is induced at the A point in the hexagonal Brillouin zone. For SrRu$_2$O$_6$, such a transition requires rather unrealistic tuning, where only the $c$ axis is reduced while other structural parameters are unchanged. However, given the larger spin-orbit coupling and smaller lattice constants in CaOs$_2$O$_6$, the desired topological transition does occur under uniform compressive strain. Our study paves a way to realize a topological insulating state in a complex oxide, which has not been experimentally demonstrated so far.

  4. Strain-induced topological transition in SrRu2O6 and CaOs2O6

    SciTech Connect

    Ochi, Masayuki; Arita, Ryotaro; Trivedi, Nandini; Okamoto, Satoshi

    2016-05-24

    The topological property of SrRu$_2$O$_6$ and isostructural CaOs$_2$O$_6$ under various strain conditions is investigated using density functional theory. Based on an analysis of parity eigenvalues, we anticipate that a three-dimensional strong topological insulating state should be realized when band inversion is induced at the A point in the hexagonal Brillouin zone. For SrRu$_2$O$_6$, such a transition requires rather unrealistic tuning, where only the $c$ axis is reduced while other structural parameters are unchanged. However, given the larger spin-orbit coupling and smaller lattice constants in CaOs$_2$O$_6$, the desired topological transition does occur under uniform compressive strain. Our study paves a way to realize a topological insulating state in a complex oxide, which has not been experimentally demonstrated so far.

  5. Lattice instability and competing spin structures in the double perovskite insulator Sr2FeOsO6.

    PubMed

    Paul, Avijit Kumar; Reehuis, Manfred; Ksenofontov, Vadim; Yan, Binghai; Hoser, Andreas; Többens, Daniel M; Abdala, Paula M; Adler, Peter; Jansen, Martin; Felser, Claudia

    2013-10-18

    The semiconductor Sr2FeOsO6, depending on temperature, adopts two types of spin structures that differ in the spin sequence of ferrimagnetic iron-osmium layers along the tetragonal c axis. Neutron powder diffraction experiments, 57Fe Mössbauer spectra, and density functional theory calculations suggest that this behavior arises because a lattice instability resulting in alternating iron-osmium distances fine-tunes the balance of competing exchange interactions. Thus, Sr2FeOsO6 is an example of a double perovskite, in which the electronic phases are controlled by the interplay of spin, orbital, and lattice degrees of freedom.

  6. Magnetic and electronic properties of La3 MO7 and possible polaron formation in hole-doped La3 MO7 (M  =  Ru and Os)

    NASA Astrophysics Data System (ADS)

    Gao, Bin; Weng, Yakui; Zhang, Jun-Jie; Zhang, Huimin; Zhang, Yang; Dong, Shuai

    2017-03-01

    Oxides with 4d/5d transition metal ions are physically interesting for their particular crystalline structures as well as the spin–orbit coupled electronic structures. Recent experiments revealed a series of 4d/5d transition metal oxides R 3 MO7 (R: rare earth; M: 4d/5d transition metal) with unique quasi-one-dimensional M chains. Here first-principles calculations have been performed to study the electronic structures of La3OsO7 and La3RuO7. Our study confirm both of them to be Mott insulating antiferromagnets with identical magnetic order. The reduced magnetic moments, which are much smaller than the expected value for ideal high-spin state (3 t 2g orbitals occupied), are attributed to the strong p  ‑  d hybridization with oxygen ions, instead of the spin–orbit coupling. The Ca-doping to La3OsO7 and La3RuO7 can not only modulate the nominal carrier density but also affect the orbital order as well as the local distortions. The Coulombic attraction and particular orbital order would prefer to form polarons, which might explain the puzzling insulating behavior of doped 5d transition metal oxides. In addition, our calculations predict that the Ca-doping can trigger ferromagnetism in La3RuO7 but not in La3OsO7.

  7. Highly textured Sr, Nb co-doped BiFeO{sub 3} thin films grown on SrRuO{sub 3}/Si substrates by rf- sputtering

    SciTech Connect

    Ostos, C.; Raymond, O.; Siqueiros, J. M.; Suarez-Almodovar, N.; Bueno-Baques, D.; Mestres, L.

    2011-07-15

    In this study, (011)-highly oriented Sr, Nb co-doped BiFeO{sub 3} (BFO) thin films were successfully grown on SrRuO{sub 3}/Si substrates by rf-magnetron sputtering. The presence of parasite magnetic phases was ruled out based on the high resolution x-ray diffraction data. BFO films exhibited a columnar-like grain growth with rms surface roughness values of {approx_equal}5.3 nm and average grain sizes of {approx_equal}65-70 nm for samples with different thicknesses. Remanent polarization values (2P{sub r}) of 54 {mu}C cm{sup -2} at room temperature were found for the BFO films with a ferroelectric behavior characteristic of an asymmetric device structure. Analysis of the leakage mechanisms for this structure in negative bias suggests Schottky injection and a dominant Poole-Frenkel trap-limited conduction at room temperature. Oxygen vacancies and Fe{sup 3+}/Fe{sup 2+} trap centers are consistent with the surface chemical bonding states analysis from x-ray photoelectron spectroscopy data. The (011)-BFO/SrRuO{sub 3}/Si film structure exhibits a strong magnetic interaction at the interface between the multiferroic film and the substrate layer where an enhanced ferromagnetic response at 5 K was observed. Zero-field cooled (ZFC) and field cooled (FC) magnetization curves of this film system revealed a possible spin glass behavior at spin freezing temperatures below 30 K depending on the BFO film thickness.

  8. Magnetic structure, magnetization, and magnetotransport properties of (Ba,Sr)M2±xT4∓xO11 ( M=Fe,Co ; T=Ru,Ti )

    NASA Astrophysics Data System (ADS)

    Shlyk, L.; Ueland, B. G.; Lynn, J. W.; Huang, Q.; de Long, L. E.; Parkin, S.

    2010-05-01

    Hexagonal R -type ferrites (Ba,Sr)M2±xT4∓xO11 ( M=Fe,Co ; T=Ru,Ti ) were studied via neutron and x-ray diffraction, magnetization, and electrical transport measurements. Magnetization data for single-crystal BaFe3.26Ti2.74O11 reveal two magnetic transitions at T1=250K and T2=84K , which indicates complex magnetic order driven by competing interactions on a frustrated lattice with a noncentrosymmetric structure. Magnetization data for single-crystal BaCo1.85Ru4.15O11 reveal soft ferromagnetic order at TC=105K with an easy direction perpendicular to the c axis. Neutron diffraction data for polycrystalline BaCo1.68Ru4.32O11 indicate a nearly compensated arrangement of spins lying within the a-b plane with a possible canting out of the plane that yields nonzero scalar spin chirality. The transverse magnetoresistivity ρxy of single-crystal BaCo1.85Ru4.15O11 for current J∥H⊥c axis is typical of an anomalous Hall effect observed in ferromagnets, whereas for J⊥H∥c axis, ρxy is a nonmonotonic function of the magnetic field, consistent with a topological Hall effect that depends upon scalar spin chirality. Neutron diffraction reveals transitions to ferrimagnetic order at TC=262(1)K for single-crystal SrFe2.6Ru3.4O11 , and at TC=403K for polycrystalline SrFe2.96Ru3.04O11 (refined as a collinear structure at T=5K ).

  9. Reproducible resistive switching in the super-thin Bi2FeCrO6 epitaxial film with SrRuO3 bottom electrode

    NASA Astrophysics Data System (ADS)

    Xu, Wenting; Sun, Jiao; Xu, Xijun; Yuan, Guoliang; Zhang, Yongjun; Liu, Junming; Liu, Zhiguo

    2016-10-01

    The reproducible and reliable resistive switching is observed in the ultrathin Bi2FeCrO6 (BFCO) epitaxial film on (001) SrTiO3 substrate with SrRuO3 as the bottom electrode. The as-grown BFCO film allows its ferroelectric polarization switching under external electric field. With a 100-nm-radius tip contacting film surface, a stable bipolar resistive switching was observed through the conductive atomic force microscope. Furthermore, the resistive switching at negative bias was observed and its high/low current ratio is above 15 among a thousand of current versus voltage curves measured by the scanning tunneling microscope with a non-contacting nm-scale tip. It is argued that this transport mechanism is due to quantum tunneling, and the resistive switching in these junctions is because of ferroelectric switching.

  10. Evolution of the interfacial magnetic anisotropy in MgO/CoFeB/Ta/Ru based multilayers as a function of annealing temperature

    SciTech Connect

    Aleksandrov, Yuriy Kowalska, Ewa; Fowley, Ciarán; Sluka, Volker; Yıldırım, Oğuz; Lindner, Jürgen; Fassbender, Jürgen; Deac, Alina M.; Ocker, Berthold

    2016-06-15

    We report the effect of annealing temperature on the dynamic and static magnetic properties of MgO/CoFeB/Ta/Ru multilayers. Angular resolved ferromagnetic resonance measurement results show that the as-deposited film exhibits in-plane magnetic anisotropy, whereas in the annealed films the magnetic easy-axis is almost along the direction perpendicular to the plane of the layers. The extracted interfacial anisotropy energy, K{sub i}, is maximized at an annealing temperature 225{sup ∘}C, in agreement with the vibrating sample magnetometry results. Although the magnetization is not fully out-of-plane, controlling the degree of the magnetization obliqueness may be advantageous for specific applications such as spin-transfer oscillators.

  11. Strain-mediated electric-field control of exchange bias in a Co90Fe10/BiFeO3/SrRuO3/PMN-PT heterostructure

    PubMed Central

    Wu, S. Z.; Miao, J.; Xu, X. G.; Yan, W.; Reeve, R.; Zhang, X. H.; Jiang, Y.

    2015-01-01

    The electric-field (E-field) controlled exchange bias (EB) in a Co90Fe10/BiFeO3 (BFO)/SrRuO3/PMN-PT heterostructure has been investigated under different tensile strain states. The in-plane tensile strain of the BFO film is changed from +0.52% to +0.43% as a result of external E-field applied to the PMN-PT substrate. An obvious change of EB by the control of non-volatile strain has been observed. A magnetization reversal driven by E-field has been observed in the absence of magnetic field. Our results indicate that a reversible non-volatile E-field control of a ferromagnetic layer through strain modulated multiferroic BFO could be achieved at room temperature. PMID:25752272

  12. Strain-mediated electric-field control of exchange bias in a Co90Fe10/BiFeO3/SrRuO3/PMN-PT heterostructure

    NASA Astrophysics Data System (ADS)

    Wu, S. Z.; Miao, J.; Xu, X. G.; Yan, W.; Reeve, R.; Zhang, X. H.; Jiang, Y.

    2015-03-01

    The electric-field (E-field) controlled exchange bias (EB) in a Co90Fe10/BiFeO3 (BFO)/SrRuO3/PMN-PT heterostructure has been investigated under different tensile strain states. The in-plane tensile strain of the BFO film is changed from +0.52% to +0.43% as a result of external E-field applied to the PMN-PT substrate. An obvious change of EB by the control of non-volatile strain has been observed. A magnetization reversal driven by E-field has been observed in the absence of magnetic field. Our results indicate that a reversible non-volatile E-field control of a ferromagnetic layer through strain modulated multiferroic BFO could be achieved at room temperature.

  13. Strain-mediated electric-field control of exchange bias in a Co90Fe10/BiFeO3/SrRuO3/PMN-PT heterostructure.

    PubMed

    Wu, S Z; Miao, J; Xu, X G; Yan, W; Reeve, R; Zhang, X H; Jiang, Y

    2015-03-10

    The electric-field (E-field) controlled exchange bias (EB) in a Co90Fe10/BiFeO3 (BFO)/SrRuO3/PMN-PT heterostructure has been investigated under different tensile strain states. The in-plane tensile strain of the BFO film is changed from +0.52% to +0.43% as a result of external E-field applied to the PMN-PT substrate. An obvious change of EB by the control of non-volatile strain has been observed. A magnetization reversal driven by E-field has been observed in the absence of magnetic field. Our results indicate that a reversible non-volatile E-field control of a ferromagnetic layer through strain modulated multiferroic BFO could be achieved at room temperature.

  14. Magnetic anomalies in self-assembled SrRuO3 -CoFe2O4 nanostructures studied by Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Chen, Yi-Chun; Huang, Yen-Chin; Chien, Chia-Hsien; Liu, Heng-Jui; Chu, Ying-Hao

    2015-03-01

    Self-assembled nanostructures with high interface-to-volume ratio usually possess interesting physical properties through the coupling between neighboring materials. In complex-oxide nanocomposites, the interplay of spin, charge, orbital, and lattice degrees of freedom especially provides various functionalities. Our recent study had shown photo-induced magnetization switching in a self-assembled system, CoFe2O4 (CFO)- SrRuO3(SRO), where the CFO nanopillars were embedded in the SRO matrix. Moreover, this system also has significant magnetoresistance behaviors. In this study, we used Raman spectroscopy to investigate the magnetic coupling mechanisms in CFO-SRO nanostructures. Compared to the pure CFO films, the CFO nano-pillars under out-of-plane compressive strain show a slightly increase of A1g(Co)/A1g(Fe) intensity ratio, which corresponds to a migration of Co ions from O-site (oxygen octahedron) to T-site (oxygen tetrahedron). This behavior can be further tuned by external stimulus, such as magnetic fields and temperatures. A strong increase of A1g(Co)/A1g(Fe) ratio together with a discontinuous A1g frequency shift occur at the SRO magnetic transition temperature. This result indicated that the spin-orbital interaction in CFO can be modulated by the SRO magnetic orderings.

  15. Time-reversal-breaking topological phases in antiferromagnetic Sr2FeOsO6 films

    NASA Astrophysics Data System (ADS)

    Dong, Xiao-Yu; Kanungo, Sudipta; Yan, Binghai; Liu, Chao-Xing

    2016-12-01

    In this work, we studied time-reversal-breaking topological phases as a result of the interplay between antiferromagnetism and inverted band structures in antiferromagnetic double perovskite transition-metal Sr2FeOsO6 films. By combining the first-principles calculations and analytical models, we demonstrate that the quantum anomalous Hall phase and chiral topological superconducting phase can be realized in this system. We find that to achieve time-reversal-breaking topological phases in antiferromagnetic materials, it is essential to break the combined symmetry of time reversal and inversion, which generally exists in antiferromagnetic structures. As a result, we can utilize an external electric gate voltage to induce the phase transition between topological phases and trivial phases, thus providing an electrically controllable topological platform for future transport experiments.

  16. NMR and NQR study of the electronic and structural properties of Al-Cu-Fe and Al-Cu-Ru quasicrystals

    SciTech Connect

    Shastri, A.; Borsa, F.; Torgeson, D.R.; Shield, J.E.; Goldman, A.I. )

    1994-12-01

    [sup 27]Al and [sup 63,65]Cu NMR is reported for powdered stable Al-Cu-Fe and Al-Cu-Ru icosahedral quasicrystals and crystalline approximants, and for an Al-Pd-Mn single-grain quasicrystal. [sup 27]Al NQR spectra at 4.2 K were observed in Al-Cu-Fe and Al-Cu-Ru samples. From quadrupole-perturbed NMR spectra at different magnetic fields, and from zero-field NQR spectra, a wide distribution of local electric-field gradient (EFG) tensor components and principal-axis-system orientations was found at the Al site. A model EFG calculation based on a 1/1 Al-Cu-Fe approximant successfully explained the observed NQR spectra. The average local gradient is largely determined by the [ital p]-electron wave function at the Al site, while the width of the distribution is due to EFG lattice contribution. Comparison of [sup 63]Cu and [sup 27]Al NMR shows the EFG distribution at the two sites is similar, but the electronic contribution to the EFG is considerably smaller at the Cu site, in agreement with a more [ital s]-type wave function of the conduction electrons. Overall spread of EFG values is well reproduced by calculation based on the approximant. However, the experimental spectra indicate a much larger number of nonequivalent sites when compared with the simulated NQR spectra based on the 1/1 approximant. The short-range, local chemical order is well represented by the approximant, but differences in coordination must be included at intermediate range in the quasicrystal. Measured [sup 27]Al Knight shift, magnetic susceptibility, and nuclear spin-lattice relaxation time as a function of temperature indicate reduced density of states at the Fermi level by a factor of 7 or 8 from the value in Al metal, consistent with the notion of a pseudogap for these quasicrystals. No differences in measured parameters were detected as a function of composition of the quasicrystalline alloys.

  17. Hydrogen dissociation and diffusion on transition metal (= Ti, Zr, V, Fe, Ru, Co, Rh, Ni, Pd, Cu, Ag)-doped Mg(0001) surfaces

    NASA Astrophysics Data System (ADS)

    Pozzo, M.; Alfè, D.

    2009-02-01

    The kinetics of hydrogen absorption by magnesium bulk is affected by two main activated processes: the dissociation of the H2 molecule and the diffusion of atomic H into the bulk. In order to have fast absorption kinetics both activated processed need to have a low barrier. Here we report a systematic ab initio density functional theory investigation of H2 dissociation and subsequent atomic H diffusion on TM (= Ti, V, Zr, Fe, Ru, Co, Rh, Ni, Pd, Cu, Ag)-doped Mg(0001) surfaces. The calculations show that doping the surface with TMs on the left of the periodic table eliminates the barrier for the dissociation of the molecule, but the H atoms bind very strongly to the TM, therefore hindering diffusion. Conversely, TMs on the right of the periodic table do not bind H, however, they do not reduce the barrier to dissociate H2 significantly. Our results show that Fe, Ni and Rh, and to some extent Co and Pd, are all exceptions, combining low activation barriers for both processes, with Ni being the best possible choice.

  18. Spin density wave (SDW) transition in Ru doped BaFeAs2 investigated by AC steady state calorimetry

    NASA Astrophysics Data System (ADS)

    Vinod, K.; Sharma, Shilpam; Sundar, C. S.; Bharathi, A.

    2015-06-01

    Heat capacity measurements were done on sub-micron sized BaFe2-xRuxAs2 single crystals using thin film membrane based the AC steady state calorimetry technique. Noticeable thermal hysteresis is observed in the heat capacity of the BaFe2-xRuxAs2 during cooling and warming cycles, indicating first order nature of the SDW transition.

  19. High-temperature ferrimagnetism driven by lattice distortion in double perovskite Ca2FeOsO6.

    PubMed

    Feng, Hai L; Arai, Masao; Matsushita, Yoshitaka; Tsujimoto, Yoshihiro; Guo, Yanfeng; Sathish, Clastin I; Wang, Xia; Yuan, Ya-Hua; Tanaka, Masahiko; Yamaura, Kazunari

    2014-03-05

    5d and 3d hybrid solid-state oxide Ca2FeOsO6 crystallizes into an ordered double-perovskite structure with a space group of P2₁/n with high-pressures and temperatures. Ca2FeOsO6 presents a long-range ferrimagnetic transition at a temperature of ~320 K (T(c)) and is not a band insulator, but is electrically insulating like the recently discovered Sr2CrOsO6 (T(c) ~725 K). The electronic stat of Ca2FeOsO6 is adjacent to a half-metallic state as well as that of Sr2CrOsO6. In addition, the high-T(c) ferrimagnetism was driven by lattice distortion, which was observed for the first time among double-perovskite oxides and represents complex interplays between spins and orbitals. Unlike conventional ferrite and garnet, the interplays likely play a pivotal role of the ferrimagnetism. A new class of 5d-3d hybrid ferrimagnetic insulators with high-T(c) is established to develop practically and scientifically useful spintronic materials.

  20. High-Pressure Synthesis and Ferrimagnetic Ordering of the B-Site-Ordered Cubic Perovskite Pb2FeOsO6.

    PubMed

    Zhao, Qing; Liu, Min; Dai, Jianhong; Deng, Hongshan; Yin, Yunyu; Zhou, Long; Yang, Junye; Hu, Zhiwei; Agrestini, Stefano; Chen, Kai; Pellegrin, Eric; Valvidares, Manuel; Nataf, Lucie; Baudelet, François; Tjeng, L H; Yang, Yi-Feng; Jin, Changqing; Long, Youwen

    2016-10-03

    Pb2FeOsO6 was prepared for the first time by using high-pressure and high-temperature synthesis techniques. This compound crystallizes into a B-site-ordered double-perovskite structure with cubic symmetry Fm3̅m, where the Fe and Os atoms are orderly distributed with a rock-salt-type manner. Structure refinement shows an Fe-Os antisite occupancy of about 16.6%. Structural analysis and X-ray absorption spectroscopy both demonstrate the charge combination to be Pb2Fe(3+)Os(5+)O6. A long-range ferrimagnetic transition is found to occur at about 280 K due to antiferromagnetic interactions between the adjacent Fe(3+) and Os(5+) spins with a straight (180°) Fe-O-Os bond angle, as confirmed by X-ray magnetic circular-dichroism measurements. First-principles theoretical calculations reveal the semiconducting behavior as well as the Fe(3+)(↑)Os(5+)(↓) antiferromagnetic coupling originating from the superexchange interactions between the half-filled 3d orbitals of Fe and t2g orbitals of Os.

  1. Cross sections of X-ray production induced by C and Si ions with energies up to 1 MeV/u on Ti, Fe, Zn, Nb, Ru and Ta

    NASA Astrophysics Data System (ADS)

    Prieto, José Emilio; Zucchiatti, Alessandro; Galán, Patricia; Prieto, Pilar

    2017-09-01

    X-ray production differential cross sections induced by C and Si ions with energies from 1 MeV/u down to 0.25 MeV/u, produced by the CMAM 5 MV tandem accelerator, have been measured for thin targets of Ti, Fe, Zn, Nb, Ru and Ta in a direct way. X-rays have been detected by a fully characterized silicon drift diode and beam currents have been measured by a system of two Faraday cups. Measured cross sections agree in general with previously published results. The ECPSSR theory with the united atoms correction gives absolute values close to the experimental ones for all the studied elements excited by C ions and for Ta, Nb and Ru excited by Si ions. For Ti, Fe and Zn excited by Si, the matching with theory is poor since even the ionization cross section is below the measured data.

  2. Predicting a Ferrimagnetic-Ferroelectric Phase of Zn2FeOsO6 with Strong Magnetoelectric Coupling

    NASA Astrophysics Data System (ADS)

    Xiang, Hongjun; Wang, P. S.; Ren, Wei; Bellaiche, L.

    2015-03-01

    Multiferroic materials, in which ferroelectric and magnetic ordering coexist, are of fundamental interest for the development of novel memory devices that allow for electrical writing and non-destructive magnetic readout operation. The great challenge is to create room temperature multiferroic materials with strongly coupled ferroelectric and ferromagnetic (or ferrimagnetic) orderings. BiFeO3 has been the most heavily investigated single-phase multiferroic to date due to the coexistence of its magnetic order and ferroelectric order at room temperature. However, there is no net magnetic moment in the cycloidal (antiferromagnetic-like) magnetic state of bulk BiFeO3, which severely limits its realistic applications in electric field controlled spintronic devices. Here, we predict that double perovskite Zn2FeOsO6 is a new multiferroic with properties superior to BiFeO3. First, there are strong ferroelectricity and strong ferrimagnetism at room temperature in Zn2FeOsO6. Second, the easy-plane of the spontaneous magnetization can be switched by an external electric field, evidencing the strong magnetoelectric coupling existing in this system. Our results suggest that ferrimagnetic 3d-5d double perovskite may therefore be used to achieve voltage control of magnetism in future spintronic devices.

  3. 3D Nanostructured Palladium-Functionalized Graphene-Aerogel-Supported Fe3O4 for Enhanced Ru(bpy)3(2+)-Based Electrochemiluminescent Immunosensing of Prostate Specific Antigen.

    PubMed

    Yang, Lei; Li, Yueyuan; Zhang, Yong; Fan, Dawei; Pang, Xuehui; Wei, Qin; Du, Bin

    2017-10-11

    We developed a novel Ru(bpy)3(2+)-based electrochemiluminescence (ECL) immunosensor utilizing palladium nanoparticle (Pd NP)-functionalized graphene-aerogel-supported Fe3O4 (FGA-Pd) for real-sample analysis of prostate specific antigen (PSA). 3D nanostructured FGA-Pd, as a novel ECL carrier, was prepared by in situ reduction. Large amounts of Ru(bpy)3(2+) could combine with FGA-Pd via electrostatic interaction to establish a brand-new ECL emitter (Ru@FGA-Pd) for improving ECL efficiency. The obtained Ru@FGA-Pd composite was utilized to label the secondary antibody, which generated strong ECL signals with tripropylamine (TPrA) as a coreactant. Furthermore, we demonstrated that the participation of Pd NPs endowed FGA with favorable electrocatalytic ability in the luminescence process to produce more excited state [Ru(bpy)3(2+)]* for realizing desirable signal amplification. In addition, the primary antibody was captured by gold nanoparticle (Au NP)-functionalized Fe2O3 nanodendrites (Au-FONDs), which possessed good electrical conductivity and favorable biocompatibility. Under optimum conditions, the fabricated sandwich-type ECL immunosensor showed a sensitive response to PSA with a low detection limit of 0.056 pg/mL (S/N = 3) and a calibration range of 0.0001-50 ng/mL. Featuring favorable selectivity, stability, and repeatability, the proposed immunosensor is expected to blaze a novel trail for the real sample detection of PSA and other biomarkers.

  4. Optical properties of epitaxial BiFeO3 thin film grown on SrRuO3-buffered SrTiO3 substrate

    PubMed Central

    2014-01-01

    The BiFeO3 (BFO) thin film was deposited by pulsed-laser deposition on SrRuO3 (SRO)-buffered (111) SrTiO3 (STO) substrate. X-ray diffraction pattern reveals a well-grown epitaxial BFO thin film. Atomic force microscopy study indicates that the BFO film is rather dense with a smooth surface. The ellipsometric spectra of the STO substrate, the SRO buffer layer, and the BFO thin film were measured, respectively, in the photon energy range 1.55 to 5.40 eV. Following the dielectric functions of STO and SRO, the ones of BFO described by the Lorentz model are received by fitting the spectra data to a five-medium optical model consisting of a semi-infinite STO substrate/SRO layer/BFO film/surface roughness/air ambient structure. The thickness and the optical constants of the BFO film are obtained. Then a direct bandgap is calculated at 2.68 eV, which is believed to be influenced by near-bandgap transitions. Compared to BFO films on other substrates, the dependence of the bandgap for the BFO thin film on in-plane compressive strain from epitaxial structure is received. Moreover, the bandgap and the transition revealed by the Lorentz model also provide a ground for the assessment of the bandgap for BFO single crystals. PMID:24791162

  5. Optical properties of epitaxial BiFeO3 thin film grown on SrRuO3-buffered SrTiO3 substrate.

    PubMed

    Xu, Ji-Ping; Zhang, Rong-Jun; Chen, Zhi-Hui; Wang, Zi-Yi; Zhang, Fan; Yu, Xiang; Jiang, An-Quan; Zheng, Yu-Xiang; Wang, Song-You; Chen, Liang-Yao

    2014-01-01

    The BiFeO3 (BFO) thin film was deposited by pulsed-laser deposition on SrRuO3 (SRO)-buffered (111) SrTiO3 (STO) substrate. X-ray diffraction pattern reveals a well-grown epitaxial BFO thin film. Atomic force microscopy study indicates that the BFO film is rather dense with a smooth surface. The ellipsometric spectra of the STO substrate, the SRO buffer layer, and the BFO thin film were measured, respectively, in the photon energy range 1.55 to 5.40 eV. Following the dielectric functions of STO and SRO, the ones of BFO described by the Lorentz model are received by fitting the spectra data to a five-medium optical model consisting of a semi-infinite STO substrate/SRO layer/BFO film/surface roughness/air ambient structure. The thickness and the optical constants of the BFO film are obtained. Then a direct bandgap is calculated at 2.68 eV, which is believed to be influenced by near-bandgap transitions. Compared to BFO films on other substrates, the dependence of the bandgap for the BFO thin film on in-plane compressive strain from epitaxial structure is received. Moreover, the bandgap and the transition revealed by the Lorentz model also provide a ground for the assessment of the bandgap for BFO single crystals.

  6. Positive exchange-bias and giant vertical hysteretic shift in La0.3Sr0.7FeO3/SrRuO3 bilayers

    PubMed Central

    Rana, Rakesh; Pandey, Parul; Singh, R. P.; Rana, D. S.

    2014-01-01

    The exchange-bias effects in the mosaic epitaxial bilayers of the itinerant ferromagnet (FM) SrRuO3 and the antiferromagnetic (AFM) charge-ordered La0.3Sr0.7FeO3 were investigated. An uncharacteristic low-field positive exchange bias, a cooling-field driven reversal of positive to negative exchange-bias and a layer thickness optimised unusual vertical magnetization shift were all novel facets of exchange bias realized for the first time in magnetic oxides. The successive magnetic training induces a transition from positive to negative exchange bias regime with changes in domain configurations. These observations are well corroborated by the hysteretic loop asymmetries which display the modifications in the AFM spin correlations. These exotic features emphasize the key role of i) mosaic disorder induced subtle interplay of competing AFM-superexchange and FM double exchange at the exchange biased interface and, ii) training induced irrecoverable alterations in the AFM spin structure. PMID:24569516

  7. Effects of pressure and composition on Pt-Re-Os partitioning behavior between solid and liquid metal in the Fe-Ni-S system: Implication for Os isotopic anomalies in plume-derived lavas

    NASA Astrophysics Data System (ADS)

    Hayashi, H.; Ohtani, E.; Terasaki, H.; Ito, Y.

    2008-12-01

    Coupled 186Os/188Os and 187Os/188Os enrichments of plume-derived lavas have been suggested to reflect material contribution from the outer core (e.g., Brandon, 1998). This geochemical hypothesis is based on an assumption that the outer core shows coupled enrichments in 186Os/ 188Os and 187Os/ 188Os ratio, reflecting the decay of 190Pt and 187Re to 186Os and 187Os, respectively. In order to examine this hypothesis, partitioning experiments of Pt-Re-Os between solid metal and liquid metal were performed using an MA-8 Kawai-type multi-anvil apparatus at 5-20 GPa and 1250-1400C. Starting materials of Fe metal, Ni (7 wt.%) metal and FeS (5 wt.% S in the bulk) were doped with 3 wt.% of Pt, Re and Os metals. Concentrations of all elements were determined using JXA-8800M electron probe microanalyzer with wave-dispersive spectrometry. Measured partition coefficients of Pt, Re and Os increase with increasing sulfur content and almost constant with increasing pressure. Therefore, the effect of liquid composition on the partitioning behavior of highly siderophile elements is much more significant compared to the effect of pressure and temperature. On the basis of the present experimental results, it is unlikely to generate the required Pt-Re-Os fractionation during inner core crystallization assuming that the light element in the Earth"fs core is sulfur only.

  8. Solvent dependences of spectral and redox properties of pyrazine (pz) complexes of ruthenium and osmium pentaammines: Ru(NH/sub 3/)/sub 5/pzCH/sub 3//sup 3 +/, Os(NH/sub 3/)/sub 5/pzCH/sub 3//sup 3 +/, and (Ru(NH/sub 3/)/sub 5/)/sup 2/pz/sup 5 +/

    SciTech Connect

    Creutz, C.; Chou, M.H.

    1987-09-09

    Near-IR-vis spectra and cyclic voltammetric parameters are reported for the title compounds in the solvent series nitromethane, acetonitrile, propylene carbonate, N,N-dimethylformamide, and dimethyl sulfoxide (over which Gutmann donor number (DN) ranges from 2.7 to 29.8). As has been found in related systems, the E/sup 0/ of (NH/sub 3/)/sub 5/M/sup III/II/ decreases with donor number, with the magnitude of the response to solvent being quantitatively similar (0.025 +/- 0.002 V/DN) for all of the couples examined. (Consequently the stability of (Ru(NH/sub 3/)/sub 5/)/sub 2/pz/sup 5 +/ with respect to disproportionation is solvent independent within experimental error.) By contrast, the vis nu/sub h/) and near-IR (nu/sub 1/) absorption bands exhibit very different solvent dependences. For Ru(NH/sub 3/)/sub 5/pzCH/sub 3//sup 3 +/, the position of nu/sub h/ is solvent independent, but nu/sub 1/ exhibits a typical MLCT solvent dependence. For Os(NH/sub 3/)/sub 5/pzCH/sub 3//sup 3 +/, nu/sub 1/ shifts to longer wavelength with increasing donor number (MLCT character) while nu/sub h/ exhibits the opposite behavior. Both vis and near-IR bands of (Ru(NH/sub 3/)/sub 5/)/sub 2/pz/sup 5 +/ shift only very slightly with solvent, but the vis band of (Ru(NH/sub 3/)/sub 5/)/sub 2/pz/sup 4 +/ is more solvent dependent - about 80% as much as Ru(NH/sub 3/)/sub 5/pz/sup 2 +/. The spectral shifts are discussed in terms of a simplified molecular orbital scheme for the M-pz back-bonding interaction, and the nature of the solvent sensitivity is found to be related to the metal and pyrazine character of the MO's involved in the transition. 51 references, 5 figures, 4 tables.

  9. Heavy-impurity resonance, hybridization, and phonon spectral functions in Fe1-xMxSi, M=Ir,Os

    DOE PAGES

    Delaire, O.; Al-Qasir, Iyad I.; May, Andrew F.; ...

    2015-03-31

    The vibrational behavior of heavy substitutional impurities (M=Ir,Os) in Fe1-xMxSi (x = 0, 0.02, 0.04, 0.1) was investigated with a combination of inelastic neutron scattering (INS), transport measurements, and first-principles simulations. In this paper, our INS measurements on single-crystals mapped the four-dimensional dynamical structure factor, S(Q;E), for several compositions and temperatures. Our results show that both Ir and Os impurities lead to the formation of a weakly dispersive resonance vibrational mode, in the energy range of the acoustic phonon dispersions of the FeSi host. We also show that Ir doping, which introduces free carriers and increases electron-phonon coupling, leads tomore » softened interatomic force-constants compared to doping with Os, which is isoelectronic to Fe. We analyze the phonon S(Q,E) from INS through a Green's function model incorporating the phonon self-energy based on first-principles density functional theory (DFT) simulations. Calculations of the quasiparticle spectral functions in the doped system reveal the hybridization between the resonance and the acoustic phonon modes. Finally, our results demonstrate a strong interaction of the host acoustic dispersions with the resonance mode, likely leading to the large observed suppression in lattice thermal conductivity.« less

  10. Heavy-impurity resonance, hybridization, and phonon spectral functions in Fe1-xMxSi (M =Ir , Os )

    NASA Astrophysics Data System (ADS)

    Delaire, O.; Al-Qasir, I. I.; May, A. F.; Li, C. W.; Sales, B. C.; Niedziela, J. L.; Ma, J.; Matsuda, M.; Abernathy, D. L.; Berlijn, T.

    2015-03-01

    The vibrational behavior of heavy substitutional impurities (M = Ir,Os) in Fe1-xMxSi (x =0 ,0.02 ,0.04 ,0.1 ) was investigated with a combination of inelastic neutron scattering (INS), transport measurements, and first-principles simulations. Our INS measurements on single crystals mapped the four-dimensional dynamical structure factor, S (Q ,E ) , for several compositions and temperatures. Our results show that both Ir and Os impurities lead to the formation of a weakly dispersive resonance vibrational mode, in the energy range of the acoustic phonon dispersions of the FeSi host. We also show that Ir doping, which introduces free carriers, leads to softened interatomic force constants compared to doping with Os, which is isoelectronic to Fe. We analyze the phonon S (Q ,E ) from INS through a Green's-function model incorporating the phonon self-energy based on first-principles density functional theory simulations, and we study the disorder-induced lifetimes on large supercells. Calculations of the quasiparticle spectral functions in the doped system reveal the hybridization between the resonance and the acoustic phonon modes. Our results demonstrate a strong interaction of the host acoustic dispersions with the resonance mode, likely leading to the large observed suppression in lattice thermal conductivity.

  11. High-density gold nanoparticles supported on a [Ru(bpy)(3)](2+)-doped silica/Fe3O4 nanocomposite: facile preparation, magnetically induced immobilization, and applications in ECL detection.

    PubMed

    Guo, Shaojun; Li, Jing; Wang, Erkang

    2008-09-01

    A large-scale process combined sonication with self-assembly techniques for the preparation of high-density gold nanoparticles supported on a [Ru(bpy)(3)](2+)-doped silica/Fe(3)O(4) nanocomposite (GNRSF) is provided. The obtained hybrid nanomaterials containing Fe(3)O(4) spheres have high saturation magnetization, which leads to their effective immobilization on the surface of an ITO electrode through simple manipulation by an external magnetic field (without the need of a special immobilization apparatus). Furthermore, this hybrid nanomaterial film exhibits a good and very stable electrochemiluminescence (ECL) behavior, which gives a linear response for tripropylamine (TPA) concentrations between 5 muM and 0.21 mM, with a detection limit in the micromolar range. The sensitivity of this ECL sensor can be easily controlled by the amount of [Ru(bpy)(3)](2+) immobilized on the hybrid nanomaterials (that is, varying the amount of [Ru(bpy)(3)](2+) during GNRSF synthesis).

  12. Redox controls on Ni-Fe-PGE mineralization and Re/Os fractionation during serpentinization of abyssal peridotite

    NASA Astrophysics Data System (ADS)

    Foustoukos, Dionysis I.; Bizimis, Michael; Frisby, Carl; Shirey, Steven B.

    2015-02-01

    Awaruite (Ni2Fe to Ni3Fe) is often used to infer fugacity and redox gradients in hydrothermally altered peridotites. However, discrepant petrological and thermodynamic data suggest that the fO2-fS2 stability field of awaruite is not well constrained. In this study, we assess the thermodynamic properties of awaruite and re-evaluate the Fe-Ni-S systematics of hydrothermally altered peridotites. New experimental data indicate that awaruite is stable at higher fO2 than previously thought, supporting the common occurrence of awaruite in the reaction zone of modern and ancient ultramafic-hosted hydrothermal vent systems. Awaruite is known to catalyze the abiogenic synthesis of methane during active serpentinization, contributing to methanogenesis at modern oceanic hydrothermal systems and potentially on early Earth. The enhanced stability field of awaruite determined here suggests that abiogenic methanogenesis may be active at a broad range of redox conditions. Serpentinized peridotites also contain platinum-group element (PGE)-Re sulfides and metal alloys that can be derived from desulfurization of primary mantle sulfides under low fS2. Thermodynamic calculations suggest that Os will exist as metal and Re as ReS2 in the redox stability field of awaruite. Under a relatively broad range of fS2-fO2 conditions, hydrothermal alteration and desulfurization of primary mantle may produce open system behavior in the Re/Os system and variable Re-PGE ratios and contribute over time to the Os isotopic heterogeneity of the mantle, through subduction and recycling of altered oceanic lithosphere. PGE-metal alloys occur at such low abundances in peridotite that they often are nearly impossible to find. The stability of awaruite at higher fO2 suggests that it can coexist with Os-Ir-Pt metal alloys, making it an important indicator mineral for their presence in hydrothermally altered peridotites.

  13. Layer-by-layer growth of SrFeO 3- δ thin films on atomically flat single-terminated SrRuO 3/SrTiO 3 (111) surfaces

    NASA Astrophysics Data System (ADS)

    Chang, Jaewan; Lee, Jong-Woo; Kim, Sang-Koog

    2010-02-01

    We successfully grew SrFeO 3- δ thin films in a layer-by-layer manner by pulsed laser deposition (PLD). When the SrFeO 3- δ films were directly grown on atomically flat Ti 4+-terminated SrTiO 3 (1 1 1) substrates, the oscillatory reflection-high-energy-electron-diffraction intensity was completely damped after its third oscillation. By contrast, the introduction of SrRuO 3 buffer layers onto the SrTiO 3 substrates allowed the SFO thin films to grow in a layer-by-layer manner over a far-extended thickness range. The probable mechanism of that growth is electronic reconstruction-reduced electrostatic potential divergence. With that result, the present study provides a means of growing pseudocubic (1 1 1)-oriented SrFeO 3- δ heterointerfaces, making possible the fabrication of high-functionality oxide heterostructures.

  14. The partitioning of Pt-Re-Os between solid and liquid metal in the Fe-Ni-S system at high pressure: Implications for inner core fractionation

    NASA Astrophysics Data System (ADS)

    Hayashi, Hiromi; Ohtani, Eiji; Terasaki, Hidenori; Ito, Yoshinori

    2009-08-01

    Coupled 186Os/ 188Os and 187Os/ 188Os enrichments of plume-derived lavas have been suggested to reflect contributions of materials from the outer core ( Brandon et al., 1998). This hypothesis is based on the assumption that the Earth's liquid outer core has high Pt/Os and slightly high Re/Os ratios as a result of the crystallization of the solid inner core, and shows coupled enrichments in the 186Os/ 188Os and 187Os/ 188Os ratios, reflecting the decay of 190Pt and 187Re to 186Os and 187Os, respectively. Partitioning experiments of Pt-Re-Os between solid and liquid metal were performed at 5-20 GPa and 1250-1400 °C, to examine the effects of pressure in the Fe-Ni-S system. The ratios ( DOs/ DPt, DOs/ DRe) of measured partition coefficients of Pt, Re and Os are almost constant with increasing pressure. DOs/ DPt increases significantly, whereas DOs/ DRe decreases, with increasing sulphur content in the liquid metal. On the basis of the present experimental results, it is unlikely that the required Pt-Re-Os fractionation is generated during inner core crystallization, assuming that the light element in the Earth's core is sulphur.

  15. Two closely related structure types with unprecedented bioctahedral rare-earth-metal clusters centered by transition metals: A{sub 2}R{sub 10}I{sub 17}Z{sub 2} (A = Rb, Cs; R = La, Ce, Pr; Z = Co, Ni, Ru, Os) and La{sub 10}I{sub 15}Os{sub 2}

    SciTech Connect

    Lulei, M.; Martin, J.D.; Hoistad, L.M.; Corbett, J.D.

    1997-01-22

    A family of compounds has been discovered in which pairs of octahedral rare-earth-metal clusters, each centered by a late transition metal Z, share a common edge. This R{sub 10}Z{sub 2} units, sheathed and interbridged by iodine atoms, occur in the quaternary phases Rb{sub 2}La{sub 10}I{sub 17}Co{sub 2}, Cs{sub 2}La{sub 10}I{sub 17}Z{sub 2} (Z = Co, Ni, Ru, Os), Cs{sub 2}Ce{sub 10}I{sub 17}Os{sub 2}, and Cs{sub 2}Pr{sub 10}I{sub 17}Z{sub 2}(Z = Co, Ru, Os) and in the ternary La{sub 10} I{sub 15}Os{sub 2}. All are obtained as black, air-sensitive crystals from reactions of RI{sub 3}, R, Z, and RbI or CsI as appropriate in welded Nb containers at 800-850{degree}C. The structure of Cs{sub 2} Ce{sub 10}I{sub 17}Os{sub 2} has been refined by single-crystal X-ray diffraction methods for comparison with the isotypic Cs{sub 2}La{sub 10}I{sub 17}Co{sub 2}, and the structure of a unique ternary La{sub 10}I{sub 15}Os{sub 2} has been defined. These new bioctahedral clusters may be regarded as the missing links between discrete clusters and infinite chains of condensed octahedral clusters among rare-earth-metal cluster halides that are stabilized by interstitial transition metals. The biclusters in both structures are extensively interconnected into three-dimensional arrays through bridging iodine atoms. The structural interconversion between Cs{sub 2}La{sub 10}I{sub 17}Os{sub 2} and La{sub 10}I{sub 15}Os{sub 2} + 2CsI may be easily visualized in terms of changes in iodide bridging modes and accommodation of cesium cations. 29 refs., 7 figs., 7 tabs.

  16. Ru(II) and Os(II) complexes based on terpyridyl-imidazole ligand rigidly linked to pyrene: synthesis, structure, photophysics, electrochemistry, and anion-sensing studies.

    PubMed

    Maity, Dinesh; Bhaumik, Chanchal; Mondal, Debiprasad; Baitalik, Sujoy

    2013-12-16

    We report in this work a new family of bis-tridentate ruthenium(II) and osmium(II) complexes bearing a terpyridyl ligand rigidly link to pyrenyl-benzimidazole moiety (tpy-HImzPy = 10-(4-[2,2':6',2''-terpyridine]terpyridin-4'-yl-phenyl)-9H-9,11-diaza-cyclopenta[e]pyrene) along with other tridentate ligands such as 4'-(2-naphthyl)-2,2':6',2″-terpyridine (tpy-NaPh) and 2,6-bis(benzimidazole-2-yl)pyridine (H2pbbzim). All the complexes are thoroughly characterized by their elemental analysis, ESI mass spectrometry, and (1)H NMR spectroscopy. The molecular structures of two complexes [Ru(tpy-HImzPy)2](ClO4)2 (3) and [(pbbzim)Ru(tpy-HImzPy)] (2a) in the solid state were determined by X-ray crystallography. The absorption, steady-state, and time-resolved luminescence and electrochemical properties of all the four compounds have been studied. On excitation at their MLCT bands, all four compounds exhibit moderately strong room-temperature luminescence with lifetimes ranging between 3.8 and 161.1 ns in aerated condition, whereas in the deaerated (N2 purged) condition, the lifetimes vary between 8.2 and 199.1 ns, depending upon the nature of the solvents. The presence of imidazole N-H protons in all the complexes motivates us to study anion sensing properties of the complexes in solution through different channels. Spectrophotometeric, fluorometric, (1)H NMR spectroscopic, and cyclic voltammetric studies of the complexes in presence of anions reveal that the complexes sense principally F(-), CN(-), and to a lesser extent for AcO(-). Multichannel anion sensing studies also indicate that anion-induced deprotonation of the imidazole N-H protons occur in all four compounds. The equilibrium constant of this deprotonation steps have been estimated from UV-vis absorption and emission titration data. Anion-induced modulation of lifetimes makes all the four complexes suitable for lifetime-based sensors for selective anions.

  17. Synthesis, crystal structure, and magnetic properties of Li3Mg2OsO6, a geometrically frustrated osmium(V) oxide with an ordered rock salt structure: comparison with isostructural Li3Mg2RuO6.

    PubMed

    Nguyen, Phuong-Hieu T; Ramezanipour, Farshid; Greedan, John E; Cranswick, Lachlan M D; Derakhshan, Shahab

    2012-11-05

    The novel osmium-based oxide Li(3)Mg(2)OsO(6) was synthesized in polycrystalline form by reducing Li(5)OsO(6) by osmium metal and osmium(IV) oxide in the presence of stoichiometric amounts of magnesium oxide. The crystal structure was refined using powder X-ray diffraction data in the orthorhombic Fddd space group with a = 5.88982(5) Å, b = 8.46873(6) Å, and c = 17.6825(2) Å. This compound is isostructural and isoelectronic with the ruthenium-based system Li(3)Mg(2)RuO(6). The magnetic ion sublattice Os(5+) (S = 3/2) consists of chains of interconnected corner- and edge-shared triangles, which brings about the potential for geometric magnetic frustration. The Curie-Weiss law holds over the range 80-300 K with C = 1.42(3) emu·K/mol [μ(eff) = 3.37(2) μ(B)] and θ(C) = -105.8(2) K. Below 80 K, there are three anomalies at 75, 30, and 8 K. Those at 75 and 30 K are suggestive of short-range antiferromagnetic correlations, while that at 8 K is a somewhat sharper maximum showing a zero-field-cooled/field-cooled divergence suggestive of perhaps spin freezing. The absence of magnetic Bragg peaks at 3.9 K in the neutron diffraction pattern supports this characterization, as does the absence of a sharp peak in the heat capacity, which instead shows only a very broad maximum at ∼12 K. A frustration index of f = 106/8 = 13 indicates a high degree of frustration. The magnetic properties of the osmium phase differ markedly from those of the isostructural ruthenium material, which shows long-range antiferromagnetic order below 17 K, f = 6, and no unusual features at higher temperatures. Estimates of the magnetic exchange interactions at the level of spin-dimer analysis for both the ruthenium and osmium materials support a more frustrated picture for the latter. Errors in the calculation and assignment of the exchange pathways in the previous report on Li(3)Mg(2)RuO(6) are identified and corrected.

  18. Varied roles of Pb in transition-metal PbMO3 perovskites (M = Ti, V, Cr, Mn, Fe, Ni, Ru).

    PubMed

    Goodenough, John B; Zhou, Jianshi

    2015-06-01

    Different structural chemistries resulting from the Pb(2+) lone-pair electrons in the PbMO3 perovskites are reviewed. The Pb(2+) lone-pair electrons enhance the ferroelectric transition temperature in PbTiO3, stabilize vanadyl formation in PbVO3, and induce a disproportionation reaction of Cr(IV) in PbCrO3. A Pb(2+) + Ni(IV) = Pb(4+) + Ni(II) reaction in PbNiO3 stabilizes the LiNbO3 structure at ambient pressure, but an A-site Pb(4+) in an orthorhombic perovskite PbNiO3 is stabilized at modest pressures at room temperature. In PbMnO3, a ferroelectric displacement due to the lone pair electron effect is minimized by the spin-spin exchange interaction and the strong octahedral site preference of the Mn(IV/III) cation. PbRuO3 is converted under pressure from the defective pyrochlore to the orthorhombic (Pbnm) perovskite structure where Pb-Ru interactions via a common O -2p orbital stabilize at low temperature a metallic Imma phase at ambient pressure. Above Pc [Formula: see text] a covalent Pb-Ru bond is formed by Pb(2+) + Ru(IV) = Pb(4+) + Ru(II) electron sharing.

  19. Unusual nodal behaviors of the superconducting gap in the iron-based superconductor Ba(Fe0.65Ru0.35)2As2 : Effects of spin-orbit coupling

    DOE PAGES

    Liu, L.; Okazaki, K.; Yoshida, T.; ...

    2017-03-06

    Here we have investigated the superconducting (SC) gap on hole Fermi surfaces (FSs) of optimally substituted Ba (Fe0.65 Ru0.35)2 As2 by angle-resolved photoemission spectroscopy (APRES) using bulk-sensitive 7 eV laser and synchrotron radiation. It was found that, whereas the gap is isotropic in the kx - ky plane, the gap magnitudes of two resolved hole FSs show similar kz dependences and decrease as kz approaches ~ 2 π/c (i.e., around the Z point), unlike the other Fe-based superconductors reported so far, where the SC gap of only one hole FS shows a strong k z dependence. This unique gap structuremore » can be understood in the scenario that the dz₂ orbital character is mixed into both hole FSs due to finite spin-orbit coupling (SOC) and is reproduced by calculation within the random phase approximation including the SOC.« less

  20. Chemical pressure tuning of URu2Si2 via isoelectronic substitution of Ru with Fe

    SciTech Connect

    Das, Pinaki; Kanchanavatee, N.; Helton, J. S.; Huang, K.; Baumbach, R. E.; Bauer, E. D.; White, B. D.; Burnett, V. W.; Maple, M. B.; Lynn, J. W.; Janoschek, M.

    2015-02-26

    We have used specific heat and neutron diffraction measurements on single crystals of URu2–xFexSi₂ for Fe concentrations x ≤ 0.7 to establish that chemical substitution of Ru with Fe acts as “chemical pressure” Pch as previously proposed by Kanchanavatee et al. [Phys. Rev. B 84, 245122 (2011)] based on bulk measurements on polycrystalline samples. Neutron diffraction reveals a sharp increase of the uranium magnetic moment at x = 0.1, reminiscent of the behavior at the “hidden order” to large moment antiferromagnetic (LMAFM) phase transition observed at a pressure Px ≈ 0.5-0.7 GPa in URu₂Si₂. Using the unit cell volume determined from our measurements and an isothermal compressibility κT = 5.2×10⁻³ GPa⁻¹ for URu₂Si₂, we determine the chemical pressure Pch in URu2-xFexSi₂ as a function of x. The resulting temperature T-chemical pressure Pch phase diagram for URu2-xFexSi₂ is in agreement with the established temperature T-external pressure P phase diagram of URu₂Si₂.

  1. Oxygen trapped by rare earth tetrahedral clusters in Nd4FeOS6: Crystal structure, electronic structure, and magnetic properties

    DOE PAGES

    Lin, Qisheng; Taufour, Valentin; Zhang, Yuemei; ...

    2015-05-22

    Single crystals of Nd4FeOS6 were grown from an Fe-S eutectic solution. Single crystal X-ray diffraction analysis revealed a Nd4MnOSe6-type structure (P63mc, a = 9.2693(1) Å, c = 6.6650(1) Å, V = 495.94(1) Å3, Z = 2), featuring parallel chains of face-sharing [FeS6x1/2]4- trigonal antiprisms and interlinked [Nd4OS3]4+ cubane-like clusters. Oxygen atoms were found to be trapped by Nd4 clusters in the [Nd4OS3]4+ chains. Structural differences among Nd4MnOSe6-type Nd4FeOS6 and the related La3CuSiS7- and Pr8CoGa3-type structures have been described. Magnetic susceptibility measurements on Nd4FeOS6 suggested the dominance of antiferromagnetic interactions at low temperature, but no magnetic ordering down to 2 Kmore » was observed. Spin-polarized electronic structure calculations revealed magnetic frustration with dominant antiferromagnetic interactions.« less

  2. Multi-pyridine decorated Fe(II) and Ru(II) complexes by Pd(0)-catalysed cross couplings: new building blocks for metallosupramolecular assemblies.

    PubMed

    Yang, Jiajia; Clegg, Jack K; Jiang, Qibai; Lui, Xiaoming; Yan, Hong; Zhong, Wei; Beves, Jonathon E

    2013-11-28

    Eight metal complexes of the type [M(tpy)2](2+) (tpy = 2,2':6',2''-terpyridine) featuring four pendant pyridine rings are reported and characterised by NMR, MS, absorption spectroscopy and electrochemical methods. Palladium-mediated Suzuki and Sonogashira cross-coupling reactions were performed on both free 4'-(3,5-dibromophenyl)-tpy and its Ru(II) complex in good yields. The ready N-alkylation of the pendant pyridyl units has significant influence on the absorption and electrochemical reduction of the complexes, processes which are localised on the periphery and leaves the [Ru(tpy)2](2+) core essentially unaffected. The binding of metal ions by the free pyridines is also demonstrated as means of assembling larger ordered non-covalent structures.

  3. Syntheses, structures and redox properties of some complexes containing the Os(dppe)Cp* fragment, including [{Os(dppe)Cp*}2(mu-C triple bondCC triple bond C)].

    PubMed

    Bruce, Michael I; Costuas, Karine; Davin, Thomas; Halet, Jean-François; Kramarczuk, Kathy A; Low, Paul J; Nicholson, Brian K; Perkins, Gary J; Roberts, Rachel L; Skelton, Brian W; Smith, Mark E; White, Allan H

    2007-12-14

    The sequential conversion of [OsBr(cod)Cp*] (9) to [OsBr(dppe)Cp*] (10), [Os([=C=CH2)(dppe)Cp*]PF6 ([11]PF6), [Os(C triple bond CH)(dppe)Cp*] (12), [{Os(dppe)Cp*}2{mu-(=C=CH-CH=C=)}][PF6]2 ([13](PF6)2) and finally [{Os(dppe)Cp*}(2)(mu-C triple bond CC triple bond C)] (14) has been used to make the third member of the triad [{M(dppe)Cp*}2(mu-C triple bond CC triple bond C)] (M = Fe, Ru, Os). The molecular structures of []PF6, 12 and 14, together with those of the related osmium complexes [Os(NCMe)(dppe)Cp*]PF6 ([15]PF6) and [Os(C triple bond CPh)(dppe)Cp*] (16), have been determined by single-crystal X-ray diffraction studies. Comparison of the redox properties of 14 with those of its iron and ruthenium congeners shows that the first oxidation potential E1 varies as: Fe approximately Os < Ru. Whereas the Fe complex has been shown to undergo three sequential 1-electron oxidation processes within conventional electrochemical solvent windows, the Ru and Os compounds undergo no fewer than four sequential oxidation events giving rise to a five-membered series of redox related complexes [{M(dppe)Cp*}2(mu-C4)]n+ (n = 0, 1, 2, 3 and 4), the osmium derivatives being obtained at considerably lower potentials than the ruthenium analogues. These results are complimented by DFT and DT DFT calculations.

  4. Hybridization gaps and antiferromagnetic gap in the Kondo semiconductors Ce T2Al10 (T =Fe and Os) observed by break-junction tunneling spectroscopy

    NASA Astrophysics Data System (ADS)

    Kawabata, J.; Ekino, T.; Yamada, Y.; Sakai, Y.; Sugimoto, A.; Muro, Y.; Takabatake, T.

    2015-11-01

    CeOs2Al10 exhibits Kondo semiconducting properties, yet orders antiferromagnetically at a rather high temperature, TN=28.5 K. We have performed break-junction tunneling measurements on single crystals of CeOs2Al10 and the nonmagnetic Kondo semiconductor CeFe2Al10 . Upon cooling CeFe2Al10 , two hybridization gaps successively appear in the tunneling spectra, while another gap opens in CeOs2Al10 below TN. For both compounds, the ratio of the two hybridization gap widths is approximately 4, in agreement with the hybridization gap model for the crystal-field ground state of Ce3 + with | Jz>=|±3 /2 > . Furthermore, we found that the gap widths are well scaled by the Kondo temperature among Ce-based Kondo semimetals/semiconductors with orthorhombic structures.

  5. Oxygen trapped by rare earth tetrahedral clusters in Nd4FeOS6: Crystal structure, electronic structure, and magnetic properties

    SciTech Connect

    Lin, Qisheng; Taufour, Valentin; Zhang, Yuemei; Wood, Max; Drtina, Thomas; Bud’ko, Sergey L.; Canfield, Paul C.; Miller, Gordon J.

    2015-05-22

    Single crystals of Nd4FeOS6 were grown from an Fe-S eutectic solution. Single crystal X-ray diffraction analysis revealed a Nd4MnOSe6-type structure (P63mc, a = 9.2693(1) Å, c = 6.6650(1) Å, V = 495.94(1) Å3, Z = 2), featuring parallel chains of face-sharing [FeS6x1/2]4- trigonal antiprisms and interlinked [Nd4OS3]4+ cubane-like clusters. Oxygen atoms were found to be trapped by Nd4 clusters in the [Nd4OS3]4+ chains. Structural differences among Nd4MnOSe6-type Nd4FeOS6 and the related La3CuSiS7- and Pr8CoGa3-type structures have been described. Magnetic susceptibility measurements on Nd4FeOS6 suggested the dominance of antiferromagnetic interactions at low temperature, but no magnetic ordering down to 2 K was observed. Spin-polarized electronic structure calculations revealed magnetic frustration with dominant antiferromagnetic interactions.

  6. Re-Os isotopic ages of pyrite and chemical composition of magnetite from the Cihai magmatic-hydrothermal Fe deposit, NW China

    NASA Astrophysics Data System (ADS)

    Huang, Xiao-Wen; Zhou, Mei-Fu; Qi, Liang; Gao, Jian-Feng; Wang, Yu-Wang

    2013-12-01

    The Eastern Tianshan Orogenic Belt of the Central Asian Orogenic Belt and the Beishan terrane of the Tarim Block, NW China, host numerous Fe deposits. The Cihai Fe deposit (>90 Mt at 45.6 % Fe) in the Beishan terrane is diabase-hosted and consists of the Cihai, Cinan, and Cixi ore clusters. Ore minerals are dominantly magnetite, pyrite, and pyrrhotite, with minor chalcopyrite, galena, and sphalerite. Gangue minerals include pyroxene, garnet, hornblende and minor plagioclase, biotite, chlorite, epidotite, quartz, and calcite. Pyrite from the Cihai and Cixi ore clusters has similar Re-Os isotope compositions, with ˜14 to 62 ppb Re and ≤10 ppt common Os. Pyrrhotite has ˜5 to 39 ppb Re and ˜0.6 ppb common Os. Pyrite has a mean Re-Os model age of 262.3 ± 5.6 Ma ( n = 13), in agreement with the isochron regression of 187Os vs. 187Re. The Re-Os age (˜262 Ma) for the Cihai Fe deposit is within uncertainty in agreement with a previously reported Rb-Sr age (268 ± 25 Ma) of the hosting diabase, indicating a genetic relationship between magmatism and mineralization. Magnetite from the Cihai deposit has Mg, Al, Ti, V, Cr, Co, Ni, Mn, Zn, Ga, and Sn more elevated than that of typical skarn deposits, but both V and Ti contents lower than that of magmatic Fe-Ti-V deposits. Magnetite from these two ore clusters at Cihai has slightly different trace element concentrations. Magnetite from the Cihai ore cluster has relatively constant trace element compositions. Some magnetite grains from the Cixi ore cluster have higher V, Ti, and Cr than those from the Cihai ore cluster. The compositional variations of magnetite between the ore clusters are possibly due to different formation temperatures. Combined with regional tectonic evolution of the Beishan terrane, the Re-Os age of pyrite and the composition of magnetite indicate that the Cihai Fe deposit may have derived from magmatic-hydrothermal fluids related to mafic magmatism, probably in an extensional rift environment.

  7. [Serotype distribution of Streptococcus pneumoniae isolated from invasive infections at the Hospital de Niños of Santa Fe].

    PubMed

    Mayoral, C; Baroni, M R; Giani, R; Virgolini, S; Zurbriggen, L; Regueira, M

    2008-01-01

    The serotype distribution of Streptococcus pneumoniae varies through time. The introduction of pneumococcal conjugate vaccines showed a decreased prevalence of pneumococcal invasive isolates belonging to serotype 14 and an increase of serotypes not therein included. In 1993, the Hospital de Niños of Santa Fe began surveillance of the serotype distribution of invasive S. pneumoniae disease. In the period 2003-2005, 76 isolates were analysed by studying the correlation between serotype and pathology, age and MIC of penicillin. Serotype 14 was the most frequent followed by serotypes 1, 6B, 18C, 7F, 19 F and 5. Serotype 14 showed a statistically significant correlation with MICs of penicillin ranging from 0,5 to 2 mg/l. Although this serotype was more frequently observed in pneumonia than in meningitis, there was not a significant association with any particular pathology. Serotypes 14 and 1, were prevalent among children under and over 2 years old, respectively. Most of these isolates with MICs of penicillin = 2 mg/l, were from patients with pneumonia and not with meningitis. The serotype distribution was similar to that during the period 1993-99, with the exception of serotypes 18C, 4, 12F and 22F which had never been found before. The emergence of these serotypes makes it essential to continue surveillance to determine which conjugated vaccine formulation would be suitable to prevent the most frequent pneumococcal invasive infections.

  8. Synthesis and characterization of (smif)2M(n) (n = 0, M = V, Cr, Mn, Fe, Co, Ni, Ru; n = +1, M = Cr, Mn, Co, Rh, Ir; smif =1,3-di-(2-pyridyl)-2-azaallyl).

    PubMed

    Frazier, Brenda A; Bartholomew, Erika R; Wolczanski, Peter T; DeBeer, Serena; Santiago-Berrios, Mitk'El; Abruña, Hector D; Lobkovsky, Emil B; Bart, Suzanne C; Mossin, Susanne; Meyer, Karsten; Cundari, Thomas R

    2011-12-19

    A series of Werner complexes featuring the tridentate ligand smif, that is, 1,3-di-(2-pyridyl)-2-azaallyl, have been prepared. Syntheses of (smif)(2)M (1-M; M = Cr, Fe) were accomplished via treatment of M(NSiMe(3))(2)(THF)(n) (M = Cr, n = 2; Fe, n = 1) with 2 equiv of (smif)H (1,3-di-(2-pyridyl)-2-azapropene); ortho-methylated ((o)Mesmif)(2)Fe (2-Fe) and ((o)Me(2)smif)(2)Fe (3-Fe) were similarly prepared. Metatheses of MX(2) variants with 2 equiv of Li(smif) or Na(smif) generated 1-M (M = Cr, Mn, Fe, Co, Ni, Zn, Ru). Metathesis of VCl(3)(THF)(3) with 2 Li(smif) with a reducing equiv of Na/Hg present afforded 1-V, while 2 Na(smif) and IrCl(3)(THF)(3) in the presence of NaBPh(4) gave [(smif)(2)Ir]BPh(4) (1(+)-Ir). Electrochemical experiments led to the oxidation of 1-M (M = Cr, Mn, Co) by AgOTf to produce [(smif)(2)M]OTf (1(+)-M), and treatment of Rh(2)(O(2)CCF(3))(4) with 4 equiv Na(smif) and 2 AgOTf gave 1(+)-Rh. Characterizations by NMR, EPR, and UV-vis spectroscopies, SQUID magnetometry, X-ray crystallography, and DFT calculations are presented. Intraligand (IL) transitions derived from promotion of electrons from the unique CNC(nb) (nonbonding) orbitals of the smif backbone to ligand π*-type orbitals are intense (ε ≈ 10,000-60,000 M(-1)cm(-1)), dominate the UV-visible spectra, and give crystals a metallic-looking appearance. High energy K-edge spectroscopy was used to show that the smif in 1-Cr is redox noninnocent, and its electron configuration is best described as (smif(-))(smif(2-))Cr(III); an unusual S = 1 EPR spectrum (X-band) was obtained for 1-Cr.

  9. Adsorptive Separation of Methanol-Acetone on Isostructural Series of Metal-Organic Frameworks M-BTC (M = Ti, Fe, Cu, Co, Ru, Mo): A Computational Study of Adsorption Mechanisms and Metal-Substitution Impacts.

    PubMed

    Wu, Ying; Chen, Huiyong; Xiao, Jing; Liu, Defei; Liu, Zewei; Qian, Yu; Xi, Hongxia

    2015-12-09

    The adsorptive separation properties of M-BTC isostructural series (M = Ti, Fe, Cu, Co, Ru, Mo) for methanol-acetone mixtures were investigated by using various computational procedures of grand canonical Monte Carlo simulations (GCMC), density functional theory (DFT), and ideal adsorbed solution theory (IAST), following with comprehensive understanding of adsorbate-metal interactions on the adsorptive separation behaviors. The obtained results showed that the single component adsorptions were driven by adsorbate-framework interactions at low pressures and by framework structures at high pressures, among which the mass effects, electrostatics, and geometric accessibility of the metal sites also played roles. In the case of methanol-acetone separation, the selectivity of methanol on M-BTCs decreased with rising pressures due to the pressure-dependent separation mechanisms: the cooperative effects between methanol and acetone hindered the separation at low pressures, whereas the competitive effects of acetone further resulted in the lower selectivity at high pressures. Among these M-BTCs, Ti and Fe analogues exhibited the highest thermodynamic methanol/acetone selectivity, making them promising for adsorptive methanol/acetone separation processes. The investigation provides mechanistic insights on how the nature of metal centers affects the adsorption properties of MOFs, and will further promote the rational design of new MOF materials for effective gas mixture separation.

  10. Bulk modulus and specific heat of B-site doped (La0.3Pr0.7)0.65Ca0.35Mn1-xBxO3 (B=Fe, Cr, Ru, Al, Ga)

    NASA Astrophysics Data System (ADS)

    Srivastava, Archana; Thakur, Rasna; Gaur, N. K.

    2014-04-01

    Specific heat (Cp) thermal expansion (α) and Bulk modulus (BT) of lightly doped Rare Earth manganites (La0.3Pr0.7)0.65Ca0.35Mn1-xBxO3 (B3+ = Fe3+,Cr3+,Ga3+,Al3+,Ru4+); (0.3Fe0.03O3 as a function of temperature (10K≤T≤ 200K) is found to be in agreement with the published data. The trend of variation of Debye temperature with B-site cationic radius is predicted probably for the first time for the B-site doped rare earth manganites.

  11. Molecule-based magnets formed by bimetallic three-dimensional oxalate networks and chiral tris(bipyridyl) complex cations. The series [ZII(bpy)3][ClO4][MIICrIII(ox)3] (ZII = Ru, Fe, Co, and Ni; MII = Mn, Fe, Co, Ni, Cu, and Zn; ox = oxalate dianion).

    PubMed

    Coronado, E; Galán-Mascarós, J R; Gómez-García, C J; Martínez-Agudo, J M

    2001-01-01

    The synthesis, structure, and physical properties of the series of molecular magnets formulated as [ZII(bpy)3][ClO4][MIICrIII(ox)3] (ZII = Ru, Fe, Co, and Ni; MII = Mn, Fe, Co, Ni, Cu, and Zn; ox = oxalate dianion) are presented. All the compounds are isostructural to the [Ru(bpy)3][ClO4][MnCr(ox)3] member whose structure (cubic space group P4(1)32 with a = 15.506(2) A, Z = 4) consists of a three-dimensional bimetallic network formed by alternating MII and CrIII ions connected by oxalate anions. The identical chirality (lambda in the solved crystal) of all the metallic centers determines the 3D chiral structure adopted by these compounds. The anionic 3D sublattice leaves some holes where the chiral [Z(bpy)3]2+ and ClO4- counterions are located. These compounds behave as soft ferromagnets with ordering temperatures up to 6.6 K and coercive fields up to 8 mT.

  12. Synthesis, crystal structure investigation and magnetism of the complex metal-rich boride series Cr{sub x}(Rh{sub 1-y}Ru{sub y}){sub 7-x}B{sub 3} (x=0.88-1; y=0-1) with Th{sub 7}Fe{sub 3}-type structure

    SciTech Connect

    Misse, Patrick R.N.; Mbarki, Mohammed; Fokwa, Boniface P.T.

    2012-08-15

    Powder samples and single crystals of the new complex boride series Cr{sub x}(Rh{sub 1-y}Ru{sub y}){sub 7-x}B{sub 3} (x=0.88-1; y=0-1) have been synthesized by arc-melting the elements under purified argon atmosphere on a water-cooled copper crucible. The products, which have metallic luster, were structurally characterized by single-crystal and powder X-ray diffraction as well as EDX measurements. Within the whole solid solution range the hexagonal Th{sub 7}Fe{sub 3} structure type (space group P6{sub 3}mc, no. 186, Z=2) was identified. Single-crystal structure refinement results indicate the presence of chromium at two sites (6c and 2b) of the available three metal Wyckoff sites, with a pronounced preference for the 6c site. An unexpected Rh/Ru site preference was found in the Ru-rich region only, leading to two different magnetic behaviors in the solid solution: The Rh-rich region shows a temperature-independent (Pauli) paramagnetism whereas an additional temperature-dependent paramagnetic component is found in the Ru-rich region. - Graphical abstract: The new complex boride series Cr{sub x}(Rh{sub 1-y}Ru{sub y}){sub 7-x}B{sub 3} (x=0.88-1; y=0-1) has been synthesized by arc melting the elements under purified argon atmosphere. Beside the 3d/4d site preference within the whole solid solution, an unexpected Rh/Ru site preference was found in the Ru-rich region only, leading to two different magnetic behaviors: The Rh-rich region shows a temperature-independent (Pauli) paramagnetism whereas an additional temperature-dependent paramagnetic component is found in the Ru-rich region. Highlights: Black-Right-Pointing-Pointer Synthesis of a new boride series fulfilling Vegard Acute-Accent s rule. Black-Right-Pointing-Pointer 3d/4d site preference. Black-Right-Pointing-Pointer Unexpected Ru/Rh site preference. Black-Right-Pointing-Pointer Rh-rich region is Pauli paramagnetic. Black-Right-Pointing-Pointer Ru-rich region is Pauli and temperature-dependent paramagnetic.

  13. Magnetic properties of RT2Zn20; R = rare earth, T = Fe, Co, Ru, Os and Ir

    SciTech Connect

    Jia, Shuang

    2008-01-01

    It is well known that rare earth intermetallic compounds have versatile, magnetic properties associated with the 4f electrons: a local moment associated with the Hund's rule ground state is formed in general, but a strongly correlated, hybridized state may also appear for specific 4f electronic configuration (eg. for rare earth elements such as Ce or Yb). On the other hand, the conduction electrons in rare earth intermetallic compounds, certainly ones associated with non hybridizing rare earths, usually manifest non-magnetic behavior and can be treated as a normal, non-interacted Fermi liquid, except for some 3d-transition metal rich binary or ternary systems which often manifest strong, itinerant, d electron dominant magnetic behavior. Of particular interest are examples in which the band filling of the conduction electrons puts the system in the vicinity of a Stoner transition: such systems, characterized as nearly or weakly ferromagnet, manifest strongly correlated electronic properties [Moriya, 1985]. For rare earth intermetallic compounds, such systems provide an additional versatility and allow for the study of the behaviors of local moments and hybridized moments which are associated with 4f electron in a correlated conduction electron background.

  14. Fragility of ferromagnetic double exchange interactions and pressure tuning of magnetism in 3 d -5 d double perovskite Sr 2 FeOsO 6

    SciTech Connect

    Veiga, L. S. I.; Fabbris, G.; van Veenendaal, M.; Souza-Neto, N; Feng, H. L.; Yamaura, K.; Haskel, D.

    2015-06-19

    The ability to tune exchange (magnetic) interactions between 3d transition metals in perovskite structures has proven to be a powerful route to discovery of novel properties. Here we demonstrate that the introduction of 3d-5d exchange pathways in double perovskites enables additional tunability, a result of the large spatial extent of 5d wave functions. Using x-ray probes of magnetism and structure at high pressure, we show that compression of Sr2FeOsO6 drives an unexpected continuous change in the sign of Fe-Os exchange interactions and a transition from antiferromagnetic to ferrimagnetic order. We analyze the relevant electron-electron interactions, shedding light into fundamental differences with the more thoroughly studied 3d-3d systems.

  15. Fragility of ferromagnetic double exchange interactions and pressure tuning of magnetism in 3d–5d double perovskite Sr₂FeOsO₆

    DOE PAGES

    Veiga, L. S. I.; Fabbris, G.; van Veenendaal, M.; ...

    2015-06-19

    The ability to tune exchange (magnetic) interactions between 3d transition metals in perovskite structures has proven to be a powerful route to discovery of novel properties. Here we demonstrate that the introduction of 3d-5d exchange pathways in double perovskites enables additional tunability, a result of the large spatial extent of 5d wave functions. Using x-ray probes of magnetism and structure at high pressure, we show that compression of Sr₂FeOsO₆ drives an unexpected continuous change in the sign of Fe-Os exchange interactions and a transition from antiferromagnetic to ferrimagnetic order. We analyze the relevant electron-electron interactions, shedding light into fundamental differencesmore » with the more thoroughly studied 3d-3d systems.« less

  16. Fragility of ferromagnetic double exchange interactions and pressure tuning of magnetism in 3d–5d double perovskite Sr₂FeOsO₆

    SciTech Connect

    Veiga, L. S. I.; Fabbris, G.; van Veenendaal, M.; Souza-Neto, N. M.; Feng, H. L.; Yamaura, K.; Haskel, D.

    2015-06-19

    The ability to tune exchange (magnetic) interactions between 3d transition metals in perovskite structures has proven to be a powerful route to discovery of novel properties. Here we demonstrate that the introduction of 3d-5d exchange pathways in double perovskites enables additional tunability, a result of the large spatial extent of 5d wave functions. Using x-ray probes of magnetism and structure at high pressure, we show that compression of Sr₂FeOsO₆ drives an unexpected continuous change in the sign of Fe-Os exchange interactions and a transition from antiferromagnetic to ferrimagnetic order. We analyze the relevant electron-electron interactions, shedding light into fundamental differences with the more thoroughly studied 3d-3d systems.

  17. The End of Monterey Submarine Canyon Incision and Potential River Source Areas-Os, Nd, and Pb Isotope Constraints from Hydrogenetic Fe-Mn Crusts

    NASA Astrophysics Data System (ADS)

    Conrad, T. A.; Nielsen, S.; Ehrenbrink, B. P. E.; Blusztajn, J.; Hein, J. R.; Paytan, A.

    2015-12-01

    The Monterey Canyon off central California is the largest submarine canyon off North America and is comparable in scale to the Grand Canyon. The age and history of the Monterey Canyon are poorly constrained due to thick sediment cover and sediment disruption from turbidity currents. To address this deficit we analyzed isotopic proxies (Os, Pb, Nd) from hydrogenetic ferromanganese (Fe-Mn) crusts, which grow over millions of years on elevated rock surfaces by precipitation of metals from seawater. Fe-Mn crusts were studied from Davidson Seamount near the base of the Monterey submarine fan, the Taney Seamount Chain, and from Hoss Seamount, which serves as a regional control (Fig.). Fe-Mn crusts were dated using Os isotope ratios compared to those that define the Cenozoic Os isotope seawater curve. Four Fe-Mn crust samples from Davidson and Taney Seamounts deviate from the Os isotopic seawater curve towards radiogenic values after 4.5±1 Ma. Osmium is well mixed in the global ocean and is not subject to significant diffusive reequilibration in Fe-Mn crusts. We therefore attribute deviations from the Os isotope seawater curve to large-scale terrestrial input that ended about 4.5±1 Ma. The two Davidson samples also show more radiogenic Nd isotope values from about 4.5±1 Ma. Lead isotopes in one Davidson Seamount crust, measured by LA-ICPMS, deviate from regional values after 4.5±1 Ma for about 500 ka towards terrestrial sources. The Taney Seamount Fe-Mn crust does not deviate from regional Nd nor Pb isotope values due to its greater distance from Monterey Canyon and the shorter marine residence times of Nd and Pb. Isotope plots of our crust data and compiled data for potential source rocks indicate that the river that carved Monterey Canyon carried sediment with values closer to the Sierra Nevada than to a Colorado Plateau source, with cessation of major riverine input occurring approximately 4.5±1 Ma, an age that we interpret as the end of the Monterey Canyon

  18. Heavy-impurity resonance, hybridization, and phonon spectral functions in Fe1-xMxSi, M=Ir,Os

    SciTech Connect

    Delaire, O.; Al-Qasir, Iyad I.; May, Andrew F.; Sales, Brian C.; Niedziela, Jennifer L.; Ma, Jie; Matsuda, Masaaki; Abernathy, Douglas L.; Berlijn, Tom

    2015-03-31

    The vibrational behavior of heavy substitutional impurities (M=Ir,Os) in Fe1-xMxSi (x = 0, 0.02, 0.04, 0.1) was investigated with a combination of inelastic neutron scattering (INS), transport measurements, and first-principles simulations. In this paper, our INS measurements on single-crystals mapped the four-dimensional dynamical structure factor, S(Q;E), for several compositions and temperatures. Our results show that both Ir and Os impurities lead to the formation of a weakly dispersive resonance vibrational mode, in the energy range of the acoustic phonon dispersions of the FeSi host. We also show that Ir doping, which introduces free carriers and increases electron-phonon coupling, leads to softened interatomic force-constants compared to doping with Os, which is isoelectronic to Fe. We analyze the phonon S(Q,E) from INS through a Green's function model incorporating the phonon self-energy based on first-principles density functional theory (DFT) simulations. Calculations of the quasiparticle spectral functions in the doped system reveal the hybridization between the resonance and the acoustic phonon modes. Finally, our results demonstrate a strong interaction of the host acoustic dispersions with the resonance mode, likely leading to the large observed suppression in lattice thermal conductivity.

  19. Ultrasound-activated piezoelectric P(VDF-TrFE)/boron nitride nanotube composite films promote differentiation of human SaOS-2 osteoblast-like cells.

    PubMed

    Genchi, Giada Graziana; Sinibaldi, Edoardo; Ceseracciu, Luca; Labardi, Massimiliano; Marino, Attilio; Marras, Sergio; De Simoni, Giorgio; Mattoli, Virgilio; Ciofani, Gianni

    2017-05-26

    Piezoelectric films of poly(vinylidenedifluoride-trifluoroethylene) (P(VDF-TrFE)) and of P(VDF-TrFE)/boron nitride nanotubes (BNNTs) were prepared by cast-annealing and used for SaOS-2 osteoblast-like cell culture. Films were characterized in terms of surface and bulk features, and composite films demonstrated enhanced piezoresponse compared to plain polymeric films (d31 increased by ~80%). Osteogenic differentiation was evaluated in terms of calcium deposition, collagen I secretion, and transcriptional levels of marker genes (Alpl, Col1a1, Ibsp, and Sparc) in cells either exposed or not to ultrasounds (US); finally, a numerical model suggested that the induced voltage (~20-60 mV) is suitable for cell stimulation. Although preliminary, our results are extremely promising and encourage the use of piezoelectric P(VDF-TrFE)/BNNT films in bone tissue regeneration. Copyright © 2017 Elsevier Inc. All rights reserved.

  20. Influence of the central diamagnetic cyanidometal on the distant magnetic interaction in cyanide-bridged Fe(III)-M(II)-Fe(III) complexes.

    PubMed

    Wang, Yong; Lin, Chensheng; Ma, Xiao; Xue, Zhenzhen; Zhu, Xiaoquan; Cao, Wenhai; Hu, Shengmin; Sheng, Tianlu; Wu, Xintao

    2015-04-28

    To investigate how the central diamagnetic cyanidometal influences the distant magnetic interaction of cyanide-bridged Fe(III)-M(II)-Fe(III) complexes, cis-[Cp(dppe)Fe(II)(NC)M(II)(L)2(CN)Fe(II)(dppe) Cp][PF6]2 (M = Os, L = bpy 1; M = Os, L = phen 2; M = Fe, L = bpy 3; M = Fe, L = phen 4), and their one-electron oxidation products 5–7 and two-electron oxidation products 8–11 were synthesized and fully characterized. The cyclic voltammetry of complexes 1–4 suggests that both NC-Os(II)(L)2-CN and NC-Fe(II)(L)2-CN have electronic communication ability. The electronic absorption spectroscopy suggests the presence of the central M(II) to the terminal Fe(III) and the terminal Fe(II) to the terminal Fe(III) metal to metal charge transfers (MMCTs) in 5-7 and the central M(II) to the terminal Fe(III) MMCTs in 8-11. Moreover, for the two-electron oxidation products the MMCT energy increases with the central metal in the order Fe < Os < Ru. The two-electron oxidation complexes 8 and 9 exhibit a strong antiferromagnetic coupling (J ≈ -26 cm(-1)) between the two distant Fe(III) ions although separated by the diamagnetic cyanidometal NC-Os(II)(L)2-CN bridge. To the best of our knowledge, this is the strongest magnetic coupling between the distant paramagnetic metal ions across a diamagnetic cyanidometal bridge reported by far. For the two-electron oxidation complexes 10 and 11 with the diamagnetic NC-Fe(II)(L)2-CN bridge, however, the distant two Fe(III) ions possess only very weak antiferromagnetic coupling (J = -0.15 and -0.19 cm(-1)). Combined with our previous reported results, it could be found that the magnetic coupling strength between the distant Fe(III) ions increases with the diamagnetic cyanidometal bridge in the order of Fe < Ru < Os.

  1. Lattice-distortion Induced Magnetic Transition from Low-temperature Antiferromagnetism to High-temperature Ferrimagnetism in Double Perovskites A2FeOsO6 (A = Ca, Sr).

    PubMed

    Hou, Y S; Xiang, H J; Gong, X G

    2015-08-20

    High-temperature insulating ferrimagnetism is investigated in order to further reveal its physical mechanisms, as well as identify potentially important scientific and practical applications relative to spintronics. For example, double perovskites such as Sr2FeOsO6 and Ca2FeOsO6 are shown to have puzzling magnetic properties. The former is a low-temperature antiferromagnet while the latter is a high-temperature insulating ferrimagnet. In order to understand the underlying mechanisms, we have investigated the frustrated magnetism of A2FeOsO6 by employing density functional theory and maximally-localized Wannier functions. We find lattice distortion enhances the antiferromagnetic nearest-neighboring Fe-O-Os interaction, however weakens the antiferromagnetic interactions via the Os-O-O-Os and Fe-O-Os-O-Fe paths, so is therefore responsible for the magnetic transition from the low-temperature antiferromagnetism to the high-temperature ferrimagnetism as the decrease of the A(2+) ion radii. Also discussed is the 5d(3)-3d(5) superexchange. We propose that such superexchange is intrinsically antiferromagnetic instead of ferromagnetic as previously thought. Our work clearly illustrates the magnetic frustration can be effectively relieved by lattice distortion, thus paving the way for tuning of complex magnetism in yet other 3d-5d (4d) double perovskites.

  2. Lattice-distortion Induced Magnetic Transition from Low-temperature Antiferromagnetism to High-temperature Ferrimagnetism in Double Perovskites A2FeOsO6 (A = Ca, Sr)

    PubMed Central

    Hou, Y. S.; Xiang, H. J.; Gong, X. G.

    2015-01-01

    High-temperature insulating ferrimagnetism is investigated in order to further reveal its physical mechanisms, as well as identify potentially important scientific and practical applications relative to spintronics. For example, double perovskites such as Sr2FeOsO6 and Ca2FeOsO6 are shown to have puzzling magnetic properties. The former is a low-temperature antiferromagnet while the latter is a high-temperature insulating ferrimagnet. In order to understand the underlying mechanisms, we have investigated the frustrated magnetism of A2FeOsO6 by employing density functional theory and maximally-localized Wannier functions. We find lattice distortion enhances the antiferromagnetic nearest-neighboring Fe-O-Os interaction, however weakens the antiferromagnetic interactions via the Os-O-O-Os and Fe-O-Os-O-Fe paths, so is therefore responsible for the magnetic transition from the low-temperature antiferromagnetism to the high-temperature ferrimagnetism as the decrease of the A2+ ion radii. Also discussed is the 5d3-3d5 superexchange. We propose that such superexchange is intrinsically antiferromagnetic instead of ferromagnetic as previously thought. Our work clearly illustrates the magnetic frustration can be effectively relieved by lattice distortion, thus paving the way for tuning of complex magnetism in yet other 3d–5d (4d) double perovskites. PMID:26289139

  3. Lattice-distortion Induced Magnetic Transition from Low-temperature Antiferromagnetism to High-temperature Ferrimagnetism in Double Perovskites A2FeOsO6 (A = Ca, Sr)

    NASA Astrophysics Data System (ADS)

    Hou, Y. S.; Xiang, H. J.; Gong, X. G.

    2015-08-01

    High-temperature insulating ferrimagnetism is investigated in order to further reveal its physical mechanisms, as well as identify potentially important scientific and practical applications relative to spintronics. For example, double perovskites such as Sr2FeOsO6 and Ca2FeOsO6 are shown to have puzzling magnetic properties. The former is a low-temperature antiferromagnet while the latter is a high-temperature insulating ferrimagnet. In order to understand the underlying mechanisms, we have investigated the frustrated magnetism of A2FeOsO6 by employing density functional theory and maximally-localized Wannier functions. We find lattice distortion enhances the antiferromagnetic nearest-neighboring Fe-O-Os interaction, however weakens the antiferromagnetic interactions via the Os-O-O-Os and Fe-O-Os-O-Fe paths, so is therefore responsible for the magnetic transition from the low-temperature antiferromagnetism to the high-temperature ferrimagnetism as the decrease of the A2+ ion radii. Also discussed is the 5d3-3d5 superexchange. We propose that such superexchange is intrinsically antiferromagnetic instead of ferromagnetic as previously thought. Our work clearly illustrates the magnetic frustration can be effectively relieved by lattice distortion, thus paving the way for tuning of complex magnetism in yet other 3d-5d (4d) double perovskites.

  4. Structural Analysis of Novel Antiferromagnetic Material CeRu2Al10 and Its Related Compounds under Pressure

    NASA Astrophysics Data System (ADS)

    Kawamura, Yukihiro; Hayashi, Junichi; Takeda, Keiki; Sekine, Chihiro; Tanida, Hiroshi; Sera, Masafumi; Nishioka, Takashi

    2016-04-01

    We performed synchrotron X-ray studies of orthorhombic CeRu2Al10 and its related compounds CeT2Al10 (T = Fe, Os) and RRu2Al10 (R = La, Yb, Lu). The results of the X-ray studies indicate that all of the compounds retain their orthorhombic crystal structures and that their lattice parameters all monotonically decrease with pressure; that is, no structural changes or distortions occur below 10 GPa within the experimental accuracy of this study. In addition, we evaluated the bulk moduli of the compounds, which are mainly affected by the transition metal in RT2Al10 systems. All of the compounds exhibited crystal structures that were harder along the b-axis than along the a- or c-axes. Furthermore, anisotropic shrinkage induced a difference between the physical pressure of CeRu2Al10 and the chemical pressure of Ce(Ru1-xFex)2Al10 (0 ≤ x ≤ 1). Thus, the physical properties of CeRu2Al10 under pressure were observed to be strongly affected by crystal structure shrinkage along the a- and c-axes.

  5. London penetration depth measurements in Ba (Fe1-xTx)2As2(T=Co,Ni,Ru,Rh,Pd,Pt,Co+Cu) superconductors

    SciTech Connect

    Gordon, Ryan T.

    2011-01-01

    The London penetration depth has been measured in various doping levels of single crystals of Ba(Fe1-xTx)2As2 (T=Co,Ni,Ru,Rh,Pd,Pt,Co+Cu) superconductors by utilizing a tunnel diode resonator (TDR) apparatus. All in-plane penetration depth measurements exhibit a power law temperature dependence of the form Δλab(T) = CTn, indicating the existence of low-temperature, normal state quasiparticles all the way down to the lowest measured temperature, which was typically 500 mK. Several different doping concentrations from the Ba(Fe1-xTx)2As2 (T=Co,Ni) systems have been measured and the doping dependence of the power law exponent, n, is compared to results from measurements of thermal conductivity and specific heat. In addition, a novel method has been developed to allow for the measurement of the zero temperature value of the in-plane penetration depth, λab(0), by using TDR frequency shifts. By using this technique, the doping dependence of λab(0) has been measured in the Ba(Fe1-xCox)2As2 series, which has allowed also for the construction of the doping-dependent superfluid phase stiffness, ρs(T) = [λ(0)/λ(T)]2. By studying the effects of disorder on these superconductors using heavy ion irradiation, it has been determined that the observed power law temperature dependence likely arises from pair-breaking impurity scattering contributions, which is consistent with the proposed s±-wave symmetry of the superconducting gap in the dirty scattering limit. This hypothesis is supported by the measurement of an exponential temperature dependence of the penetration depth in the intrinsically clean LiFeAs, indicative of a nodeless superconducting gap.

  6. La{sub 3}Ru{sub 8}B{sub 6} and Y{sub 3}Os{sub 8}B{sub 6}, new members of a homologous series R(A){sub n}M{sub 3n-1}B{sub 2n}

    SciTech Connect

    Sologub, O.L.; Noel, H.; Roisnel, T.; Goncalves, A.P.

    2007-10-15

    Two new compounds, La{sub 3}Ru{sub 8}B{sub 6} and Y{sub 3}Os{sub 8}B{sub 6}, were synthesized by arc melting the elements. Their structural characterization was carried out at room temperature on as-cast samples by using X-ray diffractometry. According to X-ray single-crystal diffraction results these borides crystallize in Fmmm space group (no. 69), Z=4, a=5.5607(1) A, b=9.8035(3) A, c=17.5524(4) A, {rho}=8.956 Mg/m{sup 3}, {mu}=25.23 mm{sup -1} for La{sub 3}Ru{sub 8}B{sub 6} and a=5.4792(2) A, b=9.5139(4) A, c=17.6972(8) A, {rho}=13.343 Mg/m{sup 3}, {mu}=128.23 mm{sup -1} for Y{sub 3}Os{sub 8}B{sub 6}. The crystal structure of La{sub 3}Ru{sub 8}B{sub 6} was confirmed from Rietveld refinement of X-ray powder diffraction data. Both La{sub 3}Ru{sub 8}B{sub 6} and Y{sub 3}Os{sub 8}B{sub 6} compounds are isotypic with the Ca{sub 3}Rh{sub 8}B{sub 6} compound and their structures are built up from CeCo{sub 3}B{sub 2}-type and CeAl{sub 2}Ga{sub 2}-type structural fragments taken in ratio 2:1. They are the members of structural series R(A){sub n}M{sub 3n-1}B{sub 2n} with n=3 (R is the rare earth metal, A the alkaline earth metal, and M the transition metal). Structural and atomic parameters were also obtained for La{sub 0.94}Ru{sub 3}B{sub 2} compound from Rietveld refinement (CeCo{sub 3}B{sub 2}-type structure, P6/mmm space group (no. 191), a=5.5835(9) A, c=3.0278(6) A). - Graphical abstract: Two new compounds, La{sub 3}Ru{sub 8}B{sub 6} and Y{sub 3}Os{sub 8}B{sub 6}, were synthesized by arc melting the elements. From room temperature X-ray single-crystal and powder diffraction, both compounds were found to be isotypic with Ca{sub 3}Rh{sub 8}B{sub 6} compound (Fmmm space group (no. 69), Z=4) and their structures are built up from CeCo{sub 3}B{sub 2}-type and CeAl{sub 2}Ga{sub 2}-type structural fragments taken in ratio 2:1. They are the members of structural series R(A){sub n}M{sub 3n-1}B{sub 2n} with n=3 (R is the rare earth metal, A the alkaline earth metal, and M the

  7. Ru/FTO: Heterogeneous catalyst for glycerol hydrogenolysis

    NASA Astrophysics Data System (ADS)

    Samad, Wan Zurina; Isahak, Wan Nor Roslam Wan; Liew, Kin Hong; Nordin, Norazzizi; Yarmo, Mohd Ambar; Yusop, Muhammad Rahimi

    2014-09-01

    An introduction of Fluorine-doped tin oxide (FTO) as new catalyst support with Ru metal had enhanced the conversion and selectivity for glycerol hydrogenolysis. A small cluster of Ru were highly dispersed and intercalated over FTO via simple chemical mixture and reduction method. In comparison with various metal (Pd, Os, Cu), Ru/FTO catalyst showed the highest conversion (100%) and highly selectivity of 1,2-propanediol (94%) in the hydrogenolysis of glycerol. The reaction was optimally conducted at 150 °C, 20 bar of H2 pressure and at 8 hours. Ru/FTO catalyst was ascribed as active catalyst due to the amphoteric sites of FTO and small size of Ru metal. This provides high surface concentration of reduction process that involves the chemical bond dissociation in the glycerol hydrogenolysis.

  8. Updating RU 486 development.

    PubMed

    Baulieu, E E

    1992-01-01

    Recent innovations in the procedure for early abortion with RU-486, expansion of its distribution range to other countries, medical considerations for new licensing, and potential new users of RU-486 are discussed. In France, the usual routine for an early abortion involves a diagnostic visit, a visit 1 week later to get RU-486, another visit 48 hours later to receive prostaglandin, and a fourth follow-up visit. The prostaglandin used is 2 tablets of 200 mcg Misoprostol, with a third dose given if expulsion does not occur in 4 hours. Ru-486 is licensed n France and the UK, and applications are in progress in Germany, Spain, and Canada. In the US Misoprostol is available and abortion is legal, but licensing is held up because Hoechst-Celanese, the US based subsidiary of Hoechst, a major shareholder of Roussel-Uclaf, does not want to enter the field of reproductive medicine. RU-486 seems simple to use, but medical supervision is necessary to diagnose and date the pregnancy, ensure that ectopic pregnancy has not occurred, provide contraceptive counseling, perform evacuation if the expulsion is not complete, and give the woman the medical care every pregnant woman deserves. The denial of "contraceptive" therapy to women who need this existing technology constitutes sex discrimination in a pluralistic society. New indications for RU-486 being researched are monthly menstrual induction, post-ovulatory anti-implantation contraception, anti-ovulation contraception, and continuous low-dose cyclic intake for contraception.

  9. Semiconducting behaviour of RuGa/sub 2/

    SciTech Connect

    Evers, J.; Meyer, H.; Oehlinger, G.

    1984-09-01

    RuGa/sub 2/ with TiSi/sub 2/-type structure was prepared by inductively heating ruthenium and gallium in a water-cooled copper boat under an argon atmosphere. The electric conductivity of a polycrystalline sample of nearly rectangular shape (7 x 5 x 4 mm/sup 3/) was measured in the temperature range from 20 to 400/sup 0/C by the four-point technique. RuGa/sub 2/ is a semiconductor with an electric resistivity of 0.2 ohm.cm at room temperature and a band gap of about 0.42 eV. Semiconducting properties have been qualitatively demonstrated for RuA1/sub 2/ (TiSi/sub 2/-type structure) and for Os/sub 2/Si/sub 3/ (Ru/sub 2/Si/sub 3/-type structure, defect TiSi/sub 2/-structure).

  10. Mössbauer Spectroscopy, NAA and PIXE Study on Some Archeological Problems of Ancient Chinese Ru Celadon

    NASA Astrophysics Data System (ADS)

    Zhang, B.; Liu, Y. L.; Gao, Z. Y.; Zhao, W. J.; Li, G. X.; Cheng, H. S.

    2005-06-01

    By Mössbauer spectroscopy, NAA and optical spectroscopy, the coloring and the firing technology of ancient Ru celadon were studied. Also, the relationship between Ru Kuan celadon from Qingliang Temple and Ru celadon from Zhanggongxiang was studied by PIXE. The glaze color of Ru celadon depends on the ratio of the structural iron ions, i.e. the Fe2+/Fe3+ ratio. Further, it depends on the firing conditions. As the Fe2+/Fe3+ ratio gradually increases, the glaze color of Ru celadon will gradually change from pea green to sky green. All the Ru celadons were fired in a reducing atmosphere. The sky green Ru celadon was fired in the most reducing atmosphere and at the highest temperature, the powder green in a more reducing atmosphere and at a lower temperature and the pea green in a lightly reducing atmosphere and at the lowest temperature. The PIXE experimental results showed that Ru Kuan celadon from Qingliang Temple and Ru celadon from Zhanggongxiang were incompletely identical in the recipe of glaze and they could be differentiated by the cluster analysis of the major element concentration of glaze.

  11. The "ethics" of RU486.

    PubMed

    Hunt, M

    1993-01-01

    The use of RU-486 to induce abortion represents a new era in reproductive technology and merits ethical attention. The feminists principles of concern for women's well-being, paying attention to the specific needs of women in specific circumstances, and balancing risks and benefits can be applied to an examination of RU-486. RU-486 has invoked the image of women's medical empowerment and has been deemed "the moral property of women." Support for RU-486 has come from major international health and feminist organizations, while the opposition of the anti-choice forces has been matched by that of the Feminist International Network of Resistance to Reproductive and Genetic Engineering. Issues critical to the introduction of RU-486 include 1) access and suitability, 2) whether RU-486 increases women's control over reproduction in a safe manner, and 3) the political problems involved when feminist leaders press for testing and attempt to explain varied and even opposing feminist positions in productive ways.

  12. Precious metal enrichment at low-redox in terrestrial native Fe-bearing basalts investigated using laser-ablation ICP-MS

    NASA Astrophysics Data System (ADS)

    Howarth, Geoffrey H.; Day, James M. D.; Pernet-Fisher, John F.; Goodrich, Cyrena A.; Pearson, D. Graham; Luo, Yan; Ryabov, Viktor V.; Taylor, Lawrence A.

    2017-04-01

    Primary native Fe is a rare crystallizing phase from terrestrial basaltic magmas, requiring highly reducing conditions (fO2 Fe alloy liquid. If this liquid also contains sufficient sulfur, it can undergo further division into conjugate Fe-C-rich and a Fe-S-rich immiscible melts that can effectively scavenge the highly siderophile elements (HSE: Re, Au, and the platinum group elements [PGE], Pd, Pt, Rh, Ru, Ir, Os), as well as Ni and Cu, to economic abundances. Three localities are known globally where native Fe bearing mafic rocks occur: (1) Paleocene basalts of Disko Island, West Greenland; (2) a Miocene lava of the Bühl basalts, Germany; and (3) mafic intrusions associated with the Late Permian Siberian flood basalts. In this contribution, we report major- and minor-element compositions and HSE concentrations for the main alloy phases (FeNi metal and cohenite) and sulfide, for all three known global occurrences of native Fe bearing basalt. Total HSE abundances in metal grains, obtained by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), are lowest in the Bühl basalt, (∼0.05 ppm), intermediate in the Disko Island basalts (4-8 ppm), and highest the Siberian Khungtukun and Dzhaltul intrusions (10-30 ppm). These differences demonstrate that, while native Fe formation is the result of carbonaceous crustal assimilation, HSE enrichment is not ubiquitous during this process. The Siberian occurrences are characterized by Pt PGE (PPGE: Pt, Pd) enrichment relative to the Ir PGE (IPGE: Rh, Ru, Ir, Os), consistent with models of early stage fractionation of olivine, chromite and metallic IPGE in staging magma reservoirs, prior to the addition of C-rich crustal materials in the shallow crust. Relative to Noril'sk Ni-Cu-PGE sulfide ores

  13. Ca2+-sequestering smooth endoplasmic reticulum in an invertebrate photoreceptor. I. Intracellular topography as revealed by OsFeCN staining and in situ Ca accumulation

    PubMed Central

    1982-01-01

    Two ultrastructural approaches were used in photoreceptor cells of the leech, Hirudo medicinalis, to (a) investigate the intracellular topography of the smooth endoplasmic reticulum (SER) and (b) identify among the various subregions of the SER those which might function as Ca-sequestering sites. When the cells are prefixed with CaCl2- containing glutaraldehyde and postfixed with osmium tetroxide- ferricyanide (OsFeCN), only a part of the total SER is specifically stained. The stained SER cisternae include the submicrovillar cisternae (SMC), subsurface cisternae (SSC), the nuclear envelope, Golgi- associated SER, paracrystalline SER, and SER associated with glycogen areas. An extensive tubular SER cisternal system always remains unstained. When the cells are permeabilized by saponin and subsequently incubated with Ca2+, MgATP, and oxalate, the SMC (Walz, 1979, Eur. J. Cell Biol. 20:83-91), the SSC and the nuclear envelope contain electron- opaque Ca-oxalate precipitates indicating their ability to function as an effective Ca2+ sink. The results show that the very elaborate SER in this photoreceptor cell includes many functionally heterogeneous subregions. Of special physiological significance are those components (SMC and SSC) which are effective in Ca2+-buffering in the immediate vicinity of the plasma membrane. PMID:6181073

  14. Meteorite - Impact Melt Mixing: PGE and Re-Os Evidence from the Morokweng Impact, South Africa

    NASA Astrophysics Data System (ADS)

    Hart, R.; Andreoli, M.; Cloete, M.; McDonald, I.; Carlson, R. W.; Tredoux, M.

    2001-12-01

    Preserved within the 870m thick impact melt sheet of the 144 Ma Morokweng impact structure, South Africa (1,2) are small (mm-cm) inclusions that are interpreted to be remnants of the impactor. Inclusions are disseminated throughout the melt sheet and consist of ultramafic silicate clasts with segregations of Ni-rich sulfides and oxides. The silicate component in the inclusions displays remnant fabric and, where unaltered, has mineral compositions consistent with ordinary chondrites (3). The sulfide-oxide component of the inclusions is Ni-rich, has high PGE contents (Ir = 16.7 x chondrite) and fractionated PGE ratios compared to chondrites and to the bulk impact melt which reflects the signature of the ordinary chondrite impactor (4). Specifically, the oxides show depletion in Pd, while the sulfide is slightly enriched in Rh and Pt and strongly enriched in Pd relative to Ir and Ru. Significantly, Ru and Ir (the high temperature PGE's) are not fractionated from one another. Initial Os isotopic compositions of the inclusion sulfides and oxides (0.1335 - 0.1358) are slightly more radiogenic than found in the melt rock (0.1301 - 0.1324), but both are substantially less radiogenic than a sample of the basement granite (0.259). The 1/Os vs 187Os/188Os correlation displayed by the bulk melt rocks is consistent with the presence of 1-3 wt% chondritic impactor in the crustal melt. The more radiogenic Os found in the inclusion minerals indicates that the inclusions contain a larger crustal PGE component than the melt rock. Though Os concentration is well correlated with Os isotopic composition in the melt rock, Re concentration is not. Thus, simple binary mixing between crustal melt and meteorite cannot explain the Re-Os systematics. The Re-Os and PGE fractionation observed in inclusion minerals suggests that meteorite-impact melt mixing occurred first through chemical exchange between oxidized melt and reduced, metal or sulfur-rich, impactor. Lithophile elements (e.g. Fe

  15. Ru-Containing Magnetically Recoverable Catalysts: A Sustainable Pathway from Cellulose to Ethylene and Propylene Glycols.

    PubMed

    Manaenkov, Oleg V; Mann, Joshua J; Kislitza, Olga V; Losovyj, Yaroslav; Stein, Barry D; Morgan, David Gene; Pink, Maren; Lependina, Olga L; Shifrina, Zinaida B; Matveeva, Valentina G; Sulman, Esther M; Bronstein, Lyudmila M

    2016-08-24

    Biomass processing to value-added chemicals and biofuels received considerable attention due to the renewable nature of the precursors. Here, we report the development of Ru-containing magnetically recoverable catalysts for cellulose hydrogenolysis to low alcohols, ethylene glycol (EG) and propylene glycol (PG). The catalysts are synthesized by incorporation of magnetite nanoparticles (NPs) in mesoporous silica pores followed by formation of 2 nm Ru NPs. The latter are obtained by thermal decomposition of ruthenium acetylacetonate in the pores. The catalysts showed excellent activities and selectivities at 100% cellulose conversion, exceeding those for the commercial Ru/C. High selectivities as well as activities are attributed to the influence of Fe3O4 on the Ru(0)/Ru(4+) NPs. A facile synthetic protocol, easy magnetic separation, and stability of the catalyst performance after magnetic recovery make these catalysts promising for industrial applications.

  16. Superconductivity at 3.1 K in the orthorhombic ternary silicide ScRuSi

    NASA Astrophysics Data System (ADS)

    Ruan, Bin-Bin; Wang, Xiao-Chuan; Yu, Jia; Pan, Bo-Jin; Mu, Qing-Ge; Liu, Tong; Chen, Gen-Fu; Ren, Zhi-An

    2017-02-01

    We report the synthesis, crystal structure, superconductivity and physical property characterizations of the ternary equiatomic compound ScRuSi. Polycrystalline samples of ScRuSi were prepared by an arc-melting method. The as-prepared samples were identified as the orthorhombic Co2P-type o-ScRuSi by powder x-ray diffraction analysis. Electrical resistivity measurements show o-ScRuSi to be a metal which superconducts below a T c of 3.1 K; the upper critical field μ 0 H c2(0) is estimated to be 0.87 T. The magnetization and specific heat measurements confirm the bulk type-II superconductivity in o-ScRuSi, with a specific heat jump within the BCS weak coupling limit. o-ScRuSi is the first Co2P-type superconductor to contain scandium. After annealing at 1273 K for a week, o-ScRuSi transforms into hexagonal Fe2P-type h-ScRuSi, which is a Pauli-paramagnetic metal with no superconductivity observed above 1.8 K.

  17. High resolution spectroscopy of 102Ru(d, p) 103Ru and 104Ru(p, d) 103Ru reactions

    NASA Astrophysics Data System (ADS)

    Berg, G. P. A.; Demarteau, M.; Hardt, A.; Hürlimann, W.; Martin, S. A.; Meissburger, J.; Oelert, W.; Seyfarth, H.; Styczen, B.; Köhler, M.; Oelrich, I.; Scheerer, J.

    1982-04-01

    The high resolution magnetic spectrometer BIG KARL was used to investigate the low-lying states of 103Ru by 102Ru(d, p) and 104Ru(p,d) reactions at Ed = 45 MeV andEp = 29 MeV. The resolution of {ΔE}/{E} = (1.7-2.5) × 10 -4 was sufficient to separate most of the known states up to Ex = 1 MeV excitation energy. For these levels differential cross sections have been measured in the range of θ lab = 4°-43°. A DWBA analysis has been employed in order to determine orbital angular momenta and obtain spectroscopic factors. These were used to make a number of tentative spin and parity assignments. In addition several weakly excited states in 103Ru could be identified and excitation energies have been determined to about ±2 keV.

  18. Distribution of platinum-group elements and Os isotopes in chromite ores from Mayarí-Baracoa Ophiolitic Belt (eastern Cuba)

    NASA Astrophysics Data System (ADS)

    Gervilla, F.; Proenza, J. A.; Frei, R.; González-Jiménez, J. M.; Garrido, C. J.; Melgarejo, J. C.; Meibom, A.; Díaz-Martínez, R.; Lavaut, W.

    2005-12-01

    The Mayarí-Baracoa ophiolitic belt in eastern Cuba hosts abundant chromite deposits of historical economic importance. Among these deposits, the chemistry of chromite ore is very variable, ranging from high Al (Cr#=0.43-0.55) to high Cr (Cr#=0.60-0.83) compositions. Platinum-group element (PGE) contents are also variable (from 33 ppb to 1.88 ppm) and correlate positively with the Cr# of the ore. Bulk PGE abundances correlate negatively with the Pd/Ir ratio showing that chromite concentrates mainly Os, Ir and Ru which gives rise to the characteristic negatively sloped, chrondrite-normalized PGE patterns in many chromitites. This is consistent with the mineralogy of PGEs, which is dominated by members of the laurite-erlichmanite solid solution series (RuS2-OsS2), with minor amounts of irarsite (IrAsS), Os-Ir alloys, Ru-Os-Ir-Fe-Ni alloys, Ni-Rh-As, and sulfides of Ir, Os, Rh, Cu, Ni, and/or Pd. Measured 187Os/188Os ratios (from 0.1304 to 0.1230) are among the lower values reported for podiform chromitites. The 187Os/188Os ratios decrease with increasing whole-rock PGE contents and Cr# of chromite. Furthermore, γOs values of all but one of the chromitite samples are negative indicating a subchondiritc mantle source. γOs decrease with increasing bulk Os content and decreasing 187Re/188Os ratios. These mineralogical and geochemical features are interpreted in terms of chromite crystallization from melts varying in composition from back-arc basalts (Al-rich chromite) to boninites (Cr-rich chromite) in a suprasubduction zone setting. Chromite crystallization occurs as a consequence of magma mixing and assimilation of preexisting gabbro sills at the mantle-crust transition zone. Cr#, PGE abundances, and bulk Os isotopic composition of chromitites are determined by the combined effects of mantle source heterogeneity, the degree of partial melting, the extent of melt-rock interactions, and the local sulfur fugacity. Small-scale (μm to cm) chemical and isotopic

  19. Role of RuO3 for the formation of RuO2 nanorods

    NASA Astrophysics Data System (ADS)

    Music, Denis; Breunung, Johannes; Mráz, Stanislav; Schneider, Jochen M.

    2012-01-01

    We have observed Ru hyperoxides (RuO3 and RuO4) in Ru-O2-Ar plasmas using mass-energy analysis. Based on ab initio adsorption data, a nanorod formation model is presented. RuO3 exhibits the strongest adsorption on RuO2(001). Adatoms impinging on these RuO3 islands are likely to contribute towards three-dimensional growth due to Ehrlich-Schwoebel barriers. We propose that RuO3 islands act as nucleation sites for the nanorod formation. Our model is consistent with available experimental data.

  20. Bulk modulus and specific heat of B-site doped (La{sub 0.3}Pr{sub 0.7}){sub 0.65}Ca{sub 0.35}Mn{sub 1−x}B{sub x}O{sub 3} (B=Fe, Cr, Ru, Al, Ga)

    SciTech Connect

    Srivastava, Archana; Thakur, Rasna; Gaur, N. K.

    2014-04-24

    Specific heat (C{sub p}) thermal expansion (α) and Bulk modulus (B{sub T}) of lightly doped Rare Earth manganites (La{sub 0.3}Pr{sub 0.7}){sub 0.65}Ca{sub 0.35}Mn{sub 1−x}B{sub x}O{sub 3} (B{sup 3+} = Fe{sup 3+},Cr{sup 3+},Ga{sup 3+},Al{sup 3+},Ru4+); (0.3Fe{sub 0.03}O{sub 3} as a function of temperature (10K≤T≤ 200K) is found to be in agreement with the published data. The trend of variation of Debye temperature with B-site cationic radius is predicted probably for the first time for the B-site doped rare earth manganites.

  1. The role of recycled oceanic crust in magmatism and metallogeny: Os-Sr-Nd isotopes, U-Pb geochronology and geochemistry of picritic dykes in the Panzhihua giant Fe-Ti oxide deposit, central Emeishan large igneous province, SW China

    NASA Astrophysics Data System (ADS)

    Hou, Tong; Zhang, Zhaochong; Encarnacion, John; Santosh, M.; Sun, Yali

    2013-04-01

    The picritic dykes occurring within fine-grained gabbro in the marginal zone and in the surrounding Proterozoic wall-rock marbles of the Panzhihua Fe-Ti oxide deposit closely correspond in bulk composition with the nearby Panzhihua intrusion. These dykes offer important constraints on the nature of the mantle source of the Panzhihua ore-bearing intrusion and its possible link to the Emeishan plume. U-Pb zircon dating of the picritic dyke yields a crystallization age of 261.4 ± 4.6 Ma, coeval with the timing of the main Panzhihua gabbroic intrusion and Late Permian Emeishan flood basalts. The Panzhihua picritic dykes contain 37.63-43.41 wt% SiO2, 1.15-1.56 wt% TiO2, 11.43-13.25 wt% TFe2O3, and 20.96-28.87 wt% MgO. Primitive-mantle-normalized patterns of the rocks are comparable to those of ocean island basalt. The rocks define a relatively small range of Os isotopic compositions and a low Os signature of -0.13 to +2.76 for γOs (261 Ma). In combination with their Sr-Nd-Os isotopic compositions, we interpret that these rocks were derived from the Emeishan plume sources as well as the interactions of plume melts with the overlying lithosphere which had been extensively affected by eclogite-derived melts from the deep-subducted oceanic slab. Partial melting induced by an upwelling mantle plume that involved an eclogite or pyroxenite component in the lithospheric mantle could have produced the parental Fe-rich magma. Our study suggests that plume-lithosphere interaction might have played a key role in generating many world-class Fe-Ti oxide deposits clustered in the Panxi area.

  2. CO chemisorption and dissociation at high coverages during CO hydrogenation on Ru catalysts.

    PubMed

    Loveless, Brett T; Buda, Corneliu; Neurock, Matthew; Iglesia, Enrique

    2013-04-24

    Density functional theory (DFT) and infrared spectroscopy results are combined with mechanism-based rate equations to assess the structure and thermodynamics of chemisorbed CO (CO*) and its activation during Fischer-Tropsch synthesis (FTS). CO* binding becomes weaker with increasing coverage on Ru(0001) and Ru201 clusters, but such decreases in binding energy occur at higher coverages on Ru201 clusters than on Ru(0001) surfaces (CO*/Ru = 1.55 to 0.75); such differences appear to reflect weaker repulsive interactions on the curved surfaces prevalent on small Ru201 clusters. Ru201 clusters achieve stable supramonolayer coverages (CO*/Ru > 1) by forming geminal dicarbonyls at low-coordination corner/edge atoms. CO* infrared spectra on Ru/SiO2 (~7 nm diameter) detect mobile adlayers that anneal into denser structures at saturation. Mechanism-based FTS rate equations give activation energies that reflect the CO*-saturated surfaces prevalent during catalysis. DFT-derived barriers show that CO* predominantly reacts at (111) terraces via H-assisted reactions, consistent with measured effects of H2 and CO pressures and cluster size effects on rates and O-rejection selectivities. Barriers are much higher for unassisted CO* dissociation on (111) terraces and low-coordination atoms, including step-edge sites previously proposed as active sites for CO* dissociation during FTS. DFT-derived barriers indicate that unassisted CO* dissociation is irreversible, making such steps inconsistent with measured rates. The modest activation barriers of H-assisted CO* dissociation paths remove a requirement for special low-coordination sites for unassisted CO* activation, which is inconsistent with higher rates on larger clusters. These conclusions seem generally applicable to Co, Fe, and Ru catalysts, which show similar FTS rate equations and cluster size effects. This study also demonstrates the feasibility and relevance of DFT treatments on the curved and crowded cluster surfaces where

  3. The series of carbon-chain complexes {Ru(dppe)Cp*}₂{μ-(C≡C)x} (x = 4–8, 11): Synthesis, structures, properties and some reactions

    SciTech Connect

    Bruce, Michael I.; Cole, Marcus L.; Ellis, Benjamin G.; Gaudio, Maryka; Nicholson, Brian K.; Parker, Christian R.; Skelton, Brian W.; White, Allan H.

    2015-01-28

    The construction of a series of compounds {Ru(dppe)Cp*}2(μ-C2x) (Ru*-C2x-Ru*, x = 4–8, 11)) is described. A direct reaction between RuCl(dppe)Cp* and Me3Si(Ctriple bond; length of mdashC)4SiMe3 afforded Ru*-C8-Ru* in 89% yield. The Pd(0)/Cu(I)-catalysed coupling of Ru{Ctriple bond; length of mdashCCtriple bond; length of mdashCAu(PPh3)}(dppe)Cp*Ru*-C4-Au (2 equiv.) with diiodoethyne gave Ru*-C10-Ru* (64%), or of 1 equiv. with I(Ctriple bond; length of mdashC)3I gave Ru*-C14-Ru* (36%); similarly, Ru{(Ctriple bond; length of mdashC)4Au(PPh3)}(dppe)Cp*Ru*-C8-Au and I(Ctriple bond; length of mdashC)3I gave Ru*-C22-Ru* (12%). Desilylation (TBAF) of Ru{(Ctriple bond; length of mdashC)xSiMe3}(dppe)Cp*Ru*-C2x-Si (x = 3, 4) followed by oxidative coupling [Cu(OAc)2/py] gave Ru*-C12-Ru* (82%) and Ru*-C16-Ru* (58%), respectively. Similar oxidative coupling of Ru(Ctriple bond; length of mdashCCtriple bond; length of mdashCH)(dppe)Cp* was a second route to Ru*-C8-Ru* (82%). Appropriate precursors are already known, or obtained by coupling of Ru*-C2x-Si (x = 2, 4) with AuCl(PPh3)/NaOMe [Ru*-C4-Au, 95%; Ru*-C8-Au, 74%] or from Pd(0)/Cu(I) catalysed coupling of Ru*-C2x-Au (x = 2, 3) with I(Ctriple bond; length of mdashC)2SiMe3 (Ru*-C8-Si, 64%; Ru*-C10-Si, 2%). Reactions between Ru*-C2x-Ru* (x = 3, 4) and Fe2(CO)9 gave {Fe3(CO)9}{μ3-CCtriple bond; length of mdashC[Ru(dppe)Cp*]}2Fe(C3-Ru*)2 and {Fe3(CO)9}{μ3-CCtriple bond; length of mdashC[Ru(dppe)Cp*]}{μ3-C(Ctriple bond; length of mdashC)2[Ru(dppe)Cp*]} Fe(C3-Ru*)(C5-Ru*), respectively. The redox properties of the series of complexes with 2x = 2–16 were measured and showed a diminution of the

  4. Infrared spectra of RuTPP, RuCOTPP, and Ru(CO)2TPP isolated in solid argon.

    PubMed

    Krim, Lahouari; Sorgues, Sébastien; Soep, Benoit; Shafizadeh, Niloufar

    2005-09-22

    Infrared spectra of unstable species such as CO-free ruthenium tetraphenylporphyrin RuTPP and RuCOTPP (species with vacant coordination sites) isolated in solid argon at 8 K have been recorded. Selective deposition conditions allow the isolation of either RuTPP and RuCOTPP or RuCOTPP and Ru(CO)2TPP. This depends on the preparation conditions of the sample. A specific Ru-CO bending mode has been characterized at 590.1 cm(-1) for Ru(CO)2TPP. The behavior of each vibrational mode of RuTPP, RuCOTPP, and Ru(CO)2TPP has been analyzed. Modes such as gamma8 at 721.3 cm(-1) (out-of-plane stretching mode gamma(Cbeta-H)sym) and nu41 at 1342.8 cm(-1) (nuCalpha-N coupled with deltaCalpha-Cm) reflect the charge transfer in the porphyrin. Indeed, the addition of one or two CO ligands to RuTPP reduces the charge transfer between the metal center and the porphyrin, which appears as an increase in the frequency of the nu41 mode and in a decrease in that of the gamma8 mode.

  5. Chemical doping effect in the LaRu3Si2 superconductor with a kagome lattice

    NASA Astrophysics Data System (ADS)

    Li, Baoxuan; Li, Sheng; Wen, Hai-Hu

    2016-09-01

    LaRu3Si2 is a superconductor with a kagome lattice and transition temperature of 7 K. By doping different rare-earth and transition-metal elements on the La and Ru sites, the evolution of superconductivity has been extensively investigated. It is found that, except for doping Fe to Ru sites, all other dopants with rare-earth (Y, Lu, and Ce) or transition metals (Ni, Cr, and Cu) seem to suppress superconducting transition temperature in LaRu3Si2 very slowly. The quick suppression of superconductivity by Fe doping can be described by the Abrikosov-Gorkov relation. By fitting and analyzing the magnetic susceptibility data under a high magnetic field with the Curie-Weiss law, we find that the effective magnetic moments for Ni and Cr doped samples are very small, indicating that these ions actually do not behave like strong magnetic scattering centers as Fe ions do in the present environment. Our experiments on systematically doped samples and related analysis indicate that the superconducting gap in LaRu3Si2 has no sign change.

  6. Effect of Ru thickness on spin pumping in Ru/Py bilayer

    SciTech Connect

    Behera, Nilamani; Singh, M. Sanjoy; Chaudhary, Sujeet; Pandya, Dinesh K. Muduli, P. K.

    2015-05-07

    We report the effect of Ru thickness (t{sub Ru}) on ferromagnetic resonance (FMR) line-width of Ru(t{sub Ru})/Py(23 nm) bilayer samples grown on Si(100)/SiO{sub 2} substrates at room temperature by magnetron sputtering. The FMR line-width is found to vary linearly with frequency for all thicknesses of Ru, indicating intrinsic origin of damping. For Ru thicknesses below 15 nm, Gilbert-damping parameter, α is almost constant. We ascribe this behavior to spin back flow that is operative for Ru thicknesses lower than the spin diffusion length in Ru, λ{sub sd}. For thicknesses >15 nm (>λ{sub sd}), the damping constant increases with Ru thickness, indicating spin pumping from Py into Ru.

  7. Galactose adsorption on Ru(0001)

    NASA Astrophysics Data System (ADS)

    Alatalo, Matti; Puisto, Mikko

    2014-03-01

    In order to understand the valorisation of biomass, it is essential to study the behavior of sugar molecules on catalytic surfaces. We have studied the adsorption of galactose molecules on the Ru(0001) surface using first principles calculations. We present results for the fully relaxed configurations of the molecule at different adsorption sites. We also compare the effect of the inclusion of the van der Waals interactions on both the energetics of the free galactose molecule and the adsorption energy of galactose on Ru(0001). We compare our results, obtained using periodically repeated supercells, to those obtained with cluster calculations.

  8. Soret separation of highly siderophile elements in Fe-Ni-S melts: Implications for solid metal-liquid metal partitioning

    NASA Astrophysics Data System (ADS)

    Brenan, James M.; Bennett, Neil

    2010-10-01

    Soret separation of melts consisting of Fe (+ 1-10 wt.% Ni) with added C, Si or S and trace highly siderophile elements (HSE; Ru, Rh, Pd, Re, Os, Ir, Pt and Au) was investigated in experiments done at 2 GPa, T hot ~ 2000 °C and T hot-T cold ~ 250 °C. Experiments with added C and Si produced homogeneous samples, whereas those with S resulted in significant compositional gradients, with S enriched at the hot end of the sample, and Fe and HSE enriched at the cold end. The magnitude of the separation of the HSE is not the same for each, but varies in the order (smallest to largest) Pd~AuRu~Pt. We show that the observed distribution of HSE within experiments is consistent with the variation in activity coefficients for these elements as predicted by the non-metal avoidance model of Jones and Malvin (1990). Thus, our results indicate that the melt composition effect on solid metal-liquid metal partitioning can be captured in a single thermal diffusion experiment. The magnitude of the melt composition effect, as judged by the Jones-Malvin interaction parameter, β, varies with metal size in a manner similar to solid metal-liquid metal partition coefficients, suggesting like origins of the HSE "selectivity" for Fe-rich solid or liquid structures.

  9. Quantifying the Carbon Abundances in the Secondary Stars of SS Cygni, RU Pegasi, and GK Persei

    NASA Astrophysics Data System (ADS)

    Harrison, Thomas E.; Hamilton, Ryan T.

    2015-11-01

    We use a modified version of MOOG to generate large grids of synthetic spectra in an attempt to derive quantitative abundances for three CVs (GK Per, RU Peg, and SS Cyg) by comparing the models to moderate resolution (R ˜ 25,000) K-band spectra obtained with NIRSPEC on Keck. For each of the three systems we find solar, or slightly sub-solar values for [Fe/H], but significant deficits of carbon: for SS Cyg we find [C/Fe] = -0.50, for RU Peg [C/Fe] = -0.75, and for GK Per [C/Fe] = -1.00. We show that it is possible to use lower resolution (R ˜ 2000) spectra to quantify carbon deficits. We examine realistic veiling scenarios and find that emission from H i or CO cannot reproduce the observations.

  10. QUANTIFYING THE CARBON ABUNDANCES IN THE SECONDARY STARS OF SS CYGNI, RU PEGASI, AND GK PERSEI

    SciTech Connect

    Harrison, Thomas E.; Hamilton, Ryan T. E-mail: rthamilton@sofia.usra.edu

    2015-11-15

    We use a modified version of MOOG to generate large grids of synthetic spectra in an attempt to derive quantitative abundances for three CVs (GK Per, RU Peg, and SS Cyg) by comparing the models to moderate resolution (R ∼ 25,000) K-band spectra obtained with NIRSPEC on Keck. For each of the three systems we find solar, or slightly sub-solar values for [Fe/H], but significant deficits of carbon: for SS Cyg we find [C/Fe] = −0.50, for RU Peg [C/Fe] = −0.75, and for GK Per [C/Fe] = −1.00. We show that it is possible to use lower resolution (R ∼ 2000) spectra to quantify carbon deficits. We examine realistic veiling scenarios and find that emission from H i or CO cannot reproduce the observations.

  11. RU-486: a continuing saga.

    PubMed

    1988-12-01

    A month after the approved marketing of RU-486 in France as a nonsurgical option for abortion, the company Roussel-Ulcaf withdrew the product in response to boycott threats and threats to company officials and their families. The government of France approved the drug on an experimental basis under the name of Mifepristone; the conditions of the approval were that the drug had to be used within the 1st 49 days after the 1st day of last menstruation and had to be administered under medical supervision at a hospital with the expertise to perform an abortion. Following trials in France, China, and the United Kingdom, RU-486, when administered in a single dose of 3 pills, was observed to have a 95% success and to be very safe. The international boycott and personal threats propelled a convention of more than 1,000 physicians in the World Congress of Gynecology and Obstetrics in Rio de Janeiro to sign a petition that advocated to Roussel-Uclaf the importance of insuring "that women have access to the benefits of scientific progress." The World Health Organization regretted the withdrawal of the drug as 1 off-shoot of the decision would be that developing companies would not be able to run clinical trials on RU-486. Shortly after the company's decision to remove the drug, the French Minister of Health, Claude Evin, ordered a continuation of experimental trials of RU-486. While no US companies have demonstrated interest in the drug, boycotts and threats exacerbate product liability coverage problems. However, should it prove effective in treating breast cancer, endometriosis or ectopic pregnancy, RU-486 may begin to increase in distribution and use.

  12. Ru doping in iron-based pnictides: The "unfolded" dominant role of structural effects for superconductivity

    NASA Astrophysics Data System (ADS)

    Reticcioli, M.; Profeta, G.; Franchini, C.; Continenza, A.

    2017-06-01

    We present an ab initio study of Ru substitution in two different compounds, BaFe2As2 and LaFeAsO, pure and F doped. Despite the many similarities among them, Ru substitution has very different effects on these compounds. By means of an unfolding technique, which allows us to trace back the electronic states into the primitive cell of the pure compounds, we are able to disentangle the effects brought by the local structural deformations and by the impurity potential to the states at the Fermi level. Our results are compared with available experiments and show (i) satisfying agreement of the calculated electronic properties with experiments, confirming the presence of a magnetic order on a short-range scale, and (ii) Fermi surfaces strongly dependent on the internal structural parameters, more than on the impurity potential. These results enter a widely discussed field in the literature and provide a better understanding of the role of Ru in iron pnictides: although isovalent to Fe, the Ru-Fe substitution leads to changes in the band structure at the Fermi level mainly related to local structural modifications.

  13. Geochemistry and Re-Os geochronology of the organic-rich sedimentary rocks in the Jingtieshan Fe-Cu deposit, North Qilian Mountains, NW China

    NASA Astrophysics Data System (ADS)

    Yang, Xiuqing; Zhang, Zuoheng; Li, Chao; Duan, Shigang; Jiang, Zongsheng

    2016-04-01

    The Jingtieshan Group in the North Qilian Mountains, NW China, is dominantly composed of banded iron formations (BIFs), copper deposits and organic-rich sedimentary rocks (ORS, carbonaceous phyllite). X-ray diffraction analysis of the ORS shows the mineral assemblage to be quartz + clay minerals. The total organic carbon contents show a range of 0.44-1.72%. Here we present the results of the geochemistry and Re-Os geochronology of the ORS from the Jingtieshan Group. The high values of Chemical Index of Alteration (CIA), Chemical Index of Weathering (CIW), Plagioclase Index of Alteration (PIA), and Th/U ratio, indicate intense weathering. The Al2O3/TiO2, Zr/Sc, Th/Sc, La/Th ratios, high rare earth elements abundances, light rare earth elements enrichment (normalized to chondrite), and distinctly negative Eu anomalies, suggest that the Jingtieshan Group ORS were derived mainly from felsic volcanic units. The new Re-Os isochron age of 1308 ± 100 Ma (2σ, n = 6, MSWD = 23) broadly overlap with the previous published ages determined using Sm-Nd and U-Pb isotope systems. The new age represents the depositional age of the Jingtieshan Group, as well that of BIF in the Jingtieshan area. Furthermore, the initial 187Os/188Os ratios (0.44 ± 0.07) indicate that the Os in the seawater was dominantly derived from hydrothermal fluids (∼75%). The Ce anomaly (Ce/Ce∗ = 0.95-1.00) and V/(V + Ni) ratios (0.71-0.86), as well as the lack of enrichment in redox-sensitive trace elements such as U, V, Zn, Pb, Cu, Ni, Cr, Co and Mn, together with the presence of overlying BIF, suggest that the Jingtieshan area represents a ferruginous deep-water succession. This, and intense submarine hydrothermal activities contributed to the deposition of the Jingtieshan BIF.

  14. Constitution and thermodynamics of the Mo-Ru, Mo-Pd, Ru-Pd and Mo-Ru-Pd systems

    NASA Astrophysics Data System (ADS)

    Kleykamp, H.

    1989-09-01

    The constitution of the Mo-Ru, Mo-Pd and Ru-Pd systems was reinvestigated between 800 and 2000°C. The Mo-Ru system is of the eutectic type, a σ-phase Mo 5Ru 3 exists between 1915 and 1143°C. The Mo-Pd system is characterized by an hcp phase Mo 9Pd 11 and by two peritectic reactions, β- Mo( Pd) + L = Mo9Pd11andMo9Pd11 + L = α- Pd( Mo). Mo 9Pd 11 decomposes eutectoidally at 1370°C. The Ru-Pd system is simple peritectic. The continuous series of the hcp solid solutions between Mo 9Pd 11 and ɛ-Ru(Mo, Pd) in the ternary Mo-Ru-Pd system observed at 1700°C are suppressed below 1370°C near the Mo-Pd boundary system by the formation of a narrow α + β + ɛ three-phase field. Relative partial molar Gibbs energies of Mo, Mo and Ru in the respective binary systems and of Mo in the ternary system were measured by the EMF method with a Zr(Ca)O 2 electrolyte. xsΔ ḠMo∞ quantities were evaluated at 1200 K which give -43 kJ/mol Mo in Ru and -94 kJ/mol Mo in Pd at infinite dilution. Gibbs energies of formation of the Mo-Ru and Mo-Pd systems were calculated.

  15. Resistive switching and magnetic behavior of Bi0.8Ba0.2FeO3 / SrRuO3 / SrTiO3 films: role of thickness-dependent strain

    NASA Astrophysics Data System (ADS)

    Vagadia, Megha; Ravalia, Ashish; Trivedi, Priyanka; Jethva, Sadaf; Katba, Savan; Kuberkar, D. G.

    2016-05-01

    The thickness-dependent resistive switching and magnetic behavior of Bi0.8Ba0.2FeO3/SRO/STO (1 0 0) films have been studied in the context of strain modifications introduced by varying the film thickness. Generation of misfit dislocation results in strain relaxation with an increase in film thickness. All films (50, 100 and 200 nm) show hysteresis in I-V behavior at room temperature with applied voltage V max  =  ±5 V. Fitting of I-V data suggests that trap-controlled SCLC governs the conduction in HRS in the 50 nm film while in the 100 nm and 200 nm films, the charge transport mechanism is ohmic-type throughout the applied field. The ON/OFF switching ratio and current retention performance decrease with an increase in film thickness, suggesting that substrate-induced strain and interface modifications play an important role in governing the resistive switching mechanism in Bi0.8Ba0.2FeO3 films. A film with lower thickness ~50 nm is found to exhibit the highest magnetization which may be attributed to the increase in oxygen vacancies and compressive strain.

  16. Superconducting transition of Ru in SQUIDs with Nb/Ru/Sr2RuO4 junctions

    NASA Astrophysics Data System (ADS)

    Nago, Y.; Ishiguro, R.; Sakurai, T.; Yakabe, M.; Nakamura, T.; Yonezawa, S.; Kashiwaya, S.; Takayanagi, H.; Maeno, Y.

    2014-12-01

    We have measured transport properties and magnetic responses of direct current superconducting quantum interference devices(dc-SQUIDs) with Nb/Ru/Sr2RuO4 junctions on the same Ru inclusion of a Sr2RuO4-Ru eutectic crystal. We observed a superconducting transition of the Ru at 0.50 K and another transition with anomalous interference patterns of the SQUID at 0.40 K. The second transition led to change of the SQUID structure due to energy competition of alternative supercurrent paths. Phase shifts of the peak of the Fraunhofer diffraction pattern were observed below the transition temperatures, implying topological effects due to a chiral p-wave state or its competition with a s-wave state.

  17. Electronic correlations, magnetism, and Hund's rule coupling in the ruthenium perovskites SrRuO3 and CaRuO3

    NASA Astrophysics Data System (ADS)

    Dang, Hung T.; Mravlje, Jernej; Georges, Antoine; Millis, Andrew J.

    2015-05-01

    A comparative density functional plus dynamical mean field theory study of the pseudocubic ruthenate materials CaRuO3 and SrRuO3 is presented. Phase diagrams are determined for both materials as a function of Hubbard repulsion U and Hund's rule coupling J . Metallic and insulating phases are found, as are ferromagnetic and paramagnetic states. The locations of the relevant phase boundaries are determined. Based on the computed phase diagrams, Mott dominated and Hund's dominated regimes of strong correlation are distinguished. Comparison of calculated properties to experiments indicates that the actual materials are in the Hund's coupling dominated region of the phase diagram so can be characterized as Hund's metals, in common with other members of the ruthenate family. Comparison of the phase diagrams for the two materials reveals the role played by rotational and tilt (GdFeO3-type) distortions of the ideal perovskite structure. The presence of magnetism in SrRuO3 and its absence in CaRuO3 despite the larger mass and larger tilt/rotational distortion amplitude of CaRuO3 can be understood in terms of density of states effects in the presence of strong Hund's coupling. Comparison of the calculated low-T properties of CaRuO3 to those of SrRuO3 provides insight into the effects of magnetic order on the properties of a Hund's metal. The study provides a simultaneous description of magnetism and correlations and explicates the roles played by band theory and Hubbard and Hund's interactions.

  18. Spectroscopic, Electrochemical and Computational Characterisation of Ru Species Involved in Catalytic Water Oxidation: Evidence for a [Ru(V) (O)(Py2 (Me) tacn)] Intermediate.

    PubMed

    Casadevall, Carla; Codolà, Zoel; Costas, Miquel; Lloret-Fillol, Julio

    2016-07-11

    A new family of ruthenium complexes based on the N-pentadentate ligand Py2 (Me) tacn (N-methyl-N',N''-bis(2-picolyl)-1,4,7-triazacyclononane) has been synthesised and its catalytic activity has been studied in the water-oxidation (WO) reaction. We have used chemical oxidants (ceric ammonium nitrate and NaIO4 ) to generate the WO intermediates [Ru(II) (OH2 )(Py2 (Me) tacn)](2+) , [Ru(III) (OH2 )(Py2 (Me) tacn)](3+) , [Ru(III) (OH)(Py2 (Me) tacn)](2+) and [Ru(IV) (O)(Py2 (Me) tacn)](2+) , which have been characterised spectroscopically. Their relative redox and pH stability in water has been studied by using UV/Vis and NMR spectroscopies, HRMS and spectroelectrochemistry. [Ru(IV) (O)(Py2 (Me) tacn)](2+) has a long half-life (>48 h) in water. The catalytic cycle of WO has been elucidated by using kinetic, spectroscopic, (18) O-labelling and theoretical studies, and the conclusion is that the rate-determining step is a single-site water nucleophilic attack on a metal-oxo species. Moreover, [Ru(IV) (O)(Py2 (Me) tacn)](2+) is proposed to be the resting state under catalytic conditions. By monitoring Ce(IV) consumption, we found that the O2 evolution rate is redox-controlled and independent of the initial concentration of Ce(IV) . Based on these facts, we propose herein that [Ru(IV) (O)(Py2 (Me) tacn)](2+) is oxidised to [Ru(V) (O)(Py2 (Me) tacn)](2+) prior to attack by a water molecule to give [Ru(III) (OOH)(Py2 (Me) tacn)](2+) . Finally, it is shown that the difference in WO reactivity between the homologous iron and ruthenium [M(OH2 )(Py2 (Me) tacn)](2+) (M=Ru, Fe) complexes is due to the difference in the redox stability of the key M(V) (O) intermediate. These results contribute to a better understanding of the WO mechanism and the differences between iron and ruthenium complexes in WO reactions.

  19. Effect of heavy-metal insertions at Fe/MgO interfaces on electric-field-induced modification of magnetocrystalline anisotropy

    NASA Astrophysics Data System (ADS)

    Nakamura, K.; Nomura, T.; Pradipto, A.-M.; Nawa, K.; Akiyama, T.; Ito, T.

    2017-05-01

    Magnetocrystalline anisotropy (MCA) at Fe/MgO interfaces with insertions of 3d (Co, Ni), 4d (Ru, Rh, Pd), and 5d (Os, Ir, Pt) elements in external electric fields was investigated from first-principles calculations. The MCA energy and the electric-field-induced MCA modification dramatically depend on the inserted elements. Large MCA modification may be achieved by heavy-metal insertions, in which the strength of spin-orbit coupling of inserted elements and the position of the Fermi level relative to d band level play key roles.

  20. Pressure Induced Enhancement of Superconductivity in LaRu2P2

    PubMed Central

    Li, Baoxuan; Liu, Jianzhong; Sun, Jian; Li, Sheng; Zhu, Xiyu; Wen, Hai-Hu

    2016-01-01

    To explore new superconductors beyond the copper-based and iron-based systems is very important. The Ru element locates just below the Fe in the periodic table and behaves like the Fe in many ways. One of the common thread to induce high temperature superconductivity is to introduce moderate correlation into the system. In this paper, we report the significant enhancement of superconducting transition temperature from 3.8 K to 5.8 K by using a pressure only of 1.74 ± 0.05 GPa in LaRu2P2 which has an iso-structure of the iron-based 122 superconductors. The ab-initio calculation shows that the superconductivity in LaRu2P2 at ambient pressure can be explained by the McMillan’s theory with strong electron-phonon coupling. However, it is difficult to interpret the enhancement of Tc versus pressure within this picture. Detailed analysis of the pressure induced evolution of resistivity and upper critical field Hc2(T) reveals that the increase of Tc with pressure may be accompanied by the involvement of extra electron-boson interaction. This suggests that the Ru-based system has some commonality as the Fe-based superconductors. PMID:27086696

  1. Pressure Induced Enhancement of Superconductivity in LaRu2P2.

    PubMed

    Li, Baoxuan; Lu, Pengchao; Liu, Jianzhong; Sun, Jian; Li, Sheng; Zhu, Xiyu; Wen, Hai-Hu

    2016-04-18

    To explore new superconductors beyond the copper-based and iron-based systems is very important. The Ru element locates just below the Fe in the periodic table and behaves like the Fe in many ways. One of the common thread to induce high temperature superconductivity is to introduce moderate correlation into the system. In this paper, we report the significant enhancement of superconducting transition temperature from 3.8 K to 5.8 K by using a pressure only of 1.74 ± 0.05 GPa in LaRu2P2 which has an iso-structure of the iron-based 122 superconductors. The ab-initio calculation shows that the superconductivity in LaRu2P2 at ambient pressure can be explained by the McMillan's theory with strong electron-phonon coupling. However, it is difficult to interpret the enhancement of Tc versus pressure within this picture. Detailed analysis of the pressure induced evolution of resistivity and upper critical field Hc2(T) reveals that the increase of Tc with pressure may be accompanied by the involvement of extra electron-boson interaction. This suggests that the Ru-based system has some commonality as the Fe-based superconductors.

  2. Pressure Induced Enhancement of Superconductivity in LaRu2P2

    NASA Astrophysics Data System (ADS)

    Li, Baoxuan; Lu, Pengchao; Liu, Jianzhong; Sun, Jian; Li, Sheng; Zhu, Xiyu; Wen, Hai-Hu

    2016-04-01

    To explore new superconductors beyond the copper-based and iron-based systems is very important. The Ru element locates just below the Fe in the periodic table and behaves like the Fe in many ways. One of the common thread to induce high temperature superconductivity is to introduce moderate correlation into the system. In this paper, we report the significant enhancement of superconducting transition temperature from 3.8 K to 5.8 K by using a pressure only of 1.74 ± 0.05 GPa in LaRu2P2 which has an iso-structure of the iron-based 122 superconductors. The ab-initio calculation shows that the superconductivity in LaRu2P2 at ambient pressure can be explained by the McMillan’s theory with strong electron-phonon coupling. However, it is difficult to interpret the enhancement of Tc versus pressure within this picture. Detailed analysis of the pressure induced evolution of resistivity and upper critical field Hc2(T) reveals that the increase of Tc with pressure may be accompanied by the involvement of extra electron-boson interaction. This suggests that the Ru-based system has some commonality as the Fe-based superconductors.

  3. Many metals make the cut: quaternary rare-earth germanides RE4M2InGe4 (M = Fe, Co, Ni, Ru, Rh, Ir) and RE4RhInGe4 derived from excision of slabs in RE2InGe2.

    PubMed

    Oliynyk, Anton O; Stoyko, Stanislav S; Mar, Arthur

    2015-03-16

    The formation of quaternary rare-earth (RE) germanides containing transition metals (M's) from groups 6 to 10 was investigated through arc-melting and annealing reactions at 800 °C; about 50 new compounds were obtained. These include several new series of quaternary germanides RE4M2InGe4 (M = Fe, Co, Ru, Rh, Ir), previously known only for M = Mn and Ni; additional members of RE4Ni2InGe4 extended to other RE substituents; and a different but closely related series RE4RhInGe4. Detailed crystal structures were determined by single-crystal X-ray diffraction studies for 20 compounds. Monoclinic structures in space group C2/m are adopted by RE4M2InGe4 (Ho4Ni2InGe4-type, a = 15.1-16.5 Å, b = 4.1-4.4 Å, c = 6.9-7.3 Å, β = 106.2-108.6°) and RE4RhInGe4 (own type, a = 20.0-20.2 Å, b = 4.2-4.3 Å, c = 10.1-10.2 Å, β = 105.0-105.3°). Both structures contain frameworks built from MGe4 tetrahedra, InGe4 square planes, and Ge2 dimers, delimiting tunnels occupied by RE atoms. These structures can also be derived by cutting slabs along different directions from the more symmetrical RE2InGe2 structure. Although the Ge2 dimers are relatively invariant, the InGe4 square planes can undergo distortion to form two sets of short versus long In-Ge distances. This distortion results from a competition between M-Ge bonding in the MGe4 tetrahedra and In-Ge bonding in the InGe4 square planes.

  4. Weathering of PGE sulfides and Pt-Fe alloys in the Freetown Layered Complex, Sierra Leone

    NASA Astrophysics Data System (ADS)

    Bowles, John F. W.; Suárez, Saioa; Prichard, Hazel M.; Fisher, Peter C.

    2017-01-01

    Fresh and weathered rocks and saprolite from Horizon B of the Freetown Layered Complex contain platinum-group minerals (PGM). The PGM in the fresh rocks are 1-7 μm across, including cooperite (PtS), isoferroplatinum (Pt3Fe), minor tetraferroplatinum (PtFe), tulameenite (Pt2FeCu), Os-bearing laurite (RuS2), and other base metal-sulfide (BMS)-bearing PGM. The weathered rocks contain fewer of those PGM but a high proportion of disordered Cu-(±Pd)-bearing Pt-Fe alloys. The saprolite hosts scarce, smaller (1-3 μm) ordered PtFe and disordered PtFe3. The Pt-Fe alloys became increasingly Fe rich as weathering proceeded. Pt-Fe oxides appeared during weathering. Copper sulfides associated with the primary PGM and cooperite (with <3% Pd) were destroyed to provide the minor Cu and Pd found in some of the disordered Pt-Fe alloys. Platinum- and Pd-bearing saprolites have retained the original rock fabric and, to a depth of about 2 m, surround residual rocks that show progressive weathering (corestones). Ground water passing through the saprolite has transported Pt and Pd (and probably Au) in solution down slope into saprolite over unmineralized rocks. Transport is marked by changes in the Pt/Pd ratio indicating that the metals have moved independently. Palladium is present in marginally higher concentrations in the deeper saprolite than in the corestones suggesting some retention of Pd in the deeper saprolite. Platinum and Pd are less concentrated in the upper saprolite than the deeper saprolite indicating surface leaching. Alteration occurred over a long period in an organic and microbial rich environment that may have contributed to the leaching and transport of PGE.

  5. Suppression of ferromagnetism and observation of quantum well states in epitaxial thin films of the cubic ruthenate BaRuO3

    NASA Astrophysics Data System (ADS)

    Burganov, Bulat; Paik, Hanjong; Shen, Kyle; Schlom, Darrell

    The pseudocubic perovskite ruthenates ARuO3, where A is alkaline earth metal, are correlated materials where Hund's coupling drives correlations and leads to a low coherence scale, large renormalization, and formation of local moments. The ferromagnetic BaRuO3 has an ideal cubic structure and a larger bandwidth, compared to its GdFeO3-distorted counterparts, CaRuO3 and SrRuO3. In stark contrast to SrRuO3, which is a Fermi liquid below TC, BaRuO3 exhibits critical fluctuations near TC that are enhanced under hydrostatic pressure, which suppresses the Fermi liquid coherence scale and TC and drives a crossover into non-FL regime. Here we use ARPES to characterize the momentum-resolved electronic structure of strained ultrathin BaRuO3 films grown in situ by molecular beam epitaxy. The films on STO (001) are metallic down to 2 u.c. thickness and manifest clearly defined subbands of well-defined quasiparticles which arise due to quantum confinement effects. We observe that the bands are moderately renormalized compared to bare GGA bands and discover that the ferromagnetism can be suppressed in the atomically thin limit. We discuss our results on BaRuO3 in the context of our recent ARPES studies of the other perovskite ruthenates, SrRuO3 and CaRuO3.

  6. Underlayer Effect on Perpendicular Magnetic Anisotropy in Co20Fe60B20\\MgO Films

    PubMed Central

    Chen, P.J.; Iunin, Y.L.; Cheng, S.F.; Shull, R.D.

    2016-01-01

    Perpendicular Magnetic Tunneling Junctions (pMTJs) with Ta\\CoFeB\\MgO have been extensively studied in recent years. However, the effects of the underlayer on the formation of the CoFeB perpendicular magnetic anisotropy (PMA) are still not well understood. Here we report the results of our systematic use of a wide range of elements (Ti, V, Cr, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Hf, Ta, W, Re, Os, Ir, Pt and Au) encompassed by columns IVA, VA, VIA, VIIA and VIIIA of the periodic table as the underlayer in a underlayer\\Co20Fe60B20\\MgO stack. Our goals were to survey more elements which could conceivably create a PMA in CoFeB and thereby to explore the mechanisms enabling these underlayers to enhance or create the PMA. We found underlayer elements having both an outer shell of 4d electrons (Zr, Nb Mo, and Pd) and 5d electrons (Hf, Ta, W, Re, Ir, and Pt) resulted in the development of a PMA in the MgO-capped Co20Fe60B20. Hybridization between the 3d electrons of the Fe or Co (in the Co20Fe60B20) at the interface with the 4d or 5d electrons of the underlayer is thought to be the cause of the PMA development. PMID:27499549

  7. Underlayer Effect on Perpendicular Magnetic Anisotropy in Co20Fe60B20\\MgO Films.

    PubMed

    Chen, P J; Iunin, Y L; Cheng, S F; Shull, R D

    2016-07-01

    Perpendicular Magnetic Tunneling Junctions (pMTJs) with Ta\\CoFeB\\MgO have been extensively studied in recent years. However, the effects of the underlayer on the formation of the CoFeB perpendicular magnetic anisotropy (PMA) are still not well understood. Here we report the results of our systematic use of a wide range of elements (Ti, V, Cr, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Hf, Ta, W, Re, Os, Ir, Pt and Au) encompassed by columns IVA, VA, VIA, VIIA and VIIIA of the periodic table as the underlayer in a underlayer\\Co20Fe60B20\\MgO stack. Our goals were to survey more elements which could conceivably create a PMA in CoFeB and thereby to explore the mechanisms enabling these underlayers to enhance or create the PMA. We found underlayer elements having both an outer shell of 4d electrons (Zr, Nb Mo, and Pd) and 5d electrons (Hf, Ta, W, Re, Ir, and Pt) resulted in the development of a PMA in the MgO-capped Co20Fe60B20. Hybridization between the 3d electrons of the Fe or Co (in the Co20Fe60B20) at the interface with the 4d or 5d electrons of the underlayer is thought to be the cause of the PMA development.

  8. Structural and Architectural Evaluation of Bimetallic Nanoparticles: A Case Study of Pt−Ru Core−Shell and Alloy Nanoparticles

    SciTech Connect

    Alayoglu, S.; Zavalij, P; Eichhorn, B; Wang, Q; Frenkel, A; Chupas, P

    2009-01-01

    A comprehensive structural/architectural evaluation of the PtRu (1:1) alloy and Ru at Pt core-shell nanoparticles (NPs) provides spatially resolved structural information on sub-5 nm NPs. A combination of extended X-ray absorption fine structure (EXAFS), X-ray absorption near edge structure (XANES), pair distribution function (PDF) analyses, Debye function simulations of X-ray diffraction (XRD), and field emission transmission electron microscopy/energy dispersive spectroscopy (FE-TEM/EDS) analyses provides complementary information used to construct a detailed picture of the core/shell and alloy nanostructures. The 4.4 nm PtRu (1:1) alloys are crystalline homogeneous random alloys with little twinning in a typical face-centered cubic (fcc) cell. The Pt atoms are predominantly metallic, whereas the Ru atoms are partially oxidized and are presumably located on the NP surface. The 4.0 nm Ru at Pt NPs have highly distorted hcp Ru cores that are primarily in the metallic state but show little order beyond 8 A. In contrast, the 1-2 monolayer thick Pt shells are relatively crystalline but are slightly distorted (compressed) relative to bulk fcc Pt. The homo- and heterometallic coordination numbers and bond lengths are equal to those predicted by the model cluster structure, showing that the Ru and Pt metals remain phase-separated in the core and shell components and that the interface between the core and shell is quite normal.

  9. Study of the double beta decays of 96Ru and 104Ru.

    PubMed

    Andreotti, Erica; Hult, Mikael; Marissens, Gerd; de Orduña, Raquel González; Vermaercke, Peter

    2012-09-01

    In this work we present new improved experimental limits for the partial half-lives of the double beta processes of (96)Ru and (104)Ru, obtained by means of a γ-ray spectrometry measurement. A disc of metallic Ru of natural isotopic abundance was sandwiched between two HPGe-detectors in the 225 m deep underground laboratory HADES. After 108 days of measurement, the lower bounds for the partial half-lives were up to 6.9×10(19) yr for (96)Ru and 1.9×10(20) yr for (104)Ru.

  10. Atomistic Modeling of RuAl and (RuNi) Al Alloys

    NASA Technical Reports Server (NTRS)

    Gargano, Pablo; Mosca, Hugo; Bozzolo, Guillermo; Noebe, Ronald D.; Gray, Hugh R. (Technical Monitor)

    2002-01-01

    Atomistic modeling of RuAl and RuAlNi alloys, using the BFS (Bozzolo-Ferrante-Smith) method for alloys is performed. The lattice parameter and energy of formation of B2 RuAl as a function of stoichiometry and the lattice parameter of (Ru(sub 50-x)Ni(sub x)Al(sub 50)) alloys as a function of Ni concentration are computed. BFS based Monte Carlo simulations indicate that compositions close to Ru25Ni25Al50 are single phase with no obvious evidence of a miscibility gap and separation of the individual B2 phases.

  11. Properties of Pd, Pt and Ru-Based Catalysts in Catalytic Oxidation of Methanol.

    PubMed

    Jung, Sang Chul; Nahm, Seung Won; Jung, Ho-young; Park, Young-kwon; Seo, Seong Gyu; Kim, Sang Chai

    2016-02-01

    Catalytic oxidation of methanol was investigated using Pd, Pt and Ru-based catalysts. Experiment was conducted at reaction temperature of 100-220 degrees C with methanol concentration of 3000 ppm and gas hourly space velocity (GHSV) of 16,000 hr(-1). Catalysts were characterized by using Brunauer-Emmett-Teller (BET) method, X-ray diffraction (XRD), field transmission electron microscopy (FE-TEM) and temperature programmed reduction (TPR). Based on complete oxidation temperature of methanol, the activity order was: 0.16 wt% Pd /0.16 wt% Pt/0.16 wt% Ru/gamma-Al2O3 > 0.5 wt% Pt/gamma-Al2O3 > 0.5 wt% Ru/gamma-AlO3 > 0.5 wt% Pd/gamma-Al2O3. Therefore, the activity of ternary metal-based catalyst was superior to single metal-based catalyst.

  12. Growth of Ru doped semi-insulating InP by low pressure metalorganic chemical vapor deposition

    NASA Astrophysics Data System (ADS)

    Dadgar, A.; Stenzel, O.; Köhne, L.; Näser, A.; Straßburg, M.; Stolz, W.; Bimberg, D.; Schumann, H.

    1998-12-01

    Ruthenium doping has been successfully applied for the growth of semi-insulating (s.i.) InP. In contrast to the 3d-transition metal (TM) Fe, the isovalent 4d-TM Ru exhibits a four orders of magnitude lower diffusion coefficient and shows no interdiffusion with p-type dopants. Most important, Ru compensates electrons as well as holes, a prerequisite for complete compensation under double injection conditions. The growth of Ru doped InP layers has been investigated using bis( η5-2,4-dimethylpentadienyl)ruthenium(II) for Ru doping, different P-precursors (PH 3, TBP, DTBP) and H 2 or N 2 carrier gas.

  13. Lifetime measurements in 100Ru

    NASA Astrophysics Data System (ADS)

    Konstantinopoulos, T.; Petkov, P.; Goasduff, A.; Arici, T.; Astier, A.; Atanasova, L.; Axiotis, M.; Bonatsos, D.; Detistov, P.; Dewald, A.; Eller, M. J.; Foteinou, V.; Gargano, A.; Georgiev, G.; Gladnishki, K.; Gottardo, A.; Harissopulos, S.; Hess, H.; Kaim, S.; Kocheva, D.; Kusoglu, A.; Lagoyannis, A.; Ljungvall, J.; Lutter, R.; Matea, I.; Melon, B.; Mertzimekis, T. J.; Nannini, A.; Petrache, C. M.; Petrovici, A.; Provatas, G.; Reiter, P.; Rocchini, M.; Roccia, S.; Seidlitz, M.; Siebeck, B.; Suzuki, D.; Warr, N.; De Witte, H.; Zerrouki, T.

    2017-01-01

    The nucleus 100Ru appears to be a good candidate for the E(5) critical point symmetry which describes the U(5)-SO(6) shape phase transition. To investigate this point with respect to the electromagnetic transition strengths, lifetime measurements of its yrast states have been performed using the recoil distance Doppler shift technique as well as the Doppler shift attenuation method. As a result, the lifetimes of the yrast 2+, 4+, and 8+ states were determined. The deduced transition strengths are compared to the E(5) predictions as well as to the results of excited Vampir and shell-model calculations.

  14. Distant ultrafast energy transfer in a trimetallic {Ru-Ru-Cr} complex facilitated by hole delocalization.

    PubMed

    Cadranel, Alejandro; Tate, Jaired E; Oviedo, Paola S; Yamazaki, Shiori; Hodak, José H; Baraldo, Luis M; Kleiman, Valeria D

    2017-01-25

    Multi-metallic complexes based on {Ru-Cr}, {Ru-Ru} and {Ru-Ru-Cr} fragments are investigated for their light-harvesting and long-range energy transfer properties. We report the synthesis and characterization of [Ru(tpy)(bpy)(μ-CN)Ru(py)4Cl](2+) and [Ru(tpy)(bpy)(μ-CN)Ru(py)4(μ-NC)Cr(CN)5]. The intercalation of {Ru(II)(py)4} linked by cyanide bridges between {Ru(tpy)(bpy)} and {Cr(CN)5} results in efficient, distant energy transfer followed by emission from the Cr moiety. Characterization of the energy transfer process based on photophysical and ultrafast time-resolved absorption suggests the delocalization of holes in the excited state, providing a pathway for energy transfer between the end moieties. The proposed mechanism opens the door to utilize this family of complexes as an appealing platform for the design of antenna compounds as the properties of the fragments could be tuned independently.

  15. Theoretical calculations for structural, elastic, and thermodynamic properties of RuN{sub 2} under high pressure

    SciTech Connect

    Dong, Bing; Zhou, Xiao-Lin E-mail: lkworld@126.com; Chang, Jing; Liu, Ke E-mail: lkworld@126.com

    2014-08-07

    The structural and elastic properties of RuN{sub 2} were investigated through the first-principles calculation using generalized gradient approximation (GGA) and local density approximation (LDA) within the plane-wave pseudopotential density functional theory. The obtained equilibrium structure and mechanical properties are in excellent agreement with other theoretical results. Then we compared the elastic modulus of RuN{sub 2} with several other isomorphic noble metal nitrides. Results show that RuN{sub 2} can nearly rival with OsN{sub 2} and IrN{sub 2}, which indicate RuN{sub 2} is a potentially ultra-incompressible and hard material. By the elastic stability criteria, it is predicted that RuN{sub 2} is stable in our calculations (0–100 GPa). The calculated B/G ratios indicate that RuN{sub 2} possesses brittle nature at 0 GPa and when the pressure increases to 13.4 GPa (for LDA) or 20.8 GPa (for GGA), it begins to prone to ductility. Through the quasi-harmonic Debye model, we also investigated the thermodynamic properties of RuN{sub 2}.

  16. Interpenetrating Diruthenium Tetraformate Monocation, [RuII/III2(O2CH)4]+, Based 3-D Molecule-based Magnets

    SciTech Connect

    Kennon, B.; Stone, K; Stephens, P; Miller, J

    2009-01-01

    Synthesis of [Ru{sub 2}(O{sub 2}CH){sub 4}]{sub 3}[MIII(CN){sub 6}] (M = Co, Fe) possessing an interpenetrating body center cubic (bcc) lattices was investigated utilizing several synthetic methods. The targeted interpenetrating bcc [a = 12.6621(3) {angstrom}] structure was obtained for [Ru{sub 2}(O{sub 2}CH){sub 4}]{sub 3}[Co(CN){sub 6}], and it exhibits {chi}T(T) that is fit to a model which includes zero field splitting. Cyanide abstraction from [Cr(CN){sub 6}]{sup 3-} occurs thwarting the formation of [Ru{sub 2}(O{sub 2}CH){sub 4}]{sub 3}[M(CN){sub 6}]. [Ru{sub 2}(O{sub 2}CH){sub 4}]{sub 3}[Fe(CN){sub 6}] also exhibits the desired bcc structure [12.7071(3) {angstrom}], and its 13.4 K T{sub c} is a 6-fold enhancement with respect to that observed for [Ru{sub 2}(O{sub 2}CMe){sub 4}]{sub 3}[Fe(CN){sub 6}].

  17. Quantitative photochemical formation of [Ru(tpy)(bpy)H]+.

    PubMed

    Matsubara, Yasuo; Konno, Hideo; Kobayashi, Atsuo; Ishitani, Osamu

    2009-11-02

    Quantitative photochemical production of [Ru(tpy)(bpy)H](+) (Ru-H(+)) was achieved by irradiation of [Ru(tpy)(bpy)(DMF)](2+) (Ru-DMF(2+); DMF = N,N-dimethylformamide) in a tetrahydrofuran (THF) solution containing excess triethylamine (NEt(3)). The mechanism of the Ru-H(+) formation was investigated in detail. A photochemical ligand substitution reaction of Ru-DMF(2+) in THF proceeded to give [Ru(tpy)(bpy)(THF)](2+) (Ru-THF(2+)) with a quantum yield of (7.6 +/- 0.7) x 10(-2). In the presence of NEt(3), a similar photochemical ligand substitution reaction also proceeded quickly, but the products were an equilibrium mixture of Ru-THF(2+) and [Ru(tpy)(bpy)(NEt(3))](2+) (Ru-NEt(3)(2+)) with a considerable amount of Ru-H(+) even in the first stage of the photochemical reaction. The equilibrium constant between Ru-THF(2+) and Ru-NEt(3)(2+) was determined as 6.9 +/- 2.1. Irradiation to Ru-NEt(3)(2+) gave Ru-H(+) with a quantum yield of (9.1 +/- 0.5) x 10(-3). An important intermediate, Ru-NEt(3)(2+), was isolated, and its properties were investigated in detail.

  18. The structure and mechanical properties of Ru-Cu and Ru-Ti nanolayer composites

    SciTech Connect

    Kung, H.; Nastasi, M.; Jervis, T.R.; Hubbard, K.; Mitchell, T.E.; Messner, R.M.; Embury, J.D.

    1993-06-01

    Multilayers of Ru-Cu and Ru-Ti have been prepared by electron beam evaporation technique. One set of composites has Ru thickness varying from 250 to 2500{Angstrom} alternating with Cu or Ti of 15{Angstrom}. The other set has 250{Angstrom} of Ru and the Cu or Ti layer varies between 15 and 200{Angstrom}. Nanoindentation measurements show that there is no significant change in hardness as either Ru or Cu/Ti thickness varies. However, the Ru-Cu multilayer has twice the hardness of the Ru-Ti system. The strengthening mechanism proposed by Koehler predicts that Ru-Ti composites would have a higher strength than Ru-Cu due to larger modulus difference between Ru and Ti. Discrepancy between prediction and experiment suggests that other strengthening mechanism(s) may be operating. We have proposed two models based on a ``shear`` mechanism to explain the differences observed between these two systems. Effects of these mechanisms in controlling the deformation process in nanolayer composites are discussed.

  19. Simulating Ru L 3 -Edge X-ray Absorption Spectroscopy with Time-Dependent Density Functional Theory: Model Complexes and Electron Localization in Mixed-Valence Metal Dimers

    SciTech Connect

    Van Kuiken, Benjamin E.; Valiev, Marat; Daifuku, Stephanie L.; Bannan, Caitlin; Strader, Matthew L.; Cho, Hana; Huse, Nils; Schoenlein, Robert W.; Govind, Niranjan; Khalil, Munira

    2013-05-30

    Ruthenium L3-edge X-ray absorption (XA) spectroscopy probes unoccupied 4d orbitals of the metal atom and is increasingly being used to investigate the local electronic structure in ground and excited electronic states of Ru complexes. The simultaneous development of computational tools for simulating Ru L3-edge spectra is crucial for interpreting the spectral features at a molecular level. This study demonstrates that time-dependent density functional theory (TDDFT) is a viable and predictive tool for simulating ruthenium L3-edge XA spectroscopy. We systematically investigate the effects of exchange correlation functional and implicit and explicit solvent interactions on a series of RuII and RuIII complexes in their ground and electronic excited states. The TDDFT simulations reproduce all of the experimentally observed features in Ru L3-edge XA spectra within the experimental resolution (0.4 eV). Our simulations identify ligand-specific charge transfer features in complicated Ru L3-edge spectra of [Ru(CN)6]4- and RuII polypyridyl complexes illustrating the advantage of using TDDFT in complex systems. We conclude that the B3LYP functional most accurately predicts the transition energies of charge transfer features in these systems. We use our TDDFT approach to simulate experimental Ru L3-edge XA spectra of transition metal mixed-valence dimers of the form [(NC)5MII-CN-RuIII(NH3)5] (where M = Fe or Ru) dissolved in water. Our study determines the spectral signatures of electron delocalization in Ru L3-edge XA spectra. We find that the inclusion of explicit solvent molecules is necessary for reproducing the spectral features and the experimentally determined valencies in these mixed-valence complexes. This study validates the use of TDDFT for simulating Ru 2p excitations using popular quantum chemistry codes and providing a powerful interpretive tool for equilibrium and ultrafast Ru L3-edge XA spectroscopy.

  20. Chemistry and petrology of Fe-Ni beads from different types of cosmic spherules: Implication for precursors

    NASA Astrophysics Data System (ADS)

    Rudraswami, N. G.; Prasad, M. Shyam; Babu, E. V. S. S. K.; Kumar, T. Vijaya

    2014-11-01

    Fe-Ni beads are observed to occur in all three (Stony, Glass, Iron) types of cosmic spherules collected from deep sea sediments of the Indian Ocean. Fe-Ni beads in cosmic spherules can provide insights for understanding metal segregation mechanisms and their refractory metal element (RME: Re, Os, W, Ir, Ru, Mo, Pt, Rh including Pd) compositions can help ascertain their precursor meteorites. We measured RME compositions of 55 Fe-Ni beads using LA-ICP-MS in all three basic types of cosmic spherules selected after examining ∼2000 cosmic spherules. The RMEs of Fe-Ni beads provide unique information on formation and differentiation during atmospheric entry. The variability in the concentration of the RMEs depends on the initial mass of the cosmic spherules, volatility, temperature attained and efficiency in metal segregation during entry. The CI chondrite and Os normalized RME compositions of the beads display a pattern that is close to CI chondritic composition. The presence of Pd, a non-refractory metal having condensation temperature similar to Fe, in Fe-Ni beads of all types of cosmic spherules indicates that the heating undergone was below its vaporization temperature. Not all parent bodies lead to the formation of beads, the precursor needs to exceed a certain minimum size and temperature to facilitate the metal to get segregated into beads. The minimum size of a parent particle that could enclose a Fe-Ni bead is estimated to have a size ∼1 mm. This places constraints on the sizes of materials that are ablated during entry, and the accompanying mass loss during entry. Our study further points out that all the three basic types of cosmic spherules have a chondritic origin based on their RME distribution patterns. Only metal-rich carbonaceous chondrites contain the required quantities of metal for the formation of Fe-Ni beads during atmospheric entry and during this process the RMEs are also efficiently segregated into these beads.

  1. Petrology of Al- and Cr-rich ophiolitic chromitites from the Muğla, SW Turkey: implications from composition of chromite, solid inclusions of platinum-group mineral, silicate, and base-metal mineral, and Os-isotope geochemistry

    NASA Astrophysics Data System (ADS)

    Uysal, Ibrahim; Tarkian, Mahmud; Sadiklar, M. Burhan; Zaccarini, Federica; Meisel, Thomas; Garuti, Giorgio; Heidrich, Stefanie

    2009-11-01

    Ultramafic rocks around the city of Muğla in SW Turkey are represented by mantle peridotites depleted to various degrees, ranging from cpx-rich harzburgites to depleted harzburgite and dunite. Cpx-rich harzburgites are thought to be the residua left after extraction of MORB-type basalt, from which high-Al chromitite [49.2 < Cr# = 100 × Cr/(Cr + Al) < 53.5] crystallised with a higher proportion of 187Os/188Os (average of 0.1361). However, depleted harzburgites are assumed to be the residua left after extraction of hydrous boninitic melt produced by second stage partial melting of already depleted mantle due to a subducting slab, from which high-Cr chromitites (64.2 < Cr# < 85.9) with lower and heterogeneous 187Os/188Os ratio (average of 0.1324) were crystallised as a result of melt-rock interaction in a supra-subduction environment. Dunites around the chromite deposits are considered to be the product of melt-peridotite interaction. Most of the chromitites contain high-Cr chromite and display enrichment in IPGE (Os, Ir, Ru) over PPGE (Rh, Pt, Pd), with PGE concentrations between 61 and 1,305 ppb. Consistently, laurite-erlichmanite series minerals with various Os concentrations are found to be the most abundant PGM inclusions in chromite. Os-Ir-Ru alloy, irarsite, and kashinite, as well as Pt-Fe alloy and Pt-oxide, which are not common in ophiolitic chromitites, were also detected as magmatic PGM inclusions. Pentlandite, millerite, and, rarely heazlewoodite form the magmatic inclusions of base-metal sulphide. The presence of olivine and clinopyroxene, as well as hydrous silicate inclusions such as amphibole and phlogopite, in high-Cr chromitite supports the idea that high-Cr chromitites were formed in a supra-subduction environment.

  2. Progress of Multi Functional Properties of Organic-Inorganic Hybrid System, A[FeIIFeIIIX3] (A = (n-CnH2n+1)4N, Spiropyran; X = C2O2S2, C2OS3, C2O3S)

    PubMed Central

    Kojima, Norimichi; Enomoto, Masaya; Kida, Noriyuki; Kagesawa, Koichi

    2010-01-01

    In the case of mixed-valence systems whose spin states are situated in the spin crossover region, new types of conjugated phenomena coupled with spin and charge are expected. From this viewpoint, we have investigated the multifunctional properties coupled with spin, charge and photon for the organic-inorganic hybrid system, A[FeIIFeIIIX3](A = (n-CnH2n+1)4N, spiropyran; X = dto(C2O2S2), tto(C2OS3), mto(C2O3S)). A[FeIIFeIII(dto)3] and A[FeIIFeIII(tto)3] undergo the ferromagnetic phase transitions, while A[FeIIFeIII(mto)3] undergoes a ferrimagnetic transition. In (n-CnH2n+1)4N [FeIIFeIII(dto)3](n = 3,4), a new type of phase transition called charge transfer phase transition (CTPT) takes place around 120 K, where the thermally induced charge transfer between FeII and FeIII occurs reversibly. At the CTPT, the iron valence state dynamically fluctuated with a frequency of about 0.1 MHz, which was confirmed by means of muon spin relaxation. The charge transfer phase transition and the ferromagnetic transition for (n-CnH2n+1)4N[FeIIFeIII(dto)3] remarkably depend on the size of intercalated cation. In the case of (SP)[FeIIFeIII(dto)3](SP = spiropyran), the photoinduced isomerization of SP under UV irradiation induces the charge transfer phase transition in the [FeIIFeIII(dto)3] layer and the remarkable change of the ferromagnetic transition temperature. In the case of (n-CnH2n+1)4N[FeIIFeIII(mto)3](mto = C2O3S), a rapid spin equilibrium between the high-spin state (S = 5/2) and the low-spin state (S = 1/2) at the FeIIIO3S3 site takes place in a wide temperature range, which induces the valence fluctuation of the FeS3O3 and FeO6 sites through the ferromagnetic coupling between the low spin state (S = 1/2) of the FeIIIS3O3 site and the high spin state (S = 2) of the FeIIO6 site.

  3. Ru(4+) induced colossal magnetoimpedance in Ru doped perovskite manganite at room temperature.

    PubMed

    Singh, Brajendra

    2016-05-14

    We have demonstrated Ru(4+) induced colossal magnetoimpedance (MI) at room temperature in a ∼1 Tesla magnetic field with a pulsed laser deposited La0.7Ca0.3Mn0.7Ru0.3O3 thin film. This composition showed a large negative ∼12% MI in the low frequency range (<5 MHz), a colossal positive MI > 120% in the intermediate frequency range (5 MHz to ∼13 MHz) and a negative MI in the high frequency range (∼13 MHz to 40 MHz) at room temperature. XAS data confirmed the predominant Ru valence state was 4+ in La0.7Ca0.3Mn0.7Ru0.3O3. Ru(4+) induced (i) charge carrier localization and (ii) reduced hole carrier density enhances the MI in this composition, which otherwise was not significant in mixed valences Mn(3+)/Mn(4+) containing La0.7Ca0.3MnO3 and Ru(4+)/Ru(5+) and Mn(3+)/Mn(4+) mixed valences containing Ru = 0.1 and Ru = 0.2 compositions in La0.7Ca0.3Mn1-xRuxO3 (0 ≤x≤ 0.3) thin films.

  4. Ru-Ag and Ru-Au dicarbene complexes from an abnormal carbene ruthenium system.

    PubMed

    Bitzer, Mario J; Pöthig, Alexander; Jandl, Christian; Kühn, Fritz E; Baratta, Walter

    2015-07-14

    Reaction of [Ru(OAc)2(PPh3)2] with a P-functionalized imidazolium bromide easily affords a cationic abnormal carbene Ru system. Metalation with Ag2O yields a Ru-Ag complex containing an anionic dicarbene ligand, while subsequent transmetalation with Au(tht)Cl leads to the corresponding Ru-Au system. The bimetallic complexes were characterized by single crystal X-ray diffraction and are the first examples of complexes bearing anionic dicarbene ligands connecting two different d-block elements.

  5. Differentiation of metal-rich meteoritic parent bodies: I. Measurements of PGEs, Re, Mo, W, and Au in meteoritic Fe-Ni metal

    NASA Astrophysics Data System (ADS)

    Petaev, M. I.; Jacobsen, S. B.

    2004-10-01

    We describe an analytical technique for measurements of Fe, Ni, Co, Mo, Ru, Rh, W, Re, Os, Ir, Pt, and Au in bulk samples of iron meteorites. The technique involves EPMA (Fe, Ni, Co) and LA-ICP-MS analyses of individual phases of iron meteorites, followed by calculation of bulk compositions based on the abundances of these phases. We report, for the first time, a consistent set of concentrations of Mo, Ru, Rh, Pd, W, Re, Os, Ir, Pt, and Au in the iron meteorites Arispe, Bennett County, Grant, Cape of Good Hope, Cape York, Carbo, Chinga, Coahuila, Duchesne, Gibeon, Henbury, Mundrabilla, Negrillos, Odessa, Sikhote-Alin, and Toluca and the Divnoe primitive achondrite. The comparison of our LA-ICP-MS data for a number of iron meteorites with high-precision isotope dilution and INAA data demonstrates the good precision and accuracy of our technique. The narrow ranges of variations of Mo and Pd concentrations within individual groups of iron meteorites suggest that these elements can provide important insights into the evolution of parent bodies of iron meteorites. Under certain assumptions, the Mo concentrations can be used to estimate mass fractions of the metal-sulfide cores in the parent bodies of iron meteorites. It appears that a range of Pd variations within a group of iron meteorites can serve as a useful indicator of S content in the core of its parent body.

  6. Interface Control of Ferroelectricity in an SrRuO3 /BaTiO3 /SrRuO3 Capacitor and its Critical Thickness.

    PubMed

    Shin, Yeong Jae; Kim, Yoonkoo; Kang, Sung-Jin; Nahm, Ho-Hyun; Murugavel, Pattukkannu; Kim, Jeong Rae; Cho, Myung Rae; Wang, Lingfei; Yang, Sang Mo; Yoon, Jong-Gul; Chung, Jin-Seok; Kim, Miyoung; Zhou, Hua; Chang, Seo Hyoung; Noh, Tae Won

    2017-05-01

    The atomic-scale synthesis of artificial oxide heterostructures offers new opportunities to create novel states that do not occur in nature. The main challenge related to synthesizing these structures is obtaining atomically sharp interfaces with designed termination sequences. In this study, it is demonstrated that the oxygen pressure (PO2) during growth plays an important role in controlling the interfacial terminations of SrRuO3 /BaTiO3 /SrRuO3 (SRO/BTO/SRO) ferroelectric (FE) capacitors. The SRO/BTO/SRO heterostructures are grown by a pulsed laser deposition method. The top SRO/BTO interface, grown at high PO2 (around 150 mTorr), usually exhibits a mixture of RuO2 -BaO and SrO-TiO2 terminations. By reducing PO2, the authors obtain atomically sharp SRO/BTO top interfaces with uniform SrO-TiO2 termination. Using capacitor devices with symmetric and uniform interfacial termination, it is demonstrated for the first time that the FE critical thickness can reach the theoretical limit of 3.5 unit cells. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Interface Control of Ferroelectricity in an SrRuO3/BaTiO3/SrRuO3 Capacitor and its Critical Thickness

    DOE PAGES

    Shin, Yeong Jae; Kim, Yoonkoo; Kang, Sung -Jin; ...

    2017-03-03

    Here, the atomic-scale synthesis of artificial oxide heterostructures offers new opportunities to create novel states that do not occur in nature. The main challenge related to synthesizing these structures is obtaining atomically sharp interfaces with designed termination sequences. In this study, it is demonstrated that the oxygen pressure (PO2) during growth plays an important role in controlling the interfacial terminations of SrRuO3/BaTiO3/SrRuO3 (SRO/BTO/SRO) ferroelectric (FE) capacitors. The SRO/BTO/SRO heterostructures are grown by a pulsed laser deposition method. The top SRO/BTO interface, grown at high PO2 (around 150 mTorr), usually exhibits a mixture of RuO2-BaO and SrO-TiO2 terminations. By reducing PO2,more » the authors obtain atomically sharp SRO/BTO top interfaces with uniform SrO-TiO2 termination. Using capacitor devices with symmetric and uniform interfacial termination, it is demonstrated for the first time that the FE critical thickness can reach the theoretical limit of 3.5 unit cells.« less

  8. Nanoscale decomposition of Nb-Ru-O

    NASA Astrophysics Data System (ADS)

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

    2016-11-01

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

  9. RU 486: an alternative to surgical abortion.

    PubMed

    Donaldson, K; Briggs, J; McMaster, D

    1994-09-01

    After 5 years of use in more than 100,000 European women, RU 486, an antiprogestin medication used as a medical abortifacient, has recently come under scrutiny in the United States. This article discusses the current and potential uses of RU 486. Also addressed are the history, advantages, and disadvantages of medical abortion (including the acceptability of the method from a woman-centered perspective); new clinical trials; and ethical issues.

  10. RU 486 research forges on, despite political hurdles.

    PubMed

    Watanabe, M E

    1994-01-24

    One year after US President Bill Clinton lifted the ban on importation of RU-486, there has been no increase in new research on RU-486 and no increase in the modest amount of RU-486 projects receiving federal support. One theory is that the stigma of RU-486 being an abortifacient carries over to nonabortion related uses. Political and economic pressures within Roussel (the only source of RU-486 and a major supplier of research funds) and its parent firm, Hoechst AG in Berlin, are responsible for the limited research on RU-486. The lack of federal funding on RU-486 may be because many persons perceive RU-486 to be a women's drug and women's diseases receive little federal funding. Nevertheless, some research of RU-486 in nonabortifacient use is occurring. RU-486's ability to interact with progesterone receptors make it a candidate for treating diseases not related to reproductive function. RU-486 also has a strong antiglucocorticoid effect. A Colorado researcher receives funding from the National Cancer Institute (NCI) to examine whether RU-486 can treat breast cancer. A small clinical trial will soon be conducted in California where women with advanced breast cancer will be treated with RU-486. NCI is supporting a Phase III clinical trial of the effects of RU-486 on nonresectable meningiomas (which have many progesterone receptors). A California researcher has conducted several small clinical trials of RU-486's effect on endometriosis and on leiomyoma. The findings so far suggest that RU-486 demonstrates greater improvement with fewer side effects than other drugs. Findings of a clinical trial in Illinois suggest that RU-486 stimulates labor in women with dead fetuses. Some researchers at the National Institute of Child Health and Human Development use RU-486 to treat some patients with a subtype of Cushing's syndrome. A clinical trial is examining whether RU-486 can improve memory in Alzheimer's disease patients.

  11. Guided ion beam and theoretical study of the reactions of Os{sup +} with H{sub 2}, D{sub 2}, and HD

    SciTech Connect

    Hinton, Christopher S.; Citir, Murat; Armentrout, P. B.

    2011-12-21

    Reactions of the third-row transition metal cation Os{sup +} with H{sub 2}, D{sub 2}, and HD to form OsH{sup +} (OsD{sup +}) were studied using a guided ion beam tandem mass spectrometer. A flow tube ion source produces Os{sup +} in its {sup 6}D (6s{sup 1}5d{sup 6}) electronic ground state level. Corresponding state-specific reaction cross sections are obtained. The kinetic energy dependences of the cross sections for the endothermic formation of OsH{sup +} and OsD{sup +} are analyzed to give a 0 K bond dissociation energy of D{sub 0}(Os{sup +}-H) = 2.45 {+-} 0.10 eV. Quantum chemical calculations are performed here at several levels of theory, with B3LYP approaches generally overestimating the experimental bond energy whereas results obtained using BHLYP and CCSD(T), coupled-cluster with single, double, and perturbative triple excitations, levels show good agreement. Theory also provides the electronic structures of these species and the potential energy surfaces for reaction. Results from the reactions with HD provide insight into the reaction mechanism and indicate that Os{sup +} reacts via a direct reaction. We also compare this third-row transition metal system with the first-row and second-row congeners, Fe{sup +} and Ru{sup +}, and find that Os{sup +} reacts more efficiently with dihydrogen, forming a stronger M{sup +}-H bond. These differences can be attributed to the lanthanide contraction and relativistic effects.

  12. Three Types of Condensed Cluster Phases of Rare-Earth Metal Iodides with Transition Metal Interstitials: Pr 4I 5Ni, Pr 3I 3Os, Pr 2INi 2, and La 2IZ 2

    NASA Astrophysics Data System (ADS)

    Park, Younbong; Martin, James D.; Corbett, John D.

    1997-03-01

    Syntheses of the title compounds result from appropriate reactions of the elements andRI3(R=La, Pr) in sealed Nb containers at, variously, 800-990°C. The structures of three were detailed by single crystal X-ray diffraction: Pr4I5Ni,Pmmn,Z=2,R(F)/Rw=3.6/5.3%; Pr3I3Os,P21/m,Z=2,R/Rw2.4/2.8%; Pr2INi2,P63/mmc,Z=2,R/Rw=2.2/3.6. The new compounds La2IZ2,Z=Fe, Co, Ru, Os, were shown to be isostructural with Pr2INi2(Gd2IFe2) by Guinier powder diffraction. Pr4I5Ni, the first orthorhombic example among theR4I5Zseries, consists ofR6Zoctahedra condensed into chains. The new example contains the most extremeR:Zsize proportions and clearly lacks the strongdπ-dπbonding betweenZand apicalRseen within other members. Pr3I3Os, previously known only with a cubic Gd3Cl3C-(Ca3I3P-)-type structure, also occurs as a relatively undistorted member of the monoclinic Pr3I3Ru (double chain) family. Apical Pr-Osπ-bonding appears significant, with Pr-Os distances that are 0.24 Å shorter than the average within the waist of the parent octahedra. TheR2IZ2phases expand the number of examples of the unusual Gd2IFe2structure, which contains AlB2-like slabs; namely, graphite-likeZ2nets between eclipsed pairs ofRlayers that are in turn separated by single iodine layers. Notable distances in Pr2INi2are Ni-Ni, 2.36 Å, and Pr-Ni, 2.98 Å. Charge-consistent, extended Hückel band calculations in La2IFe2(in contrast with results reported for Gd2IFe2) demonstrate a strong mixing of La-Fe and Fe-Fe bonding in a partially filled band, the Fe states on balance falling only slightly below those of La.

  13. Reactivity of diaminogermylenes with ruthenium carbonyl: Ru3Ge3 and RuGe2 derivatives.

    PubMed

    Cabeza, Javier A; García-Álvarez, Pablo; Polo, Diego

    2011-07-04

    The nature of the products of the reactions of [Ru(3)(CO)(12)] with diaminogermylenes depends upon the volume and the cyclic or acyclic structure of the latter. Thus, the triruthenium cluster [Ru(3){μ-Ge(NCH(2)CMe(3))(2)C(6)H(4)}(3)(CO)(9)], which has a planar Ru(3)Ge(3) core and an overall C(3h) symmetry, has been prepared in quantitative yield by treating [Ru(3)(CO)(12)] with an excess of the cyclic 1,3-bis(neo-pentyl)-2-germabenzimidazol-2-ylidene in toluene at 100 °C, but under analogous reaction conditions, the acyclic and bulkier Ge(HMDS)(2) (HMDS = N(SiMe(3))(2)) quantitatively leads to the mononuclear ruthenium(0) derivative [Ru{Ge(HMDS)(2)}(2)(CO)(3)]. Mixtures of products have been obtained from the reactions of [Ru(3)(CO)(12)] with the cyclic and very bulky 1,3-bis(tert-butyl)-2-germaimidazol-2-ylidene under various reaction conditions. The Ru(3)Ge(3) and RuGe(2) products reported in this paper are the first ruthenium complexes containing diaminogermylene ligands.

  14. Ru-NQR Study for Novel Phase Transition in CeRu2Al10

    NASA Astrophysics Data System (ADS)

    Matsumura, Masahiro; Tomita, Naoya; Matsuoka, Junichirou; Kishimoto, Yasuki; Kato, Harukazu; Kitagawa, Kentaro; Nishioka, Takashi; Tanida, Hiroshi; Sera, Masafumi

    2014-10-01

    We have performed Ru-NQR measurements on CeRu2Al10 exhibiting novel phase transition at an abnormally high temperature T0 = 27.3 K and on NdRu2Al10 with a magnetic transition temperature Tm = 2.4 K as a reference RKKY system. The splitting of the NQR line due to internal fields below T0 shows a mean-field-like monotonic increase, indicating no change in the magnetic structure below T0. The internal field strength is one order larger than those at Al sites in CeRu2Al10, and is comparable to that at the Ru site in NdRu2Al10 despite the sevenfold smaller magnitude of the 4f moment, being indicative of an enhanced conduction electron polarization at the Ru site. One of the causes of the high T0 might be the enhanced exchange coupling through the Ce-Ru-Ce path mediated by the enhanced conduction electron polarization. Being similar to that in the Al site, the nuclear spin-lattice relaxation rate 1/T1 shows a gap-like decrease below T0 without enhancement owing to a critical slowing down at T0, in contrast to the mean field 2nd-order transition.

  15. Ru(0) and Ru(II) nitrosyl pincer complexes: structure, reactivity, and catalytic activity.

    PubMed

    Fogler, Eran; Iron, Mark A; Zhang, Jing; Ben-David, Yehoshoa; Diskin-Posner, Yael; Leitus, Gregory; Shimon, Linda J W; Milstein, David

    2013-10-07

    Despite considerable interest in ruthenium carbonyl pincer complexes and their substantial catalytic activity, there has been relatively little study of the isoelectronic ruthenium nitrosyl complexes. Here we describe the synthesis and reactivity of several complexes of this type as well as the catalytic activity of complex 6. Reaction of the PNP ligand (PNP = 2,6-bis((t)Bu2PCH2)pyridine) with RuCl3(NO)(PPh3)2 yielded the Ru(II) complex 3. Chloride displacement by BAr(F-) (BAr(F-) = tetrakis(3,5-bis(trifluoromethyl)phenyl)borate) gave the crystallographicaly characterized, linear NO Ru(II) complex 4, which upon treatment with NaBEt3H yielded the Ru(0) complexes 5. The crystallographically characterized Ru(0) square planar complex 5·BF4 bears a linear NO ligand located trans to the pyridilic nitrogen. Further treatment of 5·BF4 with excess LiOH gave the crystallographicaly characterized Ru(0) square planar, linear NO complex 6. Complex 6 catalyzes the dehydrogenative coupling of alcohols to esters, reaching full conversion under air or under argon. Reaction of the PNN ligand (PNN = 2-((t)Bu2PCH2)-6-(Et2NCH2)pyridine) with RuCl3(NO)(H2O)2 in ethanol gave an equilibrium mixture of isomers 7a and 7b. Further treatment of 7a + 7b with 2 equivalent of sodium isopropoxide gave the crystallographicaly characterized, bent-nitrosyl, square pyramidal Ru(II) complex 8. Complex 8 was also synthesized by reaction of PNN with RuCl3(NO)(H2O)2 and Et3N in ethanol. Reaction of the "long arm" PN(2)N ligand (PN(2)N = 2-((t)Bu2PCH2-)-6-(Et2NCH2CH2)pyridine) with RuCl3(NO)(H2O)2 in ethanol gave complex 9, which upon treatment with 2 equiv of sodium isopropoxide gave complex 10. Complex 10 was also synthesized directly by reaction of PN(2)N with RuCl3(NO)(H2O)2 and a base in ethanol. A noteworthy aspect of these nitrosyl complexes is their preference for the Ru(0) oxidization state over Ru(II). This preference is observed with both aromatized and dearomatized pincer ligands, in

  16. Enhanced interlayer exchange coupling in antiferromagnetically coupled ultrathin (Co70Fe30/Pd) multilayers

    NASA Astrophysics Data System (ADS)

    Meng, Zhaoliang; Qiu, Jinjun; Han, Guchang; Teo, Kie Leong

    2015-12-01

    We report the studies of magnetization reversal and magnetic interlayer coupling in synthetic antiferromagnetic (SAF) [Pd/Co70Fe30]9/Ru(tRu)/Pd(tPd)/[Co70Fe30/Pd]9 structure as functions of inserted Pd layer (tPd) and Ru layer (tRu) thicknesses. We found the exchange coupling field (Hex) and perpendicular magnetic anisotropy (PMA) can be controlled by both the tPd and tRu, The Hex shows a Ruderman-Kittel-Kasuya-Yosida-type oscillatory decay dependence on tRu and a maximum interlayer coupling strength Jex = 0.522 erg/cm2 is achieved at tPd + tRu ≈ 0.8 nm in the as-deposited sample. As it is known that a high post-annealing stability of SAF structure is required for magnetic random access memory applications, the dependence of Hex and PMA on the post-annealing temperature (Ta) is also investigated. We found that both high PMA of the top Co70Fe30/Pd multilayer is maintained and Hex is enhanced with increasing Ta up to 350 °C for tRu > 0.7 nm in our SAF structure.

  17. Synthesis of novel Ru2C under high pressure-high temperature conditions.

    PubMed

    Sanjay Kumar, N R; Chandra Shekar, N V; Chandra, Sharat; Basu, Joysurya; Divakar, R; Sahu, P Ch

    2012-09-12

    We report here, for the first time, synthesis of the Fe(2)N type hexagonal phase of ruthenium carbide by a high pressure-high temperature technique using a laser heated diamond anvil cell (LHDAC). The synthesis is carried out by laser heating a mixture of pure elements, Ru and C, at very low 'pressure' of 5 GPa and T ~ 2000 K. The structure of the temperature quenched high pressure phase is characterized by in situ high pressure x-ray diffraction (HPXRD) and is corroborated by ex situ TEM imaging and diffraction, carried out for the first time on the retrieved sample synthesized by LHDAC. The lattice parameters of Ru(2)C at ambient pressure are found to be a = 2.534 Å and c = 4.147 Å. In situ HPXRD studies up to 14.2 GPa yield a bulk modulus of 178(4) GPa. Electronic structure calculations reveal the system to be metallic in nature with a degree of covalence along the Ru-C bond. As ruthenium is isoelectronic to osmium, this result for Ru(2)C has significant implications in the synthesis and study of osmium carbides.

  18. Influence of steric confinement within zeolite Y on photoinduced energy transfer between [Ru(bpy)3]2+ and iron polypyridyl complexes.

    PubMed

    Sewell, Gavin; Forster, Robert J; Keyes, Tia E

    2008-02-07

    The spectroscopic and photophysical properties of zeolite-Y-entrapped [Ru(bpy)3]2+ co-doped with either [Fe(bpy)3]2+ or [Fe(tpy)2]2+ over a range of iron complex loadings are presented. In solution, [Ru(bpy)3]2+ undergoes efficient bimolecular energy transfer to [Fe(bpy)3]2+, whereas only radiative or trivial energy transfer occurs between [Ru(bpy)3]2+ and [Fe(tpy)2]2+. In sharp contrast, within zeolite Y, both [Fe(bpy)3]2+ and [Fe(tpy)2]2+ were found to effectively quench the donor emission. Fitting the Perrin model to the photophysical data yields an effective quenching radius of 32 and 27 A, respectively, for [Fe(bpy)3]2+ and [Fe(tpy)2]2+. The long-range nature of the quenching suggests Förster energy transfer. Detailed spectroscopic investigations indicate that [Fe(tpy)2]2+ bound within zeolite Y undergoes significant distortion from octahedral geometry. This distortion results in increased oscillator strength and enhanced spectral overlap, between the [Ru(bpy)3]2+ (3)d pi-pi* donor emission and the co-incident acceptor (1)T2-(1)A1 ligand field absorption compared with solution. This turns on an efficient energy transfer to [Fe(tpy)2]2+ within the confinement of the zeolite Y supercage. Overall, this is an interesting example of the ability of the zeolite environment to provoke new photophysical processes not possible in solution.

  19. Excited-state spectroscopic investigations of multinuclear complexes based on [Ru(bpy)3](2+) moieties connected to 2,2'-bipyridine and 2,2';6',2''-terpyridine ligands.

    PubMed

    Horvath, Raphael; Lombard, Jean; Leprêtre, Jean-Claude; Collomb, Marie-Noëlle; Deronzier, Alain; Chauvin, Jérôme; Gordon, Keith C

    2013-12-21

    A number of multinuclear assemblies based on [Ru(bpy)3](2+) photosensitive moieties covalently linked to Fe(II), Co(II) or Zn(II) polypyridyl complexes are investigated regarding their initial and thermally equilibrated excited states. Ground state absorption and vibrational spectroscopic techniques are carried out, along with resonance Raman, transient absorption, and time resolved resonance Raman measurements. These methods are also supplemented by computational modelling. In all systems, the results clearly show that under visible irradiation, the substituted bpy linker ligand is involved in the initial (1)MLCT excitation of the Ru(II) subunit. For the Ru(II)/Fe(II) linked assemblies, absorption due to [Ru(bpy)3](2+) and [Fe(tpy)2](2+) subunits are identified to give rise to differing resonance Raman spectra. Transient absorption spectra of complexes containing two [Ru(bpy)3](2+) and one [Fe(tpy)2](2+) subunits show a strong depletion for the [Fe(tpy)2](2+) absorption peaks, which decay on a much faster timescale than the remainder of the transient features. This is consistent with a single excitation of the multimetallic assembly, followed by fast depletion (<10 ns) of the spectral signal from the bpy ligand bound to the Fe subunit. The results are supported by time resolved resonance Raman measurements where a number of features assigned to the linker are found at early time-scales. Using transient absorption this process can be followed for most complexes.

  20. Al 2O 3 supported Ru catalysts prepared by thermolysis of Ru 3(CO) 12 for catalytic wet air oxidation

    NASA Astrophysics Data System (ADS)

    Yu, Chaoying; Zhao, Peiqing; Chen, Gexin; Hu, Bin

    2011-06-01

    Low loading catalysts Ru/γ-Al 2O 3 and Ru-Ce/γ-Al 2O 3 were prepared by thermolysis of Ru 3(CO) 12 on γ-Al 2O 3. The catalysts were characterized by XPS, XRD and SEM. Two new Ru species (Ru A and Ru B) were detected during the Ru 3(CO) 12 decomposition process due to chemical interaction with the active OH groups on the surface of Al 2O 3 support, and the reduction of them can lead to more dispersed metallic phases. The sample was completely decomposed at 673 K in H 2, and RuO 2 was formed with minor amounts of Ru 0. When the temperature was increased to 773 K to heat the sample, the ratio of Ru 0 to RuO 2 increased. However, after the addition of CeO 2, only RuO 2 was detected on surface. The catalysts exhibited high activities in Catalytic Wet Air Oxidation (CWAO) of different organic compounds at high concentration such as isopropyl alcohol, phenol, acetic acids and N,N-dimethylformamide, which is attributed to the better dispersion of Ru particles and the addition of CeO 2 further enhanced number of effectively active sites on the cluster-derived catalyst surface.

  1. Itinerant Antiferromagnetism in RuO2

    DOE PAGES

    Berlijn, Tom; Snijders, Paul C.; Delaire, Oliver A.; ...

    2017-02-15

    Bulk rutile RuO2 has long been considered a Pauli paramagnet. Here, in this article, we report that RuO2 exhibits a hitherto undetected lattice distortion below approximately 900 K. The distortion is accompanied by antiferromagnetic order up to at least 300 K with a small room temperature magnetic moment of approximately 0.05μB as evidenced by polarized neutron diffraction. Density functional theory plus U(DFT+U) calculations indicate that antiferromagnetism is favored even for small values of the Hubbard U of the order of 1 eV. The antiferromagnetism may be traced to a Fermi surface instability, lifting the band degeneracy imposed by the rutilemore » crystal field. The combination of high Néel temperature and small itinerant moments make RuO2 unique among ruthenate compounds and among oxide materials in general.« less

  2. Itinerant Antiferromagnetism in RuO2

    NASA Astrophysics Data System (ADS)

    Berlijn, T.; Snijders, P. C.; Delaire, O.; Zhou, H.-D.; Maier, T. A.; Cao, H.-B.; Chi, S.-X.; Matsuda, M.; Wang, Y.; Koehler, M. R.; Kent, P. R. C.; Weitering, H. H.

    2017-02-01

    Bulk rutile RuO2 has long been considered a Pauli paramagnet. Here we report that RuO2 exhibits a hitherto undetected lattice distortion below approximately 900 K. The distortion is accompanied by antiferromagnetic order up to at least 300 K with a small room temperature magnetic moment of approximately 0.05 μB as evidenced by polarized neutron diffraction. Density functional theory plus U (DFT +U ) calculations indicate that antiferromagnetism is favored even for small values of the Hubbard U of the order of 1 eV. The antiferromagnetism may be traced to a Fermi surface instability, lifting the band degeneracy imposed by the rutile crystal field. The combination of high Néel temperature and small itinerant moments make RuO2 unique among ruthenate compounds and among oxide materials in general.

  3. Neutron-spectroscopic strength in Ru isotopes

    SciTech Connect

    Duarte, J.L.M.; Borello-Lewin, T.; Horodynski-Matsushigue, L.B. )

    1994-08-01

    A systematic, high resolution (6--8 keV) study of ([ital d],[ital t]) reactions on [sup 100,102,104]Ru is reported. Spectroscopic factors were extracted by comparison of experimental angular distributions with distorted wave Born approximation predictions. All of the information for [sup 99]Ru and, for excitation energies above 0.9 MeV, for [sup 103]Ru is new. Most of the strength expected for the 50--82 neutron shell was found. The strength distributions are discussed, also in comparison with the corresponding stripping reactions. Special attention is focused on extremely low and relatively intense [ital l]=3 excitations and on the [ital l]=4 transfer pattern observed.

  4. Skeletal Ru/Cu catalysts prepared from crystalline and quasicrystalline ternary alloy precursors: characterization by X-ray absorption spectroscopy and CO oxidation.

    PubMed

    Highfield, James; Liu, Tao; Loo, Yook Si; Grushko, Benjamin; Borgna, Armando

    2009-02-28

    . Preliminary studies in CO and H(2) oxidation were made in a DRIFTS flow reactor with on-line MS, and their activities and selectivities were compared against skeletal Ru and Cu controls, Ru/Al(2)O(3), and Au/Fe(2)O(3). All samples were active in CO oxidation above approximately 50 degrees C, showing light-off temperatures in the range 60-70 degrees C. Ru(22)Cu(7) and Ru(17)Cu(12.5) also showed good selectivities (vs. H(2) oxidation), attributed tentatively to Ru-modified Cu surfaces of varying thickness. These compositions are promising candidates to test in a (PROX) fuel processor to supply purified (CO-free) H(2) to a PEM fuel cell.

  5. The role of the non-magnetic material in spin pumping and magnetization dynamics in NiFe and CoFeB multilayer systems

    NASA Astrophysics Data System (ADS)

    Ruiz-Calaforra, A.; Brächer, T.; Lauer, V.; Pirro, P.; Heinz, B.; Geilen, M.; Chumak, A. V.; Conca, A.; Leven, B.; Hillebrands, B.

    2015-04-01

    We present a study of the effective magnetization M eff and the effective damping parameter α eff by means of ferromagnetic resonance spectroscopy on the ferromagnetic (FM) materials Ni81Fe19 (NiFe) and Co40Fe40B20 (CoFeB) in FM/Pt, FM/NM, and FM/NM/Pt systems with the non-magnetic (NM) materials Ru, Cr, Al, and MgO. Moreover, for NiFe layer systems, the influence of interface effects is studied by way of thickness dependent measurements of M eff and α eff . Additionally, spin pumping in NiFe/NM/Pt is investigated by means of inverse spin Hall effect (ISHE) measurements. We observe a large dependence of M eff and α eff of the NiFe films on the adjacent NM layer. While Cr and Al do not induce a large change in the magnetic properties, Ru, Pt, and MgO affect M eff and α eff in different degrees. In particular, NiFe/Ru and NiFe/Ru/Pt systems show a large perpendicular surface anisotropy and a significant enhancement of the damping. In contrast, the magnetic properties of CoFeB films do not have a large influence of the NM adjacent material and only CoFeB/Pt systems present an enhancement of α eff . However, this enhancement is much more pronounced in NiFe/Pt. By the introduction of the NM spacer material, this enhancement is reduced. Furthermore, a difference in symmetry between NiFe/NM/Pt and NiFe/NM systems in the output voltage signal from the ISHE measurements reveals the presence of spin pumping into the Pt layer in all-metallic NiFe/NM/Pt and NiFe/Pt systems.

  6. Petrology of high-Cr and high-Al ophiolitic chromitites from the Muǧla, SW Turkey: Implications from composition of chromite, solid inclusions of Platinum-group mineral (PGM), silicate, and base-metal mineral (BMM), and Os-isotope geochemistry

    NASA Astrophysics Data System (ADS)

    Uysal, I.; Tarkian, M.; Sadiklar, M. B.; Zaccarini, F.; Meisel, T.; Garuti, G.; Heidrich, S.

    2009-04-01

    Ultramafic rocks around the city of Muğla in SW-Turkey are represented by various degree depleted mantle peridotites ranging from cpx-rich harzburgites to depleted harzburgite and dunite. Cpx-rich harzburgite are thought to be the residua left after extraction of MORB-type basalt, from which high-Al chromitite (49.2 < Cr# < 53.5) crystallized with a higher content of 187Os/188Os (average of 0.1361). However, depleted harzburgites are assumed to be residua left after extraction of hydrous boninitic melt, produced by second stage partial melting of already depleted mantle due to subducting slab, from which high-Cr chromitites (64.2 < Cr# < 85.9) with lower and heterogeneous 187Os/188Os ratio (average of 0.1324) were crystallized as a result of melt-rock interaction in a suprasubduction environment. Dunites around the chromite deposits are considered to be the product of melt-peridotite interaction. Most of the chromitites contain high-Cr chromite and display enrichment in IPGE (Os, Ir, Ru) over PPGE (Rh, Pt, Pd), with concentrations of PGE between 61 and 1305 ppb. Consistently, laurite-erlichmanite serie minerals with various Os concentrations are found to be the most abundant PGM inclusions in chromite. Os-Ir-Ru alloys, irarsite, kashinite, and Pt-Fe alloys which is not common in ophiolitic chromitites were also detected as magmatic PGM inclusions as well as pentlandite, millerite, and rare heazlewoodite as base metal sulfide. The presence of olivine and clinopyroxene as well as hydrous silicate inclusions such as amphibole and phlogopite in high-Cr chromitite support the idea that high-Cr chromitites were formed in a suprasubduction environment.

  7. Temperature-induced transformation of electrochemically formed hydrous RuO2 layers over Ru(0001) model electrodes

    NASA Astrophysics Data System (ADS)

    Krause, Philipp P. T.; Camuka, Hava; Leichtweiss, Thomas; Over, Herbert

    2016-07-01

    Hydrous RuO2 reveals excellent performance both as a supercapacitor and as a heterogeneous oxidation catalyst. Molecular understanding of these processes needs, however, a model system with preferably low structural and morphological complexity. This goal is partly accomplished here by using single crystalline Ru(0001) as a template on which hydrous RuO2 is electrochemically formed. The hydrous RuO2 layers on Ru(0001) and their temperature induced transformation under ultra high vacuum (UHV) conditions are comprehensively characterized by scanning electron microscopy and X-ray photoemission spectroscopy. The hydrous RuO2 layer grows with an intricate morphology governed by the presence of step bunching regions of the Ru(0001) surface. Upon annealing to 200 °C in UHV the hydrous RuO2 layer transforms mostly into flat metallic Ru islands and occasionally into (100) and (111) oriented RuO2 particles aligned along the high symmetry direction of Ru(0001).Hydrous RuO2 reveals excellent performance both as a supercapacitor and as a heterogeneous oxidation catalyst. Molecular understanding of these processes needs, however, a model system with preferably low structural and morphological complexity. This goal is partly accomplished here by using single crystalline Ru(0001) as a template on which hydrous RuO2 is electrochemically formed. The hydrous RuO2 layers on Ru(0001) and their temperature induced transformation under ultra high vacuum (UHV) conditions are comprehensively characterized by scanning electron microscopy and X-ray photoemission spectroscopy. The hydrous RuO2 layer grows with an intricate morphology governed by the presence of step bunching regions of the Ru(0001) surface. Upon annealing to 200 °C in UHV the hydrous RuO2 layer transforms mostly into flat metallic Ru islands and occasionally into (100) and (111) oriented RuO2 particles aligned along the high symmetry direction of Ru(0001). Electronic supplementary information (ESI) available. See DOI: 10

  8. Multiple pathways for benzyl alcohol oxidation by Ru(V)═O3+ and Ru(IV)═O2+.

    PubMed

    Paul, Amit; Hull, Jonathan F; Norris, Michael R; Chen, Zuofeng; Ess, Daniel H; Concepcion, Javier J; Meyer, Thomas J

    2011-02-21

    Significant rate enhancements are found for benzyl alcohol oxidation by the Ru(V)═O(3+) form of the water oxidation catalyst [Ru(Mebimpy)(bpy)(OH(2))](2+) [Mebimpy = 2,6-bis(1-methylbenzimidazol-2-yl)pyridine; bpy = 2,2'-bipyridine] compared to Ru(IV)═O(2+) and for the Ru(IV)═O(2+) form with added bases due to a new pathway, concerted hydride proton transfer (HPT).

  9. Bulk Electronic Structure of Superconducting LaRu2P2 Single Crystals Measured by Soft-X-Ray Angle-Resolved Photoemission Spectroscopy

    NASA Astrophysics Data System (ADS)

    Razzoli, E.; Kobayashi, M.; Strocov, V. N.; Delley, B.; Bukowski, Z.; Karpinski, J.; Plumb, N. C.; Radovic, M.; Chang, J.; Schmitt, T.; Patthey, L.; Mesot, J.; Shi, M.

    2012-06-01

    We present a soft x-ray angle-resolved photoemission spectroscopy (SX-ARPES) study of the stoichiometric pnictide superconductor LaRu2P2. The observed electronic structure is in good agreement with density functional theory (DFT) calculations. However, it is significantly different from its counterpart in high-temperature superconducting Fe pnictides. In particular, the bandwidth renormalization present in the Fe pnictides (˜2-3) is negligible in LaRu2P2 even though the mass enhancement is similar in both systems. Our results suggest that the superconductivity in LaRu2P2 has a different origin with respect to the iron pnictides. Finally, we demonstrate that the increased probing depth of SX-ARPES, compared to the widely used ultraviolet ARPES, is essential in determining the bulk electronic structure in the experiment.

  10. Metal-metal and metal-ligand bonding at a QTAIM catastrophe: a combined experimental and theoretical charge density study on the alkylidyne cluster Fe3(μ-H)(μ-COMe)(CO)10.

    PubMed

    Farrugia, Louis J; Senn, Hans Martin

    2010-12-30

    The charge density in the tri-iron methoxymethylidyne cluster Fe(3)(μ-H)(μ-COMe)(CO)(10) (1) has been studied experimentally at 100 K and by DFT calculations on the isolated molecule using the Quantum Theory of Atoms in Molecules (QTAIM). The COMe ligand acts as a nearly symmetric bridge toward two of the Fe atoms (Fe-C = 1.8554(4), 1.8608(4) Å) but with a much longer interaction to the third Fe atom, Fe-C = 2.6762(4) Å. Complex 1 provides a classic example where topological QTAIM catastrophes render an exact structure description ambiguous. While all experimental and theoretical studies agree in finding no direct metal-metal interaction for the doubly bridged Fe-Fe vector, the chemical bonding between the Fe(CO)(4) unit and the Fe(2)(μ-H)(μ-COMe)(CO)(6) moiety in terms of conventional QTAIM descriptors is much less clear. Bond paths implying direct Fe-Fe interactions and a weak interaction between the COMe ligand and the Fe(CO)(4) center are observed, depending on the experimental or theoretical density model examined. Theoretical studies using the Electron Localizability Indicator (ELI-D) suggest the metal-metal bonding is more significant, while the delocalization indices imply that both Fe-Fe bonding and Fe···C(alkylidyne) bonding are equally important. The source functions at various interfragment reference points are similar and highly delocalized. The potential-energy surface (PES) for the migration of the alkylidyne group from a μ(2) to a semi-μ(3) coordination mode has been explored by DFT calculations on 1 and the model complexes M(3)(μ-H)(μ-CH)(CO)(10) (M = Fe, 2; Ru, 3; and Os, 4). These calculations confirm a semi-μ(3) bridging mode for the alkylidyne ligand as the minimum-energy geometry for compounds 2-4 and demonstrate that, for 1, both Fe-Fe and Fe···C(alkylidyne) interactions are important in the cluster bonding. The PES between μ(2) and semi-μ(3) alkylidyne coordination for 1 is extremely soft, and the interconversion between

  11. Mössbauer study of the (Ru1-xFex)Sr2GdCu2O8-δ system and two of its possible impurities: SrRuO3 and Gd2CuO4

    NASA Astrophysics Data System (ADS)

    Gómez, R.; Marquina, V.; Arévalo, A.; Pérez, J. L.; Ridaura, R.; Marquina, M. L.; Escamilla, R.; Akachi, T.

    2006-07-01

    Mössbauer spectra of a series of samples of the weak ferromagnetic 2!1!+- % feaaeaart1ev0aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn % hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr % 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9 % vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x % fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaWaaeWaaeaaru % qqYLwySbacfaGaa8Nuaiaa-vhadaWgaaWcbaGaa8xmaiaa-1cacaWF % 4baabeaakiaa-zeacaWFLbWaaSbaaSqaaiaa-HhaaeqaaaGccaGLOa % GaayzkaaGaa83uaiaa-jhadaWgaaWcbaGaa8NmaaqabaGccaWFhbGa % a8hzaiaa-neacaWF1bWaaSbaaSqaaiaa-jdaaeqaaOGaa83tamaaBa % aaleaacaWF4aGaa8xlaiabes7aKbqabaaaaa!4BBA! {left( {Ru_{{1 - x}} Fex } right)}Sr2 GdCu2 O_{{8 - δ }} system reveal the existence of three dissimilar sites where the Fe atoms can go into the structure. The Mössbauer parameters of the three observed quadrupole doublets, together with the relative population on each site, allow the following site assignment for the iron atoms: Fe3+ in four-fold planar coordination at Ru sites; Fe3+ in five-fold pyramidal coordination also at Ru sites and Fe2+ or Fe3+ in five-fold coordination at Cu sites. This assignment implies the formation of oxygen-vacancies at the charge reservoir (the RuO2 planes) that affect the structure and the superconducting and magnetic properties of the undoped system. Moreover, a close correlation between the oxygen content, calculated through the Mössbauer data, and the measured cell volume is established. We also report the Mössbauer spectra of two compounds (SrRu0.95Fe0.05O3 and Gd2Cu0.95Fe0.05O4) that could be formed as impurities during the synthesis of our samples.

  12. Carbon coated face-centered cubic Ru-C nanoalloys.

    PubMed

    Zhao, Zhisheng; Meng, Chuanmin; Li, Peifang; Zhu, Wenjun; Wang, Qianqian; Ma, Yanming; Shen, Guoyin; Bai, Ligang; He, Hongliang; He, Duanwei; Yu, Dongli; He, Julong; Xu, Bo; Tian, Yongjun

    2014-09-07

    Carbon-encapsulated ruthenium-carbon (Ru-C) nanoalloys were synthesized by dynamic shocks. The Ru-C alloy shows a new fcc structure different from the original hcp structure of metal Ru. This fcc phase is assigned to a Ru32C4 solid solution with a lattice parameter of 3.868(2) Å and a bulk modulus KT0 of 272(12) GPa. The small amount of carbon in the solid solution enhances the thermodynamic and chemical stabilities with respect to pure Ru, as well as induces changes in the electronic properties, which have direct applications in improving the material's catalytic activity and selectivity.

  13. Congress delves into science with RU-486.

    PubMed

    Kaeser, L

    1998-12-01

    In June 1998, a conservative, Republican member of the US House of Representatives attempted to amend the 1999 bill authorizing funding for the US Food and Drug Administration (USFDA) to prevent government funds from being used to test, develop, or approve "any drug for the chemical inducement of abortion." This bill was designed to halt the approval process for RU-486, a drug that was deemed "approvable" by the USFDA in 1996. Arguments mounted against the amendment by medical, health, and research groups stated that 1) RU-486 is an advance because it permits abortions early in pregnancies, 2) it is improper for the US Congress to impose a scientific judgement on the USFDA, and 3) this amendment has adverse implications for a wide range of drugs and devices that might have an abortifacient effect but be approved for other uses. The House of Representatives passed the amendment but the Senate rejected it, and it was deleted from the final version of the legislation. The amendment is expected to resurface next year. The Congressional debate on RU-486 also spilled over into the appointment hearings for the nomination of Jane Henney as USFDA commissioner. During her confirmation process, Henney was grilled about whether she would grant final approval to RU-486. Henney's nomination was approved by committee but has not yet been considered by the full Senate.

  14. Lubiprostone: RU 0211, SPI 0211.

    PubMed

    2005-01-01

    Lubiprostone [RU 0211, SPI 0211] is a bicyclic fatty acid that acts as a chloride channel opener, increasing intestinal water secretion. Lubiprostone, an orally-administered formulation, is one of a series of functional fatty acid compounds discovered by Dr Ryuji Ueno, and is currently undergoing development for the treatment of constipation, constipation-predominant irritable bowel syndrome (IBS-C) and postoperative ileus with Sucampo Pharmaceutical's. Lubiprostone activates a specific chloride channel (CLC2) on cells lining the gut, thereby naturally increasing intestinal fluid secretion. The increased fluid level softens the stool, promotes spontaneous bowel movements, and reduces abdominal discomfort/pain and bloating. The chloride channel is a protein that controls cell membrane transport of chloride ion. Lubiprostone acts on the ClC-2 chloride channel, which is located in the apical intestinal membrane. In November 2004, Takeda Pharmaceuticals entered into a collaboration and licensing agreement for Lubiprostone with Sucampo Pharmaceuticals for the treatment of chronic constipation and constipation-predominant Irritable Bowel Syndrome (c-IBS). Under the terms of the agreement, Takeda received the right to market the product in the US and Canada, while Sucampo reserved the co-promotion rights for these countries. Takeda's wholly-owned US subsidiary, Takeda Pharmaceuticals North America Inc., will sell lubiprostone once the product is approved by the US FDA. Takeda will also receive an option for marketing rights in other territories, including Japan and Europe. Takeda and Sucampo agreed on the exclusive manufacturing and supply of Lubiprostone by R-Tech Ueno, Ltd, a member of the Sucampo Group. Sucampo has the potential to receive up to dollar US 210 million in initial and milestone payments, some of which are contingent upon the successful achievement of several milestones. Takeda will fund a major part of development costs not only for chronic constipation

  15. Seven new rare-earth transition-metal oxychalcogenides: Syntheses and characterization of Ln{sub 4}MnOSe{sub 6} (Ln=La, Ce, Nd), Ln{sub 4}FeOSe{sub 6} (Ln=La, Ce, Sm), and La{sub 4}MnOS{sub 6}

    SciTech Connect

    Ijjaali, Ismail; Deng Bin; Ibers, James A. . E-mail: ibers@chem.northwestern.edu

    2005-05-15

    The quaternary oxychalcogenides Ln{sub 4}MnOSe{sub 6} (Ln=La, Ce, Nd), Ln{sub 4}FeOSe{sub 6} (Ln=La, Ce, Sm), and La{sub 4}MnOS{sub 6} have been synthesized by the reactions of Ln (Ln=La, Ce, Nd, Sm), M (M=Mn, Fe), Se, and SeO{sub 2} at 1173K for the selenides or by the reaction of La{sub 2}S{sub 3} and MnO at 1173K for the sulfide. Warning: These reactions frequently end in explosions. These isostructural compounds crystallize with two formula units in space group C{sub 6v}{sup 4}-P6{sub 3}mc of the hexagonal system. The cell constants (a, c in A) at 153K are: La{sub 4}MnOSe{sub 6}, 9.7596(3), 7.0722(4); La{sub 4}FeOSe{sub 6}, 9.7388(4), 7.0512(5); Ce{sub 4}MnOSe{sub 6}, 9.6795(4), 7.0235(5); Ce{sub 4}FeOSe{sub 6}, 9.6405(6), 6.9888(4); Nd{sub 4}MnOSe{sub 6}, 9.5553(5), 6.9516(5); Sm{sub 4}FeOSe{sub 6}, 9.4489(5), 6.8784(5); and La{sub 4}MnOS{sub 6}, 9.4766(6), 6.8246(6). The structure of these Ln{sub 4}MOQ{sub 6} compounds comprises a three-dimensional framework of interconnected LnOQ{sub 7} bicapped trigonal prisms, MQ{sub 6} octahedra, and the unusual LnOQ{sub 6} tricapped tetrahedra.

  16. Heat capacity and heat content measurements on binary compounds in the Ru-Si, Ru-Ge, and Ru-Sn systems

    SciTech Connect

    Kuntz, J.J.; Gachon, J.C.; Feschotte, P.; Perring, L. |

    1997-11-01

    Molar heat capacities of Ru{sub 0.5}Si{sub 0.5} Ru{sub 0.4}Si{sub 0.6}, Ru{sub 0.5}Ge{sub 0.5}, Ru{sub 0.4}Ge{sub 0.6}, Ru{sub 0.4}Sn{sub 0.6}, and Ru{sub 0.3}Sn{sub 0.7} were determined every 10 K by differential scanning calorimetry in the temperature range from 310 to 1080 K. The present results have been fitted by a polynomial function of temperature: C{sub p} = a+bT-cT{sup -2}. Heat contents of the six phases have been verified by drop calorimetry. Standard enthalpies of formation are given for the studied compounds.

  17. Ferromagnetism and Ru-Ru distance in SrRuO3 thin film grown on SrTiO3 (111) substrate

    PubMed Central

    2014-01-01

    Epitaxial SrRuO3 thin films were grown on both (100) and (111) SrTiO3 substrates with atomically flat surfaces that are required to grow high-quality films of materials under debate. The following notable differences were observed in the (111)-oriented SrRuO3 films: (1) slightly different growth mode, (2) approximately 10 K higher ferromagnetic transition temperature, and (3) better conducting behavior with higher relative resistivity ratio, than (100)c-oriented SrRuO3 films. Together with the reported results on SrRuO3 thin films grown on (110) SrTiO3 substrate, the different physical properties were discussed newly in terms of the Ru-Ru nearest neighbor distance instead of the famous tolerance factor. PACS 75.70.Ak; 75.60.Ej; 81.15.Fg PMID:24393495

  18. Integration of antiferromagnetic Heusler compound Ru2MnGe into spintronic devices

    NASA Astrophysics Data System (ADS)

    Balluff, Jan; Huminiuc, Teodor; Meinert, Markus; Hirohata, Atsufumi; Reiss, Günter

    2017-07-01

    We report on the integration of an antiferromagnetic Heusler compound acting as a pinning layer into magnetic tunneling junctions (MTJs). The antiferromagnet Ru2MnGe is used to pin the magnetization direction of a ferromagnetic Fe layer in MgO based thin film tunneling magnetoresistance stacks. The samples were prepared using magnetron co-sputtering. We investigate the structural properties by X-ray diffraction and reflection, as well as atomic force and high-resolution transmission electron microscopy. We find an excellent crystal growth quality with a low interface roughnesses of 1-3 Å, which is crucial for the preparation of working tunneling barriers. Using Fe as a ferromagnetic electrode material, we prepared magnetic tunneling junctions and measured the magnetoresistance. We find a sizeable maximum magnetoresistance value of 135%, which is comparable to other common Fe based MTJ systems.

  19. Thiol, disulfide, and trisulfide complexes of Ru porphyrins: potential models for iron-sulfur bonds in heme proteins.

    PubMed

    Rebouças, Júlio S; Patrick, Brian O; James, Brian R

    2012-02-22

    Thirty-two Ru(porp)L(2) complexes have been synthesized, where porp = the dianion of meso-tetramesitylporphyrin (TMP) or meso-tetrakis(4-methylphenyl)porphyrin (H(2)T-pMe-PP), and L = a thiol, a sulfide, a disulfide, or a trisulfide. Species studied were with RSH [R = Me, Et, (n)Pr, (i)Pr, (t)Bu, Bn (benzyl), and Ph], RSR (R = Me, Bn), RSSR (R = Me, Et, (n)Pr, Bn) and MeSS(t)Bu, and RSSSR (R = Me, Bn). All the species except two, which were the isolated Ru(T-pMe-PP)((t)BuSH)(2) and Ru(TMP)(MeSSMe)(2), were characterized in situ. The disulfide complex was characterized by X-ray analysis. (1)H NMR data for the coordinated thiols are the first reported within metalloporphyrin systems, and are especially informative because of the upfield shifts of the axial sulfur-containing ligands due to the porphyrin π-ring current effect, which is also present in the di- and trisulfide species. The disulfide in the solid state structure of Ru(TMP)(MeSSMe)(2) is η(1)(end-on) coordinated, the first example of such bonding in a nontethered, acyclic dialkyl disulfide; (1)H-(1)H EXSY NMR data in solution show that the species undergoes 1,2-S-metallotropic shifts. Stepwise formation of the bis(disulfide) complex from Ru(TMP)(MeCN)(2) in solution occurs with a cooperativity effect, resembling behavior of Fe(II)-porphyrin systems where crystal field effects dominate, but ligand trans-effects are more likely in the Ru system. The η(1)(end-on) coordination mode is also favored for the trisulfide ligand. Discussed also are the remarkable linear correlations that exist between the ring-current shielding shifts for the axial ligand C(1) protons of Ru(porp)(RS(x)R)(2) and x (the number of S atoms). The Introduction briefly reviews literature on Ru- and Fe porphyrins (including heme proteins) with sulfur-containing ligands or substrates, and relationships between our findings and this literature are discussed throughout the paper.

  20. Ru-assisted synthesis of Pd/Ru nanodendrites with high activity for ethanol electrooxidation

    NASA Astrophysics Data System (ADS)

    Zhang, Ke; Bin, Duan; Yang, Beibei; Wang, Caiqin; Ren, Fangfang; Du, Yukou

    2015-07-01

    Due to the specific physical and chemical properties of a highly branched noble metal, the controllable synthesis has attracted much attention. This article reports the synthesis of Pd/Ru nanodendrites by a facile method using an oil bath in the presence of polyvinyl pyrrolidone, potassium bromide and ascorbic acid. The morphology, structure, and composition of the as-prepared catalysts were characterized by means of X-ray diffraction, X-ray photoelectron spectroscopy and transmission electron microscopy. In the electrochemical measurement, the as-prepared Pd7/Ru1 bimetallic nanodendrites provide a large electrochemically active surface area and exhibit high peak current density in the forward scan toward ethanol electrooxidation, which is nearly four times higher than those of a pure Pd catalyst. The as-prepared Pd7/Ru1 catalysts also exhibit significantly enhanced cycling stability toward ethanol oxidation in alkaline medium, which are mainly ascribed to the synergetic effect between Pd and Ru. This indicates that the Pd7/Ru1 catalysts should have great potential applications in direct ethanol fuel cells.Due to the specific physical and chemical properties of a highly branched noble metal, the controllable synthesis has attracted much attention. This article reports the synthesis of Pd/Ru nanodendrites by a facile method using an oil bath in the presence of polyvinyl pyrrolidone, potassium bromide and ascorbic acid. The morphology, structure, and composition of the as-prepared catalysts were characterized by means of X-ray diffraction, X-ray photoelectron spectroscopy and transmission electron microscopy. In the electrochemical measurement, the as-prepared Pd7/Ru1 bimetallic nanodendrites provide a large electrochemically active surface area and exhibit high peak current density in the forward scan toward ethanol electrooxidation, which is nearly four times higher than those of a pure Pd catalyst. The as-prepared Pd7/Ru1 catalysts also exhibit significantly

  1. 186Os-187Os and highly siderophile element abundance systematics of the mantle revealed by abyssal peridotites and Os-rich alloys

    NASA Astrophysics Data System (ADS)

    Day, James M. D.; Walker, Richard J.; Warren, Jessica M.

    2017-03-01

    Abyssal peridotites are oceanic mantle fragments that were recently processed through ridges and represent residues of both modern and ancient melting. To constrain the nature and timing of melt depletion processes, and the composition of the mantle, we report high-precision Os isotope data for abyssal peridotites from three ocean basins, as well as for Os-rich alloys, primarily from Mesozoic ophiolites. These data are complemented by whole-rock highly siderophile element (HSE: Os, Ir, Ru, Pt, Pd, Re), trace- and major-element abundances for the abyssal peridotites, which are from the Southwest Indian (SWIR), Central Indian (CIR), Mid-Atlantic (MAR) and Gakkel Ridges. The results reveal a limited role for melt refertilization or secondary alteration processes in modifying abyssal peridotite HSE compositions. The abyssal peridotites examined have experienced variable melt depletion (2% to >16%), which occurred >0.5 Ga ago for some samples. Abyssal peridotites typically exhibit low Pd/Ir and, combined with high-degrees of estimated total melt extraction, imply that they were relatively refractory residues prior to incorporation into their present ridge setting. Recent partial melting processes and mid-ocean ridge basalt (MORB) generation therefore played a limited role in the chemical evolution of their precursor mantle domains. The results confirm that many abyssal peridotites are not simple residues of recent MORB source melting, having a more complex and long-lived depletion history. Peridotites from the Gakkel Ridge, SWIR, CIR and MAR indicate that the depleted MORB mantle has 186Os/188Os of 0.1198356 ± 21 (2SD). The Phanerozoic Os-rich alloys yield an average 186Os/188Os within uncertainty of abyssal peridotites (0.1198361 ± 20). Melt depletion trends defined between Os isotopes and melt extraction indices (e.g., Al2O3) allow an estimate of the primitive mantle (PM) composition, using only abyssal peridotites. This yields 187Os/188Os (0.1292 ± 25), and 186Os

  2. Magnetic phases and structural properties in Co/Ru superlattices

    NASA Astrophysics Data System (ADS)

    Alayo, W.; Tafur, Miguel; Baggio-Saitovitch, E.; Pelegrini, F.; Nascimento, V. P.

    2009-05-01

    We report studies by x-ray diffraction, ferromagnetic resonance (FMR), and x-ray magnetic circular dichroism (XMCD) in Co/Ru superlattices grown by magnetron sputtering. We studied the [Co(50Å)/Ru(tRu)]20 samples, which were deposited at room temperature on Si substrates with the Ru thicknesses, tRu, varying between 9 and 33 Å. The main and secondary uniform absorption modes, observed in the FMR spectra, are associated with the Co/Ru interfaces and the bulk Co regions, respectively. The main mode becomes more intense than the secondary one for increasing tRu. This is attributed to the roughness and/or atomic interdiffusion, which leads, with increasing tRu, to an increasing volume of Co/Ru interfacial regions and a decreasing volume of pure Co regions. The XMCD measurements provide Co spin magnetic moments lower than the bulk Co value, confirming the presence of a Co magnetic region with a lower local effective magnetization attributed to the Co/Ru interfaces.

  3. Ru-assisted synthesis of Pd/Ru nanodendrites with high activity for ethanol electrooxidation.

    PubMed

    Zhang, Ke; Bin, Duan; Yang, Beibei; Wang, Caiqin; Ren, Fangfang; Du, Yukou

    2015-08-07

    Due to the specific physical and chemical properties of a highly branched noble metal, the controllable synthesis has attracted much attention. This article reports the synthesis of Pd/Ru nanodendrites by a facile method using an oil bath in the presence of polyvinyl pyrrolidone, potassium bromide and ascorbic acid. The morphology, structure, and composition of the as-prepared catalysts were characterized by means of X-ray diffraction, X-ray photoelectron spectroscopy and transmission electron microscopy. In the electrochemical measurement, the as-prepared Pd7/Ru1 bimetallic nanodendrites provide a large electrochemically active surface area and exhibit high peak current density in the forward scan toward ethanol electrooxidation, which is nearly four times higher than those of a pure Pd catalyst. The as-prepared Pd7/Ru1 catalysts also exhibit significantly enhanced cycling stability toward ethanol oxidation in alkaline medium, which are mainly ascribed to the synergetic effect between Pd and Ru. This indicates that the Pd7/Ru1 catalysts should have great potential applications in direct ethanol fuel cells.

  4. Laser Spectroscopy of Ruthenium Containing Diatomic Molecules: RuH/D and RuP.

    NASA Astrophysics Data System (ADS)

    Adam, Allan G.; Konder, Ricarda M.; Nickerson, Nicole M.; Linton, Colan; Tokaryk, D. W.

    2015-06-01

    In the last few years, the Cheung group in Hong Kong and the Steimle group in Arizona have successfully studied several ruthenium containing diatomic molecules, RuX (X =C, O, N, B, using the laser-ablation molecular jet technique. Based on this success, the UNB spectroscopy group decided to try and find the optical signatures of other RuX molecules. Using CH_3OH and PH_3 as reactant gases, the RuH and RuP diatomic molecules have been detected in surveys of the 420 - 675 nm spectral region. RuD has also been made using fully deuterated methanol as a reactant. Dispersed fluorescence experiments have been performed to determine ground state vibrational frequencies and the presence of any low-lying electronic states. Rotationally resolved spectra for these molecules have also been taken and the analysis is proceeding. The most recent results will be presented. F. Wang et al., Journal of Chemical Physics 139, 174318 (2013). N. Wang et al., Journal of Physical Chemistry A 117, 13279 (2013). T. Steimle et al., Journal of Chemical Physics 119, 12965 (2003). N. Wang et al., Chemical Physics Letters 547, 21 (2012).

  5. Iron deficiency regulated OsOPT7 is essential for iron homeostasis in rice.

    PubMed

    Bashir, Khurram; Ishimaru, Yasuhiro; Itai, Reiko Nakanishi; Senoura, Takeshi; Takahashi, Michiko; An, Gynheung; Oikawa, Takaya; Ueda, Minoru; Sato, Aiko; Uozumi, Nobuyuki; Nakanishi, Hiromi; Nishizawa, Naoko K

    2015-05-01

    The molecular mechanism of iron (Fe) uptake and transport in plants are well-characterized; however, many components of Fe homeostasis remain unclear. We cloned iron-deficiency-regulated oligopeptide transporter 7 (OsOPT7) from rice. OsOPT7 localized to the plasma membrane and did not transport Fe(III)-DMA or Fe(II)-NA and GSH in Xenopus laevis oocytes. Furthermore OsOPT7 did not complement the growth of yeast fet3fet4 mutant. OsOPT7 was specifically upregulated in response to Fe-deficiency. Promoter GUS analysis revealed that OsOPT7 expresses in root tips, root vascular tissue and shoots as well as during seed development. Microarray analysis of OsOPT7 knockout 1 (opt7-1) revealed the upregulation of Fe-deficiency-responsive genes in plants grown under Fe-sufficient conditions, despite the high Fe and ferritin concentrations in shoot tissue indicating that Fe may not be available for physiological functions. Plants overexpressing OsOPT7 do not exhibit any phenotype and do not accumulate more Fe compared to wild type plants. These results indicate that OsOPT7 may be involved in Fe transport in rice.

  6. Magnetic phase transitions and magnetization reversal in MnRuP

    NASA Astrophysics Data System (ADS)

    Lampen-Kelley, P.; Mandrus, D.

    The ternary phosphide MnRuP is an incommensurate antiferromagnetic metal crystallizing in the non-centrosymmetric Fe2P-type crystal structure. Below the Neel transition at 250 K, MnRuP exhibits hysteretic anomalies in resistivity and magnetic susceptibility curves as the propagation vectors of the spiral spin structure change discontinuously across T1 = 180 K and T2 = 100 K. Temperature-dependent X-ray diffraction data indicate that the first-order spin reorientation occurs in the absence of a structural transition. A strong magnetization reversal (MR) effect is observed upon cooling the system through TN in moderate dc magnetic fields. Positive magnetization is recovered on further cooling through T1 and maintained in subsequent warming curves. The field dependence and training of the MR effect in MnRuP will be discussed in terms of the underlying magnetic structures and compared to anomalous MR observed in vanadate systems. This work is supported by the Gordon and Betty Moore Foundation GBMF4416 and U.S. DOE, Office of Science, BES, Materials Science and Engineering Division.

  7. The Loopy Ultraviolet Line Profiles of RU Lupi: Accretion, Outflows, and Fluorescence

    NASA Astrophysics Data System (ADS)

    Herczeg, Gregory J.; Walter, Frederick M.; Linsky, Jeffrey L.; Gahm, Gösta F.; Ardila, David R.; Brown, Alexander; Johns-Krull, Christopher M.; Simon, Michal; Valenti, Jeff A.

    2005-06-01

    We present far-ultraviolet (FUV) spectra of the classical T Tauri star RU Lup covering the 912-1710 Å spectral range, as observed by the Hubble Space Telescope STIS and the Far Ultraviolet Spectroscopic Explorer satellite. We use these spectra, which are rich in emission and absorption lines, to probe both the accreting and outflowing gas. Absorption in the Lyα profile constrains the extinction to AV~0.07 mag, which we confirm with other diagnostics. We estimate a mass accretion rate of (5+/-2)×10-8 Msolar yr-1 using the optical-NUV accretion continuum. The accreting gas is also detected in bright, broad lines of C IV, Si IV, and N V, which all show complex structures across the line profile. Many other emission lines, including those of H2 and Fe II, are pumped by Lyα. RU Lup's spectrum varies significantly in the FUV; our STIS observations occurred when RU Lup was brighter than several other observations in the FUV, possibly because of a high mass accretion rate.

  8. Re-Os and S isotope evidence for the origin of Platreef mineralization (Bushveld Complex)

    NASA Astrophysics Data System (ADS)

    Yudovskaya, M.; Belousova, E.; Kinnaird, J.; Dubinina, E.; Grobler, D. F.; Pearson, N.

    2017-10-01

    The Bushveld Complex contains the largest platinum-group element (PGE) deposits of the world that are represented by persistent stratiform reefs highly enriched with PGE with respect to underlying and overlying rocks. New Re-Os isotope and elemental LA MC-ICPMS data on platinum-group minerals (PGM) from the mineralized reefs are presented with implications to correlation between the different segments of the Bushveld Complex and a role of superimposed processes at the reef formation. We analyzed laurite (RuS2), hollingworthite (RhAsS), sperrylite (PtAs2) and Pt-Fe alloys from the Merensky Reef, Pseudoreef and the PGE reef of the Platreef. The measured 187Os/188Os value for Platreef laurite is 0.1751 ± 0.0004 whereas the ratios for sperrylite and hollingworthite range to slightly higher values (0.1713-0.1818 and 0.1744-0.1835 respectively). The observed textures of the analyzed PGM, such as Pt-Fe symplectites in base metal sulfides (BMS), laurite inclusions in chromite and sperrylite rims around sulfide-silicate aggregates, are interpreted as features of primary magmatic crystallization whereas hollingworthite overgrowths and exsolutions in sperrylite are likely to have originated from later solid state transformation or metasomatic processes. The Platreef is a composite sill-like body in the northern limb correlative to the Critical Zone in terms of stratigraphic position, whole-rock geochemistry and isotope characteristics. The pristine magmatic character of sulfides and PGM in the stratiform reefs at the top of the Platreef strongly resembles the style of Merensky Reef mineralization. However, the basal part of the Platreef pyroxenitic sequence is variably contaminated and mineralized with a significant hydrothermal overprint. Sulfides from underlying Lower Zone peridotite yield δ34S values varying from +9‰ to +14.2‰ that are much higher than the values for the overlying Platreef and are a consequence of sulfur assimilation from sedimentary sulfates. The

  9. Ru sub 3 (CO) sub 12 and Mo(CO) sub 6 adsorbed on Ru(001) and Au/Ru: An infrared reflection-absorption study

    SciTech Connect

    Malik, I.J.; Hrbek, J.

    1990-01-01

    We obtained IRAS and TDS data for Ru{sub 3}(CO){sub 12}/Ru(001) and Mo(CO){sub 6}/Au/Ru systems for metal carbonyl coverages between submonolayer and approximately 20 monolayers. We characterized the C-O stretching mode of both systems (4 cm{sup {minus}1} FWHM) and a deformation mode of Mo(CO){sub 6} at 608 cm{sup {minus}1} (1 cm{sup {minus}1} FWHM). Both IRAS and TDS data suggest adsorption and desorption of metal carbonyls as molecular species with a preferential orientation in the overlayers. The IR intensity of the C-O stretch per a C-O bond projected onto the surface normal is approximately twice (five times) larger for Ru{sub 3}(CO){sub 12} (Mo(CO){sub 6}) at submonolayer coverages than for CO/Ru(001) at {theta}{sub CO}=0.68. 31 refs., 4 figs.

  10. Effect of Geomagnetism on 101Ru Nuclear Quadrupole Resonance Measurements of CeRu2

    NASA Astrophysics Data System (ADS)

    Manago, Masahiro; Ishida, Kenji; Matsuda, Tatsuma D.; Ōnuki, Yoshichika

    2015-11-01

    We performed 101Ru nuclear quadrupole resonance (NQR) measurements on the s-wave superconductor CeRu2 and found oscillatory behavior in the spin-echo amplitude at the | ± 1/2> ≤ftrightarrow | ± 3/2> transitions but not at the | ± 3/2> ≤ftrightarrow | ± 5/2> transitions. The modulation disappears in the superconducting state or in a magnetic shield, which implies a geomagnetic field effect. Our results indicate that the NQR spin-echo decay curve at the | ± 1/2> ≤ftrightarrow | ± 3/2> transitions is sensitive to a weak magnetic field.

  11. Comparative antianaerobic activities of the ketolides HMR 3647 (RU 66647) and HMR 3004 (RU 64004).

    PubMed Central

    Ednie, L M; Jacobs, M R; Appelbaum, P C

    1997-01-01

    HMR 3647 (RU 66647) and HMR 3004 (RU 64004), two ketolides, had MICs at which 50% of the strains are inhibited (MIC50s) of 0.06 to 0.125 microg/ml and MIC90s of 16.0 microg/ml against 352 anaerobes. MIC50s and MIC90s of erythromycin, azithromycin, clarithromycin, and roxithromycin were 0.5 to 2.0 microg/ml and 32.0 to >64.0 microg/ml, respectively. HMR 3647 and HMR 3004 were more active against non-Bacteroides fragilis-group anaerobes (other than Fusobacterium mortiferum, Fusobacterium varium, and Clostridium difficile). PMID:9303406

  12. CIAO? ADiOS!

    NASA Astrophysics Data System (ADS)

    Korn, Andreas

    At the New Horizons in Globular Cluster Astronomy conference (Padova, June 2002), two members of the VLT globular cluster team presented different views on the importance of heavy-element sedimentation in Population II stars: ``The lack of evidence for depletion of Fe and Li in the atmospheres of globular cluster subgiants led some people to suspect that, for unknown reasons, Population II stars are not affected by this mechanism.'' \\citep{Castellani_2003} and ``There should be some mechanism that prevents sedimentation.'' \\citep{Gratton_2003}. In this review, I will argue that the scepticism behind both these statements is justified. We recently revisited the results on sedimentation in NGC 6397 stars presented by {\\citet{Gratton_etal_2001}} using higher-quality VLT/FLAMES-UVES data \\citep{Korn_etal_2006,Korn_etal_2007}. Element-specific abundance trends were identified which agree with atomic-diffusion predictions, if turbulent mixing below the convective envelope is accounted for in a parametrized way. Have we thus detected signatures of Atomic Diffusion in Old Stars (ADiOS)? Or are these trends mere artefacts of Conspiring Inaccuracies in Abundance Observations (CIAO)?

  13. Graphene Growth by Metal Etching on Ru (0001)

    SciTech Connect

    Loginova, Elena; Maier, Sabine; Stass, Ingeborg; Bartelt, Norman; Feibelman, Peter; Salmeron, Miquel; McCarty, Kevin

    2009-09-14

    Low-energy electron microscopy (LEEM) reveals a new mode of graphene growth on Ru(0001) in which Ru atoms from a step edge are injected under a growing graphene sheet. The injected atoms can form under-graphene islands, or incorporate into the topmost Ru layer, thereby increasing its density and forming dislocation networks. Density functional calculations imply that Ru islands nucleated between the graphene layer and the substrate are energetically stable; scanning tunneling microscopy (STM) reveals that dislocation networks exist near step edges.

  14. Supergene neoformation of Pt-Ir-Fe-Ni alloys: multistage grains explain nugget formation in Ni-laterites

    NASA Astrophysics Data System (ADS)

    Aiglsperger, Thomas; Proenza, Joaquín A.; Font-Bardia, Mercè; Baurier-Aymat, Sandra; Galí, Salvador; Lewis, John F.; Longo, Francisco

    2016-11-01

    Ni-laterites from the Dominican Republic host rare but extremely platinum-group element (PGE)-rich chromitites (up to 17.5 ppm) without economic significance. These chromitites occur either included in saprolite (beneath the Mg discontinuity) or as `floating chromitites' within limonite (above the Mg discontinuity). Both chromitite types have similar iridium-group PGE (IPGE)-enriched chondrite normalized patterns; however, chromitites included in limonite show a pronounced positive Pt anomaly. Investigation of heavy mineral concentrates, obtained via hydroseparation techniques, led to the discovery of multistage PGE grains: (i) Os-Ru-Fe-(Ir) grains of porous appearance are overgrown by (ii) Ni-Fe-Ir and Ir-Fe-Ni-(Pt) phases which are overgrown by (iii) Pt-Ir-Fe-Ni mineral phases. Whereas Ir-dominated overgrowths prevail in chromitites from the saprolite, Pt-dominated overgrowths are observed within floating chromitites. The following formation model for multistage PGE grains is discussed: (i) hypogene platinum-group minerals (PGM) (e.g. laurite) are transformed to secondary PGM by desulphurization during serpentinization; (ii) at the stages of serpentinization and/or at the early stages of lateritization, Ir is mobilized and recrystallizes on porous surfaces of secondary PGM (serving as a natural catalyst) and (iii) at the late stages of lateritization, biogenic mediated neoformation (and accumulation) of Pt-Ir-Fe-Ni nanoparticles occurs. The evidence presented in this work demonstrates that in situ growth of Pt-Ir-Fe-Ni alloy nuggets of isometric symmetry is possible within Ni-laterites from the Dominican Republic.

  15. Os isotopic composition of steels: Constraints on sources of Os in steel & crustal isotopic evolution of iron ores

    NASA Astrophysics Data System (ADS)

    Chatterjee, R. N.; Lassiter, J. C.

    2013-12-01

    Metal contamination during sample processing is a potential concern in Os-isotope studies. We examined Os concentrations and Os isotopes in industrial steels. Samples include high Cr stainless steels (>10.5% Cr), low alloy steels (>=92% Fe) and high alloy steels (<92% Fe). The chief components used to make steel are iron ore, chromites and coke. Coke is derived from coals that have low Os concentration (~36 ppt) [1]. Chromites in steels are mined from chromitites, which have high average Os concentrations and mantle-like 187Os/188Os ratios (~88 ppb Os, 187Os/188Os ≈ 0.127×24) [2]. Iron ores used in US steel manufacturing derive chiefly from magnetites mined from iron-bearing formations such as Banded Iron Formations (BIF), which have median Os concentration of ~4.8 ppb and radiogenic 187Os/188Os ≈ 0.358×388 [3]. Os concentrations in the measured steels span a wide range, from 0.03 to 22 ppb. The 187Os/188Os ratios vary from 0.144-4.12. Such high Os concentrations and radiogenic isotopic compositions confirm that metal contamination can affect Os-isotope compositions during sample processing, particularly for low-[Os] samples. There is no correlation between C and Os concentration in steel, indicating that coke is not a major Os source in steels. Os concentrations in steels are positively correlated with Cr content, suggesting that chromite-derived Os dominates the Os budget in stainless steels. 187Os/188Os is negatively correlated with Cr content, ranging from 0.144-0.195 in high-Cr (>10.5 % Cr) steels but from 0.279-4.12 in low-Cr steels. In addition, there is a positive correlation between 1/Os and 187Os/188Os, consistent with two-component mixing of Os derived from magnetite ore and chromites. Lower Os concentrations in steels than expected from simple mixing of magnetite and chromitite suggest some volatile Os loss during smelting. Although the current data is limited, the 186Os-187Os trend defined by the steel analyses can be utilized to extrapolate

  16. AuRu/AC as an effective catalyst for hydrogenation reactions

    DOE PAGES

    Villa, Alberto; Chan-Thaw, Carine E.; Campisi, Sebastiano; ...

    2015-03-23

    AuRu bimetallic catalysts have been prepared by sequential deposition of Au on Ru or vice versa obtaining different nanostructures: when Ru has been deposited on Au, a Aucore–Rushell has been observed, whereas the deposition of Au on Ru leads to a bimetallic phase with Ru enrichment on the surface. In the latter case, the unexpected Ru enrichment could be attributed to the weak adhesion of Ru on the carbon support, thus allowing Ru particles to diffuse on Au particles. Both structures result very active in catalysing the liquid phase hydrogenolysis of glycerol and levulinic acid but the activity, the selectivitymore » and the stability depend on the structure of the bimetallic nanoparticles. Ru@Au/AC core–shell structure mostly behaved as the monometallic Ru, whereas the presence of bimetallic AuRu phase in Au@Ru/AC provides a great beneficial effect on both activity and stability.« less

  17. Tandem hydroformylation/hydrogenation of alkenes to normal alcohols using Rh/Ru dual catalyst or Ru single component catalyst.

    PubMed

    Takahashi, Kohei; Yamashita, Makoto; Nozaki, Kyoko

    2012-11-14

    The catalyst system for tandem hydroformylation/hydrogenation of terminal alkenes to the corresponding homologated normal alcohol was developed. The reaction mechanism for the Rh/Ru dual catalyst was investigated by real-time IR monitoring experiments and (31)P NMR spectroscopy, which proved the mutual orthogonality of Rh-catalyzed hydroformylation and Ru-catalyzed hydrogenation. Detailed investigation about Ru-catalyzed hydrogenation of undecanal under H(2)/CO pressure clarified different kinetics from the hydrogenation under H(2) and gave a clue to design more active hydrogenation catalysts under H(2)/CO atmosphere. The solely Ru-catalyzed normal selective hydroformylation/hydrogenation is also reported.

  18. Ab-initio calculations of electric field gradient in Ru compounds and their implication on the nuclear quadrupole moments of ^{99}Ru and ^{101}Ru

    NASA Astrophysics Data System (ADS)

    Mishra, S. N.

    2017-08-01

    The nuclear quadrupole moments, Q, for the ground and first excited states in ^{99}Ru and ground state of ^{101}Ru have been determined by comparing the experimentally observed quadrupole interaction frequencies ν _Q with calculated electric field gradient (EFG) for a large number of Ru-based compounds. The ab-initio calculations of EFG were performed using the all-electron augmented plane wave + local orbital (APW + lo) method of the density functional theory (DFT). From the slope of the linear correlation between theoretically calculated EFGs and experimentally observed ν _Q, we obtain the quadrupole moment for the (5/2^+) ground state in ^{99}Ru and ^{101}Ru as 0.0734(17) b and 0.431(14) b respectively, showing excellent agreement with the values reported in literature. For 3/2^+, the quadrupole moment of the first excited state in ^{99}Ru is obtained as +0.203(3) b, which is considerably lower than the commonly accepted literature value of +0.231(12) b. The results presented in this paper would be useful for the precise determination of quadrupole moment of high spin states in other Ru isotopes and is likely to stimulate further shell model calculations for an improved understanding of nuclear shape in these nuclei.

  19. The knockdown of OsVIT2 and MIT affects iron localization in rice seed.

    PubMed

    Bashir, Khurram; Takahashi, Ryuichi; Akhtar, Shamim; Ishimaru, Yasuhiro; Nakanishi, Hiromi; Nishizawa, Naoko K

    2013-11-20

    The mechanism of iron (Fe) uptake in plants has been extensively characterized, but little is known about how Fe transport to different subcellular compartments affects Fe localization in rice seed. Here, we discuss the characterization of a rice vacuolar Fe transporter 2 (OsVIT2) T-DNA insertion line (osvit2) and report that the knockdown of OsVIT2 and mitochondrial Fe transporter (MIT) expression affects seed Fe localization. osvit2 plants accumulated less Fe in their shoots when grown under normal or excess Fe conditions, while the accumulation of Fe was comparable to that in wild-type (WT) plants under Fe-deficient conditions. The accumulation of zinc, copper, and manganese also changed significantly in the shoots of osvit2 plants. The growth of osvit2 plants was also slow compared to that of WT plants. The concentration of Fe increased in osvit2 polished seeds. Previously, we reported that the expression of OsVIT2 was higher in MIT knockdown (mit-2) plants, and in this study, the accumulation of Fe in mit-2 seeds decreased significantly. These results suggest that vacuolar Fe trafficking is important for plant Fe homeostasis and distribution, especially in plants grown in the presence of excess Fe. Moreover, changes in the expression of OsVIT2 and MIT affect the concentration and localization of metals in brown rice as well as in polished rice seeds.

  20. OsIRO2 is responsible for iron utilization in rice and improves growth and yield in calcareous soil.

    PubMed

    Ogo, Yuko; Itai, Reiko N; Kobayashi, Takanori; Aung, May Sann; Nakanishi, Hiromi; Nishizawa, Naoko K

    2011-04-01

    Iron (Fe) deficiency, a worldwide agricultural problem on calcareous soil with low Fe availability, is also a major human nutritional deficit. Plants induce Fe acquisition systems under conditions of low Fe availability. Previously, we reported that an Fe-deficiency-inducible basic helix-loop-helix (bHLH) transcription factor, OsIRO2, is responsible for regulation of the genes involved in Fe homeostasis in rice. Using promoter-GUS transformants, we showed that OsIRO2 is expressed throughout a plant's lifetime in a spatially and temporally similar manner to the genes OsNAS1, OsNAS2 and TOM1, which is involved in Fe absorption and translocation. During germination, OsIRO2 expression was detected in embryos. OsIRO2 expression in vegetative tissues was restricted almost exclusively to vascular bundles of roots and leaves, and to the root exodermis under Fe-sufficient conditions, and expanded to all tissues of roots and leaves in response to Fe deficiency. OsIRO2 expression was also detected in flowers and developing seeds. Plants overexpressing OsIRO2 grew better, and OsIRO2-repressed plants showed poor growth compared to non-transformant rice after germination. OsIRO2 overexpression also resulted in improved tolerance to low Fe availability in calcareous soil. In addition to increased Fe content in shoots, the overexpression plants accumulated higher amounts of Fe in seeds than non-transformants when grown on calcareous soil. These results suggest that OsIRO2 is synchronously expressed with genes involved in Fe homeostasis, and performs a crucial function in regulation not only of Fe uptake from soil but also Fe transport during germination and Fe translocation to grain during seed maturation.

  1. High-Spin Structure of 102Ru

    SciTech Connect

    Sohler, D.; Timar, J.; Molnar, J.; Algora, A.; Dombradi, Zs.; Krasznahorkay, A.; Zolnai, L.; Rainovski, G.; Joshi, P.; Wadsworth, R.; Jenkins, D.G.; Raddon, P.M.; Simons, A.J.; Wilkinson, A.R.; Starosta, K.; Fossan, D.B.; Bednarczyk, P.; Curien, D.; Duchene, G.; Gizon, A.

    2005-11-21

    High-spin states in the nucleus 102Ru have been studied through the 96Zr(13C,{alpha}3n) reaction using the EUROBALL IV {gamma}-ray spectrometer accompanied by the DIAMANT array for the detection of charged particles. All previously known bands have been extended to higher spins and additional bands have been found. Comparing the experimental Routhians and aligned angular momenta to the predictions of Woods-Saxon TRS calculations, vh11/2(d5/2,g7/2) configurations have been assigned to the observed negative-parity bands.

  2. Ru nanoframes with an fcc structure and enhanced catalytic properties

    SciTech Connect

    Ye, Haihang; Wang, Qingxiao; Catalano, Massimo; Lu, Ning; Vermeylen, Joseph; Kim, Moon J.; Liu, Yuzi; Sun, Yugang; Xia, Xiaohu

    2016-03-21

    Noble-metal nanoframes are of great interest to many applications due to their unique open structures. Among various noble metals, Ru has never been made into nanoframes. In this study, we report for the first time an effective method based on seeded growth and chemical etching for the facile synthesis of Ru nanoframes with high purity. The essence of this approach is to induce the preferential growth of Ru on the corners and edges of Pd truncated octahedra as the seeds by kinetic control. The resultant Pd–Ru core–frame octahedra could be easily converted to Ru octahedral nanoframes of ~2 nm in thickness by selectively removing the Pd cores through chemical etching. Most importantly, in this approach the face-centered cubic (fcc) crystal structure of Pd seeds was faithfully replicated by Ru that usually takes an hcp structure. Furthermore, the fcc Ru nanoframes showed higher catalytic activities toward the reduction of p-nitrophenol by NaBH4 and the dehydrogenation of ammonia borane compared with hcp Ru nanowires with roughly the same thickness.

  3. Ru nanoframes with an fcc structure and enhanced catalytic properties

    DOE PAGES

    Ye, Haihang; Wang, Qingxiao; Catalano, Massimo; ...

    2016-03-21

    Noble-metal nanoframes are of great interest to many applications due to their unique open structures. Among various noble metals, Ru has never been made into nanoframes. In this study, we report for the first time an effective method based on seeded growth and chemical etching for the facile synthesis of Ru nanoframes with high purity. The essence of this approach is to induce the preferential growth of Ru on the corners and edges of Pd truncated octahedra as the seeds by kinetic control. The resultant Pd–Ru core–frame octahedra could be easily converted to Ru octahedral nanoframes of ~2 nm inmore » thickness by selectively removing the Pd cores through chemical etching. Most importantly, in this approach the face-centered cubic (fcc) crystal structure of Pd seeds was faithfully replicated by Ru that usually takes an hcp structure. Furthermore, the fcc Ru nanoframes showed higher catalytic activities toward the reduction of p-nitrophenol by NaBH4 and the dehydrogenation of ammonia borane compared with hcp Ru nanowires with roughly the same thickness.« less

  4. RuO2 Thermometer for Ultra-Low Temperatures

    NASA Technical Reports Server (NTRS)

    Hait, Thomas; Shirron, Peter J.; DiPirro, Michael

    2009-01-01

    A small, high-resolution, low-power thermometer has been developed for use in ultra-low temperatures that uses multiple RuO2 chip resistors. The use of commercially available thick-film RuO2 chip resistors for measuring cryogenic temperatures is well known due to their low cost, long-term stability, and large resistance change.

  5. Ru Nanoframes with an fcc Structure and Enhanced Catalytic Properties.

    PubMed

    Ye, Haihang; Wang, Qingxiao; Catalano, Massimo; Lu, Ning; Vermeylen, Joseph; Kim, Moon J; Liu, Yuzi; Sun, Yugang; Xia, Xiaohu

    2016-04-13

    Noble-metal nanoframes are of great interest to many applications due to their unique open structures. Among various noble metals, Ru has never been made into nanoframes. In this study, we report for the first time an effective method based on seeded growth and chemical etching for the facile synthesis of Ru nanoframes with high purity. The essence of this approach is to induce the preferential growth of Ru on the corners and edges of Pd truncated octahedra as the seeds by kinetic control. The resultant Pd-Ru core-frame octahedra could be easily converted to Ru octahedral nanoframes of ∼2 nm in thickness by selectively removing the Pd cores through chemical etching. Most importantly, in this approach the face-centered cubic (fcc) crystal structure of Pd seeds was faithfully replicated by Ru that usually takes an hcp structure. The fcc Ru nanoframes showed higher catalytic activities toward the reduction of p-nitrophenol by NaBH4 and the dehydrogenation of ammonia borane compared with hcp Ru nanowires with roughly the same thickness.

  6. OsNRAMP5, a major player for constitutive iron and manganese uptake in rice.

    PubMed

    Ishimaru, Yasuhiro; Bashir, Khurram; Nakanishi, Hiromi; Nishizawa, Naoko K

    2012-07-01

    Manganese (Mn) and iron (Fe) are essential mineral micronutrients for plants and their deficiency and or toxicity represents a serious agricultural problem. In rice the information about genes involved in Mn uptake from soil is scarce. Recently, we showed that OsNRAMP5 is a plasma membrane protein involved in Mn and Fe transport. The concentration of Mn in roots, shoots and xylem sap of OsNRAMP5 RNAi (OsNRAMP5i) plants was significantly reduced compared with WT plants. The expression of OsNRAMP5 is not controlled by Fe deficiency in root and was also observed in pistil, ovary, lemma and palea. These data show that rice would utilize OsNRAMP5 for constitutive Fe and Mn uptake, while OsNRAMP5 would also play a role in Fe and Mn transport during flowering and seed development.

  7. Ru isotope heterogeneity in the solar protoplanetary disk

    NASA Astrophysics Data System (ADS)

    Fischer-Gödde, Mario; Burkhardt, Christoph; Kruijer, Thomas S.; Kleine, Thorsten

    2015-11-01

    Nucleosynthetic isotope anomalies in bulk chondrites and differentiated meteorites reflect variable proportions of isotopically diverse presolar components in bulk planetary bodies, but the origin of these heterogeneities is not well understood. Here, the Ru isotope composition of a comprehensive suite of iron meteorites and bulk samples of ordinary, enstatite and carbonaceous chondrites, as well as acid leachates and an insoluble residue of the Allende chondrite are examined using newly developed multi-collector inductively coupled plasma mass spectrometry techniques. Except for IAB iron meteorites and enstatite chondrites, all investigated meteorites show well-resolved Ru isotope anomalies. Of these, within-group Ru isotopic variations observed for samples from a given chemical group of iron meteorites reflect secondary neutron capture induced Ru isotope shifts during prolonged cosmic ray-exposure. After correction of these cosmogenic effects using Pt isotopes as a neutron-dose monitor, the remaining Ru isotope anomalies are nucleosynthetic in nature and are consistent with a deficit in s-process Ru in iron meteorite parent bodies. Similarly, Ru isotope anomalies in bulk ordinary and carbonaceous chondrites also reflect a deficiency in s-process Ru. The sequential dissolution of Allende reveals the presence of an HF-soluble s-process carrier, which is either an unidentified presolar phase or a component that incorporated s-process Ru liberated from SiC grains during nebular or parent body processes. We show that varying proportions of the s-process carrier identified in Allende resulted in the correlated Ru isotope anomalies observed for bulk meteorites, and that all meteorites (except possibly IAB irons and enstatite chondrites) are depleted in this s-process component relative to Ru from the Earth's mantle. Bulk meteorites exhibit correlated Ru and Mo isotope anomalies, reflecting variable deficits of a common s-process component, but some iron meteorites and

  8. Spectroscopic studies of three Cepheids with high positive pulsation period increments: SZ Cas, BY Cas, and RU Sct

    NASA Astrophysics Data System (ADS)

    Usenko, I. A.; Klochkova, V. G.

    2015-07-01

    circumstellar envelopes around all three Cepheids. We have determined the atmospheric parameters and chemical composition of the program Cepheids. An appreciable carbon underabundance, a nitrogen overabundance (the result was obtained only for BY Cas), a nearly solar oxygen abundance, a sodium overabundance, and solar magnesium and aluminum abundances have been revealed in all stars, suggesting that these yellow supergiants has already passed the first dredge-up. The abundances of the Fe-peak elements, a-elements, and r- and s-process elements are nearly solar. [Fe/H] = -0.05 dex for SZ Cas and [Fe/H]= +0.05 dex for RU Sct can be used to estimate the metallicities of the open clusters χ and h Per and Trump 35, respectively.

  9. Endemic Ru Isotopic Anomalies in Iron Meteorites and in Allende

    NASA Technical Reports Server (NTRS)

    Chen, J. H.; Papanastassiou, D. A.; Wasserburg, G. J.

    2003-01-01

    Small variations for Mo isotopes have been observed recently in the Allende meteorite and in iron meteorites, mesosiderites, and pallasites, using ICPMS. Large effects for Mo have been reported for leaches of Orgueil and in SiC and graphite from Murchison. Variations for Mo in bulk Allende and in Murchison have also been presented by NTIMS. Effects in Ru isotopes can define further the preserved exotic r, s, and p contributions in this mass region, and possible effects in Ru-98 and Ru-99 from Tc-98 (4.2 Ma half-life) and Tc-99 (0.21 Ma half-life). Previous attempts at determination of Ru isotopes yielded no resolved effects. The present work represents a substantial improvement in precision over the earlier work. Chemical and mass spectrometric analytical techniques are presented to determine the Ru isotope compositions in terrestrial standards and in meteorites.

  10. Bifunctional electrocatalysis in pt-ru nanoparticle systems.

    PubMed

    Roth, C; Benker, N; Theissmann, R; Nichols, R J; Schiffrin, D J

    2008-03-04

    Pt-Ru alloys are prominent electrocatalysts in fuel cell anodes as they feature a very high activity for the oxidation of reformate and methanol. The improved CO tolerance of these alloys has been discussed in relation to the so-called ligand and bifunctional mechanisms. Although these effects have been known for many years, they are still not completely understood. A new approach that bridges the gap between single crystals and practical catalysts is presented in this paper. Nanoparticulate model systems attached to an oxidized glassy carbon electrode were prepared by combining both ligand-stabilized and spontaneously deposited Pt and Ru nanoparticles. These electrodes showed very different voltammetric responses for CO and methanol oxidation. The cyclic voltammograms were deconvoluted into contributions attributed to Pt, Ru, and Pt-Ru contact regions to quantify the contribution of the latter to the bifunctional mechanism. Scanning transmission electron microscopy confirmed the proximity of Pt and Ru nanoparticles in the different samples.

  11. Endemic Ru Isotopic Anomalies in Iron Meteorites and in Allende

    NASA Technical Reports Server (NTRS)

    Chen, J. H.; Papanastassiou, D. A.; Wasserburg, G. J.

    2003-01-01

    Small variations for Mo isotopes have been observed recently in the Allende meteorite and in iron meteorites, mesosiderites, and pallasites, using ICPMS. Large effects for Mo have been reported for leaches of Orgueil and in SiC and graphite from Murchison. Variations for Mo in bulk Allende and in Murchison have also been presented by NTIMS. Effects in Ru isotopes can define further the preserved exotic r, s, and p contributions in this mass region, and possible effects in Ru-98 and Ru-99 from Tc-98 (4.2 Ma half-life) and Tc-99 (0.21 Ma half-life). Previous attempts at determination of Ru isotopes yielded no resolved effects. The present work represents a substantial improvement in precision over the earlier work. Chemical and mass spectrometric analytical techniques are presented to determine the Ru isotope compositions in terrestrial standards and in meteorites.

  12. Thermal conductivity of ruthenium aluminide (RuAl)

    SciTech Connect

    Anderson, S.A.; Lang, C.I.

    1998-01-06

    Ruthenium aluminide (RuAl) is an intermetallic compound which exhibits strength at high temperatures together with attractive room temperature toughness. This combination of properties makes it a promising material for use at higher temperatures than currently possible with conventional titanium and nickel based alloys. Although high temperature applications will demand a knowledge and understanding of the thermal properties of RuAl, no such information is available in the scientific literature. In this paper, measurements of the thermal conductivity of RuAl are reported for the first time. Although the electrical properties of RuAl have previously been investigated, further electrical resistivity measurements have been made, using the same samples used to measure thermal conductivity. This allows a direct, meaningful comparison of electrical and thermal conductivity data, offering insights into the thermal transport mechanisms in RuAl. Microstructure is shown to have a significant influence on thermal and electrical properties.

  13. s-Process Os isotope enrichment in ureilites by planetary processing

    NASA Astrophysics Data System (ADS)

    Goderis, S.; Brandon, A. D.; Mayer, B.; Humayun, M.

    2015-12-01

    Ubiquitous nucleosynthetic isotope anomalies relative to the terrestrial isotopic composition in Mo, Ru, and other elements are known from both bulk chondrites and differentiated meteorites, but Os isotope ratios reported from such meteorites have been found to be indistinguishable from the terrestrial value. The carriers of s- and r-process Os must thus have been homogeneously distributed in the solar nebula. As large Os isotope anomalies are known from acid leachates and residues of primitive chondrites, the constant relative proportions of presolar s- and r-process carriers in such chondrites must have been maintained during nebular processes. It has long been assumed that partial melting of primitive chondrites would homogenize the isotopic heterogeneity carried by presolar grains. Here, ureilites, carbon-rich ultramafic achondrites dominantly composed of olivine and low-Ca pyroxene, are shown to be the first differentiated bulk Solar System materials for which nucleosynthetic Os isotope anomalies have been identified. These anomalies consist of enrichment in s-process Os heterogeneously distributed in different ureilites. Given the observed homogeneity of Os isotopes in all types of primitive chondrites, this Os isotope variability among ureilites must have been caused by selective removal of s-process-poor Os host phases, probably metal, during rapid localized melting on the ureilite parent body. While Mo and Ru isotope anomalies for all meteorites measured so far exhibit s-process deficits relative to the Earth, the opposite holds for the Os isotope anomalies in ureilites reported here. This might indicate that the Earth preferentially accreted olivine-rich restites and inherited a s-process excess relative to smaller meteorite bodies, consistent with Earth's high Mg/Si ratio and enrichment of s-process nuclides in Mo, Ru, and Nd isotopes. Our new Os isotope results imply that caution must be used when applying nucleosynthetic isotope anomalies as provenance

  14. Electronic structure and spectra of [Ru(NH{sub 3}){sub 5}pyz]{sup 2+} and [(NH{sub 3}){sub 5}Ru-pyz-Ru(NH{sub 3}){sub 5}]{sup 4+}

    SciTech Connect

    Sizova, O.V.; Ivanova, N.V.; Baranovskii, V.I.; Nikolskii, A.B.

    1995-01-01

    The electronic structure and spectra of [Ru(NH{sub 3}){sub 5}pyz]{sup 2+} and [(NH{sub 3}){sub 5}]{sup 4+} are calculated by the INDO (CINDO-E/S) method. Changes in molecular orbitals, charge distributions, and bond order indices of the pyrazine molecule and [Ru(NH{sub 3}){sub 5}pyz]{sup 2+} complex in the [(NH{sub 3}){sub 5}Ru-pyz-Ru(NH{sub 3}){sub 5}Ru-pyz-Ru(NH{sub 3}){sub 5}]{sup 4+} binuclear complex are analyzed.

  15. One-Pot Process for Hydrodeoxygenation of Lignin to Alkanes Using Ru-Based Bimetallic and Bifunctional Catalysts Supported on Zeolite Y.

    PubMed

    Wang, Hongliang; Ruan, Hao; Feng, Maoqi; Qin, Yuling; Job, Heather; Luo, Langli; Wang, Chongmin; Engelhard, Mark H; Kuhn, Erik; Chen, Xiaowen; Tucker, Melvin P; Yang, Bin

    2017-04-22

    The synthesis of high-efficiency and low-cost catalysts for hydrodeoxygenation (HDO) of waste lignin to advanced biofuels is crucial for enhancing current biorefinery processes. Inexpensive transition metals, including Fe, Ni, Cu, and Zn, were severally co-loaded with Ru on HY zeolite to form bimetallic and bifunctional catalysts. These catalysts were subsequently tested for HDO conversion of softwood lignin and several lignin model compounds. Results indicated that the inexpensive earth-abundant metals could modulate the hydrogenolysis activity of Ru and decrease the yield of low-molecular-weight gaseous products. Among these catalysts, Ru-Cu/HY showed the best HDO performance, affording the highest selectivity to hydrocarbon products. The improved catalytic performance of Ru-Cu/HY was probably a result of the following three factors: (1) high total and strong acid sites, (2) good dispersion of metal species and limited segregation, and (3) high adsorption capacity for polar fractions, including hydroxyl groups and ether bonds. Moreover, all bifunctional catalysts proved to be superior over the combination catalysts of Ru/Al2 O3 and HY zeolite. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. One-pot process for hydrodeoxygenation of lignin to alkanes using Ru-based bimetallic and bifunctional catalysts supported on zeolite Y

    DOE PAGES

    Wang, Hongliang; Ruan, Hao; Feng, Maoqi; ...

    2017-02-22

    Here, the synthesis of high-efficiency and low-cost catalysts for hydrodeoxygenation (HDO) of waste lignin to advanced biofuels is crucial for enhancing current biorefinery processes. Inexpensive transition metals, including Fe, Ni, Cu, and Zn, were severally co-loaded with Ru on HY zeolite to form bimetallic and bifunctional catalysts. These catalysts were subsequently tested for HDO conversion of softwood lignin and several lignin model compounds. Results indicated that the inexpensive earth-abundant metals could modulate the hydrogenolysis activity of Ru and decrease the yield of low-molecular-weight gaseous products. Among these catalysts, Ru-Cu/HY showed the best HDO performance, affording the highest selectivity to hydrocarbonmore » products. The improved catalytic performance of Ru-Cu/HY was probably a result of the following three factors: (1) high total and strong acid sites, (2) good dispersion of metal species and limited segregation, and (3) high adsorption capacity for polar fractions, including hydroxyl groups and ether bonds. Moreover, all bifunctional catalysts proved to be superior over the combination catalysts of Ru/Al2O3 and HY zeolite.« less

  17. Ordered phases in ruthenium binary alloys from high-throughput first-principles calculations

    NASA Astrophysics Data System (ADS)

    Jahnátek, Michal; Levy, Ohad; Hart, Gus L. W.; Nelson, Lance J.; Chepulskii, Roman V.; Xue, J.; Curtarolo, Stefano

    2011-12-01

    Despite the increasing importance of ruthenium in numerous technological applications, e.g., catalysis and electronic devices, experimental and computational data on its binary alloys are sparse. In particular, data are scant on those binary systems believed to be phase-separating. We performed a comprehensive study of ruthenium binary systems with the 28 transition metals, using high-throughput first-principles calculations. These computations predict novel unsuspected compounds in 7 of the 16 binary systems previously believed to be phase-separating and in two of the three systems reported with only a high-temperature σ phase. They also predict a few unreported compounds in five additional systems and indicate that some reported compounds may actually be unstable at low temperature. These new compounds may be useful in the rational design of new Ru-based catalysts. The following systems are investigated: AgRu, AuRu, CdRu, CoRu, CrRu, CuRu, FeRu, HfRu, HgRu, IrRu, MnRu, MoRu, NbRu, NiRu, OsRu, PdRu, PtRu, ReRu, RhRu, RuSc, RuTa, RuTc, RuTi, RuV, RuW, RuY, RuZn, and RuZr (a star denotes systems in which the ab initio method predicts that no compounds are stable).

  18. Fischer–Tropsch Synthesis: Effect of Reducing Agent for Aqueous-Phase Synthesis Over Ru Nanoparticle and Supported Ru Catalysts

    SciTech Connect

    Pendyala, Venkat Ramana Rao; Shafer, Wilson D.; Jacobs, Gary; Graham, Uschi M.; Khalid, Syed; Davis, Burtron H.

    2014-12-27

    The effect of the reducing agent on the performance of a ruthenium nanoparticle catalyst was investigated during aqueous-phase Fischer–Tropsch synthesis using a 1 L stirred tank reactor in the batch mode of operation. For the purpose of comparison, the activity and selectivity of NaY zeolite supported Ru catalyst were also studied. NaBH4 and hydrogen were used as reducing agents in our study, and hydrogen reduced catalysts exhibited higher activities than the NaBH4 reduced catalysts, because of higher extent of reduction and a relatively lower tendency toward agglomeration of Ru particles. The Ru nanoparticle catalyst displayed higher activities than the NaY zeolite supported Ru catalyst for both reducing agents. NaBH4 reduced catalysts are less active and the carbon dioxide selectivity is higher than the hydrogen reduced catalysts. The activity of the supported Ru catalyst (Ru/NaY) was 75 % of that of the Ru nanoparticle catalyst, and has the benefit of easy wax/catalyst slurry separation by filtration. Finally, the hydrogen reduced supported Ru catalyst exhibited superior selectivity towards hydrocarbons (higher C5+ selectivity and lower selectivity to methane) than all other catalysts tested.

  19. Brassinosteroids are involved in Fe homeostasis in rice (Oryza sativa L.).

    PubMed

    Wang, Baolan; Li, Gen; Zhang, Wen-Hao

    2015-05-01

    Brassinosteroids (BRs) are steroid hormones that modulate numerous physiological processes in plants. However, few studies have focused on the involvement of BRs in sensing and responding to the stress of mineral nutrient deficiency. In the present study, we evaluated the roles of BRs in the response of rice (Oryza sativa) to iron (Fe) deficiency during Fe uptake, transport, and translocation. Exogenous application of 24-epibrassinolide (EBR) to wild-type (WT) plants exaggerated leaf symptoms of Fe deficiency and suppressed growth. EBR increased and decreased Fe concentrations in roots and shoots, respectively, under both Fe-deficient and Fe-sufficient conditions. Transcripts involved in Fe homeostasis, including OsIRT1, OsYSL15, OsYSL2, OsNAS1, and OsNAS2, were enhanced by EBR under Fe-deficient conditions. EBR depressed expression of OsNAS1, OsNAS2, and OsYSL2 in shoots, and inhibited Fe transport and translocation via the phloem. Rice mutant d2-1, which is defective in BR biosynthesis, was more tolerant to Fe deficiency than the WT, and accumulated greater amounts of Fe in roots than the WT under Fe-sufficient conditions. A greater upregulation of OsIRT1, OsYSL15, OsYSL2, OsNAS1, and OsNAS2 in the d2-1 mutant compared to the WT was found under Fe-sufficient conditions, while expression of these genes in the d2-1 mutant was lower than in the WT under Fe-deficient conditions. The greater tolerance of the d2-1 mutant could be partly mitigated by exogenous application of EBR. These novel findings highlight the important role of BR in mediating the response of strategy II plants to Fe deficiency by regulating Fe uptake and translocation in rice.

  20. Brassinosteroids are involved in Fe homeostasis in rice (Oryza sativa L.)

    PubMed Central

    Wang, Baolan; Li, Gen; Zhang, Wen-Hao

    2015-01-01

    Brassinosteroids (BRs) are steroid hormones that modulate numerous physiological processes in plants. However, few studies have focused on the involvement of BRs in sensing and responding to the stress of mineral nutrient deficiency. In the present study, we evaluated the roles of BRs in the response of rice (Oryza sativa) to iron (Fe) deficiency during Fe uptake, transport, and translocation. Exogenous application of 24-epibrassinolide (EBR) to wild-type (WT) plants exaggerated leaf symptoms of Fe deficiency and suppressed growth. EBR increased and decreased Fe concentrations in roots and shoots, respectively, under both Fe-deficient and Fe-sufficient conditions. Transcripts involved in Fe homeostasis, including OsIRT1, OsYSL15, OsYSL2, OsNAS1, and OsNAS2, were enhanced by EBR under Fe-deficient conditions. EBR depressed expression of OsNAS1, OsNAS2, and OsYSL2 in shoots, and inhibited Fe transport and translocation via the phloem. Rice mutant d2-1, which is defective in BR biosynthesis, was more tolerant to Fe deficiency than the WT, and accumulated greater amounts of Fe in roots than the WT under Fe-sufficient conditions. A greater upregulation of OsIRT1, OsYSL15, OsYSL2, OsNAS1, and OsNAS2 in the d2-1 mutant compared to the WT was found under Fe-sufficient conditions, while expression of these genes in the d2-1 mutant was lower than in the WT under Fe-deficient conditions. The greater tolerance of the d2-1 mutant could be partly mitigated by exogenous application of EBR. These novel findings highlight the important role of BR in mediating the response of strategy II plants to Fe deficiency by regulating Fe uptake and translocation in rice. PMID:25770588

  1. Suppression of proximity effect and the enhancement of p-wave superconductivity in the Sr2RuO4-Ru system.

    PubMed

    Ying, Y A; Xin, Y; Clouser, B W; Hao, E; Staley, N E; Myers, R J; Allard, L F; Fobes, D; Liu, T; Mao, Z Q; Liu, Y

    2009-12-11

    We report unexpected phenomena observed on the Sr2RuO4-Ru eutectic phase featuring Ru islands embedded in a bulk crystal of the chiral p-wave superconductor Sr2RuO4. It was found that the Sr2RuO4/Ru interface is atomically sharp, terminated uniformly by a Sr/O layer. Surprisingly, the proximity-induced p-wave superconducting energy gap predicted by theory was not detected inside Ru islands. Our results suggest that the previously observed enhancement of superconductivity in this eutectic phase occurs away from rather than near the Sr2RuO4/Ru interface, where dislocations and phonon hardening were found.

  2. Ru101 Knight-shift measurement of Sr2RuO4 in low fields applied parallel to the RuO2 plane

    NASA Astrophysics Data System (ADS)

    Murakawa, Hiroshi; Ishida, Kenji; Kitagawa, Kentaro; Mao, Z. Q.; Maeno, Yoshiteru

    2007-03-01

    We have measured Ru101 Knight shift (K101) in the spin triplet superconductor Sr2RuO4 in various magnetic fields applied parallel and perpendicular to the RuO2 plane to determine the spin direction of the Cooper pair. We measured temperature dependence of K101 in 0.15 and 0.055 T parallel to the RuO2 plane using nuclear-quadrupole-resonance (NQR) technique. We found that K101 is invariant with temperature in both fields on passing through the superconducting (SC) transition temperature. These results indicate that the spin susceptibility parallel to the RuO2 plane does not change in the field greater than 0.055 T, suggesting that the SC d-vector is along the c-axis when the magnetic field greater than 0.055 T is applied along to the RuO2 plane. The possible spin state in magnetic fields is discussed on the basis of the Knight-shift measurements so far.

  3. Intrinsic relation between catalytic activity of CO oxidation on Ru nanoparticles and Ru oxides uncovered with ambient pressure XPS.

    PubMed

    Qadir, Kamran; Joo, Sang Hoon; Mun, Bongjin S; Butcher, Derek R; Renzas, J Russell; Aksoy, Funda; Liu, Zhi; Somorjai, Gabor A; Park, Jeong Young

    2012-11-14

    Recent progress in colloidal synthesis of nanoparticles with well-controlled size, shape, and composition, together with development of in situ surface science characterization tools, such as ambient pressure X-ray photoelectron spectroscopy (APXPS), has generated new opportunities to unravel the surface structure of working catalysts. We report an APXPS study of Ru nanoparticles to investigate catalytically active species on Ru nanoparticles under oxidizing, reducing, and CO oxidation reaction conditions. The 2.8 and 6 nm Ru nanoparticle model catalysts were synthesized in the presence of poly(vinyl pyrrolidone) polymer capping agent and deposited onto a flat Si support as two-dimensional arrays using the Langmuir-Blodgett deposition technique. Mild oxidative and reductive characteristics indicate the formation of surface oxide on the Ru nanoparticles, the thickness of which is found to be dependent on nanoparticle size. The larger 6 nm Ru nanoparticles were oxidized to a smaller extent than the smaller Ru 2.8 nm nanoparticles within the temperature range of 50-200 °C under reaction conditions, which appears to be correlated with the higher catalytic activity of the bigger nanoparticles. We found that the smaller Ru nanoparticles form bulk RuO(2) on their surfaces, causing the lower catalytic activity. As the size of the nanoparticle increases, the core-shell type RuO(2) becomes stable. Such in situ observations of Ru nanoparticles are useful in identifying the active state of the catalysts during use and, hence, may allow for rational catalyst designs for practical applications.

  4. Low-temperature specific heat and magnetic properties of the filled skutterudite ferromagnet NdRu4As12

    NASA Astrophysics Data System (ADS)

    Rudenko, A.; Henkie, Z.; Cichorek, T.

    2016-09-01

    We present the low-temperature specific heat and magnetic properties of the filled skutterudite compound NdRu4As12 that exhibits a ferromagnetic transition at TC ≃ 2.3 K . Magnetic entropy considerations point at a quartet ground state of the Nd3+ ions. Deep in the ferromagnetic state, the heat capacity shows a Schottky anomaly that we ascribe to the Zeeman splitting in the presence of a molecular field. Comparison of the specific heats of NdRu4As12 and its Os-based homologue near their Curie temperatures supports our earlier observation suggesting an unusual lowering of the Th cubic point symmetry in the latter filled skutterudite.

  5. Dependency of anti-ferro-magnetic coupling strength on Ru spacer thickness of [Co/Pd]{sub n}-synthetic-anti-ferro-magnetic layer in perpendicular magnetic-tunnel-junctions fabricated on 12-inch TiN electrode wafer

    SciTech Connect

    Chae, Kyo-Suk; Shim, Tae-Hun; Park, Jea-Gun

    2014-07-21

    We investigated the Ru spacer-thickness effect on the anti-ferro-magnetic coupling strength (J{sub ex}) of a [Co/Pd]{sub n}-synthetic-anti-ferro-magnetic layer fabricated with Co{sub 2}Fe{sub 6}B{sub 2}/MgO based perpendicular-magnetic-tunneling-junction spin-valves on 12-in. TiN electrode wafers. J{sub ex} peaked at a certain Ru spacer-thickness: specifically, a J{sub ex} of 0.78 erg/cm{sup 2} at 0.6 nm, satisfying the J{sub ex} criteria for realizing the mass production of terra-bit-level perpendicular-spin-transfer-torque magnetic-random-access-memory. Otherwise, J{sub ex} rapidly degraded when the Ru spacer-thickness was less than or higher than 0.6 nm. As a result, the allowable Ru thickness variation should be controlled less than 0.12 nm to satisfy the J{sub ex} criteria. However, the Ru spacer-thickness did not influence the tunneling-magneto-resistance (TMR) and resistance-area (RA) of the perpendicular-magnetic-tunneling-junction (p-MTJ) spin-valves since the Ru spacer in the synthetic-anti-ferro-magnetic layer mainly affects the anti-ferro-magnetic coupling efficiency rather than the crystalline linearity of the Co{sub 2}Fe{sub 6}B{sub 2} free layer/MgO tunneling barrier/Co{sub 2}Fe{sub 6}B{sub 2} pinned layer, although Co{sub 2}Fe{sub 6}B{sub 2}/MgO based p-MTJ spin-valves ex-situ annealed at 275 °C achieved a TMR of ∼70% at a RA of ∼20 Ω μm{sup 2}.

  6. Os-187/Os-188 and Highly Siderophile Element Systematics of Apollo 17 Aphanitic Melt Rocks

    NASA Technical Reports Server (NTRS)

    Puchtel, I. S.; Walker, R. J.; James, O. B.

    2005-01-01

    Introduction: Generally chondritic relative abundances and high absolute abundances of the highly siderophile elements (HSE: Ru, Rh, Pd, Re, Os, Ir, Pt, Au) in Earth s upper mantle provide strong evidence that these elements were added to the Earth following the last major interaction between its metallic core and silicate fraction. So called "late accretion" may have added materials comprising as much as 0.8% of the total mass of the Earth and possibly a similar proportion of mass to the Moon. We have begun to study the chemical nature of late accreted materials to the Earth - Moon system by examining the HSE contained in lunar impact-melt rocks. The HSE contained in melt rocks were largely added to the Moon during the period of time from the origin of the lunar highlands crust (4.4- 4.5 Ga) to the end of the late bombardment period (ca. 3.9 Ga). These materials provide the only direct chemical link to the late accretionary period. The chemical fingerprints of the HSE in late accreted materials may enable us to ascertain under what conditions and where in the solar system the late accreted materials formed. The Os-187/Os-188 ratios (reflecting long-term Re/Os), coupled with ratios of other HSE, can be diagnostic for identifying the nature of the impactor. A critical issue, however, will be deconvolving the exogenous from indigenous components.

  7. RU-486: learning more about the French abortion drug.

    PubMed

    Smith, L

    1994-05-24

    RU-486 is a compound manufactured by Roussel Uclaf which blocks the functioning of progesterone, a hormone necessary for the maintenance of pregnancy. RU-486 is used widely outside of the US as a "morning after" pill to prevent a fertilized egg from implanting in the uterus after unprotected sexual intercourse. RU-486 will also cause a developing embryo to detach from the uterus. Accordingly, RU-486 is widely used as an abortion-inducing drug in Europe and China. Prostaglandins are typically administered one-two days after RU-486 to induce the uterus to expel the embryo. The treatment is given during the early weeks after conception, is painful, and usually takes two-three days. A woman visits a doctor several times over the course of treatment. By using RU-486, women avoid surgery and anesthesia, can terminate their pregnancies shortly after conception, have privacy, and can secure an abortion from any physician trained in pregnancy and its complications instead of having to go to centers where surgical abortions are performed. A surgical abortion, however, takes less time, is slightly more effective, and requires fewer office visits; women also usually experience less cramping and notice a lighter blood flow than they do with RU-486. The Population Council, a nonprofit contraceptive research organization in New York, holds the US patent rights to RU-486. The organization will soon select sites for clinical trials involving 2000 women required by the US Food and Drug Administration before the drug can be made available to the public. Approval is expected in two years. Use of the drug as a morning-after pill is being tested at the University of California, San Francisco. The manufacturer recommends women over age 35, who are smokers, and who have any other cardiovascular risks to not use RU-486.

  8. Atomic and molecular adsorption on Ru(0001)

    SciTech Connect

    Herron, Jeffrey A.; Tonelli, Scott; Mavrikakis, Manos

    2013-08-01

    The adsorption properties of a variety of atoms (H, O, N, S, and C), molecules (N2, HCN, CO, NO, and NH3) and molecular fragments (CN, NH2, NH, CH3, CH2, CH, HNO, NOH, and OH) are calculated on the (0001) facet of ruthenium using periodic, self-consistent, density functional theory calculations (DFT-GGA) at 1/4 ML coverage. For each species, we determine the optimal binding geometry and corresponding binding energy. The vibrational frequencies of these adsorbed species are calculated and are found to be in good agreement with experimental values that have been reported in the literature. From the binding energies, we calculate potential energy surfaces for the decomposition of NO, CO, N2, NH3, and CH4 on Ru(0001), showing that the decomposition of all of these molecules is thermochemically preferred to their desorption.

  9. Properties of Semiconducting Ru_2Ge_3

    NASA Technical Reports Server (NTRS)

    Fleurial, Jean-Pierre; Borshchevsky, Alex

    1993-01-01

    Transport properties of large single crystalline samples of Ru_2Ge_3 grown from the melt have been investigated in a 25-1000 C temperature range. A diffusionless transition between 500 and 550C from a high temperature tetragonal structure to a low temperature orthorhombic structure was clearly observed. Results showed that both the low temperature orthorhombic and the high temperature structural tetragonal phase are semiconductors. Some anisotropy of the transport coefficients was determined by measuring the samples in orientations parallel and perpendicular to the preferential direction of crystal growth. Large Seebeck coefficient (up to 400 microVK^(-1)) and low thermal conductivity (as low as 20x10^(-3) Wcm^(-1)K^(-1)) were achieved for the low temperature orthorhombic phase. Difficulties in preparing heavily doped samples and low Hall mobilities have limited values for the maximum figure of merit to 0.5 x 10^(-3) K^(-1) at 500 C.

  10. RU 486, mifepristone: a review of a controversial drug.

    PubMed

    DiPierri, D

    1994-06-01

    RU 486 (mifepristone), commonly referred to as the French abortion pill, has received much attention in the popular media. Much of this information has clouded the facts, and has been shrouded by controversy. Political, religious, and personal bias have slanted the presentation of the potential uses of this drug. Health care practitioners must be able to provide clients with the most accurate and factual information available. This article details the physiological effects of RU 486, as well as research data regarding uses and side effects. RU 486's most well publicized use, and efficacy, as an abortifacient are discussed in detail.

  11. Ordered Porous Pd Octahedra Covered with Monolayer Ru Atoms.

    PubMed

    Ge, Jingjie; He, Dongsheng; Bai, Lei; You, Rui; Lu, Haiyuan; Lin, Yue; Tan, Chaoliang; Kang, Yan-Biao; Xiao, Bin; Wu, Yuen; Deng, Zhaoxiang; Huang, Weixin; Zhang, Hua; Hong, Xun; Li, Yadong

    2015-11-25

    Monolayer Ru atoms covered highly ordered porous Pd octahedra have been synthesized via the underpotential deposition and thermodynamic control. Shape evolution from concave nanocube to octahedron with six hollow cavities was observed. Using aberration-corrected high-resolution transmission electron microscopy and X-ray photoelectron spectroscopy, we provide quantitative evidence to prove that only a monolayer of Ru atoms was deposited on the surface of porous Pd octahedra. The as-prepared monolayer Ru atoms covered Pd nanostructures exhibited excellent catalytic property in terms of semihydrogenation of alkynes.

  12. MoRu/Be multilayers for extreme ultraviolet applications

    DOEpatents

    Bajt, Sasa C.; Wall, Mark A.

    2001-01-01

    High reflectance, low intrinsic roughness and low stress multilayer systems for extreme ultraviolet (EUV) lithography comprise amorphous layers MoRu and crystalline Be layers. Reflectance greater than 70% has been demonstrated for MoRu/Be multilayers with 50 bilayer pairs. Optical throughput of MoRu/Be multilayers can be 30-40% higher than that of Mo/Be multilayer coatings. The throughput can be improved using a diffusion barrier to make sharper interfaces. A capping layer on the top surface of the multilayer improves the long-term reflectance and EUV radiation stability of the multilayer by forming a very thin native oxide that is water resistant.

  13. /sup 97/Ru-DMSA for delayed renal imaging. [Dogs

    SciTech Connect

    Oster, Z.H.; Som, P.; Gil, M.C.; Goldman, A.G.; Fairchild, R.G.; Meinken, G.E.; Srivastava, S.C.; Atkins, H.L.; Richards, P.; Brill, A.B.

    1981-01-01

    Dimercaptosuccinic acid (DMSA) was labeled with /sup 97/Ru both with and without the addition of SnCl.2H/sub 2/O. The tin-containing preparation was found to induce higher cortical deposition of /sup 97/Ru-DMSA than the tin-free preparation. Visualization of the renal cortex was excellent 4 to 48 hours after injection in normal dogs with renal insufficiency. It is concluded that /sup 97/Ru-(Sn+/sup 2/)-DMSA is a potentially useful renal imaging agent when delayed scintigraphy is necessary because of decompensaton of the kidneys.

  14. /sup 97/Ru-DMSA for delayed renal imaging

    SciTech Connect

    Oster, Z.H.; Som, P.; Gil, M.C.

    1981-10-01

    Dimercaptosuccinic acid (DMSA) was labeled with /sup 97/Ru both with and without the addition of SnCl-2H/sub 2/O. The tin-containing preparation was found to induce higher cortical deposition of /sup 97/Ru-DMSA than the tin-free preparation. Visualization of the renal cortex was excellent 4 to 48 hours after injection in normal dogs and in dogs with renal insufficiency. It is concluded that /sup 97/Ru-(SN/sup 2 +/)-DMSA is a potentially useful renal imaging agent when delayed scintigraphy is necessary because of decompensation of the kidneys.

  15. Growth of RuO2 nanorods in reactive sputtering

    NASA Astrophysics Data System (ADS)

    Lin, Yu-Tsun; Chen, Chun-Yu; Hsiung, Chang-Po; Cheng, Kai-Wen; Gan, Jon-Yiew

    2006-08-01

    The synthesis of RuO2 nanorods with reactive sputtering was demonstrated in this work. The synthesis process is very much like the metal organic chemical vapor deposition, except that RuO3 generated with reactive sputtering under high oxygen-to-argon flow ratio (>5SCCM /15SCCM) (SCCM denotes cubic centimeter per minute at STP) and high substrate temperature (>300°C) is used in place of the metal organic precursor. RuO2 nanorods tend to grow steadily with constant aspect ratio (˜27) and the field-emission characteristics appear very sensitive to their spatial distribution.

  16. Adsorption of formaldehyde and formyl intermediates on Pt, PtRu-, and PtRuMo-alloy surfaces: A density functional study

    NASA Astrophysics Data System (ADS)

    Cahyanto, Wahyu Tri; Shukri, Ganes; Agusta, Mohammad Kemal; Kasai, Hideaki

    2013-02-01

    Stable binding configuration for formaldehyde (H2CO) and formyl (HCO) adsorption on Pt, PtRu, and PtRuMo are studied within the frame of density functional theory (DFT). We address this study to investigate the role of Ru and Mo on the binding characteristic of formaldehyde and formyl adsorption with respect to interaction strength and charge analysis. Several binding conformation on all possible surface adsorption sites are considered in determining the most stable adsorption geometry on three surfaces. Our results show that the presence of Ru in PtRu and Mo in PtRuMo stabilize the formaldehyde and formyl, which are indicated by stronger bond strength. Further electronic structure analysis shows that the addition of Ru in PtRu and Mo in PtRuMo modifies the electronic structure of Pt's surface significantly. The presence of both impurities shifted the derived anti-bonding state - which is originally located below the fermi level in pure Pt surface - to be above the fermi level in PtRu and PtRuMo systems. This fact explains the stronger adsorption found on PtRu & PtRuMo as compared to pure Pt surface.

  17. Comparative NMR studies on Ca3LiRuO6 and Ca3NaRuO6

    NASA Astrophysics Data System (ADS)

    Chakrabarty, T.; Paulose, P. L.

    2016-06-01

    We report a comparative study of two ruthanate compounds, Ca3LiRuO6 and Ca3NaRuO6 by magnetic measurements, heat capacity and NMR. Ca3LiRuO6 is a weak ferromagnet with a magnetic ordering temperature of 115 K. The 7Li NMR linewidth of Ca3LiRuO6 displays a broad shoulder above the magnetic ordering temperature. Anomalous shoulder of this type is observed in the susceptibility data also. The origin of these phenomena is not clear but could possibly be attributed to low dimensional magnetism. A contrasting magnetic behavior is seen in Ca3NaRuO6, an antiferromagnet with a transition temperature at 87 K. The NMR study shows that the Knight shift is proportional to the magnetic susceptibility. Also, in Ca3NaRuO6, the Knight shift and the linewidth of the spectra change differently compared to Ca3LiRuO6. The heat capacity of both compounds show a λ-type anomaly at respective magnetic transition temperatures. However, in both the systems the entropy change (Δ S) is much less than that of an ordered S  =  3/2 system.

  18. A new dinuclear Ru-Hbpp based water oxidation catalyst with a trans-disposition of the Ru-OH.

    PubMed

    Mola, Joaquim; Dinoi, Chiara; Sala, Xavier; Rodríguez, Montserrat; Romero, Isabel; Parella, Teodor; Fontrodona, Xavier; Llobet, Antoni

    2011-04-14

    The bis(2-pyridyl)ethylamine (bpea) ligand has been used as a starting material for the synthesis of dinuclear Ru complexes of general formula trans,fac-{[Ru(n)X(bpea)](2)(μ-bpp)}(m+) (for X = Cl, n = II, m = 1, trans-Ru(II)-Cl, 1(+); for X = OH, n = III, m = 3, trans-Ru(III)-OH, 2(3+)) where the 3,5-bis(2-pyridyl)pyrazolate anionic ligand (bpp) acts as bridging dinucleating ligand, the bpea ligand coordinates in a facial manner and the monodentate ligands X are situated in a trans fashion with regard to one another. These complexes have been characterized in solution by 1D and 2D NMR spectroscopy, UV-vis and electrochemical techniques and in the solid state by X-ray diffraction analysis. The reaction of 1(PF(6)) with Ag(+) generates the corresponding solvated complex where the Cl ligand has been removed as insoluble AgCl, followed by the oxidation of Ru(II) to Ru(III) to generate the corresponding dinuclear complex trans-Ru(III)-OH, 2(PF(6))(3). The latter has been shown to catalytically oxidize water to molecular dioxygen using Ce(IV) as oxidant. Quantitative gas evolution as a function of time has been monitored on line by both manometry and mass spectroscopy (MS) techniques. Relative initial velocities of oxygen formation together with structural considerations rule out an intramolecular O-O bond formation pathway.

  19. Materials Data on Zr2RuOs (SG:225) by Materials Project

    SciTech Connect

    Kristin Persson

    2016-09-01

    Computed materials data using density functional theory calculations. These calculations determine the electronic structure of bulk materials by solving approximations to the Schrodinger equation. For more information, see https://materialsproject.org/docs/calculations

  20. Materials Data on Ti2RuOs (SG:225) by Materials Project

    SciTech Connect

    Kristin Persson

    2016-08-05

    Computed materials data using density functional theory calculations. These calculations determine the electronic structure of bulk materials by solving approximations to the Schrodinger equation. For more information, see https://materialsproject.org/docs/calculations

  1. Materials Data on Ho2RuOs (SG:225) by Materials Project

    SciTech Connect

    Kristin Persson

    2016-08-27

    Computed materials data using density functional theory calculations. These calculations determine the electronic structure of bulk materials by solving approximations to the Schrodinger equation. For more information, see https://materialsproject.org/docs/calculations

  2. Submonolayered Ru Deposited on Ultrathin Pd Nanosheets used for Enhanced Catalytic Applications.

    PubMed

    Zhang, Zhicheng; Liu, Ye; Chen, Bo; Gong, Yue; Gu, Lin; Fan, Zhanxi; Yang, Nailiang; Lai, Zhuangchai; Chen, Ye; Wang, Jie; Huang, Ying; Sindoro, Melinda; Niu, Wenxin; Li, Bing; Zong, Yun; Yang, Yanhui; Huang, Xiao; Huo, Fengwei; Huang, Wei; Zhang, Hua

    2016-12-01

    Ultrathin Pd nanosheets (NSs) coated with submonolayered Ru, referred to as Pd@Ru NSs, are synthesized via a seed-mediated growth method. The underpotential deposition can be the driving force for the formation of Pd@Ru NSs. The Pd@Ru NSs exhibit superior catalytic properties in the reduction of 4-nitrophenol and the semihydrogenation of 1-octyne, compared to the pure Pd NSs and Ru NSs.

  3. Adsorption and diffusion of Ru adatoms on Ru(0001)-supported graphene: Large-scale first-principles calculations

    SciTech Connect

    Han, Yong; Evans, James W.

    2015-10-27

    Large-scale first-principles density functional theory calculations are performed to investigate the adsorption and diffusion of Ru adatoms on monolayer graphene (G) supported on Ru(0001). The G sheet exhibits a periodic moiré-cell superstructure due to lattice mismatch. Within a moiré cell, there are three distinct regions: fcc, hcp, and mound, in which the C6-ring center is above a fcc site, a hcp site, and a surface Ru atom of Ru(0001), respectively. The adsorption energy of a Ru adatom is evaluated at specific sites in these distinct regions. We find the strongest binding at an adsorption site above a C atom in the fcc region, next strongest in the hcp region, then the fcc-hcp boundary (ridge) between these regions, and the weakest binding in the mound region. Behavior is similar to that observed from small-unit-cell calculations of Habenicht et al. [Top. Catal. 57, 69 (2014)], which differ from previous large-scale calculations. We determine the minimum-energy path for local diffusion near the center of the fcc region and obtain a local diffusion barrier of ~0.48 eV. We also estimate a significantly lower local diffusion barrier in the ridge region. These barriers and information on the adsorption energy variation facilitate development of a realistic model for the global potential energy surface for Ru adatoms. Furthermore, this in turn enables simulation studies elucidating diffusion-mediated directed-assembly of Ru nanoclusters during deposition of Ru on G/Ru(0001).

  4. Adsorption and diffusion of Ru adatoms on Ru(0001)-supported graphene: Large-scale first-principles calculations

    SciTech Connect

    Han, Yong; Evans, James W.

    2015-10-28

    Large-scale first-principles density functional theory calculations are performed to investigate the adsorption and diffusion of Ru adatoms on monolayer graphene (G) supported on Ru(0001). The G sheet exhibits a periodic moiré-cell superstructure due to lattice mismatch. Within a moiré cell, there are three distinct regions: fcc, hcp, and mound, in which the C{sub 6}-ring center is above a fcc site, a hcp site, and a surface Ru atom of Ru(0001), respectively. The adsorption energy of a Ru adatom is evaluated at specific sites in these distinct regions. We find the strongest binding at an adsorption site above a C atom in the fcc region, next strongest in the hcp region, then the fcc-hcp boundary (ridge) between these regions, and the weakest binding in the mound region. Behavior is similar to that observed from small-unit-cell calculations of Habenicht et al. [Top. Catal. 57, 69 (2014)], which differ from previous large-scale calculations. We determine the minimum-energy path for local diffusion near the center of the fcc region and obtain a local diffusion barrier of ∼0.48 eV. We also estimate a significantly lower local diffusion barrier in the ridge region. These barriers and information on the adsorption energy variation facilitate development of a realistic model for the global potential energy surface for Ru adatoms. This in turn enables simulation studies elucidating diffusion-mediated directed-assembly of Ru nanoclusters during deposition of Ru on G/Ru(0001)

  5. Adsorption and diffusion of Ru adatoms on Ru(0001)-supported graphene: Large-scale first-principles calculations

    DOE PAGES

    Han, Yong; Evans, James W.

    2015-10-27

    Large-scale first-principles density functional theory calculations are performed to investigate the adsorption and diffusion of Ru adatoms on monolayer graphene (G) supported on Ru(0001). The G sheet exhibits a periodic moiré-cell superstructure due to lattice mismatch. Within a moiré cell, there are three distinct regions: fcc, hcp, and mound, in which the C6-ring center is above a fcc site, a hcp site, and a surface Ru atom of Ru(0001), respectively. The adsorption energy of a Ru adatom is evaluated at specific sites in these distinct regions. We find the strongest binding at an adsorption site above a C atom inmore » the fcc region, next strongest in the hcp region, then the fcc-hcp boundary (ridge) between these regions, and the weakest binding in the mound region. Behavior is similar to that observed from small-unit-cell calculations of Habenicht et al. [Top. Catal. 57, 69 (2014)], which differ from previous large-scale calculations. We determine the minimum-energy path for local diffusion near the center of the fcc region and obtain a local diffusion barrier of ~0.48 eV. We also estimate a significantly lower local diffusion barrier in the ridge region. These barriers and information on the adsorption energy variation facilitate development of a realistic model for the global potential energy surface for Ru adatoms. Furthermore, this in turn enables simulation studies elucidating diffusion-mediated directed-assembly of Ru nanoclusters during deposition of Ru on G/Ru(0001).« less

  6. X-ray absorption spectroscopy study in the BaFe2As2 family

    NASA Astrophysics Data System (ADS)

    Koh, Yoonyoung; Kim, Yeongkwan; Yang, Wanli; Kim, Changyoung

    2012-02-01

    One of the representative Fe-based superconductor families, BaFe2As2 (Tc =38K) is a semimetal with the same number of hole and electron carriers, and is in a spin density wave state below 139K. It has been reported that various types of ``doped'' BaFe2As2 systems can obtained by substitution of Ba, Fe, and As atoms. However, an important issue has been recently raised regarding whether each type of substitution indeed induces effective charge doping or not. It is essential to clarify whether each type of substitution indeed induce an effective doping in BaFe2As2 system. To clarify the carrier doping issue, we performed high resolution X-ray absorption spectroscopy experiment on Ba(Fe,Co)2As2, Ba(Fe,Ru)2As2, BaFe2(As,P)2 which are representative ``doped'' BaFe2As2 systems.

  7. Photoinduced intramolecular energy transfer and anion sensing studies of isomeric RuIIOsII complexes derived from an asymmetric phenanthroline-terpyridine bridge.

    PubMed

    Maity, Dinesh; Bhaumik, Chanchal; Mondal, Debiprasad; Baitalik, Sujoy

    2014-01-28

    Two heterobimetallic Ru(II)-Os(II) complexes of compositions [(bpy)2M(II)(phen-Hbzim-tpy)M'(II)(tpy-PhCH3)](4+), where M(II) = Ru and M'(II) = Os (4) and M(II) = Os and M'(II) = Ru (5), phen-Hbzim-tpy = 2-(4-(2,6-di(pyridin-2-yl)pyridine-4-yl)phenyl)-1H-imidazole[4,5][1,10]phenanthroline, bpy = 2,2'-bipyridine, and tpy-PhCH3 = 4'-(4-methylphenyl)-2,2':6',2''-terpyridine have been synthesized and characterized by elemental analyses, ESI mass spectrometry, and (1)H NMR and UV-vis absorption spectroscopy. The absorption spectra, redox behavior, and luminescence properties of the complexes have been thoroughly investigated and compared with that of monometallic model compounds [(bpy)2M(II)(phen-Hbzim-tpy)](2+) [M(II) = Ru (1) and M(II) = Os (2)] and [(phen-Hbzim-tpy)Ru(II)(tpy-PhCH3)](2+) (3). The complexes display very intense, ligand-centered absorption bands in the UV and moderately intense MLCT bands in the visible regions. The bimetallic complexes show two successive one-electron reversible metal-centered oxidations, whereas the monometallic complexes display one-electron oxidation in the positive potential window. Steady state and time-resolved luminescence data at room temperature show that an efficient intramolecular electronic energy transfer takes place from the Ru-center to the Os-based component in both the heterometallic dyads in all the solvents. The complexes under investigation contain an imidazole NH proton which became appreciably acidic due to metal coordination and can be utilized for recognition of selective anions in solution either via hydrogen bonding interaction or by proton transfer. Accordingly, the anion binding properties of the two heterobimetallic complexes as well as parent bridging ligand, phen-Hbzim-tpy, have been studied in solutions using absorption, steady state and time-resolved luminescence spectral measurements. The metalloreceptors act as sensors for F(-), CN(-) and AcO(-) ions. It is evident from sensing studies that in the

  8. Dual emission and excited-state mixed-valence in a quasi-symmetric dinuclear Ru-Ru complex.

    PubMed

    Kreitner, Christoph; Grabolle, Markus; Resch-Genger, Ute; Heinze, Katja

    2014-12-15

    The synthesis and characterization of the new dinuclear dipeptide [(EtOOC-tpy)Ru(tpy-NHCO-tpy)Ru(tpy-NHCOCH3)](4+) 3(4+) of the bis(terpyridine)ruthenium amino acid [(HOOC-tpy)Ru(tpy-NH2)](2+) 1(2+) are described, and the properties of the dipeptide are compared to those of the mononuclear complex [(EtOOC-tpy)Ru(tpy-NHCOCH3)](2+) 4(2+) carrying the same functional groups. 3(4+) is designed to serve a high electronic similarity of the two ruthenium sites despite the intrinsic asymmetry arising from the amide bridge. This is confirmed via UV-vis absorption and NMR spectroscopy as well as cyclic voltammetry. 4(2+) and 3(4+) are emissive at room temperature, as expected. Moreover, 3(4+) exhibits dual emission from two different triplet states with different energies and lifetimes at room temperature. This is ascribed to the presence of a unique thermal equilibrium between coexisting [Ru(II)(tpy-NHCO-tpy(·-))Ru(III)] and [Ru(III)(tpy-NHCO-tpy(·-))Ru(II)] states leading to an unprecedented excited-state Ru(II)Ru(III) mixed-valent system via the radical anion bridge tpy-NHCO-tpy(·-). The mixed-valent cation 3(5+), on the other hand, shows no measurable interaction of the Ru(II)Ru(III) centers via the neutral bridge tpy-NHCO-tpy (Robin-Day class I). Reduction of 3(4+) to the radical cation 3(3+) by decamethylcobaltocene is bridge-centered as evidenced by rapid-freeze electron paramagnetic resonance spectroscopy. Interestingly, all attempts to observe 3(3+) via NMR and UV-vis absorption spectroscopy only led to the detection of the diamagnetic complex 3-H(3+) in which the bridging amide is deprotonated. Hence 3-H(3+) (and 4-H(+)) appear to reduce protons to dihydrogen. The ease of single and double deprotonation of 4(2+) and 3(4+) to 4-H(+), 3-H(3+), and 3-2H(2+) was demonstrated using a strong base and was studied using NMR and UV-vis absorption spectroscopies. The equilibrating excited triplet states of 3(4+) are reductively quenched by N,N-dimethylaniline assisted by

  9. Study of Ru{sub 2}VGe and Ru{sub 2}VSb: High-spin polarized and half-metallic Heusler alloys

    SciTech Connect

    Bhat, Idris Hamid; Gupta, Dinesh C.

    2015-06-24

    Electronic and magnetic properties of Ru{sub 2}VGe and Ru{sub 2}VSb have been investigated by ab-initio. The optimized equilibrium lattice parameters were found to be 6.032 Å for Ru{sub 2}VGe and 6.272 Å for Ru{sub 2}VSb. Both the materials have ferromagnetic ground states and V mainly contributes to the magnetic properties in these materials. The highly spin-polarized half-metallic materials have integral magnetic moments of 1.0 µ{sub B} for Ru{sub 2}VGe and 2.0 µ{sub B} for Ru{sub 2}VSb with an energy gap of 0.095 eV for Ru2VGe and 0.186 eV for Ru{sub 2}VSb in the spin-down channel.

  10. Catalytic ammonia decomposition over industrial-waste-supported Ru catalysts

    SciTech Connect

    Pei Fang Ng; Li Li; Shaobin Wang; Zhonghua Zhu; Gaoqing Lu; Zifeng Yan

    2007-05-15

    Industrial solid wastes (fly ash and red mud, a by-product of the aluminium industry) have been employed as supports for preparation of Ru-based catalysts. Physical and chemical treatments on red mud were conducted and these modified supports were also used for preparation of Ru-based catalysts. Those Ru catalysts were characterized by various techniques such as N2 adsorption, H{sub 2} adsorption, XRD, XPS, and temperature-programmed reduction (TPR), and were then tested for catalytic ammonia decomposition to hydrogen. It was found that red-mud-supported Ru catalyst exhibits higher ammonia conversion and hydrogen production than fly-ash-supported catalyst. Heat and chemical treatments of the red mud greatly improve the catalytic activity. Moreover, a combination of acid and heat treatments produces the highest catalytic conversion of ammonia. 35 refs., 4 figs., 4 tabs.

  11. Studies of quadrupole collectivity in the γ -soft 106Ru

    NASA Astrophysics Data System (ADS)

    Sanchez-Vega, M.; Mach, H.; Taylor, R. B. E.; Fogelberg, B.; Lindroth, A.; Aas, A. J.; Dendooven, P.; Honkanen, A.; Huhta, M.; Lhersonneau, G.; Oinonen, M.; Parmonen, J. M.; Penttilä, H.; Äystö, J.; Persson, J. R.; Kurpeta, J.

    2008-02-01

    Various alternative models were used to describe the structure of 106Ru . For example, the General Collective Model (GCM) predicts shape-coexistence for 106Ru with a spherical and a triaxial minimum and strongly mixed structures, while in the IBA-2 calculations, where 106Ru was considered as transitional from vibrational U(5) to γ -soft O(6) , no need was found to include the shape-coexisting configurations. In order to provide additional constraints on the model interpretations, we have applied the Advanced Time-Delayed (ATD) βγγ( t) method to measure the level lifetimes of the excited levels in 106Ru . The new results include the half-lives of T 1/2 = 183(3) ps and 7.5(30)ps for the 2+ 1 and 2+ 2 states, respectively.

  12. Internal oxidation of laminated Nb-Ru coatings

    NASA Astrophysics Data System (ADS)

    Chen, Yung-I.; Chu, Hsiu-Nuan; Kai, Wu

    2016-12-01

    A direct current magnetron cosputtering system was used to deposit Nb-Ru coatings with various chemical compositions onto silicon wafers. The Nb-Ru coatings exhibited distinct nanolaminated structures because of the cyclical gradient concentration deposition. The oxidized Nb-Ru coatings formed oxide and metal multilayers when they experienced internal oxidation at 400-600 °C in a 1% O2-99% Ar atmosphere. A two-stage parabolic-rate law was obeyed for the Nb0.49Ru0.51 coatings oxidized at 350-550 °C in 1% O2-99% Ar. The activation energies in the two-stage oxidation, dominated by oxygen dissolution and oxide formation, were calculated at 88 and 127 kJ/mol, respectively.

  13. The role of the non-magnetic material in spin pumping and magnetization dynamics in NiFe and CoFeB multilayer systems

    SciTech Connect

    Ruiz-Calaforra, A. Brächer, T.; Lauer, V.; Pirro, P.; Heinz, B.; Geilen, M.; Chumak, A. V.; Conca, A.; Leven, B.; Hillebrands, B.

    2015-04-28

    We present a study of the effective magnetization M{sub eff} and the effective damping parameter α{sub eff} by means of ferromagnetic resonance spectroscopy on the ferromagnetic (FM) materials Ni{sub 81}Fe{sub 19} (NiFe) and Co{sub 40}Fe{sub 40}B{sub 20} (CoFeB) in FM/Pt, FM/NM, and FM/NM/Pt systems with the non-magnetic (NM) materials Ru, Cr, Al, and MgO. Moreover, for NiFe layer systems, the influence of interface effects is studied by way of thickness dependent measurements of M{sub eff} and α{sub eff}. Additionally, spin pumping in NiFe/NM/Pt is investigated by means of inverse spin Hall effect (ISHE) measurements. We observe a large dependence of M{sub eff} and α{sub eff} of the NiFe films on the adjacent NM layer. While Cr and Al do not induce a large change in the magnetic properties, Ru, Pt, and MgO affect M{sub eff} and α{sub eff} in different degrees. In particular, NiFe/Ru and NiFe/Ru/Pt systems show a large perpendicular surface anisotropy and a significant enhancement of the damping. In contrast, the magnetic properties of CoFeB films do not have a large influence of the NM adjacent material and only CoFeB/Pt systems present an enhancement of α{sub eff}. However, this enhancement is much more pronounced in NiFe/Pt. By the introduction of the NM spacer material, this enhancement is reduced. Furthermore, a difference in symmetry between NiFe/NM/Pt and NiFe/NM systems in the output voltage signal from the ISHE measurements reveals the presence of spin pumping into the Pt layer in all-metallic NiFe/NM/Pt and NiFe/Pt systems.

  14. More on Ru Endemic Isotope Anomalies in Meteorites

    NASA Technical Reports Server (NTRS)

    Papanastassiou, D. A.; Chen, J. H.; Wasserburg, G. J.

    2004-01-01

    We reported last year on endemic isotope anomalies for Ru in iron meteorites, pallasites, ordinary chondrites, and on a whole-rock sample of Allende. We have extended the Ru measurements to more meteorites, to refractory Ca-Al-rich inclusions (CAI) from Allende, and to a whole rock sample of Murchison (CM2). In a companion abstract we report on new measurements for the Mo isotopes, in some of the same samples. There has been a renewed interest in searching for isotope anomalies in this nuclide region, as Ru and Mo include many isotopes from r-, s-, and p-process nucleosynhesis. Furthermore, the Ru and Mo p-process isotopes show atypically high abundances, which have been hard to explain through the standard nucleosynthetic processes. Effects are possible in Ru-98 and Ru-99 from Tc-98 (with a poorly known t(sub 1/2)=4.2 to 10Ma) and from Tc-99 (t(sub 1/2)=0.21Ma). Natural Tc is now extinct on Earth due to the short half-lives, but may have been present in the early solar system. Both radiogenic and general isotope anomalies are important in understanding the processes for the formation of the early solar system. The current emphasis on Ru and Mo is also the result of the development of Negative-ion Thermal Ionization Mass Spectrometry and of Multiple-Collector, Inductively-Coupled-Mass-Spectrometry. We have also developed specific chemical siparation techniques for Ru, which eliminated mass interference effects.

  15. Energy distribution monitoring of the T Tauri star RU LUPI

    NASA Astrophysics Data System (ADS)

    Giovannelli, F.; Vittone, A. A.; Errico, L.; Rossi, C.

    Simultaneous UV, optical and IR energy distributions of RU Lupi are presented for the period 1984-1986. The observations were obtained with the IUE satellite and optical and IR telescopes. Variations are detected in UV and optical regions. In addition, a large flare was observed on June 30, 1986. The results agree with those of Gahm et al. (1974) and suggest that the main cause of variability in RU Lupi is strong activity in the star's surface layers.

  16. More on Ru Endemic Isotope Anomalies in Meteorites

    NASA Technical Reports Server (NTRS)

    Papanastassiou, D. A.; Chen, J. H.; Wasserburg, G. J.

    2004-01-01

    We reported last year on endemic isotope anomalies for Ru in iron meteorites, pallasites, ordinary chondrites, and on a whole-rock sample of Allende. We have extended the Ru measurements to more meteorites, to refractory Ca-Al-rich inclusions (CAI) from Allende, and to a whole rock sample of Murchison (CM2). In a companion abstract we report on new measurements for the Mo isotopes, in some of the same samples. There has been a renewed interest in searching for isotope anomalies in this nuclide region, as Ru and Mo include many isotopes from r-, s-, and p-process nucleosynhesis. Furthermore, the Ru and Mo p-process isotopes show atypically high abundances, which have been hard to explain through the standard nucleosynthetic processes. Effects are possible in Ru-98 and Ru-99 from Tc-98 (with a poorly known t(sub 1/2)=4.2 to 10Ma) and from Tc-99 (t(sub 1/2)=0.21Ma). Natural Tc is now extinct on Earth due to the short half-lives, but may have been present in the early solar system. Both radiogenic and general isotope anomalies are important in understanding the processes for the formation of the early solar system. The current emphasis on Ru and Mo is also the result of the development of Negative-ion Thermal Ionization Mass Spectrometry and of Multiple-Collector, Inductively-Coupled-Mass-Spectrometry. We have also developed specific chemical siparation techniques for Ru, which eliminated mass interference effects.

  17. ARPES study of the Kitaev Candidate RuCl3

    NASA Astrophysics Data System (ADS)

    Zhou, Xiaoqing; Li, Haoxiang; Waugh, Justin; Parham, Stephen; Kim, Heung-Sik; Kee, Hae-Young; Sears, Jennifer; Kim, Young-June; Dessau, Daniel

    RuCl3 has been identified as a spin-orbital-assisted Mott insulator with possible Kitaev magnetic orders at low temperature by X-ray absorption, susceptibility, specific heat and Raman scattering. Here we report high resolution ARPES spectroscopy measurements on single crystal RuCl3, and compare it with DFT calculations with and without magnetic order. Furthermore, the possible spin-orbital-assisted Mott transition is investigated through electron doping

  18. Triggers on sulfide saturation in Fe-Ti oxide-bearing, mafic-ultramafic layered intrusions in the Tarim large igneous province, NW China

    NASA Astrophysics Data System (ADS)

    Cao, Jun; Wang, Christina Yan; Xu, Yi-Gang; Xing, Chang-Ming; Ren, Ming-Hao

    2016-08-01

    Three Fe-Ti oxide-bearing layered intrusions (Mazaertag, Wajilitag, and Piqiang) in the Tarim large igneous province (NW China) have been investigated for understanding the relationship of sulfide saturation, Platinum-group element (PGE) enrichment, and Fe-Ti oxide accumulation in layered intrusions. These mafic-ultramafic layered intrusions have low PGE concentrations (<0.4 ppb Os, <0.7 ppb Ir, <1 ppb Ru, <0.2 ppb Rh, <5 ppb Pt, and <8 ppb Pd) and elevated Cu/Pd (2.2 × 104 to 3.3 × 106). The low PGE concentrations of the rocks are mainly attributed to PGE-depleted, parental magma that was produced by low degrees of partial melting of the mantle. The least contaminated rocks of the Mazaertag and Wajilitag intrusions have slightly enriched Os isotopic compositions with γOs(t = 280 Ma) values ranging from +13 to +23, indicating that the primitive magma may have been generated from a convecting mantle, without appreciable input of lithospheric mantle. The Mazaertag and Wajilitag intrusions have near-chondritic γOs(t) values (+13 to +60) against restricted ɛ Nd(t) values (-0.4 to +2.8), indicating insignificant crustal contamination. Rocks of the Piqiang intrusion have relatively low ɛ Nd(t) values of -3.1 to +1.0, consistent with ˜15 to 25 % assimilation of the upper crust. The rocks of the Mazaertag and Wajilitag intrusions have positive correlation of PGE and S, pointing to the control of PGE by sulfide. Poor correlation of PGE and S for the Piqiang intrusion is attributed to the involvement of multiple sulfide-stage liquids with different PGE compositions or sulfide-oxide reequilibration on cooling. These three layered intrusions have little potential of reef-type PGE mineralization. Four criteria are summarized in this study to help discriminate between PGE-mineralized and PGE-unmineralized mafic-ultramafic intrusions.

  19. Enhancement of Solar Fuel Production Schemes by Using a Ru,Rh,Ru Supramolecular Photocatalyst Containing Hydroxide Labile Ligands.

    PubMed

    Rogers, Hannah Mallalieu; Arachchige, Shamindri M; Brewer, Karen J

    2015-11-16

    Polyazine-bridged Ru(II)Rh(III)Ru(II) complexes with two halide ligands, Cl(-) or Br(-), bound to the catalytically active Rh center are efficient single-component photocatalysts for H2O reduction to H2 fuel, with the coordination environment on Rh impacting photocatalysis. Herein reported is a new, halide-free Ru(II)Rh(III)Ru(II) photocatalyst with OH(-) ligands bound to Rh, further enhancing the photocatalytic reactivity of the structural motif. H2 production experiments using the photocatalyst bearing OH(-) ligands at Rh relative to the analogues bearing halides at Rh in solvents of varying polarity (DMF, CH3CN, and H2O) suggest that ion pairing with halides deactivates photocatalyst function, representing an exciting phenomenon to exploit in the development of catalysts for solar H2 production schemes.

  20. Enhanced conductivity and metal-insulator transition of ultrathin CaRuO3 in superlattices

    NASA Astrophysics Data System (ADS)

    Xu, Haoran; Chen, Binbin; Jin, Feng; Guo, Zhuang; Gao, Guanyin; Chen, Feng; Wu, Wenbin

    2016-12-01

    Transport characteristics of CaRuO3(CRO)/SmFeO3(SFO) superlattices are studied as a function of the thickness of CRO (0.8 nm ≤ t CRO ≤ 3.2 nm). An abrupt enhancement of the conductivity is observed on superlattices, although ultrathin CRO film show a very high resistance and SFO single layer is insulating. The superlattices with t CRO between 2.0 and 3.2 nm retain a metallic state. As t CRO decreases to 1.6 nm or even thinner in superlattices, the metallic state turns to insulating state. The metal-insulator transition could be attributed to the comparable scale for the disorder length and the electron travel distance at small t CRO value, which causes a change from weak localization to strong localization.

  1. Photoactivation of Anticancer Ru Complexes in Deep Tissue: How Deep Can We Go?

    PubMed

    Sun, Wen; Thiramanas, Raweewan; Slep, Leonardo D; Zeng, Xiaolong; Mailänder, Volker; Wu, Si

    2017-08-10

    Activation of anticancer therapeutics such as ruthenium (Ru) complexes is currently a topic of intense investigation. The success of phototherapy relies on photoactivation of therapeutics after the light passes through skin and tissue. In this paper, the photoactivation of anticancer Ru complexes with 671-nm red light through tissue of different thicknesses was studied. Four photoactivatable Ru complexes with different absorption wavelengths were synthesized. Two of them (Ru3 and Ru4) were responsive to wavelengths in the "therapeutic window" (650-900 nm) and could be activated using 671-nm red light after passing through tissue up to 16-mm-thick. The other two (Ru1 and Ru2) could not be activated using red light. Additionally, activated Ru4 caused inhibition of cancer cells. These results suggest that photoactivatable Ru complexes are promising for applications in deep-tissue phototherapy. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Enhancement of perpendicular magnetic anisotropy and coercivity in ultrathin Ru/Co/Ru films through the buffer layer engineering

    NASA Astrophysics Data System (ADS)

    Kolesnikov, Alexander G.; Stebliy, Maxim E.; Ognev, Alexey V.; Samardak, Alexander S.; Fedorets, Aleksandr N.; Plotnikov, Vladimir S.; Han, Xiufeng; Chebotkevich, Ludmila A.

    2016-10-01

    We present results on a study of the interplay between microstructure and the magnetic properties of ultrathin Ru/Co/Ru films with perpendicular magnetic anisotropy (PMA). To induce PMA in the Co layer, we experimentally determined thicknesses of the buffer and capping layers of Ru. The maximum value of PMA was observed for the Co thickness of 0.9 nm with the 3 nm thick capping layer. The effective anisotropy field (H eff) and coercive force (H c) of the Co layer are very sensitive to the Ru buffer layer thickness (t b). The values of H eff and H c increase approximately by two and ten times, correspondingly, when t b changes from 6 to 20 nm, owing to an increase in volume fraction of the crystalline phase as a result of the grains’ growth. PMA is found to be mainly enhanced by elastic strains induced by the lattice mismatch on the Ru/Co and Co/Ru interfaces, leading to the deformation of the Co lattice. The surface impact is determined to be less than 10% of the magneto-elastic contribution to the effective anisotropy. Observation of the magnetic domain structure by means of polar Kerr microscopy reveals that out-of-plane magnetization reversal occurs through the nucleation, growth, and annihilation of domains, where the average size drastically rises with the increasing t b.

  3. Atomic structure of an ultrathin Fe-silicate film grown on a metal: a monolayer of clay?

    PubMed

    Włodarczyk, Radosław; Sauer, Joachim; Yu, Xin; Boscoboinik, Jorge Anibal; Yang, Bing; Shaikhutdinov, Shamil; Freund, Hans-Joachim

    2013-12-26

    Ultrathin Fe-doped silicate films were prepared on a Ru(0001) surface and, as a function of the Fe/Si ratio, structurally characterized by low-energy electron diffraction, X-ray photoelectron spectroscopy, infrared reflection-absorption spectroscopy, and scanning tunneling microscopy. Density functional theory (DFT) was used to identify the atomic structure. The results show that uniform substitution of Si by Fe in the silicate bilayer frame is thermodynamically unfavorable: the film segregates into a pure silicate and an Fe-silicate phase. The DFT calculations reveal that the Fe-silicate film with an Fe/Si = 1:1 ratio consists of a monolayer of [SiO4] tetrahedra on top of an iron oxide monolayer. As such, it closely resembles the structure of the clay mineral nontronite, a representative of the Fe-rich smectites. Furthermore, the DFT calculations predict formation of bridging Fe-O-Ru bonds between the Fe-silicate film and the Ru substrate accompanied by charge transfer from the metal substrate to the film, so that iron is in the oxidation state +III as in nontronite.

  4. Opposite signs of voltage-induced perpendicular magnetic anisotropy change in CoFeB|MgO junctions with different underlayers

    NASA Astrophysics Data System (ADS)

    Shiota, Yoichi; Bonell, Frédéric; Miwa, Shinji; Mizuochi, Norikazu; Shinjo, Teruya; Suzuki, Yoshishige

    2013-08-01

    We report a voltage-induced perpendicular magnetic anisotropy (PMA) change in sputter-deposited Ta|CoFeB|MgO and Ru|CoFeB|MgO junctions. The PMA change is quantitatively evaluated by the field dependence of the tunneling magnetoresistance for various bias voltages. We find that both the sign and amplitude of the voltage effect depend on the underlayer, Ta or Ru, below the CoFeB layer. The rf voltage-induced ferromagnetic resonance spectra also support the underlayer-material-dependent direction of the voltage torque. The present study shows that the underlayer is one of the key parameters for controlling the voltage effect.

  5. A new mutation of mouse ruby-eye 2, ru2(d)/Hps5(ru2-d) inhibits eumelanin synthesis but stimulates pheomelanin synthesis in melanocytes.

    PubMed

    Hirobe, Tomohisa; Wakamatsu, Kazumasa; Ito, Shosuke

    2012-10-01

    We previously demonstrated that a novel mutation, characterized by light-colored coats and ruby eyes, which occurred spontaneously in mice in our laboratory, exhibited deletion in the Hps5 gene (ru2(d)/Hps5(ru2-d)). To clarify the mechanism of this hypopigmentation, the characteristics of the neonatal development of ru2(d)/ru2(d) melanocytes were investigated in detail with special reference to those of +/+ melanocytes. In ru2(d)/ru2(d) mice, there were fewer epidermal melanocytes than in +/+ mice, whereas there was no difference in numbers of epidermal melanoblasts in +/+ and ru2(d)/ru2(d)mice, both in dorsal and ventral skin. Epidermal melanocytes with increased dopa-melanin deposition and dendritogenesis were greatly increased by injecting L-Tyr subcutaneously into newborn ru2(d)/ru2(d) mice. The eumelanin content in the epidermis and dermis in postnatal ru2(d)/ru2(d) mice was much lower than in +/+ mice, whereas similar pheomelanin content was observed 5.5 or 7.5 days after birth both in dorsal and ventral skins. Moreover, the eumelanin content in the dorsal and ventral hairs in 5-week-old ru2(d)/ru2(d) mice was much lower than in +/+ mice, whereas pheomelanin content was two to four times greater than in +/+ mice. These results suggest that the ru2(d) allele suppresses the differentiation of melanocytes through the inhibition of eumelanin synthesis, but stimulates pheomelanin synthesis in melanocytes.

  6. Critical analysis on nanostructured CoFeB synthetic orthogonal ferrimagnet

    SciTech Connect

    Chen, Y. S.; Lin, J. G.; Cheng, Chih-Wei; Chern, G.

    2014-09-21

    Critical analysis on the magnetic properties of synthetic ferrimagnet (SyF), Ta/MgO/CoFeB/Ru/CoFeB/MgO/Ta, is demonstrated via both static and dynamic techniques. With the Ru thickness being 2.3 nm, the coupling between two CoFeB layers becomes orthogonal, which can be used for spin-transfer-torque nano-oscillator (STNO). The fitting of angular dependent ferromagnetic resonance (FMR) allows the precise determination of magnetic anisotropy of each CoFeB layer, the relative magnetizations and the exchange field near the frequency of STNO applications. In addition, the mechanism of resonance broadening at out-of-plane direction is identified to be magnetic inhomogeneity by fitting the angular dependent linewidth of FMR spectra, which provides indispensable information for the future design of STNO devices.

  7. Evolution of magnetism in single-crystal Ca2Ru1-xIrxO4(0≤x≤0.65)

    DOE PAGES

    Yuan, S. J.; Terzic, J.; Wang, J. C.; ...

    2015-07-24

    In this paper, we report structural, magnetic, transport, and thermal properties of single-crystal Ca2Ru1-xIrxO4(0≤x≤0.65). Ca2RuO4 is a structurally driven Mott insulator with a metal-insulator transition at TMI=357K, which is well separated from antiferromagnetic order at TN=110K. Substitution of a 5d element, Ir, for Ru enhances spin-orbit coupling and locking between the structural distortions and magnetic moment canting. Ir doping intensifies the distortion or rotation of Ru/IrO6 octahedra and induces weak ferromagnetic behavior along the c axis. In particular, Ir doping suppresses TN but concurrently causes an additional magnetic ordering TN2 at a higher temperature up to 210 K for x=0.65.more » The effect of Ir doping sharply contrasts with that of 3d-element doping such as Cr, Mn, and Fe, which suppresses TN and induces unusual negative volume thermal expansion. Finally, the stark difference between 3d- and 5d-element doping underlines a strong magnetoelastic coupling inherent in the Ir-rich oxides.« less

  8. Impact of rare earth magnetic moment on ordering of Ru in Sr 2RuREO 6 (RE=Gd and Eu)

    NASA Astrophysics Data System (ADS)

    Awana, V. P. S.; Tripaathi, Rahul; Sharma, V. K.; Kishan, H.; Takayama-Muromachi, E.; Felner, I.

    2007-05-01

    We report the synthesis and magnetization of Sr 2RuREO 6 (RE/Ru-211O 6) with RE=Gd and Eu. Both Gd and Eu/Ru-211O 6 are formed in distorted perovskite-type single phase with monoclinic P2 1/n space group. Magnetization ( M/ T) measurements exhibited antiferromagnetic ordering of Ru moments for both Gd and Eu compounds at a TN of around 30 K due to super-exchange Ru-O-O-Ru interaction. Interestingly enough, detailed M/ H plots of Gd/Ru-211O 6 exhibited the development of a ferromagnetic (FM) component at 20 K. Furthermore, below 10 K, the FM component disappears, and rather spin freezing field ( HSF) of around 1000 Oe is seen at 5 K. In case of Eu/Ru-211O 6, the basic antiferromagnetic ordering of Ru moments remains invariantly down to 5 K, and the appearance of the FM component is not seen. It seems that the high magnetic moment of 8 μB for Gd 3+ influences the anti ferromagnetic (AFM) ordering of Ru in case of Gd/Ru-211O 6.

  9. Erlichmanite /OsS sub 2/, a new mineral.

    NASA Technical Reports Server (NTRS)

    Snetsinger, K. G.

    1971-01-01

    Natural osmium disulfide (termed erlichmanite) was recognized in two occurrences on the basis of electron probe and X-ray data. One occurrence is in grains of platinum-metal sand from California, the other in a platinum-metal nugget from Western Ethiopian laterites. California erlichmanite has Os 68.0, Ir 2.6, Rh 3.8, Ru 0.4, Pd 0.5, and S 25.2, summation of 100.5 wt. %, the number of metal atoms being 1.06 on the basis of 2.00 sulfurs. Ethiopian material has higher Rh and Ir and lower Os. Both are optically isotropic. Spotty X-ray reflections from a 15-micron particle of California erlichmanite give rise to d spacing which match those of synthetic cubic osmium disulfide. Erlichmanite is defined as a cubic disulfide in which osmium is the most abundant metal atom.

  10. Re-Os Systematics and HSE Distribution in Metal from Ochansk (H4) Chondrite

    NASA Technical Reports Server (NTRS)

    Smoliar, M. I.; Horan, M. F.; Alexander, C. M. OD.; Walker, R. J.

    2003-01-01

    Previous studies of the Re-Os systematics of chondrites have documented considerable variation in the Re/Os ratios of whole rock samples. For some whole rock chondrites, Re-Os systematics display large deviations from the primitive isochron that are considerably larger than deviations in other isotope systems. Possible interpretation of these facts is that the Re-Os system in chondrites is particularly sensitive to post-formation alteration processes, thus providing a useful tool to examine such processes. Significant variations that have been detected in highly siderophile element (HSE) patterns for ordinary chondrites support this conclusion. We report Re-Os isotope data for metal separates from the Ochansk H4 chondrite coupled with abundance data for Ru, Pd, Ir, and Pt, determined in the same samples by isotope dilution. We chose this meteorite mainly because it is an observed fall with minimal signs of weathering, and its low metamorphic grade (H4) and shock stage (S3).

  11. Electronic structure and spectroscopy of [Ru(tpy)(2)](2+), [Ru(tpy)(bpy)(H(2)O)](2+), and [Ru(tpy)(bpy)(Cl)](+).

    PubMed

    Jakubikova, Elena; Chen, Weizhong; Dattelbaum, Dana M; Rein, Francisca N; Rocha, Reginaldo C; Martin, Richard L; Batista, Enrique R

    2009-11-16

    We use a combined, theoretical and experimental, approach to investigate the spectroscopic properties and electronic structure of three ruthenium polypyridyl complexes, [Ru(tpy)(2)](2+), [Ru(tpy)(bpy)(H(2)O)](2+), and [Ru(tpy)(bpy)(Cl)](+) (tpy = 2,2':6',2''-terpyridine and bpy = 2,2'-bipyridine) in acetone, dichloromethane, and water. All three complexes display strong absorption bands in the visible region corresponding to a metal-to-ligand-charge-transfer (MLCT) transition, as well as the emission bands arising from the lowest lying (3)MLCT state. [Ru(tpy)(bpy)(Cl)](+) undergoes substitution of the Cl(-) ligand by H(2)O in the presence of water. Density functional theory (DFT) calculations demonstrate that the triplet potential energy surfaces of these molecules are complicated, with several metal-centered ((3)MC) and (3)MLCT states very close in energy. Solvent effects are included in the calculations via the polarizable continuum model as well as explicitly, and it is shown that they are critical for proper characterization of the triplet excited states of these complexes.

  12. AuRu/AC as an effective catalyst for hydrogenation reactions

    SciTech Connect

    Villa, Alberto; Chan-Thaw, Carine E.; Campisi, Sebastiano; Bianchi, Claudia L.; Wang, Di; Kotula, Paul G.; Kübel, Christian; Prati, Laura

    2015-03-23

    AuRu bimetallic catalysts have been prepared by sequential deposition of Au on Ru or vice versa obtaining different nanostructures: when Ru has been deposited on Au, a AucoreRushell has been observed, whereas the deposition of Au on Ru leads to a bimetallic phase with Ru enrichment on the surface. In the latter case, the unexpected Ru enrichment could be attributed to the weak adhesion of Ru on the carbon support, thus allowing Ru particles to diffuse on Au particles. Both structures result very active in catalysing the liquid phase hydrogenolysis of glycerol and levulinic acid but the activity, the selectivity and the stability depend on the structure of the bimetallic nanoparticles. Ru@Au/AC core–shell structure mostly behaved as the monometallic Ru, whereas the presence of bimetallic AuRu phase in Au@Ru/AC provides a great beneficial effect on both activity and stability.

  13. Tetra- and Heptametallic Ru(II),Rh(III) Supramolecular Hydrogen Production Photocatalysts

    DOE PAGES

    Manbeck, Gerald F.; Fujita, Etsuko; Brewer, Karen J.

    2017-06-01

    Supramolecular mixed metal complexes combining the trimetallic chromophore [{(bpy)2Ru(dpp)}2Ru(dpp)]6+ (Ru3) with [Rh(bpy)Cl2]+ or [RhCl2]+ catalytic fragments to form [{(bpy)2Ru(dpp)}2Ru(dpp)RhCl2(bpy)](PF6)7 (Ru3Rh) or [{(bpy)2Ru(dpp)}2Ru(dpp)]2RhCl2(PF6)13 (Ru3RhRu3) (bpy = 2,2'-bipyridine and dpp = 2,3-bis(2-pyridyl)pyrazine) catalyze the photochemical reduction of protons to H2. This first example of a heptametallic Ru,Rh photocatalyst produces over 300 turnovers of H2 upon photolysis of a solution of acetonitrile, water, triflic acid, and N,N-dimethylaniline as an electron donor. Conversely, the tetrametallic Ru3Rh produces only 40 turnovers of H2 due to differences in the excited state properties and nature of the catalysts upon reduction as ascertained from electrochemical data, transient absorptionmore » spectroscopy, and flash-quench experiments. And while the lowest unoccupied molecular orbital of Ru3Rh is localized on a bridging ligand, it is Rh-centered in Ru3RhRu3 facilitating electron collection at Rh in the excited state and reductively quenched state. The Ru → Rh charge separated state of Ru3RhRu3 is endergonic with respect to the emissive Ru → dpp 3MLCT excited and cannot be formed by static electron transfer quenching of the 3MLCT state. Instead, a mechanism of subnanosecond charge separation from high lying states is proposed. Multiple reductions of Ru3 and Ru3Rh using sodium amalgam were carried out to compare UV–vis absorption spectra of reduced species and to evaluate the stability of highly reduced complexes. Furthermore, the Ru3 and Ru3Rh can be reduced by 10 and 13 electrons, respectively, to final states with all bridging ligands doubly reduced and all bpy ligands singly reduced.« less

  14. Triggering the generation of an iron(IV)-oxo compound and its reactivity toward sulfides by Ru(II) photocatalysis.

    PubMed

    Company, Anna; Sabenya, Gerard; González-Béjar, María; Gómez, Laura; Clémancey, Martin; Blondin, Geneviève; Jasniewski, Andrew J; Puri, Mayank; Browne, Wesley R; Latour, Jean-Marc; Que, Lawrence; Costas, Miquel; Pérez-Prieto, Julia; Lloret-Fillol, Julio

    2014-03-26

    The preparation of [Fe(IV)(O)(MePy2tacn)](2+) (2, MePy2tacn = N-methyl-N,N-bis(2-picolyl)-1,4,7-triazacyclononane) by reaction of [Fe(II)(MePy2tacn)(solvent)](2+) (1) and PhIO in CH3CN and its full characterization are described. This compound can also be prepared photochemically from its iron(II) precursor by irradiation at 447 nm in the presence of catalytic amounts of [Ru(II)(bpy)3](2+) as photosensitizer and a sacrificial electron acceptor (Na2S2O8). Remarkably, the rate of the reaction of the photochemically prepared compound 2 toward sulfides increases 150-fold under irradiation, and 2 is partially regenerated after the sulfide has been consumed; hence, the process can be repeated several times. The origin of this rate enhancement has been established by studying the reaction of chemically generated compound 2 with sulfides under different conditions, which demonstrated that both light and [Ru(II)(bpy)3](2+) are necessary for the observed increase in the reaction rate. A combination of nanosecond time-resolved absorption spectroscopy with laser pulse excitation and other mechanistic studies has led to the conclusion that an electron transfer mechanism is the most plausible explanation for the observed rate enhancement. According to this mechanism, the in-situ-generated [Ru(III)(bpy)3](3+) oxidizes the sulfide to form the corresponding radical cation, which is eventually oxidized by 2 to the corresponding sulfoxide.

  15. Triggering the Generation of an Iron(IV)-Oxo Compound and Its Reactivity toward Sulfides by RuII Photocatalysis

    PubMed Central

    2015-01-01

    The preparation of [FeIV(O)(MePy2tacn)]2+ (2, MePy2tacn = N-methyl-N,N-bis(2-picolyl)-1,4,7-triazacyclononane) by reaction of [FeII(MePy2tacn)(solvent)]2+ (1) and PhIO in CH3CN and its full characterization are described. This compound can also be prepared photochemically from its iron(II) precursor by irradiation at 447 nm in the presence of catalytic amounts of [RuII(bpy)3]2+ as photosensitizer and a sacrificial electron acceptor (Na2S2O8). Remarkably, the rate of the reaction of the photochemically prepared compound 2 toward sulfides increases 150-fold under irradiation, and 2 is partially regenerated after the sulfide has been consumed; hence, the process can be repeated several times. The origin of this rate enhancement has been established by studying the reaction of chemically generated compound 2 with sulfides under different conditions, which demonstrated that both light and [RuII(bpy)3]2+ are necessary for the observed increase in the reaction rate. A combination of nanosecond time-resolved absorption spectroscopy with laser pulse excitation and other mechanistic studies has led to the conclusion that an electron transfer mechanism is the most plausible explanation for the observed rate enhancement. According to this mechanism, the in-situ-generated [RuIII(bpy)3]3+ oxidizes the sulfide to form the corresponding radical cation, which is eventually oxidized by 2 to the corresponding sulfoxide. PMID:24568126

  16. Biochemical characterization of predicted Precambrian RuBisCO

    PubMed Central

    Shih, Patrick M.; Occhialini, Alessandro; Cameron, Jeffrey C.; Andralojc, P John; Parry, Martin A. J.; Kerfeld, Cheryl A.

    2016-01-01

    The antiquity and global abundance of the enzyme, RuBisCO, attests to the crucial and longstanding role it has played in the biogeochemical cycles of Earth over billions of years. The counterproductive oxygenase activity of RuBisCO has persisted over billions of years of evolution, despite its competition with the carboxylase activity necessary for carbon fixation, yet hypotheses regarding the selective pressures governing RuBisCO evolution have been limited to speculation. Here we report the resurrection and biochemical characterization of ancestral RuBisCOs, dating back to over one billion years ago (Gyr ago). Our findings provide an ancient point of reference revealing divergent evolutionary paths taken by eukaryotic homologues towards improved specificity for CO2, versus the evolutionary emphasis on increased rates of carboxylation observed in bacterial homologues. Consistent with these distinctions, in vivo analysis reveals the propensity of ancestral RuBisCO to be encapsulated into modern-day carboxysomes, bacterial organelles central to the cyanobacterial CO2 concentrating mechanism. PMID:26790750

  17. Biochemical characterization of predicted Precambrian RuBisCO.

    PubMed

    Shih, Patrick M; Occhialini, Alessandro; Cameron, Jeffrey C; Andralojc, P John; Parry, Martin A J; Kerfeld, Cheryl A

    2016-01-21

    The antiquity and global abundance of the enzyme, RuBisCO, attests to the crucial and longstanding role it has played in the biogeochemical cycles of Earth over billions of years. The counterproductive oxygenase activity of RuBisCO has persisted over billions of years of evolution, despite its competition with the carboxylase activity necessary for carbon fixation, yet hypotheses regarding the selective pressures governing RuBisCO evolution have been limited to speculation. Here we report the resurrection and biochemical characterization of ancestral RuBisCOs, dating back to over one billion years ago (Gyr ago). Our findings provide an ancient point of reference revealing divergent evolutionary paths taken by eukaryotic homologues towards improved specificity for CO2, versus the evolutionary emphasis on increased rates of carboxylation observed in bacterial homologues. Consistent with these distinctions, in vivo analysis reveals the propensity of ancestral RuBisCO to be encapsulated into modern-day carboxysomes, bacterial organelles central to the cyanobacterial CO2 concentrating mechanism.

  18. Diastereomeric bactericidal effect of Ru(phenanthroline)2dipyridophenazine

    PubMed Central

    Bergentall, Mattias; Tremaroli, Valentina; Lincoln, Per

    2016-01-01

    ABSTRACT Metal susceptibility assays and spot plating were used to investigate the antimicrobial activity of enantiopure [Ru(phen)2dppz]2+ (phen =1,10‐phenanthroline and dppz = dipyrido[3,2‐a:2´,3´‐c]phenazine) and [μ‐bidppz(phen)4Ru2]4 + (bidppz =11,11´‐bis(dipyrido[3,2‐a:2´,3´‐c]phenazinyl)), on Gram‐negative Escherichia coli and Gram‐positive Bacillus subtilis as bacterial models. The minimum inhibitory concentrations (MIC) and minimum bactericidal concentrations (MBC) were determined for both complexes: while [μ‐bidppz(phen)4Ru2]4 + only showed a bactericidal effect at the highest concentrations tested, the antimicrobial activity of [Ru(phen)2dppz]2+ against B. subtilis was comparable to that of tetracyline. In addition, the Δ‐enantiomer of [Ru(phen)2dppz]2+ showed a 2‐fold higher bacteriostatic and bactericidal effect compared to the Λ‐enantiomer. This was in accordance with the enantiomers relative binding affinity for DNA, thus strongly indicating DNA binding as the mode of action. PMID:27791316

  19. LiLa 6I 12Os, a substitutional derivative of rhombohedral La(La 6I 12Os)

    NASA Astrophysics Data System (ADS)

    Jensen, Elizabeth A.; Corbett, John D.

    2004-12-01

    The series of quaternary rare-earth-metal halide cluster compounds ALa 6I 12Z with transition metal interstitials Z and alkali or alkaline-earth metal cations A has been expanded to include A=Li. The compounds synthesized by high-temperature solid-state techniques for Z=Os, Ir, Pt, Ru are isotypic with rhombohedral R7X12Z ( R3¯, Z=3). The refined single X-ray crystal structure of (Li 0.967La 0.033)La 6I 12Os is reported, along with supportive results from a Rietveld analysis of neutron powder diffraction from a different sample, 7Li MAS-NMR, and electronic resistivity and magnetic susceptibility measurements. The samples show continuous Li 1-xLa x cation compositions and are generally semiconductors, but their complex paramagnetic properties are not those of simple spin-only systems.

  20. Electrical field modification of dynamic magnetic properties in FeCo films grown onto [Pb(Mg1/3Nb2/3)O3]0.68-[PbTiO3]0.32(011) piezoelectric substrates with Ru underlayers

    NASA Astrophysics Data System (ADS)

    Phuoc, Nguyen N.; Ong, C. K.

    2015-06-01

    A detailed investigation of electrical tuning of dynamic magnetization of the FeCo magnetic thin film grown onto a PMN-PT piezoelectric substrate was carried out based on the measurement of the zero-field permeability spectra under the application of a voltage across the thickness of the substrate. The resonance frequency can be tuned from 2.95 GHz to 5.9 GHz upon the application of a voltage on the sample in unpoled state. After poling, the resonance frequency of the sample can be tuned in the range from 4.75 GHz to 5.9 GHz. In addition, it was found that after poling the peak of the permeability spectra is broadened compared to before poling, which can be tentatively attributed to the magnetic anisotropy dispersion arising from the presence of the stress-induced anisotropy. The result is also discussed in conjunction with the angular measurement of the static hysteresis loops of the sample before and after poling.

  1. Photoinduced reduction of the medial FeS center in the hydrogenase small subunit HupS from Nostoc punctiforme.

    PubMed

    Raleiras, Patrícia; Hammarström, Leif; Lindblad, Peter; Styring, Stenbjörn; Magnuson, Ann

    2015-07-01

    The small subunit from the NiFe uptake hydrogenase, HupSL, in the cyanobacterium Nostoc punctiforme ATCC 29133, has been isolated in the absence of the large subunit (P. Raleiras, P. Kellers, P. Lindblad, S. Styring, A. Magnuson, J. Biol. Chem. 288 (2013) 18,345-18,352). Here, we have used flash photolysis to reduce the iron-sulfur clusters in the isolated small subunit, HupS. We used ascorbate as electron donor to the photogenerated excited state of Ru(II)-trisbipyridine (Ru(bpy)3), to generate Ru(I)(bpy)3 as reducing agent. Our results show that the isolated small subunit can be reduced by the Ru(I)(bpy)3 generated through flash photolysis. Copyright © 2015 Elsevier Inc. All rights reserved.

  2. Heteroleptic neutral Ru(II) complexes based photodiodes

    NASA Astrophysics Data System (ADS)

    Elgazzar, Elsayed; Dayan, O.; Serbetci, Z.; Dere, A.; Al-Sehemi, Abdullah G.; Al-Ghamdi, Ahmed A.; El-Tantawy, Farid; Farooq, W. A.; Yakuphanoglu, F.

    2017-07-01

    The two complexes Ru (II) containing 2,6-bis(benzimidazol-2-yl)pyridine and 2-pyridine and 2-quinoline carboxylates were synthesized to fabricate organic photodiodes. The electrical properties of Au / Ru (II) complex (I) / n - Si / Al and Au / Ru (II) complex (II) / n - Si / Al diodes were investigated by current-voltage and capacitance-voltage measurements. The fabricated devices give a high rectification behavior with rectification ratio of 2.4 × 104 -2.1 × 103 at ± 4 V. The diodes exhibited a high photoconductivity based on trap levels within band gap. The series resistance and barrier height were calculated from (C - V) measurements and compared to other of (I - V) . The obtained results indicate that the prepared photodiodes can be used as photosensor for optoelectronic applications.

  3. Enhanced thermoelectric power and electronic correlations in RuSe₂

    SciTech Connect

    Wang, Kefeng; Wang, Aifeng; Tomic, A.; Wang, Limin; Abeykoon, A. M. Milinda; Dooryhee, E.; Billinge, S. J.L.; Petrovic, C.

    2015-03-03

    We report the electronic structure, electric and thermal transport properties of Ru₁₋xIrxSe₂ (x ≤ 0.2). RuSe₂ is a semiconductor that crystallizes in a cubic pyrite unit cell. The Seebeck coefficient of RuSe₂ exceeds -200 µV/K around 730 K. Ir substitution results in the suppression of the resistivity and the Seebeck coefficient, suggesting the removal of the peaks in density of states near the Fermi level. Ru₀.₈Ir₀.₂Se₂ shows a semiconductor-metal crossover at about 30 K. The magnetic field restores the semiconducting behavior. Our results indicate the importance of the electronic correlations in enhanced thermoelectricity of RuSb₂.

  4. Enhanced thermoelectric power and electronic correlations in RuSe₂

    DOE PAGES

    Wang, Kefeng; Wang, Aifeng; Tomic, A.; ...

    2015-03-03

    We report the electronic structure, electric and thermal transport properties of Ru₁₋xIrxSe₂ (x ≤ 0.2). RuSe₂ is a semiconductor that crystallizes in a cubic pyrite unit cell. The Seebeck coefficient of RuSe₂ exceeds -200 µV/K around 730 K. Ir substitution results in the suppression of the resistivity and the Seebeck coefficient, suggesting the removal of the peaks in density of states near the Fermi level. Ru₀.₈Ir₀.₂Se₂ shows a semiconductor-metal crossover at about 30 K. The magnetic field restores the semiconducting behavior. Our results indicate the importance of the electronic correlations in enhanced thermoelectricity of RuSb₂.

  5. Two Dimensional Antiferromagnetic Chern Insulator: NiRuCl6.

    PubMed

    Zhou, P; Sun, C Q; Sun, L Z

    2016-10-12

    Density functional theory (DFT) and Berry curvature calculations show that quantum anomalous Hall effect (QAHE) can be realized in two-dimensional(2D) antiferromagnetic (AFM) NiRuCl6. The results indicate that NiRuCl6 behaves as an AFM Chern insulator and its spin-polarized electronic structure and strong spin-orbit coupling (SOC) are responsible for the QAHE. By tuning SOC, we found that the topological property of NiRuCl6 arises from its energy band inversion. Considering the compatibility between the AFM and insulators, AFM Chern insulator provides a new way to archive high temperature QAHE in experiments due to its different magnetic coupling mechanism from that of ferromagnetic (FM) Chern insulator.

  6. Synthesis of RuAl by reactive powder processing

    NASA Astrophysics Data System (ADS)

    Wolff, I. M.

    1996-11-01

    The unusual combination of high-temperature strength and room-temperature ductility makes compounds based on RuAl attractive for structural applications. Difficulties inherent in the manufacture of RuAl by melt processing can be circumvented by powder metallurgical (PM) techniques. The present work shows that reactive hot isostatic pressing (RHIPing) based on the self-propagating exothermic reaction of the constituent powders allows homogeneous, high-density material to be made. Controlled process parameters include green density, prior degassing, the powder size distribution, heating rate, pressure, and homogenizing schedule. The nature of the reaction products was found to be determined primarily by the applied pressure during combustion. While concurrent pressure is required to ensure densification, pressurization leads to the formation of a host of nonequilibrium phases that necessitate extended homogenizing practices to drive the reaction to completion. The readily assimilable process parameters allow the production of structural components based on RuAl to be envisaged.

  7. CO adsorption on a silica bilayer supported on Ru(0001)

    NASA Astrophysics Data System (ADS)

    Schlexer, Philomena; Pacchioni, Gianfranco; Włodarczyk, Radosław; Sauer, Joachim

    2016-06-01

    Silica bilayers are built up of two layers of corner sharing SiO4-tetrahedra and constitute an inert ultra-thin membrane supported on the Ru(0001) surface. We have investigated the adsorption of CO on that system using DFT with inclusion of dispersion corrections. The molecules adsorb at the interface between the SiO2 film and Ru(0001) surface. The estimated barrier for diffusion of CO through the silica bilayer is around 0.5 eV. The CO bond length, the C-O stretching frequency and the silica-ruthenium distance depend strongly on the CO coverage. The band observed at 2051 cm- 1 in previous experiments can be assigned to a CO coverage of around 0.5 ML on Ru(0001), with the silica bilayer floating above the CO molecules.

  8. Complex of transferrin with ruthenium for medical applications. [Ru 97, Ru 103

    DOEpatents

    Richards, P.; Srivastava, S.C.; Meinken, G.E.

    1980-11-03

    A novel Ruthenium-transferrin complex, prepared by reacting iron-free human transferrin dissolved in a sodium acetate solution at pH 7 with ruthenium by heating at about 40/sup 0/C for about 2 hours, and purifying said complex by means of gel chromatography with pH 7 sodium acetate as eluent. The mono- or di-metal complex produced can be used in nuclear medicine in the diagnosis and/or treatment of tumors and abscesses. Comparitive results with Ga-67-citrate, which is the most widely used tumor-localizing agent in nuclear medicine, indicate increased sensitivity of detection and greater tumor uptake with the Ru-transferrin complex.

  9. Narrow band gap and enhanced thermoelectricity in FeSb2.

    PubMed

    Sun, Peijie; Oeschler, Niels; Johnsen, Simon; Iversen, Bo B; Steglich, Frank

    2010-01-28

    FeSb(2) was recently identified as a narrow-gap semiconductor with indications of strong electron-electron correlations. In this manuscript, we report on systematic thermoelectric investigation of a number of FeSb(2) single crystals with varying carrier concentrations, together with two isoelectronically substituted FeSb(2-x)As(x) samples (x = 0.01 and 0.03) and two reference compounds FeAs(2) and RuSb(2). Typical behaviour associated with narrow bands and narrow gaps is only confirmed for the FeSb(2) and the FeSb(2-x)As(x) samples. The maximum absolute thermopower of FeSb(2) spans from 10 to 45 mV/K at around 10 K, greatly exceeding that of both FeAs(2) and RuSb(2). The relation between the carrier concentration and the maximum thermopower value is in approximate agreement with theoretical predictions of the electron-diffusion contribution which, however, requires an enhancement factor larger than 30. The isoelectronic substitution leads to a reduction of the thermal conductivity, but the charge-carrier mobility is also largely reduced due to doping-induced crystallographic defects or impurities. In combination with the high charge-carrier mobility and the enhanced thermoelectricity, FeSb(2) represents a promising candidate for thermoelectric cooling applications at cryogenic temperatures.

  10. Enantioselective light switch effect of Δ- and Λ-[Ru(phenanthroline)2 dipyrido[3,2-a:2', 3'-c]phenazine](2+) bound to G-quadruplex DNA.

    PubMed

    Park, Jin Ha; Lee, Hyun Suk; Jang, Myung Duk; Han, Sung Wook; Kim, Seog K; Lee, Young-Ae

    2017-07-04

    The interaction of Δ- and Λ-[Ru(phen)2DPPZ](2+) (DPPZ = dipyrido[3,2-a:2', 3'-c]phenazine, phen = phenanthroline) with a G-quadruplex formed from 5'-G2T2G2TGTG2T2G2-3'(15-mer) was investigated. The well-known enhancement of luminescence intensity (the 'light-switch' effect) was observed for the [Ru(phen)2DPPZ](2+) complexes upon formation of an adduct with the G-quadruplex. The emission intensity of the G-quadruplex-bound Λ-isomer was 3-fold larger than that of the Δ-isomer when bound to the G-quadruplex, which is opposite of the result observed in the case of double stranded DNA (dsDNA); the light switch effect is larger for the dsDNA-bound Δ-isomer. In the job plot of the G-quadruplex with Δ- and Λ-[Ru(phen)2DPPZ](2+), a major inflection point for the two isomers was observed at x ≈ .65, which suggests a binding stoichiometry of 2:1 for both enantiomers. When the G base at the 8th position was replaced with 6-methyl isoxanthopterin (6MI), a fluorescent guanine analog, the excited energy of 6-MI transferred to bound Δ- or Λ-[Ru(phen)2DPPZ](2+), which suggests that at least a part of both Ru(II) enantiomers is close to or in contact with the diagonal loop of the G-quadruplex. A luminescence quenching experiment using [Fe(CN)6](4-) for the G-quadruplex-bound Ru(II) complex revealed downward bending curves for both enantiomers in the Stern-Volmer plot, which suggests the presence of Ru(II) complexes that are both accessible and inaccessible to the quencher and may be related to the 2:1 binding stoichiometry.

  11. Nuclear forward scattering of synchrotron radiation by 99Ru

    DOE PAGES

    Bessas, D.; Merkel, D. G.; Chumakov, A. I.; ...

    2014-10-03

    In this study, we measured nuclear forward scattering spectra utilizing the 99Ru transition, 89.571(3) keV, with a notably mixed E2/M1 multipolarity. The extension of the standard evaluation routines to include mixed multipolarity allows us to extract electric and magnetic hyperfine interactions from 99Ru-containing compounds. This paves the way for several other high-energy Mössbauer transitions, E~90 keV. Lastly, the high energy of such transitions allows for operando nuclear forward scattering studies in real devices.

  12. Oxidation resistance of Ru-capped EUV multilayers

    SciTech Connect

    Bajt, S; Dai, Z; Nelson, E J; Wall, M A; Alameda, J; Nguyen, N; Baker, S; Robinson, J C; Taylor, J S; Clift, M; Aquila, A; Gullikson, E M; Edwards, N G

    2005-02-23

    Differently prepared Ru-capping layers, deposited on Mo/Si EUV multilayers, have been characterized using a suite of metrologies to establish their baseline structural, optical, and surface properties in as-deposited state. Same capping layer structures were tested for their thermal stability and oxidation resistance. Post-mortem characterization identified changes due to accelerated tests. The best performing Ru-capping layer structure was studied in detail with transmission electron microscopy to identify the grain microstructure and texture. This information is essential for modeling and performance optimization of EUVL multilayers.

  13. Nuclear forward scattering of synchrotron radiation by 99Ru.

    PubMed

    Bessas, D; Merkel, D G; Chumakov, A I; Rüffer, R; Hermann, R P; Sergueev, I; Mahmoud, A; Klobes, B; McGuire, M A; Sougrati, M T; Stievano, L

    2014-10-03

    We measured nuclear forward scattering spectra utilizing the (99)Ru transition, 89.571(3) keV, with a notably mixed E2/M1 multipolarity. The extension of the standard evaluation routines to include mixed multipolarity allows us to extract electric and magnetic hyperfine interactions from (99)Ru-containing compounds. This paves the way for several other high-energy Mössbauer transitions, E ∼ 90 keV. The high energy of such transitions allows for operando nuclear forward scattering studies in real devices.

  14. Mesoporous Trimetallic PtPdRu Spheres as Superior Electrocatalysts.

    PubMed

    Jiang, Bo; Ataee-Esfahani, Hamed; Li, Cuiling; Alshehri, Saad M; Ahamad, Tansir; Henzie, Joel; Yamauchi, Yusuke

    2016-05-17

    Mesoporous Trimetallic PtPdRu Spheres with well-defined spherical morphology and uniformly sized pores were synthesized in an aqueous solution using ascorbic acid as the reducing agent and triblock copolymer F127 as the pore directing agent. These mesoporous PtPdRu spheres exhibited enhanced electrocatalytic activity compared to commercial Pt black, resulting in a ∼4.9 times improvement in mass activity for the methanol oxidation reaction. The excellent electrocatalytic activity and stability are due to the unique mesoporous architecture and electronic landscape between different elements.

  15. Os trigonum syndrome.

    PubMed

    Nault, Marie-Lyne; Kocher, Mininder S; Micheli, Lyle J

    2014-09-01

    Os trigonum syndrome is the result of an overuse injury of the posterior ankle caused by repetitive plantar flexion stress. It is predominantly seen in ballet dancers and soccer players and is primarily a clinical diagnosis of exacerbated posterior ankle pain while dancing on pointe or demi-pointe or while doing push-off maneuvers. Symptoms may improve with rest or activity modification. Imaging studies, including a lateral radiographic view of the ankle in maximal plantar flexion, will typically reveal the os trigonum between the posterior tibial lip and calcaneus. If an os trigonum is absent on radiography, an MRI may reveal scar tissue behind the posterior talus, a condition associated with similar symptoms. Os trigonum syndrome is often associated with pathology of the flexor hallucis longus tendon. Treatment begins with nonsurgical measures. In addition to physical therapy, symptomatic athletes may need surgical excision of os trigonum secondary to unavoidable plantar flexion associated with their sport. This surgery can be performed using open or arthroscopic approaches.

  16. Isonitrile-functionalized ruthenium nanoparticles: intraparticle charge delocalization through Ru=C=N interfacial bonds

    NASA Astrophysics Data System (ADS)

    Zhang, Fengqi; Huang, Lin; Zou, Jiasui; Yang, Jun; Kang, Xiongwu; Chen, Shaowei

    2017-09-01

    Ruthenium nanoparticles (2.06 ± 0.46 nm in diameter) stabilized by 1-hexyl-4-isocyanobenzene (CNBH), denoted as RuCNBH, were prepared by the self-assembly of isonitrile molecules onto the surface of "bare" Ru colloids by virtue of the formation of Ru=C=N- interfacial bonds. FTIR measurements showed that the stretching vibration of the terminal -N≡C bonds at 2119 cm-1 for the monomeric ligands disappeared and concurrently three new bands at 2115, 2043, and 1944 cm-1 emerged with RuCNBH nanoparticles, which was ascribed to the transformation of -N≡C to Ru=C=N- by back donation of Ru-d electrons to the π* orbital of the organic ligands. Metathesis reaction of RuCNBH with vinyl derivatives further corroborated the nature of the Ru=C interfacial bonds. When 1-isocyanopyrene (CNPy) was bounded onto the Ru nanoparticles surface through Ru=C=N interfacial bond (denoted as RuCNPy), the emission maximum was found to red-shift by 27 nm, as compared to that of the CNPy monomers, along with a reduced fluorescence lifetime, due to intraparticle charge delocalization that arose from the conjugated Ru=C=N- interfacial bonds. The results of this study further underline the significance of metal-organic interfacial bonds in the control of intraparticle charge-transfer dynamics and the optical and electronic properties of metal nanoparticles. [Figure not available: see fulltext.

  17. Orbital entanglement and CASSCF analysis of the Ru-NO bond in a Ruthenium nitrosyl complex.

    PubMed

    Freitag, Leon; Knecht, Stefan; Keller, Sebastian F; Delcey, Mickaël G; Aquilante, Francesco; Pedersen, Thomas Bondo; Lindh, Roland; Reiher, Markus; González, Leticia

    2015-06-14

    Complete active space self-consistent field (CASSCF) wavefunctions and an orbital entanglement analysis obtained from a density-matrix renormalisation group (DMRG) calculation are used to understand the electronic structure, and, in particular, the Ru-NO bond of a Ru nitrosyl complex. Based on the configurations and orbital occupation numbers obtained for the CASSCF wavefunction and on the orbital entropy measurements evaluated for the DMRG wavefunction, we unravel electron correlation effects in the Ru coordination sphere of the complex. It is shown that Ru-NO π bonds show static and dynamic correlation, while other Ru-ligand bonds feature predominantly dynamic correlation. The presence of static correlation requires the use of multiconfigurational methods to describe the Ru-NO bond. Subsequently, the CASSCF wavefunction is analysed in terms of configuration state functions based on localised orbitals. The analysis of the wavefunctions in the electronic singlet ground state and the first triplet state provides a picture of the Ru-NO moiety beyond the standard representation based on formal oxidation states. A distinct description of the Ru and NO fragments is advocated. The electron configuration of Ru is an equally weighted superposition of Ru(II) and Ru(III) configurations, with the Ru(III) configuration originating from charge donation mostly from Cl ligands. However, and contrary to what is typically assumed, the electronic configuration of the NO ligand is best described as electroneutral.

  18. Half metallicity and magnetic properties of CrO2 doped with Ti, Sn or Ru

    NASA Astrophysics Data System (ADS)

    Yuan, C.; Lu, Z.; Liu, S.; Gan, Z.; Guo, F.; Xiong, R.; Mei, X.; Liu, H.; Shi, J.

    2016-11-01

    It is possible to stabilize CrO2 internally by doping with element such as Ti, Sn or Ru which has stable rutile structured oxide. However, the half metallicity and magnetic properties of CrO2 may also change when doped with different elements. In this study, by using first principle method, the electronic structure and magnetic properties of CrO2 doped with different amounts and different types (Ti, Sn or Ru) of dopants were studied. It was found that when doped with Ti or Sn, the half metallicity of CrO2 will keep intact even at very high dopant concentration, while for Ru-doped CrO2, the half metallicity will only be maintained at low Ru concentration. Besides, the half metallicity of Ru-doped CrO2 also depends on the relative positions of Ru atoms - the half metallicity may be destroyed even at low Ru concentration if two Ru ions are very close to each other. The magnetic properties of doped CrO2 also show dependence on dopant concentration and dopant type. The magnetocrystalline anisotropy (MAC) of Ru-doped is found to be very sensitive to both Ru concentration and relative positions of Ru atoms. Large MAC may be induced by Ru doping.

  19. Face to phase with RU Lupi

    NASA Astrophysics Data System (ADS)

    Gahm, G. F.; Stempels, H. C.; Walter, F. M.; Petrov, P. P.; Herczeg, G. J.

    2013-12-01

    Context. Some classical T Tauri stars, with intense line and continuous excess emission, show extremely complex spectral variations. Aims: We aim to map and interpret the spectral variations in one such extreme T Tauri star, namely RU Lupi, and to explore how the changes are related to stellar brightness and rotational phase. Methods: We followed the star over three observing runs, each covering a few days, collecting high-resolution optical spectra. In connection to the third run, complementary NIR spectra, multicolour photometric data, and X-ray observations were obtained. Results: The stellar photospheric absorption line spectrum is weakened by superimposed emission, and this veiling becomes extremely high on occasion. Interpreted as a variable continuous excess emission, its contribution would amount to several times the stellar continuum brightness. However, the stellar brightness does not change much when the veiling changes, and we conclude that the veiling is dominated by narrow line emission that fills in the photospheric lines. Continuous emission, originating at the hot spot on the stellar surface, plays a dominant role only at lower degrees of veiling. The radial velocity of narrow emission components in lines of He i vary periodically in anti-phase with the stellar velocity, reflecting the location and motion of the accretion footprint. The blue-shifted wings in He i, related to a stellar wind, are remarkably stable in equivalent width. This implies that the line flux responds directly to changes in the veiling, which in turn is related to the accretion rate close to the star. In contrast, the equivalent widths of the red-shifted wings change with rotational phase. From the pattern of variability we infer that these wings originate in accreting gas close to the star, and that the accretion funnels are bent and trail the hot spot. The profiles of the forbidden lines of [O I] and [S II] are very stable in strength and shape over the entire observing

  20. CaFe interstellar clouds

    NASA Astrophysics Data System (ADS)

    Bondar, A.; Kozak, M.; Gnaciński, P.; Galazutdinov, G. A.; Beletsky, Y.; Krełowski, J.

    2007-07-01

    A new kind of interstellar cloud is proposed. These are rare (just a few examples among ~300 lines of sight) objects with the CaI 4227-Å, FeI 3720-Å and 3860-Å lines stronger than those of KI (near 7699 Å) and NaI (near 3302 Å). We propose the name `CaFe' for these clouds. Apparently they occupy different volumes from the well-known interstellar HI clouds where the KI and ultraviolet NaI lines are dominant features. In the CaFe clouds we have not found either detectable molecular features (CH, CN) or diffuse interstellar bands which, as commonly believed, are carried by some complex, organic molecules. We have found the CaFe clouds only along sightlines toward hot, luminous (and thus distant) objects with high rates of mass loss. In principle, the observed gas-phase interstellar abundances reflect the combined effects of the nucleosynthetic history of the material, the depletion of heavy elements into dust grains and the ionization state of these elements which may depend on irradiation by neighbouring stars. Based on data collected using the Maestro spectrograph at the Terskol 2-m telescope, Russia; and on data collected using the ESO Feros spectrograph; and on data obtained from the ESO Science Archive Facility acquired with the UVES spectrograph, Chile. E-mail: `arctur'@rambler.ru (AB); marizak@astri.uni.torun.pl (MK); pg@iftia.univ.gda.pl (PG); gala@boao.re.kr (GAG); ybialets@eso.org (YB); jacek@astri.uni.torun.pl (JK)

  1. A Ru(II) complex with 2-(4-(methylsulfonyl)phenyl)-1H-imidazo[4,5-f][1,10]phenanthroline: synthesis, characterization, and acid-base and DNA-binding properties.

    PubMed

    Gao, Jie; Wang, Zhi-Ping; Yuan, Cui-Li; Jia, Hai-Shun; Wang, Ke-Zhi

    2011-09-01

    A new Ru(II) complex of [Ru(bpy)2(Hmspip)]Cl2 {in which bpy=2,2'-bipyridine, Hmspip=2-(4-(methylsulfonyl)phenyl)-1H-imidazo[4,5-f][1,10]phenanthroline} have been synthesized and characterized. The ground- and excited-state acid-base properties of [Ru(bpy)2(Hmspip)]Cl2 and its parent complex of [Ru(bpy)2(Hpip)]Cl2 {Hpip=2-phenyl-1H-imidazo[4,5-f][1,10]phenanthroline} have been studied by UV-visible (UV-vis) and emission spectrophotometric pH titrations. [Ru(bpy)2(Hmspip)]Cl2 acts as a calf thymus DNA intercalators with a binding constant of 4.0×10(5) M(-1) in buffered 50 mM NaCl, as evidenced by UV-vis and luminescence titrations, steady-state emission quenching by [Fe(CN)6]4-, DNA competitive binding with ethidium bromide, reverse salt titrations and viscosity measurements.

  2. A Ru(II) complex with 2-(4-(methylsulfonyl)phenyl)-1H-imidazo[4,5- f][1,10]phenanthroline: Synthesis, characterization, and acid-base and DNA-binding properties

    NASA Astrophysics Data System (ADS)

    Gao, Jie; Wang, Zhi-Ping; Yuan, Cui-Li; Jia, Hai-Shun; Wang, Ke-Zhi

    2011-09-01

    A new Ru(II) complex of [Ru(bpy) 2(Hmspip)]Cl 2 {in which bpy = 2,2'-bipyridine, Hmspip = 2-(4-(methylsulfonyl)phenyl)-1 H-imidazo[4,5- f][1,10]phenanthroline} have been synthesized and characterized. The ground- and excited-state acid-base properties of [Ru(bpy) 2(Hmspip)]Cl 2 and its parent complex of [Ru(bpy) 2(Hpip)]Cl 2 {Hpip = 2-phenyl-1H-imidazo[4,5- f][1,10]phenanthroline} have been studied by UV-visible (UV-vis) and emission spectrophotometric pH titrations. [Ru(bpy) 2(Hmspip)]Cl 2 acts as a calf thymus DNA intercalators with a binding constant of 4.0 × 10 5 M -1 in buffered 50 mM NaCl, as evidenced by UV-vis and luminescence titrations, steady-state emission quenching by [Fe(CN) 6] 4-, DNA competitive binding with ethidium bromide, reverse salt titrations and viscosity measurements.

  3. {beta}-K{sub 4}La{sub 6}I{sub 14}Os: A new structure type for rare-earth-metal cluster compounds that contains discrete tetrahedral K{sub 4}I{sup 3+} units

    SciTech Connect

    Uma, S.; Corbett, J.D.

    1999-08-23

    Suitable reactions of KI, La, LaI{sub 3}, and Os in niobium tubes at 800--850 C result in black, air- and moisture-sensitive crystals of the quaternary title phase. Isostructural K{sub 4}Pr{sub 6}I{sub 14}Z also exist for Z = Fe, Ru. The title phase was characterized by single-crystal X-ray diffraction (tetragonal, P4/ncc (No. 130), Z = 4; a = 13.117(3), c = 25.17(1) {angstrom} at 23 C). The important structural feature is the constitution (K{sub 4}I){sup 3+}(La{sub 6}I{sub 13}Os{sup 3{minus}}) with a new type of 3D anion network of [(La{sub 6}Os)I{sub 8}{sup i}I{sub 4/2}{sup i{minus}a}I{sub 4/2}{sup a{minus}i}I{sub 2/2}{sup a{minus}a}] clusters that are connected into puckered layers through I{sup i{minus}a} and I{sup a{minus}i} atom pairs that bridge diagonally in the a-b plane. These cluster layers are further interlinked along {rvec c} at trans-vertexes through simple bridging I{sup a{minus}a}. The 14th iodine atom occurs in the unique K{sub 4}I{sup 3+} ions which lie in columns that interpenetrate the La{sub 6}OsI{sub 13} network along c. The present 16-e{sup {minus}} clusters, in contrast with the optimal 18-e{sup {minus}} octahedral cluster configuration, exhibit an uncommon tetragonal elongation and evidently become closed shell, with only a small temperature-independent (van Vleck-like) paramagnetism, {approximately}4 x 10{sup {minus}4} emu mol{sup {minus}1}.

  4. Oxygen-participated electrochemistry of new lithium-rich layered oxides Li3MRuO5 (M = Mn, Fe).

    PubMed

    Laha, S; Natarajan, S; Gopalakrishnan, J; Morán, E; Sáez-Puche, R; Alario-Franco, M Á; Dos Santos-Garcia, A J; Pérez-Flores, J C; Kuhn, A; García-Alvarado, F

    2015-02-07

    We describe the synthesis, crystal structure and lithium deinsertion-insertion electrochemistry of two new lithium-rich layered oxides, Li3MRuO5 (M = Mn, Fe), related to rock salt based Li2MnO3 and LiCoO2. The Li3MnRuO5 oxide adopts a structure related to Li2MnO3 (C2/m) where Li and (Li0.2Mn0.4Ru0.4) layers alternate along the c-axis, while the Li3FeRuO5 oxide adopts a near-perfect LiCoO2 (R3[combining macron]m) structure where Li and (Li0.2Fe0.4Ru0.4) layers are stacked alternately. Magnetic measurements indicate for Li3MnRuO5 the presence of Mn(3+) and low spin configuration for Ru(4+) where the itinerant electrons occupy a π*-band. The onset of a net maximum in the χ vs. T plot at 9.5 K and the negative value of the Weiss constant (θ) of -31.4 K indicate the presence of antiferromagnetic superexchange interactions according to different pathways. Lithium electrochemistry shows a similar behaviour for both oxides and related to the typical behaviour of Li-rich layered oxides where participation of oxide ions in the electrochemical processes is usually found. A long first charge process with capacities of 240 mA h g(-1) (2.3 Li per f.u.) and 144 mA h g(-1) (1.38 Li per f.u.) is observed for Li3MnRuO5 and Li3FeRuO5, respectively. An initial sloping region (OCV to ca. 4.1 V) is followed by a long plateau (ca. 4.3 V). Further discharge-charge cycling points to partial reversibility (ca. 160 mA h g(-1) and 45 mA h g(-1) for Mn and Fe, respectively). Nevertheless, just after a few cycles, cell failure is observed. X-ray photoelectron spectroscopy (XPS) characterisation of both pristine and electrochemically oxidized Li3MRuO5 reveals that in the Li3MnRuO5 oxide, Mn(3+) and Ru(4+) are partially oxidized to Mn(4+) and Ru(5+) in the sloping region at low voltage, while in the long plateau, O(2-) is also oxidized. Oxygen release likely occurs which may be the cause for failure of cells upon cycling. Interestingly, some other Li-rich layered oxides have been reported to

  5. Heterotrimetallic Ru(II)/Pd(II)/Ru(II) complexes: Synthesis, crystalstructure, spectral characterization, DFT calculation and antimicrobial study

    NASA Astrophysics Data System (ADS)

    Al-Noaimi, Mousa; Nafady, Ayman; Warad, Ismail; Alshwafy, Rwaida; Husein, Ahmad; Talib, Wamidh H.; Hadda, Taibi Ben

    2014-03-01

    New ruthenium(II) mononuclear complexes of the type [RuCl2(PPh3)2(η2-triamine)] (2) [RuCl(PPh3)2(η3-triamine)]Cl (5) (triemine = N1-(2-aminoethyl)-1,2-ethanediamine) have been synthesized by reacting [RuCl2(PPh3)3] (1) with one mole equivalent of N1-(2-aminoethyl)-1,2-ethanediamine in dichloromethane. Reaction of (2) with half-equivalent of (PhCN)2PdCl2 or Pd(OAc)2 in dichloromethane as a solvent afforded two novel heterotrimetallic Ru(II)-Pd(II)-Ru(II) complexes, [RuIICl2(PPh3)2(triamine)]2[PdIIX2](X = Cl, OAc) (3 and 4), bearing bioactive ligand. The progress of the undertaken reactions was monitored by 31P{1H} NMR and FTIR. Crystal structure of complex 2 was confirmed by X-ray diffraction. The absorption spectrum of 2 in dichloromethane was modeled by time-dependent density functional theory (TD-DFT). The in vitro antimicrobial studies of complex 2-5 against an array of microorganisms (bacteria and fungi) were conducted. Complexes 3 and 4 exhibit high dual antibacterial and antifungal activity inhibiting microorganisms possibly via hydrolytic pathway which further evidenced by electrochemical analyses. The complexes 3 and 4 show a high inhibitory activity at 200 μg/ml concentration, suggesting that complexes 3 and 4 are two efficient catalytic inhibitor of microorganisms and further, they should be tested against cancer strains.

  6. Heterotrimetallic Ru(II)/Pd(II)/Ru(II) complexes: synthesis, crystalstructure, spectral characterization, DFT calculation and antimicrobial study.

    PubMed

    Al-Noaimi, Mousa; Nafady, Ayman; Warad, Ismail; Alshwafy, Rwaida; Husein, Ahmad; Talib, Wamidh H; Hadda, Taibi Ben

    2014-03-25

    New ruthenium(II) mononuclear complexes of the type [RuCl2(PPh3)2(η(2)-triamine)] (2) [RuCl(PPh3)2(η(3)-triamine)]Cl (5) (triemine=N(1)-(2-aminoethyl)-1,2-ethanediamine) have been synthesized by reacting [RuCl2(PPh3)3] (1) with one mole equivalent of N(1)-(2-aminoethyl)-1,2-ethanediamine in dichloromethane. Reaction of (2) with half-equivalent of (PhCN)2PdCl2 or Pd(OAc)2 in dichloromethane as a solvent afforded two novel heterotrimetallic Ru(II)-Pd(II)-Ru(II) complexes, [Ru(II)Cl2(PPh3)2(triamine)]2[Pd(II)X2](X=Cl, OAc) (3 and 4), bearing bioactive ligand. The progress of the undertaken reactions was monitored by (31)P{1H} NMR and FTIR. Crystal structure of complex 2 was confirmed by X-ray diffraction. The absorption spectrum of 2 in dichloromethane was modeled by time-dependent density functional theory (TD-DFT). The in vitro antimicrobial studies of complex 2-5 against an array of microorganisms (bacteria and fungi) were conducted. Complexes 3 and 4 exhibit high dual antibacterial and antifungal activity inhibiting microorganisms possibly via hydrolytic pathway which further evidenced by electrochemical analyses. The complexes 3 and 4 show a high inhibitory activity at 200 μg/ml concentration, suggesting that complexes 3 and 4 are two efficient catalytic inhibitor of microorganisms and further, they should be tested against cancer strains. Copyright © 2013 Elsevier B.V. All rights reserved.

  7. Variation of the Ru moment in the Ca(0.3)Sr(0.7)Ru(1-x)Mn(x)O3 system.

    PubMed

    Mizusaki, S; Naito, M; Taniguchi, T; Nagata, Y; Itou, M; Sakurai, Y; Noro, Y; Ozawa, T C; Samata, H

    2010-04-14

    The variation of the magnetic moment on Ru and Mn atoms in the Ca(0.3)Sr(0.7)Ru(1-x)Mn(x)O(3) system was investigated by the magnetic Compton scattering technique using synchrotron radiation. The Ca(0.3)Sr(0.7)Ru(1-x)Mn(x)O(3) system has ferrimagnetism with an antiferromagnetic coupling between Ru and Mn, and the dominant magnetic component changes from ferromagnetic Ru to ferromagnetic Mn at x ∼0.25 as the Mn substitution proceeds. The mechanism for the change in the magnetism of Ca(0.3)Sr(0.7)Ru(1-x)Mn(x)O(3) is discussed.

  8. The effects of structural variations of thiophene-containing Ru(II) complexes on the acid-base and DNA binding properties.

    PubMed

    Yuan, Cui-Li; Zhang, An-Guo; Zheng, Ze-Bo; Wang, Ke-Zhi

    2013-03-01

    A phenylthiophenyl-bearing Ru(II) complex of [Ru(bpy)₂(Hbptip)](PF₆)₂ {bpy = 2,2'-bipyridine, Hbptip = 2-(4-phenylthiophen-2-yl)-1H-imidazo[4,5-f][1,10]phenanthroline} was synthesized and characterized by elemental analysis, ¹H NMR spectroscopy, and electrospray ionization mass spectrometry. The ground- and excited-state acid-base properties of the complex were studied by UV-visible absorption and photoluminescence spectrophotometric pH titrations and the negative logarithm values of the ground-state acid ionization constants were derived to be pK(a1) = 1.31 ± 0.09 and pK(a2) = 5.71 ± 0.11 with the pK(a2) associated deprotonation/protonation process occurring over 3 pK(a) units more acidic than thiophenyl-free parent complex of [Ru(bpy)₂(Hpip)]²⁺ {Hpip = 2-phenyl-1H-imidazo[4,5-f][1,10]phenanthroline}. The calf thymus DNA-binding properties of [Ru(bpy)₂(Hbptip)]²⁺ in Tris-HCl buffer (pH 7.1 and 50 mM NaCl) were investigated by DNA viscosities and density functional theoretical calculations as well as UV-visible and emission spectroscopy techniques of UV-visible and luminescence titrations, steady-state emission quenching by [Fe(CN)₆]⁴⁻, DNA competitive binding with ethidium bromide, DNA melting experiments, and reverse salt effects. The complex was evidenced to bind to the DNA intercalatively with binding affinity being greater than those for previously reported analogs of [Ru(bpy)₂(Hip)]²⁺, [Ru(bpy)₂(Htip)]²⁺, and [Ru(bpy)₂(Haptip)]²⁺ {Hip = 1H-imidazo[4,5-f][1,10]phenanthroline, Htip = 2-thiophenimidazo[4,5-f][1,10]phenanthroline, Haptip = 2-(5-phenylthiophen-2-yl)-1H-imidazo[4,5-f][1,10]phenanthroline}.

  9. Hydrous RuO2 nanoparticles as highly active electrocatalysts for hydrogen evolution reaction

    NASA Astrophysics Data System (ADS)

    Lee, Jooyoung; Sher Shah, Selim Arif; Yoo, Pil J.; Lim, Byungkwon

    2017-04-01

    This letter describes an aqueous-phase synthetic route to hydrous ruthenium oxide (RuO2) nanoparticles and their conversion into crystalline ones via a thermal annealing process. Electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy were employed to characterize hydrous and crystalline RuO2 nanoparticles. The hydrous RuO2 nanoparticles exhibited higher activity for hydrogen evolution reaction than commercial Pt catalyst, while the crystalline RuO2 nanoparticles showed better performance for oxygen evolution reaction than IrO2 catalyst. With these hydrous and crystalline RuO2 catalysts, we were able to achieve highly efficient overall electrochemical water splitting.

  10. The Nanostructuring of Atomically Flat Ru(0001) upon Oxidation and Reduction

    NASA Astrophysics Data System (ADS)

    Goriachko, A.; Over, H.

    2016-12-01

    The O/Ru(0001) system is widely studied due to its rich phase variety of various stoichiometry and atomic arrangements, including the formation of a RuO2/Ru(0001) oxide layer. Apart from homogeneous ruthenium surfaces in certain oxidation states, also strongly heterogeneous surfaces can exist due to oxidation state's variation at the nanoscale. We report on a scanning tunneling microscopy (STM) study of the nanostructuring of the oxidized Ru(0001) surface as a result of its interaction with molecular oxygen at elevated temperatures and subsequent reduction of a resulting RuO2 film by CO or HCl molecules from the gas phase in high-vacuum environment.

  11. Internal oxidation of laminated ternary Ru-Ta-Zr coatings

    NASA Astrophysics Data System (ADS)

    Chen, Yung-I.; Lu, Tso-Shen

    2015-10-01

    Researchers have observed the internal oxidation phenomenon in binary alloy coatings when developing refractory alloy coatings for protective purposes by conducting annealing at high temperatures and in oxygen-containing atmospheres. The coatings were assembled using cyclical gradient concentration deposition during cosputtering by employing a substrate holder rotating at a slow speed. The internally oxidized zone demonstrated a laminated structure, comprising alternating oxygen-rich and oxygen-deficient layers stacked in a general orientation. In the current study, Ru-Ta-Zr coatings were prepared with various stacking sequences during cosputtering. The Ru-Ta-Zr coatings were annealed at 600 °C in an atmosphere continuously purged with 1% O2-99% Ar mixed gas for 30 min. A transmission electron microscope was used to examine the periods of the laminated layers and crystallinity of the annealed coatings. Depth profiles produced using an Auger electron spectroscope and X-ray photoelectron spectroscope were used to certify the periodic variation of the related constituents and chemical states of the elements, respectively. The results indicate that the internally oxidized ternary coatings are stacked of Ru-, Ta2O5-, and ZrO2-dominant sublayers and that the stacking sequences of the sublayers affect the crystalline structure of the coatings. Zr is oxidized preferentially in the Ru-Ta-Zr coatings, increasing the surface hardness of the oxidized coatings.

  12. Rotationally resolved spectra of jet-cooled RuSi

    NASA Astrophysics Data System (ADS)

    Lindholm, Ned; Morse, Michael D.

    2007-08-01

    We report the first gas-phase spectroscopic investigation of diatomic ruthenium silicide (RuSi). The molecules were produced by laser ablation of a Ru disk into a flow of helium carrier gas containing 0.5% SiH4, and were cooled in a supersonic expansion. The RuSi molecules were then studied using resonant two-photon ionization spectroscopy. Investigations conducted in the spectral range from 18800to23800cm-1 show a large number of excited vibronic levels that cannot readily be grouped into electronic band systems. The ground state is been demonstrated to be of Δ33 symmetry, deriving from the 2δ314σ1 electronic configuration. Correcting for the effects of the spin-uncoupling operator, the ground state bond length (r0) is determined to be 2.0921±0.0004Å (1σ error limit). Diatomic RuSi is shown to have strong dπ-pπ bonds, unlike the isovalent AlCo molecule.

  13. ELECTRONIC AND TRANSPORT PROPERTIES OF THERMOELECTRIC Ru2Si3

    NASA Astrophysics Data System (ADS)

    Singh, David J.; Parker, David

    2013-08-01

    We report calculations of the doping and temperature dependent thermopower of Ru2Si3 based on Boltzmann transport theory and the first principles electronic structure. We find that the performance reported to date can be significantly improved by optimization of the doping level and that ultimately n-type should have higher ZT than p-type.

  14. Insight into water oxidation by mononuclear polypyridyl Ru catalysts.

    PubMed

    Wasylenko, Derek J; Ganesamoorthy, Chelladurai; Koivisto, Bryan D; Henderson, Matthew A; Berlinguette, Curtis P

    2010-03-01

    A family of compounds based on the mononuclear coordination complex [Ru(tpy)(bpy)(OH(2))](2+) (1b; tpy = 2,2':6',2''-terpyridine, bpy = 2,2'-bipyridine) are shown to be competent catalysts in the Ce(IV)-driven oxidation of water in acidic media. The systematic installation of electron-withdrawing (e.g., -Cl, -COOH) and -donating (e.g., -OMe) groups at various positions about the periphery of the polypyridyl framework offers insight into how electronic parameters affect the properties of water oxidation catalysts. It is observed, in general, that electron-withdrawing groups (EWGs) on the bpy ligands suppress catalytic activity (k(obs)) and enhance catalytic turnover numbers (TONs); conversely, the presence of electron-donating groups (EDGs) accelerate catalytic rates while decreasing catalyst stability. We found that 2,2'-bipyridine N,N'-dioxide is produced when 1b is subject to excess Ce(IV) in acidic media, which suggests that dissociation of the bpy ligand is a source of catalyst deactivation and/or decomposition. Density functional theory (DFT) calculations corroborate these findings by showing that the Ru-N(bpy) bond trans to the O atom is weakened at higher oxidation levels while the other Ru-N bonds are affected to a lesser extent. We also show that the Ru-Cl bond is not robust in aqueous media, which has implications in studying the catalytic behavior of systems of this type.

  15. The interactions of water and perfluorodiethyl ether on Ru(100)

    SciTech Connect

    Leavitt, P.

    1990-09-21

    We have studied the interactions of water and perfluorodiethyl ether on Ru(100) in order to model the effects of surface structure and humidity on the bonding and decomposition of perfluoroalkyl ether lubricants with metal surfaces. In order to understand the interactions on Ru(100), we have first investigated the interactions of each of these adsorbates alone on the clean surface. The interactions of water with Ru(100) have been studied using both thermal desorption spectroscopy (TDS) and electron energy loss spectroscopy (EELS). From these studies we conclude that a small amount of water dissociates on this surface (5--10% of a monolayer), but water is adsorbed in a predominantly molecular form on this surface with an increasing degree of hydrogen-bonding with increasing coverage. The effects of hydrogen and oxygen coadsorption on the interactions of water with this surface have also been studied using TDS. Finally, the interactions of coadsorbed water and perfluorodiethyl ether on Ru(100) have been investigated using TDS.

  16. Switchable diode-effect mechanism in ferroelectric BiFeO{sub 3} thin film capacitors

    SciTech Connect

    Matsuo, Hiroki; Kitanaka, Yuuki; Inoue, Ryotaro; Noguchi, Yuji Miyayama, Masaru

    2015-09-21

    We investigate the mechanism of a switchable diode behavior observed in ferroelectric SrRuO{sub 3}/BiFeO{sub 3} (BFO)/SrRuO{sub 3} capacitors. We experimentally demonstrate that the switchable diode effect observed in the capacitors is induced by the polarization reversal in the BFO film. The conductivity in an Ohmic region in different oxidation states provides direct evidence that electron hole acts as the majority carrier, delivering p-type conduction. Density functional theory (DFT) calculations show that the p-type conduction arises from an unoccupied gap state of Fe{sup 4+} in an FeO{sub 5} pyramid which is derived from Bi vacancy. Our experimental and DFT study leads to the conclusion that the switchable diode effect originates from an asymmetric band bending in the top and bottom depletion layers modulated by ferroelectric polarization and oxygen vacancies.

  17. Influence of capping layers on CoFeB anisotropy and damping

    SciTech Connect

    Natarajarathinam, A.; Tadisina, Z. R.; Gupta, S.; Mewes, T.; Watts, S.; Chen, E.

    2012-09-01

    Magnetic behavior of CoFeB at various thicknesses ranging from 2 nm to 8 nm capped with different materials, such as MgO, Ta, Ru, and V have been studied. The films were sputter-deposited and subsequently characterized by magnetometry and broadband ferromagnetic resonance (FMR). There are magnetically dead layers at the interface observed with Ru and Ta capping layers, while MgO and V have almost no effect on the magnetization of the CoFeB. As the ferromagnetic layer is made thinner, the effective magnetization decreases, indicating an interfacial perpendicular anisotropy. Particularly in the case of MgO, V/Ru, and V/Ta capping layers, interfacial perpendicular anisotropy is induced in CoFeB, and the Gilbert damping parameter is also reduced. The origin of this perpendicular magnetic anisotropy (PMA) is understood to be caused by the interface anisotropy between the free layer and the capping layer. The effect of post-deposition annealing and CoFeB thickness on the anisotropy and damping of V/Ta capped samples are reported. Doping CoFeB with vanadium (V) greatly reduced the 4{pi}M{sub s} and 4{pi}M{sub eff} values, resulting in an effective increase in the PMA.

  18. Influence of capping layers on CoFeB anisotropy and damping

    NASA Astrophysics Data System (ADS)

    Natarajarathinam, A.; Tadisina, Z. R.; Mewes, T.; Watts, S.; Chen, E.; Gupta, S.

    2012-09-01

    Magnetic behavior of CoFeB at various thicknesses ranging from 2 nm to 8 nm capped with different materials, such as MgO, Ta, Ru, and V have been studied. The films were sputter-deposited and subsequently characterized by magnetometry and broadband ferromagnetic resonance (FMR). There are magnetically dead layers at the interface observed with Ru and Ta capping layers, while MgO and V have almost no effect on the magnetization of the CoFeB. As the ferromagnetic layer is made thinner, the effective magnetization decreases, indicating an interfacial perpendicular anisotropy. Particularly in the case of MgO, V/Ru, and V/Ta capping layers, interfacial perpendicular anisotropy is induced in CoFeB, and the Gilbert damping parameter is also reduced. The origin of this perpendicular magnetic anisotropy (PMA) is understood to be caused by the interface anisotropy between the free layer and the capping layer. The effect of post-deposition annealing and CoFeB thickness on the anisotropy and damping of V/Ta capped samples are reported. Doping CoFeB with vanadium (V) greatly reduced the 4πMs and 4πMeff values, resulting in an effective increase in the PMA.

  19. Planar junction tunneling study of single-crystal eutectic phases of Sr2RuO4/Sr3Ru2O7

    NASA Astrophysics Data System (ADS)

    Cai, Xinxin; Zakrzewski, Brian; Wang, H.; Andreou, C.; Schlom, D.; Mao, Z.-Q.; Cava, R. J.; Liu, Ying

    Despite of intensive study of many years, the precise value of the superconducting energy gap of the odd-parity superconductor Sr2RuO4 has not been fully settled. Many complications exist. The band dependence of superconductivity makes the results from a bulk measurement of the gap difficult to interpret quantitatively. Surface based measurements such as scanning tunneling spectroscopy have to deal with the suppression of the superconducting energy gap on the cleaved ab surface due to surface reconstruction. We performed quasi-particle tunneling measurements of the superconducting energy gap in planar junctions prepared on naturally cleaved edges of a Sr2RuO4 crystal found in the eutectic phase of Sr2RuO4 /Sr3Ru2O7. Cleaving of such eutectic crystals exposes thin Sr2RuO4 ``plates'' inserted in a Sr3Ru2O7 bulk crystal with the c axis along that of the Sr3Ru2O7 bulk, as shown by X-ray diffraction data. Results obtained on Au-Sr2RuO4/Sr3Ru2O7 tunnel junctions suggest that superconductivity survives on the surface of the ``plates'', showing a gap value of 0.2 meV, close to the BCS value for weak-coupling superconductors. Experiments on tunnel junctions made on cleaved crystals of a mesoscopic size are underway.

  20. Multiple Pathways for Benzyl Alcohol Oxidation by RuV=O3+ and RuIV=O2+

    SciTech Connect

    Paul, Amit; Hull, Jonathan F.; Norris, Michael R.; Chen, Zuofeng; Ess, Daniel H.; Concepcion, Javier J.; Meyer, Thomas J.

    2011-01-20

    Significant rate enhancements are found for benzyl alcohol oxidation by the RuV=O3+ form of the water oxidation catalyst [Ru(Mebimpy)(bpy)(OH2)]2+ [Mebimpy = 2,6-bis(1-methylbenzimidazol-2-yl)pyridine; bpy = 2,2'-bipyridine] compared to RuIV=O2+ and for the RuIV=O2+ form with added bases due to a new pathway, concerted hydride proton transfer (HPT).

  1. Multiple Pathways for Benzyl Alcohol Oxidation by RuV=O3+ and RuIV=O2+

    SciTech Connect

    Paul, Amit; Hull, Jonathan F.; Norris, Michael R.; Chen, Zuofeng; Ess, Daniel H.; Concepcion, Javier J.; Meyer, Thomas J.

    2011-01-20

    Significant rate enhancements are found for benzyl alcohol oxidation by the RuV=O3+ form of the water oxidation catalyst [Ru(Mebimpy)(bpy)(OH2)]2+ [Mebimpy = 2,6-bis(1-methylbenzimidazol-2-yl)pyridine; bpy = 2,2'-bipyridine] compared to RuIV=O2+ and for the RuIV=O2+ form with added bases due to a new pathway involving concerted hydride proton transfer (HPT).

  2. ScRu2B3 and Sc2RuB6: Borides Featuring a 2D Infinite Boron Clustering.

    PubMed

    Salamakha, Leonid P; Sologub, Oksana; Stöger, Berthold; Rogl, Peter Franz; Waas, Monika; Kapustianyk, Volodymyr B; Bauer, Ernst

    2017-09-05

    Two borides, ScRu2B3 and Sc2RuB6, were obtained by argon-arc melting of the elements followed by annealing at 800 °C. ScRu2B3 exhibits a new structure type with the space group Cmcm (a = 3.0195(2) Å, b = 15.4056(8) Å, c = 5.4492(3) Å; single crystal X-ray data; RF(2) = 0.0105). Sc2RuB6 adopts the Y2ReB6-type structure (space group Pbam; a = 8.8545(2) Å, b = 11.1620(3) Å, c = 3.4760(1) Å; single crystal X-ray data; RF(2) = 0.0185). ScRu2B3 displays an unusual intergrowth of CeCo3B2- and AlB2-related slabs; a striking feature is a boat configuration of puckered boron hexagons within infinite graphite like boron layers (6(3) nets). Sc2RuB6 presents two-dimensional planar nets of condensed boron pentagons, hexagons, and heptagons sandwiched between metal layers. In Sc/Y substituted Y2ReB6-type, Y atoms are distributed exclusively inside the boron heptagons. Exploration of the Sc-Ru-B system at 800 °C including binary boundaries employing EPMA and powder X-ray diffraction technique furthermore rules out the existence of previously reported "ScRuB4" but confirms the formation and crystal structure of Sc2Ru5B4. ScRu4B4 forms in cast alloys (LuRu4B4-type structure; space group I41/acd (No. 142), a = 7.3543(2) Å, c = 14.92137(8) Å). Cell parameters and atomic coordinates have been refined for ScRu2B3, Sc2RuB6, and ScRu4B4 in the scope of the generalized gradient approximation. Ab initio electronic structure calculations indicate a moderate electronic density of states at the Fermi level situated near the upper edge of essentially filled d-bands. Electrical resistivity measurements characterize ScRu2B3 and Sc2RuB6 as metals in concord with electronic band structure calculations.

  3. Phase stability, electronic structure, elastic properties and hardness of Ru-Ir alloys: first-principles calculations

    NASA Astrophysics Data System (ADS)

    Hu, Riming; Zhou, Zhaobo; Zhou, Xiaolong; Yu, Jie; Zhang, Kunhua

    2017-07-01

    The Phase stability, electronic structure, elastic properties and hardness of Ru-Ir alloys (Ru5Ir15, Ru6Ir14, Ru8Ir12) were investigated by first principles calculations. The negative values of cohesive energy and formation enthalpy show that these compounds are thermodynamically stable, and Ru-Ir alloys tend to exist in the form of Ru5Ir15, Ru6Ir14 and Ru8Ir12. The calculated results of electronic structure reveal that strong hybridizations exist near the Fermi level, being characteristic of Ru-d and Ir-d states, as a result, it is mainly composed of Ru-Ir bond in Ru-Ir alloy. The elastic properties were calculated, which included bulk modulus, shear modulus, Young’s modulus, Poisson’s ratio and hardness. The calculated results reveal that Ru6Ir14 compound has the highest hardness, and Ru8Ir12 compound has the maximal elastic anisotropy ratio. Meanwhile, Ru5Ir15, Ru6Ir14, Ru8Ir12 are brittle, and the vickers hardness values of these alloys are 25.29 GPa, 27.96 GPa, 27.39 GPa, respectively.

  4. Synthesis and characterization of noble metal borides: RuB{sub x}(x > 1)

    SciTech Connect

    Li, Zhifang; Zheng, Dafang; Ding, Zhanhui; Li, Yongfeng; Yao, Bin; Li, Yongsheng; Zhao, Xudong; Yu, Guichuan; Tang, Yang; Zheng, Weitao; Liu, Xiaoyang

    2016-02-15

    Highlights: • Hexagonal RuB{sub 1.1} were synthesized using ruthenium and boron powders as raw materials during ball milling process. • Orthorhombic RuB{sub 2} were synthesized under high pressure (5 GPa) and high temperature (1000 °C) conditions. • Hexagonal Ru{sub 2}B{sub 3} have been synthesized under 5 GPa and 1200 °C. - Abstract: Noble metal borides RuB{sub 1.1}, RuB{sub 2} and Ru{sub 2}B{sub 3} have been synthesized by mechanical alloying and high pressure sintering methods using ruthenium (Ru) and boron (B) powders as raw materials. The crystal structures of borides were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The results shown that only RuB{sub 1.1} with hexagonal crystal structure was synthesized during the ball milling process, the orthorhombic RuB{sub 2} was synthesized under high pressure (5 GPa) and high temperature (1000 °C) conditions, while the hexagonal Ru{sub 2}B{sub 3} can be synthesized under 5 GPa and 1200 °C. The mechanism of synthesis for the ruthenium borides (RuB{sub x}) are discussed in details.

  5. Effect of gas composition on Ru dissolution and crossover in polymer-electrolyte membrane fuel cells

    NASA Astrophysics Data System (ADS)

    Cheng, Tommy T. H.; Jia, Nengyou; Colbow, Vesna; Wessel, Silvia; Dutta, Monica

    Pt-Ru-based anodes are commonly used in polymer-electrolyte membrane fuel cells (PEMFCs) to provide improved CO tolerance for reformate fuel applications. However, Ru crossover from the anode to the cathode has been identified as a critical durability problem that has severe performance implications. In the present study, an anode accelerated stress test (AST) was used to simulate potential spikes that occur during fuel cell start-ups and shutdowns to induce Ru crossover. The effects of fuel gas composition, namely hydrogen and carbon dioxide concentrations, on Ru dissolution and crossover were investigated. The cell performance losses were correlated with the degree of Ru crossover as determined by the changes in cathode cyclic voltammetry (CV) characteristics and neutron activation analysis (NAA). It was found that higher hydrogen concentration in the fuel accelerated Ru crossover and that the presence of carbon dioxide hindered Ru crossover. In particular, the injection of 20 vol.% carbon dioxide during potential cycling resulted in very minor Ru crossover, which showed essentially identical performance losses and CV characteristic changes as a fuel cell composed of a Ru-free anode. The experimental results suggest that the Ru species in our Pt-Ru metal oxide catalysts need to go through a reduction step by hydrogen before dissolution. The presence of carbon dioxide may play a role in hindering the reduction step.

  6. Ru(III) catalyzed permanganate oxidation of aniline at environmentally relevant pH.

    PubMed

    Zhang, Jing; Zhang, Ying; Wang, Hui; Guan, Xiaohong

    2014-07-01

    Ru(III) was employed as catalyst for aniline oxidation by permanganate at environmentally relevant pH for the first time. Ru(III) could significantly improve the oxidation rate of aniline by 5-24 times with its concentration increasing from 2.5 to 15 μmol/L. The reaction of Ru(III) catalyzed permanganate oxidation of aniline was first-order with respect to aniline, permanganate and Ru(III), respectively. Thus the oxidation kinetics can be described by a third-order rate law. Aniline degradation by Ru(III) catalyzed permanganate oxidation was markedly influenced by pH, and the second-order rate constant (ktapp) decreased from 643.20 to 2.67 (mol/L)⁻¹sec⁻¹ with increasing pH from 4.0 to 9.0, which was possibly due to the decrease of permanganate oxidation potential with increasing pH. In both the uncatalytic and catalytic permanganate oxidation, six byproducts of aniline were identified in UPLC-MS/MS analysis. Ru(III), as an electron shuttle, was oxidized by permanganate to Ru(VI) and Ru(VII), which acted the co-oxidants for decomposition of aniline. Although Ru(III) could catalyze permanganate oxidation of aniline effectively, dosing homogeneous Ru(III) into water would lead to a second pollution. Therefore, efforts would be made to investigate the catalytic performance of supported Ru(III) toward permanganate oxidation in our future study.

  7. [Ru/AC catalyzed ozonation of recalcitrant organic compounds].

    PubMed

    Wang, Jian-Bing; Hou, Shao-Pei; Zhou, Yun-Rui; Zhu, Wan-Peng; He, Xu-Wen

    2009-09-15

    Ozonation and Ru/AC catalyzed ozonation of dimethyl phthalate (DMP), phenols and disinfection by-products precursors were studied. It shows that Ru/AC catalyst can obviously enhance the mineralization of organic compounds. In the degradation of DMP, TOC removal was 28.84% by ozonation alone while it was 66.13% by catalytic ozonation. In the oxidation of 23 kinds of phenols, TOC removals were 9.57%-56.08% by ozonation alone while they were 41.81%-82.32% by catalytic ozonation. Compared to ozonation alone, Ru/AC catalyzed ozonation was more effective for the reduction of disinfection by-products formation potentials in source water. The reduction of haloacetic acids formation potentials was more obvious than thichlomethane formation potentials. After the treatment by catalytic ozonation, the haloacetic acids formation potentials decreased from 144.02 microg/L to 58.50 microg/L, which was below the standard value of EPA. However ozonation alone could not make it reach the standard. The treatments of source water by BAC, O3 + BAC, O3/AC + BAC and Ru/AC + O3 + BAC were also studied. In the four processes, TOC removal was 3.80%, 20.14%, 27.45% and 48.30% respectively, COD removal was 4.37%, 27.22%, 39.91% and 50.00% respectively, UV254 removal was 8.16%, 62.24%, 67.03% and 84.95% respectively. Ru/AC + O3 + BAC process is more effective than the other processes for the removal of TOC, COD and UV254 and no ruthenium leaching observed in the solution. It is a promising process for the treatment of micro polluted source water.

  8. Introduction of RU 486 in the USA: obstacles and opportunities.

    PubMed

    Thoss, E

    1993-10-01

    On January 22, 1993, the 20th anniversary of the US Supreme Court decision Roe v. Wade, President Clinton reversed an oppressive rule relating to abortion imposed by former Presidents Reagan and Bush. In addition, the president directed the US Food and Drug Administration (FDA) to rescind the restriction on RU-486 and to promote its testing, licensing, and manufacturing in the US. On February 24 a meeting was held between the FDA commissioner and the president of Roussel-Uclaf. The Reproductive Health Technologies Project's own meeting was on April 14, 1993, to review the outlook for introduction of RU-486 in the USA. Roussel-Uclaf stated that: the company was ready to apply for FDA approval; clear guidelines should be developed on how the compound should be used; optimal care with regard to cases with complications should be guaranteed; and the method should be strictly medicalized. The Population Council has a contract with Roussel-Uclaf to conduct trials on RU-486 in the US. Meetings between the FDA, Hoechst AG, and the Population Council took place on April 20, 1993. Roussel-Uclaf agreed to license the production of RU-486 and the technology for making it to the Population Council. This agreement will take probably as much as 2 years. The Population Council will begin clinical trials for at least 2000 women shortly. The Population Council will begin putting together the documentation for a new drug application to be submitted to the FDA. Roussel-Uclaf will supply the Population Council with its toxicological, chemical, and clinical data as soon as possible. The Population Council will be responsible for finding a US manufacturer to produce RU-486. Several companies have expressed an interest already. In addition there are issues to be settled regarding the provision of services and the training of providers.

  9. Glucocorticoid receptor antagonism by cyproterone acetate and RU486.

    PubMed

    Honer, Christian; Nam, Kiyean; Fink, Cynthia; Marshall, Paul; Ksander, Gary; Chatelain, Ricardo E; Cornell, Wendy; Steele, Ronald; Schweitzer, Robert; Schumacher, Christoph

    2003-05-01

    The steroid compound cyproterone acetate was identified in a high-throughput screen for glucocorticoid receptor (GR) binding compounds. Cyproterone (Schering AG) is clinically used as an antiandrogen for inoperable prostate cancer, virilizing syndromes in women, and the inhibition of sex drive in men. Despite its progestin properties, cyproterone shares a similar pharmacological profile with the antiprogestin mifepristone (RU486; Roussel Uclaf SA). The binding affinities of cyproterone and RU486 for the GR and progesterone receptor were similar (K(d), 15-70 nM). Both compounds were characterized as competitive antagonists of dexamethasone without intrinsic transactivating properties in rat hepatocytes (K(i), 10-30 nM). In osteosarcoma cells, RU486 revealed a higher potency than cyproterone acetate to prevent responses to dexamethasone-induced GR transactivation and NF kappa B transrepression. Upon administration to Sprague-Dawley rats, both compounds were found to be orally bioavailable and to inhibit transactivation of liver GR. Molecular docking of cyproterone acetate and RU486 into the homology model for the GR ligand binding domain illustrated overlapping steroid scaffolds in the binding pocket. However, in contrast to RU486, cyproterone lacks a bulky side chain at position C11 beta that has been proposed to trigger active antagonism of nuclear receptors by displacing the C-terminal helix of the ligand-binding domain, thereby affecting activation function 2. Cyproterone may therefore inhibit transactivation of the GR by a molecular mechanism recently described as passive antagonism. New therapeutic profiles may result from compounds designed to selectively stabilize the inactive and active conformations of certain nuclear receptors.

  10. Carbon-supported bimetallic Pd–Fe catalysts for vapor-phase hydrodeoxygenation of guaiacol

    SciTech Connect

    Sun, Junming; Karim, Ayman M.; Zhang, He; Kovarik, Libor; Li, Xiaohong Shari; Hensley, Alyssa J.; McEwen, Jean-Sabin; Wang, Yong

    2013-10-01

    Abstract Carbon supported metal catalysts (Cu/C, Fe/C, Pd/C, Pt/C, PdFe/C and Ru/C) have been prepared, characterized and tested for vapor-phase hydrodeoxygenation (HDO) of guaiacol (GUA) at atmospheric pressure. Phenol was the major intermediate on all catalysts. Over the noble metal catalysts saturation of the aromatic ring was the major pathway observed at low temperature (250 °C), forming predominantly cyclohexanone and cyclohexanol. Substantial ring opening reaction was observed on Pt/C and Ru/C at higher reaction temperatures (e.g., 350 °C). Base metal catalysts, especially Fe/C, were found to exhibit high HDO activity without ring-saturation or ring-opening with the main products being benzene, phenol along with small amounts of cresol, toluene and trimethylbenzene (TMB). A substantial enhancement in HDO activity was observed on the PdFe/C catalysts. Compared with Fe/C, the yield to oxygen-free aromatic products (i.e., benzene/toluene/TMB) on PdFe/C increased by a factor of four at 350 °C, and by approximately a factor of two (83.2% versus 43.3%) at 450 °C. The enhanced activity of PdFe/C is attributed to the formation of PdFe alloy as evidenced by STEM, EDS and TPR.

  11. Re-187-Os-187, Pt-190-Os-186 Isotopic and Highly Siderophile Element Systematics of Group IVA Irons

    NASA Technical Reports Server (NTRS)

    Walker, R. J.; McCoy, T. J.; Schulte, R. F.; McDonough, W. F.; Ash, R. D.

    2005-01-01

    We have recently completed Re-187-Os-187 and Pt-190-Os-186 isotopic and elemental studies of the two largest magmatic iron meteorite groups, IIAB and IIIAB [1]. These studies revealed closed-system behavior of both isotopic systems, but complex trace element behavior for Re, Pt and Os in group IIIAB. Here we examine isotopic and trace elemental systematics of group IVA irons. The IVA irons are not as extensively fractionated as IIAB and IIIAB and their apparently less complex crystallization history may make for more robust interpretation of the relative partitioning behavior of Re, Pt and Os, as well as the other highly siderophile elements (HSE) measured here; Pd, Ru and Ir [e.g. 2]. An additional goal of our continuing research plan for iron meteorites is to assess the possibility of relating certain ungrouped irons with major groups via trace element modeling. Here, the isotopic and trace element systematics of the ungrouped irons Nedagolla and EET 83230 are compared with the IVA irons.

  12. Induction of Cytotoxicity in Pyridine Analogues of the Anti-metastatic Ru(III) Complex NAMI-A by Ferrocene Functionalization.

    PubMed

    Mu, Changhua; Chang, Stephanie W; Prosser, Kathleen E; Leung, Ada W Y; Santacruz, Stephanie; Jang, Thalia; Thompson, John R; Yapp, Donald T T; Warren, Jeffrey J; Bally, Marcel B; Beischlag, Timothy V; Walsby, Charles J

    2016-01-04

    A series of novel ferrocene (Fc) functionalized Ru(III) complexes was synthesized and characterized. These compounds are derivatives of the anti-metastatic Ru(III) complex imidazolium [trans-RuCl4(1H-imidazole) (DMSO-S)] (NAMI-A) and are derived from its pyridine analogue (NAMI-Pyr), with direct coupling of Fc to pyridine at the 4 or 3 positions, or at the 4 position via a two-carbon linker, which is either unsaturated (vinyl) or saturated (ethyl). Electron paramagnetic resonance (EPR) and UV-vis spectroscopic studies of the ligand exchange processes of the compounds in phosphate buffered saline (PBS) report similar solution behavior to NAMI-Pyr. However, the complex with Fc substitution at the 3 position of the coordinated pyridine shows greater solution stability, through resistance to the formation of oligomeric species. Further EPR studies of the complexes with human serum albumin (hsA) indicate that the Fc groups enhance noncoordinate interactions with the protein and help to inhibit the formation of protein-coordinated species, suggesting the potential for enhanced bioavailability. Cyclic voltammetry measurements demonstrate that the Fc groups modestly reduce the reduction potential of the Ru(III) center as compared to NAMI-Pyr, while the reduction potentials of the Fc moieties of the four compounds vary by 217 mV, with the longer linkers giving significantly lower values of E1/2. EPR spectra of the compounds with 2-carbon linkers show the formation of a high-spin Fe(III) species (S = 5/2) in PBS with a distinctive signal at g = 4.3, demonstrating oxidation of the Fe(II) ferrocene center and likely reflecting degradation products. Density functional theory calculations and paramagnetic (1)H NMR describe delocalization of spin density onto the ligands and indicate that the vinyl linker could be a potential pathway for electron transfer between the Ru and Fe centers. In the case of the ethyl linker, electron transfer is suggested to occur via an indirect

  13. Laser-Induced Fluorescence Spectroscopy of Two Ruthenium-Bearing Molecules: RuF and RuCl

    NASA Astrophysics Data System (ADS)

    Zarringhalam, Hanif; Adam, Allan G.; Linton, Colan; Tokaryk, Dennis W.

    2017-06-01

    This work extends the electronic spectroscopy of RuF, and reports on what we believe is the first observation of RuCl. Both molecules have been created in a laser-ablation molecular beam apparatus at UNB, and their spectra have been detected by laser-induced fluorescence. In the low-resolution survey of RuF from 400 to 770 nm, five bands were detected in the blue, green and infrared regions of the electromagnetic spectrum. Four of them were rotationally analyzed from high-resolution data. The three bands in the green region are associated with the ^4Γ_{11/2}-X^4Φ_{9/2} system first observed by Steimle et al. A new ^4Δ_{7/2}-X^4Φ_{9/2} transition in the blue region was also detected. Two high-resolution bands of RuCl were rotationally analyzed, and the ground state was also found to be X^4Φ_{9/2}. The data provide detailed structural information about the molecules, such as bond lengths, vibrational frequencies, isotopic structure, spin-orbit interactions and hyperfine interactions. T. C. Steimle, W. Virgo and T. Ma, J. Chem. Phys. 124 024309 (2006).

  14. Investigation of surrogate reactions near A=100: ^102,104Ru(,') for ^101,103Ru(n,γ)

    NASA Astrophysics Data System (ADS)

    Church, J. A.; Bernstein, L. A.; Burke, J. T.; Dietrich, F.; Escher, J.; Forssen, C.; Norman, E. B.; Ai, H.-C.; Phair, L.; Clark, R.; Fallon, P. A.; Lee, D.; Lee, I. Y.; Macchiavelli, A. O.; McMahan, P.; Sinha, S.; Stephens, M.; -Vietez, E. R.; Wiedeking, M.

    2006-10-01

    For two-step, neutron-induced reactions proceeding through an equilibrated intermediate state, an alternate, ``surrogate reaction'' technique is applicable. Measured decay probabilities for the intermediate nucleus formed via a light-ion reaction are combined with optical-model calculations for the formation of the same intermediate nucleus via the n- induced reaction, and result in the overall (n, γ/n/2n) cross sections. ^102,104Ru(,') were studied separately as surrogate reactions for ^101,103Ru (n,γ). The test, ^101Ru(n,γ), has been previously measured directly (EXFOR). The unknown, ^103Ru (n,γ), is a branch in the s-process. Energies of scattered α particles were detected in double-sided silicon detectors (STARS) over scattering angles of 42-60 degrees. Ge clover detectors (LiBerACE) were used to count γ-rays in coincidence with α particles scattered at energies corresponding to 0-3 MeV equivalent neutron energy in the desired (n,γ) reaction. Work performed under the auspices of the U.S. DOE by the Univ. of CA, LLNL contract No. W-7405-Eng-4, and DOE grants DE-FG02-91ER-40609 and DE-FG03- 03NA00081, LDRD-04-ERD-057. J.D. Cramer and H.C. Britt, Nucl. Sci. Eng., 41, 177 (1970).

  15. Quasiparticle self-consistent GW calculation of Sr2RuO4 and SrRuO3

    NASA Astrophysics Data System (ADS)

    Ryee, Siheon; Jang, Seung Woo; Kino, Hiori; Kotani, Takao; Han, Myung Joon

    2016-02-01

    By using quasiparticle self-consistent GW calculations, we reexamined the electronic structure of Sr2RuO4 and SrRuO3. Our calculations show that the correlation effects beyond the conventional local density approximation and generalized gradient approximation are reasonably well captured by the QSGW self-energy without any ad hoc parameter or any ambiguity related to the double-counting and the downfolding issues. While spectral weight transfer to the lower and upper Hubbard band is not observed, the noticeable bandwidth reduction and effective-mass enhancement are obtained. Important features in the electronic structures that have been debated over the last decades such as the photoemission spectra at around -3 eV in Sr2RuO4 and the half-metallicity for SrRuO3 are discussed in the light of our QSGW results and in comparison with the previous studies. The promising aspects of QSGW are highlighted as a first-principles calculation method to describe the moderately correlated 4 d transition-metal oxides along with the limitations of QSGW.

  16. Synthesis of Pd9Ru@Pt nanoparticles for oxygen reduction reaction in acidic electrolytes

    DOE PAGES

    Sun, Yu; Hsieh, Yu -Chi; Chang, Li -Chung; ...

    2014-11-22

    Nanoparticles of PdRu, Pd₃Ru, and Pd₉Ru are synthesized and impregnated on carbon black via a wet chemical reflux process. X-ray diffraction patterns of the as-synthesized samples, PdxRu/C (x=1/3/9), suggest succesful formation of alloy without presence of individual Pd and Ru nanoparticles. Images from transmission electron microscope confirm irregularly-shaped nanoparticles with average size below 3 nm. Analysis from extended X-ray absorption fine structure on both Pd and Ru K-edge absorption profiles indicate the Ru atoms are enriched on the surface of PdxRu/C. Among these samples, the Pd₉Ru/C exhibits the strongest electrocatalytic activity for oxygen reduction reaction (ORR) in an oxygen-saturated 0.1more » M aqueous HClO₄ solution. Subsequently, the Pd₉Ru/C undegoes Cu under potential deposition, followed by a galvanic displacement reaction to deposit a Pt monolayer on the Pd₉Ru surface (Pd₉Ru@Pt). The Pd₉Ru@Pt reveals better ORR performance than that of Pt, reaching a mass activity of 0.38 mA μg⁻¹ Pt, as compared to that of commercially available Pt nanoparticles (0.107 mA μg⁻¹ Pt). Thus, the mechanisms responsible for the ORR enhancement are attributed to the combined effects of lattice strain and ligand interaction. In addition, this core-shell Pd₉Ru@Pt electrocatalyst represents a substantial reduction in the amount of Pt consumption and raw material cost.« less

  17. Thermal Stability of Co-Sputtered Ru Ti Alloy Electrodes for Dynamic Random Access Memory Applications

    NASA Astrophysics Data System (ADS)

    Horng, Ray-Hua; Wuu, Dong-Sing; Wu, Luh-Huei; Lee, Ming-Kwei; Chan, Shih-Hsiung; Leu, Ching-Chich; Huang, Tiao-Yuan; Sze, Simon

    1998-10-01

    Ru Ti alloy films were studied for use as a bottom electrode of ferroelectric/paraelectric thin film capacitors. These thin films with different Ru/Ti compositions were first prepared by co-sputtering. The Ru/Ti ratio in the alloy was found to strongly affect the resistivity, structure formation and thermal stability. The resistivity of the as-deposited films decreases and closes to that of pure Ru metal films as the amount of Ru atoms increasing. From X-ray diffraction measurement, it was found that the RuTi phase has formed for the as-deposited sample. There also exist Ru and Ti phases for Ru-enriched and Ti-enriched samples, respectively. As-deposited alloy films were also annealed by rapid thermal processing (RTP, 600 750°C, 1 min) in oxygen ambient to simulate the processing of ferroelectric/paraelectric thin film capacitors. It was found that the composition of the thin film has a large effect on the thermal stability. The resistivity of alloy thin films is thermally stable as the Ru composition varies from 0.68 to 0.81. It may be due to the RuTiO2 formation at the surface and play an important role in preventing further oxidation of the Ru-enriched layer. This oxide also presents conductive behavior. On the other hand, the interface between Ru-enriched alloys and Si substrate was still sharp for the RTP-treated sample at 600°C for 1 min. The alloy film with high Ru composition shows excellent thermal stability and barriers against interdiffusion of Si and oxygen. These results suggest that the Ru-enriched alloy films are suitable for the bottom electrode application in ferroelectric/paraelectric thin film capacitors.

  18. Platinum Group Elements, 187OS/188OS and 87SR/86SR Isotope Systematics in Depleted Fluid-Modified Mariana Fore-Arc Peridotites

    NASA Astrophysics Data System (ADS)

    Harvey, J.; Savov, I. P.; Shirey, S. B.; Horan, M. F.; Mock, T. D.

    2012-12-01

    The serpentine mud volcanoes of the Izu-Bonin-Mariana (IBM) fore-arc, collected during Ocean Drilling Program Leg 195 [1], contain hard-rock clasts of serpentine sampled from close to the décollement, which separates the down-going Pacific slab from the overlying mantle wedge. These clasts preserve evidence for melt depletion (>25 % melt extraction in many instances) in a sub-arc environment, and extensive (40 - 100%) serpentinization due to subsequent fluid / peridotite interaction, e.g. [2]. Platinum-group element (PGE) abundances are not consistent with melt-depletion alone [3]. Fractionation between I-PGE (Os, Ir, Ru) has resulted in groups of IBM serpentinites with either a high chondrite-normalized Os/Ir ratio (OsN/IrN) or a low OsN/IrN ratio. Similarly, fractionation of P-PGE (Pt, Pd) is marked, and distinguishes the IBM serpentinites from worldwide abyssal peridotites. Interaction with high-pH fluids [4] may have partially oxidized mantle sulphide, the major primary host for PGE in these rocks, leading to partial breakdown to sulphate and the selective redistribution of certain PGE (Os, Ru, Pt), a feature normally associated with sub-aerial weathering [5], but which likely prevails in other oxidizing environments. In particular, the Re-Os systematics of the high (OsN/IrN) IBM serpentinites have been disturbed by the addition of Os. Unlike peridotite xenoliths associated with magmatic regions of subduction zones where subduction-related Os-addition is unequivocally radiogenic and derived from crustal material [6][7], where Os has been added to the IBM serpentinites it is unradiogenic and was most likely derived from within the oceanic mantle. IBM serpentinites therefore preserve osmium isotope ratios that are exclusively sub-chondritic (187Os/188Os ≤ 0.127), as previously reported [8]. These serpentinized peridotites were produced by at least a three-step process: melt depletion, serpentinization, and the mobilization of Os, Ru and Pt to produce low Os

  19. OS-10 Payload Provisions

    NASA Astrophysics Data System (ADS)

    Kemp, P.; Hempsell, C. M.

    The OS-10 is a small space station concept which is intended for commercial development and sale on the open market. It is designed to be operated as a “shelter”; that is for most of its in orbit life it operates unmanned but is supported by periodic manned servicing visits. This pattern of utilisation and the expected customer requirements led to a different approach to the provision of payload facilities when compared with past manned orbiting laboratories. The paper outlines these facilities and explains the rationale for their inclusion. While it is outside the scope of the paper to fully cover and justify the commercial and marketing aspects of the OS-10 project, some discussion of the background assumptions is required to appreciate their impact on the technical approaches.

  20. OS Friendly Microprocessor Architecture

    DTIC Science & Technology

    2017-04-01

    writes a cache bank block of data to USB controller .......34 Fig. 29 Process stack example...Architecture Block Diagram Data Bus Program Address Bus Data Address Bus Read/ Write Program Memory Extended Harvard Processor Architecture Program...Bus Data Memory Data Address Bus Read/ Write Data Address Bus Read/ Write Register Mem Pipeline State Mem OS Friendly Architecture B us se s B us se

  1. Symptomatic os infranaviculare.

    PubMed

    Kim, Jae Kwang; Roh, Kwon Jae

    2013-06-01

    The author observed a new accessory bone of the foot in the distal portion of navicular, which articulated with the medial cuneiform and the intermediate cuneiform, and named it os infranaviculare. A degenerative change was observed between the accessory bone and the navicular; this caused midfoot pain to the patient during weight-bearing. Thus, the patient was treated by excision of the accessory bone. The symptom was relieved at one-year postoperative.

  2. Symptomatic Os Infranaviculare

    PubMed Central

    Roh, Kwon Jae

    2013-01-01

    The author observed a new accessory bone of the foot in the distal portion of navicular, which articulated with the medial cuneiform and the intermediate cuneiform, and named it os infranaviculare. A degenerative change was observed between the accessory bone and the navicular; this caused midfoot pain to the patient during weight-bearing. Thus, the patient was treated by excision of the accessory bone. The symptom was relieved at one-year postoperative. PMID:23730481

  3. Development of a Ru complex-incorporated MOF photocatalyst for hydrogen production under visible-light irradiation.

    PubMed

    Toyao, Takashi; Saito, Masakazu; Dohshi, Satoru; Mochizuki, Katsunori; Iwata, Masatoshi; Higashimura, Hideyuki; Horiuchi, Yu; Matsuoka, Masaya

    2014-06-28

    A Ru complex-incorporated Ti-based MOF (Ti-MOF-Ru(tpy)2) has been synthesised by using a bis(4'-(4-carboxyphenyl)-terpyridine)Ru(ii) complex (Ru(tpy)2) as an organic linker. Ti-MOF-Ru(tpy)2 promotes photocatalytic hydrogen production from water containing a sacrificial electron donor under visible-light irradiation up to 620 nm.

  4. Precise ReOs determinations and systematics of iron meteorites

    NASA Astrophysics Data System (ADS)

    Shen, J. J.; Papanastassiou, D. A.; Wasserburg, G. J.

    1996-08-01

    The ReOs system for samples of FeNi, sulphide, and phosphide from iron meteorites was investigated. Techniques were developed which yield reproducible analyses for Re/Os at the 2%‰ level and which permit complete isotopic exchange between sample and tracer, as is necessary for concentration measurements of Re and Os by isotope dilution. High precision osmium and rhenium isotope data have been obtained using negative ion thermal ionization, with ionization efficiencies of up to 10% for Os and 20% for Re, both for normals and for Re and Os extracted from the samples. Replicate analyses of Re/Os are in good agreement, within ±2.5%o. The results show a well defined correlation line on a 187Re- 187Os evolution diagram for iron meteorites from groups IAB, IIAB, IIIAB, IVA, and IVB, all taken together. This correlation line yields a slope of 0.07863 ± 0.00031 (2σ) and initial 187Os/ 188Os = 0.09560 ± 0.00018 (2σ). If the individual groups of iron meteorites for which there is sufficient dispersion in Re/Os are considered, data on the IIAB and on the IVA irons appear to indicate a difference in age of 60 ± 45 Ma, with the IVA group being older. This age difference is qualitatively the same as obtained for PdAg data but is larger. Sulphides from two IAB iron meteorites show extremely low concentrations of Re and Os and indicate that Re and Os are not partitioned into this phase during planetary differentiation. There is evidence for recent element remobilization or contamination, corresponding to relative enrichment of Re or loss of Os in the sulphides. Schreibersites contain small but significant amounts of Re and Os, with high Re/Os relative to the metal phases and with 187Os/ 188Os much more radiogenic than in the metal. Model ages for the Schreibersites are relatively young (4.3-3.5 AE) and indicate that the Schreibersites were open-systems for ReOs at least 0.5-1 AE after the original formation of the iron meteorites. It now appears possible to use

  5. Novel 2D RuPt core-edge nanocluster catalyst for CO electro-oxidation

    NASA Astrophysics Data System (ADS)

    Grabow, Lars C.; Yuan, Qiuyi; Doan, Hieu A.; Brankovic, Stanko R.

    2015-10-01

    A single layer, bi-metallic RuPt catalyst on Au(111) is synthesized using surface limited red-ox replacement of underpotentially deposited Cu and Pb monolayers though a two-step process. The resulting 2D RuPt monolayer nanoclusters have a unique core-edge structure with a Ru core and Pt at the edge along the perimeter. The activity of this catalyst is evaluated using CO monolayer oxidation as the probe reaction. Cyclic voltammetry demonstrates that the 2D RuPt core-edge catalyst morphology is significantly more active than either Pt or Ru monolayer catalysts. Density functional theory calculations in combination with infra-red spectroscopy data point towards oscillating variations (ripples) in the adsorption energy landscape along the radial direction of the Ru core as the origin of the observed behavior. Both, CO and OH experience a thermodynamic driving force for surface migration towards the Ru-Pt interface, where they adsorb most strongly and react rapidly. We propose that the complex interplay between epitaxial strain, ligand and finite size effects is responsible for the formation of the rippled RuPt monolayer cluster, which provides optimal conditions for a quasi-ideal bi-functional mechanism for CO oxidation, in which CO is adsorbed mainly on Pt, and Ru provides OH to the active Pt-Ru interface.

  6. Synthesis, spectral and electrochemical studies of binuclear Ru(III) complexes containing dithiosemicarbazone ligand.

    PubMed

    Kanchana Devi, A; Ramesh, R

    2014-01-03

    Synthesis of several new octahedral binuclear ruthenium(III) complexes of the general composition [(EPh3)2(X)Ru-L-Ru(X)(EPh3)2] containing benzene dithiosemicarbazone ligands (where E=P or As; X=Cl or Br; L=binucleating ligands) is presented. All the complexes have been fully characterized by elemental analysis, FT-IR, UV-vis and EPR spectroscopy together with magnetic susceptibility measurements. IR study shows that the dithiosemicarbazone ligands behave as dianionic tridentate ligands coordinating through the oxygen atom of the deprotonated phenolic group, nitrogen atom of the azomethine group and thiolate sulphur. In DMF solution, all the complexes exhibit intense d-d transition and ligand-to-metal charge transfer (LMCT) transition in the visible region. The magnetic moment values of the complexes are in the range 1.78-1.82 BM, which reveals the presence of one unpaired electron on each metal ion. The EPR spectra of the liquid samples at LNT show the presence of three different 'g' values (gx≠gy≠gz) indicate a rhombic distortion around the ruthenium ion. All the complexes exhibit two quasi-reversible one electron oxidation responses (Ru(III)-Ru(III)/Ru(III)-Ru(IV); Ru(III)-Ru(IV)/Ru(IV)-Ru(IV)) within the E1/2 range of 0.61-0.74 V and 0.93-0.98 V respectively, versus Ag/AgCl.

  7. Synthesis, spectral and electrochemical studies of binuclear Ru(III) complexes containing dithiosemicarbazone ligand

    NASA Astrophysics Data System (ADS)

    Kanchana Devi, A.; Ramesh, R.

    2014-01-01

    Synthesis of several new octahedral binuclear ruthenium(III) complexes of the general composition [(EPh3)2(X)Ru-L-Ru(X)(EPh3)2] containing benzene dithiosemicarbazone ligands (where E = P or As; X = Cl or Br; L = binucleating ligands) is presented. All the complexes have been fully characterized by elemental analysis, FT-IR, UV-vis and EPR spectroscopy together with magnetic susceptibility measurements. IR study shows that the dithiosemicarbazone ligands behave as dianionic tridentate ligands coordinating through the oxygen atom of the deprotonated phenolic group, nitrogen atom of the azomethine group and thiolate sulphur. In DMF solution, all the complexes exhibit intense d-d transition and ligand-to-metal charge transfer (LMCT) transition in the visible region. The magnetic moment values of the complexes are in the range 1.78-1.82 BM, which reveals the presence of one unpaired electron on each metal ion. The EPR spectra of the liquid samples at LNT show the presence of three different 'g' values (gx ≠ gy ≠ gz) indicate a rhombic distortion around the ruthenium ion. All the complexes exhibit two quasi-reversible one electron oxidation responses (RuIII-RuIII/RuIII-RuIV; RuIII-RuIV/RuIV-RuIV) within the E1/2 range of 0.61-0.74 V and 0.93-0.98 V respectively, versus Ag/AgCl.

  8. Diamagnetic Ru(2+) in Na2La2Ti2RuO10-x (0 < x < 2): A Series of Complex Oxides Prepared by Topochemical Reduction.

    PubMed

    Pratt, Jacob A; Shepherd, Ashley M; Hayward, Michael A

    2015-11-16

    Reaction of the n = 3 Ruddlesden-Popper phase Na2La2Ti2RuO10 with a 5% H2/95% N2 atmosphere between 300 and 900 °C leads to the formation of phases of composition Na2La2Ti2RuO10-x (0 < x < 2) via topochemical reduction. Magnetization data collected from Na2La2Ti2RuO10-x samples in the range 0 < x < 1 show a rapid decline in susceptibility with increasing x, consistent with the conversion of S = 1, Ru(4+) centers at x = 0 to S = 0, Ru(2+) centers at x = 1. We believe this is the first report of diamagnetic Ru(2+) centers in an extended oxide phase. Further reduction of Na2La2Ti2RuO9 leads to the reduction of Ti(4+) to Ti(3+); however, Na2La2Ti2RuO10-x samples in the range 1 < x < 2 exhibit only a very weak paramagnetic response. Given the highly insulating nature of the phases, this suggests the electrons added on reduction of titanium are paired within a local Ti-Ti bonding network in a manner analogous to that observed for TinO2n-1 phases.

  9. Magnetic, electronic, high-spin polarization and half-metallic properties of Ru2VGe and Ru2VSb Heusler alloys: An FP-LAPW study

    NASA Astrophysics Data System (ADS)

    Gupta, Dinesh C.; Bhat, Idris H.

    2015-01-01

    Electronic and magnetic properties of Ru2VGe and Ru2VSb have been calculated using full potential linearized augmented plane wane method. The optimized equilibrium lattice constants in stable Fm-3m configuration were found to be 6.032 Å for Ru2VGe and 6.272 Å for Ru2VSb. Spin-resolved calculations show that V mainly contributes to the magnetic properties in these materials. The materials follow the Slater-Pauling rule and hence have integral magnetic moments which is due to 100% spin polarization at Fermi energy. The calculated total magnetic moments per unit cell were found to be 1.0 μB for Ru2VGe and 2.0 μB for Ru2VSb. Both the materials having ferromagnetic ground state, exhibit half-metallicity with an energy gap in the spin-down channel of 0.095 eV for Ru2VGe and 0.186 eV for Ru2VSb.

  10. RuSi@Ru(bpy)3(2+)/Au@Ag2S nanoparticles electrochemiluminescence resonance energy transfer system for sensitive DNA detection.

    PubMed

    Wu, Mei-Sheng; He, Li-Jing; Xu, Jing-Juan; Chen, Hong-Yuan

    2014-05-06

    This work describes a new electrochemiluminescence resonance energy transfer (ECL-RET) system with graphene oxide(GO)-Au/RuSi@Ru(bpy)3(2+)/chitosan (CS) composites as the ECL donor and Au@Ag2S nanoparticles (NPs) as ECL the acceptor for the first time. The ECL signal observed by the application of GO-Au/RuSi@Ru(bpy)3(2+)/CS composites was enhanced for 5-fold compared to that of RuSi@Ru(bpy)3(2+)/CS in the presence of coreactant tripropylamine (TPA) due to the increased surface area and improved electrical conductivity by using graphene oxide-gold nanoparticles (GO-Au) composite materials. In addition, we synthesized Au@Ag2S core-shell NPs, whose UV-vis absorption spectrum shows good spectral overlap with the ECL spectrum of GO-Au/RuSi@Ru(bpy)3(2+)/CS composites by adjusting the amount of Na2S and AgNO3 in the process of synthesis. The distance between energy donor and acceptor was studied to get the highly effective ECL-RET. Then, this ECL-RET system was developed for sensitive and specific detection of target DNA, and the ECL quenching efficiency (ΔI/I0, ΔI = I0 - I) was found to be logarithmically related to the concentration of the target DNA in the range from 10 aM to 10 pM.

  11. Nmr evidence for coexistence of superconductivity and ferromagnetic component in magnetic superconductor RuSr2YCu2O8: 99,101Ru and 63Cu NMR.

    PubMed

    Tokunaga, Y; Kotegawa, H; Ishida, K; Kitaoka, Y; Takagiwa, H; Akimitsu, J

    2001-06-18

    From Ru- and Cu-NMR studies, we present evidence for coexistence of superconductivity and ferromagnetism in a cuprate superconductor RuSr2YCu2O8 (RuY1212). The observation of a large enhancement of a radio-frequency field for the Ru-NMR signal at zero field reveals the existence of a ferromagnetic (FM) component in the ordered RuO2 plane below a Curie temperature of TM = 150 K. Just below the onset temperature of superconductivity T(onset)c = 45 K, a remarkable decrease of the nuclear spin-lattice relaxation rate 1/T1 was observed within the ordered RuO2 plane as well as the CuO2 plane, revealing that the superconducting gap coexists with the FM component in the RuO2 plane on a microscopic scale. In addition, from the observation of a sharp peak in 101(1/T1) at T(zero)c approximately 23 K where the resistivity becomes zero, we suggest that the motion of self-induced vortices originating from fluctuations of the FM component induces the resistivity between T(onset)c and T(zero)c in RuY1212.

  12. Adsorption and Dissociation of CO2 on Ru(0001)

    PubMed Central

    2017-01-01

    The adsorption and dissociation of carbon dioxide on a Ru(0001) single crystal surface was investigated by reflection–absorption infrared spectroscopy (RAIRS) and temperature-programmed desorption (TPD) spectroscopy for CO2 adsorbed at 85 K. RAIRS spectroscopy shows that the adsorption of CO2 on a Ru(0001) single crystal is partially dissociative, resulting in CO2 and CO. The CO vibrational mode was also observed to split into two distinct modes, indicating two general populations of CO present at the surface. Furthermore, a time-dependent blue-shift is observed, which is characteristic of increasing CO surface coverage. TPD showed that coverages of up to 0.3 ML were obtained, and no evidence for chemisorption of oxygen on ruthenium was found.

  13. Linear magnetoresistance in a topological insulator Ru2Sn3

    NASA Astrophysics Data System (ADS)

    Shiomi, Y.; Saitoh, E.

    2017-03-01

    We have studied magnetotransport properties of a topological insulator material Ru2Sn3. Bulk single crystals of Ru2Sn3 were grown by a Bi flux method. The resistivity is semiconducting at high temperatures above 160 K, while it becomes metallic below 160 K. Nonlinear field dependence of Hall resistivity in the metallic region shows conduction of multiple carriers at low temperatures. In the high-temperature semiconducting region, magnetoresistance exhibits a conventional quadratic magnetic-field dependence. In the low-temperature metallic region, however, high-field magnetoresistance is clearly linear with magnetic fields, signaling a linear dispersion in the low-temperature electronic structure. Small changes in the magnetoresistance magnitude with respect to the magnetic field angle indicate that bulk electron carriers are responsible mainly for the observed linear magnetoresistance.

  14. Silicene Evolution from Silicon Herringbones on Ru(0001)

    NASA Astrophysics Data System (ADS)

    Zhang, Yanfang; Huang, Li; Xu, Wenyan; Que, Yande; Li, En; Pan, Jinbo; Du, Shixuan; Liu, Yunqi; Zhang, Yuyang; Pantelides, Sokrates T.; Gao, Hongjun

    Silicon-based 2D materials can potentionally be integrated into Si-based electronics. Buckled silicene, an analog of graphene, was recently fabricated on a Ag (111) substrate and used to make a field effect transistor. Here, we report that, when Ru (0001) is used as a substrate, low Si coverage produces a herringbone structure, a new silicon phase. With increasing Si coverage, the elbow sites of the herringbone develop into nucleation sites of silicene. At even higher coverage, narrow Si ribbons with honeycomb structure develop between herringbones. Finally, with even higher Si coverage, a (√3 x √3) silicene monolayer forms in registry on (√7 x √7) Ru(0001). Scanning tunneling microscopy (STM) was used to image the structures. The growth process was confirmed by density functional theory (DFT) calculations. This work may contribute to precise control of growth of silicene and other silicon structures.

  15. Temperature-dependent thermal properties of Ru/C multilayers.

    PubMed

    Yan, Shuai; Jiang, Hui; Wang, Hua; He, Yan; Li, Aiguo; Zheng, Yi; Dong, Zhaohui; Tian, Naxi

    2017-09-01

    Multilayers made of Ru/C are the most promising candidates when working in the energy region 8-20 keV. The stability of its thermal properties, including thermal expansion and thermal conduction, needs to be considered for monochromator or focusing components. Ru/C multilayers with periodic thicknesses of 3, 4 and 5 nm were investigated in situ by grazing-incidence X-ray reflectometry and diffuse scattering in order to study their thermal expansion characteristics as a function of annealing temperature up to 400°C. The thermal conductivity of multilayers with the same structure was also measured by the transient hot-wire method and compared with bulk values.

  16. {sup 45}Sc Solid State NMR studies of the silicides ScTSi (T=Co, Ni, Cu, Ru, Rh, Pd, Ir, Pt)

    SciTech Connect

    Harmening, Thomas; Eckert, Hellmut; Fehse, Constanze M.; Sebastian, C. Peter; Poettgen, Rainer

    2011-12-15

    The silicides ScTSi (T=Fe, Co, Ni, Cu, Ru, Rh, Pd, Ir, Pt) were synthesized by arc-melting and characterized by X-ray powder diffraction. The structures of ScCoSi, ScRuSi, ScPdSi, and ScIrSi were refined from single crystal diffractometer data. These silicides crystallize with the TiNiSi type, space group Pnma. No systematic influences of the {sup 45}Sc isotropic magnetic shift and nuclear electric quadrupolar coupling parameters on various structural distortion parameters calculated from the crystal structure data can be detected. {sup 45}Sc MAS-NMR data suggest systematic trends in the local electronic structure probed by the scandium atoms: both the electric field gradients and the isotropic magnetic shifts relative to a 0.2 M aqueous Sc(NO{sub 3}){sub 3} solution decrease with increasing valence electron concentration and within each T group the isotropic magnetic shift decreases monotonically with increasing atomic number. The {sup 45}Sc nuclear electric quadrupolar coupling constants are generally well reproduced by quantum mechanical electric field gradient calculations using the WIEN2k code. Highlights: Black-Right-Pointing-Pointer Arc-melting synthesis of silicides ScTSi. Black-Right-Pointing-Pointer Single crystal X-ray data of ScCoSi, ScRuSi, ScPdSi, and ScIrSi. Black-Right-Pointing-Pointer {sup 45}Sc solid state NMR of silicides ScTSi.

  17. A novel solid-state electrochemiluminescence sensor for melamine with Ru(bpy)3(2+)/mesoporous silica nanospheres/Nafion composite modified electrode.

    PubMed

    Cao, Hongmei; Hu, Xiaoqing; Hu, Chenyi; Zhang, Yang; Jia, Nengqin

    2013-03-15

    A novel melamine electrochemiluminescence (ECL) sensor was developed based on mesoporous SiO(2) nanospheres/Ru(bpy)(3)(2+)/Nafion modified electrodes. The homogeneous mesoporous silica nanospheres, synthesized using modified Stöber sol-gel process, were characterized by Field Emission Scanning Electron Microscopy (FE-SEM), Transmission Electron Microscopy (TEM) and Brunauer-Emmett-Teller (BET). The ECL and electrochemistry of the modified electrodes were investigated with tri-n-propylamine (TPA) as the coreactant. Furthermore, the mesporous SiO(2) nanospheres/Ru(bpy)(3)(2+)-based modified electrodes were used for ECL determination of melamine. The analytical performances of this ECL sensor for melamine based on its enhancement ECL emission of Ru(bpy)(3)(2+) were investigated. The results indicated that the sensor exhibited excellent performance during melamine determination with a wide linear range (7.81×10(-9)-5×10(-6) M), low detection limit (2.6×10(-9) M). The high sensitivity and stability mainly resulted from the high surface area and special structure of the mesoporous silica nanospheres. The proposed ECL approach was used to analyze the melamine content in powdered milk with satisfactory results.

  18. Ru-catalyzed stereoselective addition of imides to alkynes.

    PubMed

    Goossen, Lukas J; Blanchot, Mathieu; Brinkmann, Claus; Goossen, Käthe; Karch, Ralph; Rivas-Nass, Andreas

    2006-12-08

    A catalyst system formed in situ from bis(2-methylallyl)cycloocta-1,5-dieneruthenium(II) ((cod)Ru[met]2), a phosphine, and scandium(III) trifluoromethanesulfonate (Sc(OTf)3) was found to efficiently catalyze the anti-Markovnikov addition of imides to terminal alkynes, allowing mild and atom-economic synthesis of enimides. Depending on the phosphine employed, both the (E)- and the (Z)-isomer can be accessed stereoselectively.

  19. Shape Evolution in Neutron-Rich Ru Nuclei

    NASA Astrophysics Data System (ADS)

    Söderström, P.-A.; Lorusso, G.; Watanabe, H.; Nishimura, S.; Doornenbal, P.; Browne, F.; Bruce, A. M.; Daido, R.; Fang, Y.; Gey, G.; Jung, H. S.; Nishizuka, I.; Patel, Z.; Rice, S.; Sinclair, L.; Sumikama, T.; Taprogge, J.; Vajta, Zs.; Wu, J.; Xu, Z. Y.; Baba, H.; Benzoni, G.; Carroll, R. J.; Chae, K. Y.; Crespi, F. C. L.; Fukuda, N.; Gernhäuser, R.; Ideguchi, E.; Inabe, N.; Isobe, T.; Jungclaus, A.; Kameda, D.; Kim, G. D.; Kim, Y.-K.; Kojouharov, I.; Kondev, F. G.; Kubo, T.; Kurz, N.; Kwon, Y. K.; Lalkovski, S.; Lane, G. J.; Li, Z.; Lozeva, R.; Montaner-Piza, A.; Moschner, K.; Naqvi, F.; Niikura, M.; Nishibata, H.; Odahara, A.; Orlandi, R.; Podolyak, Zs.; Regan, P. H.; Roberts, O. J.; Sakurai, H.; Schaffner, H.; Simpson, G. S.; Steiger, K.; Suzuki, H.; Takeda, H.; Tanaka, M.; Wendt, A.; Werner, V.; Wieland, O.; Yagi, A.; Yoshinaga, K.

    Recent experimental work has been carried out at the RIBF using the EURICA HPGe detector array. In this contribution, we discuss the recently published results on the shape evolution of the even-even isotopes 116,118Ru and present an outlook of β-delayed γ-ray spectroscopy of the odd-neutron nuclei and possibilities for life-time measurements of excited states.

  20. Influence of Binders and Solvents on Stability of Ru/RuOx Nanoparticles on ITO Nanocrystals as Li-O2 Battery Cathodes.

    PubMed

    Vankova, Svetoslava; Francia, Carlotta; Amici, Julia; Zeng, Juqin; Bodoardo, Silvia; Penazzi, Nerino; Collins, Gillian; Geaney, Hugh; O'Dwyer, Colm

    2017-02-08

    Fundamental research on Li-O2 batteries remains critical, and the nature of the reactions and stability are paramount for realising the promise of the Li-O2 system. We report that indium tin oxide (ITO) nanocrystals with supported 1-2 nm oxygen evolution reaction (OER) catalyst Ru/RuOx nanoparticles (NPs) demonstrate efficient OER processes, reduce the recharge overpotential of the cell significantly and maintain catalytic activity to promote a consistent cycling discharge potential in Li-O2 cells even when the ITO support nanocrystals deteriorate from the very first cycle. The Ru/RuOx nanoparticles lower the charge overpotential compared with those for ITO and carbon-only cathodes and have the greatest effect in DMSO electrolytes with a solution-processable F-free carboxymethyl cellulose (CMC) binder (<3.5 V) instead of polyvinylidene fluoride (PVDF). The Ru/RuOx /ITO nanocrystalline materials in DMSO provide efficient Li2 O2 decomposition from within the cathode during cycling. We demonstrate that the ITO is actually unstable from the first cycle and is modified by chemical etching, but the Ru/RuOx NPs remain effective OER catalysts for Li2 O2 during cycling. The CMC binders avoid PVDF-based side-reactions and improve the cyclability. The deterioration of the ITO nanocrystals is mitigated significantly in cathodes with a CMC binder, and the cells show good cycle life. In mixed DMSO-EMITFSI [EMITFSI=1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide] ionic liquid electrolytes, the Ru/RuOx /ITO materials in Li-O2 cells cycle very well and maintain a consistently very low charge overpotential of 0.5-0.8 V. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.