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Sample records for fe ru os

  1. Infrared spectra and theoretical calculations for Fe, Ru, and Os metal hydrides and dihydrogen complexes.

    PubMed

    Wang, Xuefeng; Andrews, Lester

    2009-01-22

    Laser-ablated iron, ruthenium, and osmium atoms react with hydrogen in excess argon, neon and pure hydrogen to produce the FeH(2) molecule, and the FeH(2)(H(2))(3), RuH(H(2))(4), RuH(2)(H(2))(4), and (H(2))MH complexes (M = Fe, Ru, Os), as identified through infrared spectra with D(2) and HD substitution. DFT frequency calculations support the assignment of absorptions observed experimentally. The FeH(2) molecule has a quintet ground state with a quasi-linear structure, and is repulsive to the addition of one more H(2) ligand: however, with three more H(2) ligands, stable triplet and singlet state FeH(2)(H(2))(3) supercomplexes can be formed. The quintet FeH(2) molecule and FeH(2)(H(2))(3) supercomplex undergo reversible near-ultraviolet photochemical rearrangement in solid neon and hydrogen. The RuH(2) molecule has a bent triplet ground state and forms the stable singlet RuH(2)(H(2))(4) supercomplex, but only the latter is observed in these experiments. In like fashion RuH has a quartet ground state and the doublet RuH(H(2))(4) complex is trapped in solid hydrogen. All three (H(2))MH complexes with lower energy than MH(3) are trapped, and no absorptions are observed for MH(3) molecules.

  2. Infrared spectra and theoretical calculations for Fe, Ru, and Os metal hydrides and dihydrogen complexes.

    PubMed

    Wang, Xuefeng; Andrews, Lester

    2009-01-22

    Laser-ablated iron, ruthenium, and osmium atoms react with hydrogen in excess argon, neon and pure hydrogen to produce the FeH(2) molecule, and the FeH(2)(H(2))(3), RuH(H(2))(4), RuH(2)(H(2))(4), and (H(2))MH complexes (M = Fe, Ru, Os), as identified through infrared spectra with D(2) and HD substitution. DFT frequency calculations support the assignment of absorptions observed experimentally. The FeH(2) molecule has a quintet ground state with a quasi-linear structure, and is repulsive to the addition of one more H(2) ligand: however, with three more H(2) ligands, stable triplet and singlet state FeH(2)(H(2))(3) supercomplexes can be formed. The quintet FeH(2) molecule and FeH(2)(H(2))(3) supercomplex undergo reversible near-ultraviolet photochemical rearrangement in solid neon and hydrogen. The RuH(2) molecule has a bent triplet ground state and forms the stable singlet RuH(2)(H(2))(4) supercomplex, but only the latter is observed in these experiments. In like fashion RuH has a quartet ground state and the doublet RuH(H(2))(4) complex is trapped in solid hydrogen. All three (H(2))MH complexes with lower energy than MH(3) are trapped, and no absorptions are observed for MH(3) molecules. PMID:19099441

  3. 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.

  4. Compressibility of Ru and Os in Comparison with Hcp ɛ -Fe; the lowest measured compressibility

    NASA Astrophysics Data System (ADS)

    Cynn, H.; Yoo, C.; Iota, V.; Baer, B.

    2001-12-01

    The hardness of a material is strongly correlated with its bulk modulus; thus, the search for superhard materials often becomes the search for very low compressibilities. Diamond is the hardest known material and has the highest known bulk modulus, B0 = 443 GPa (or the lowest compressibility, β = 0.226 Mbar-1). In this paper, we present surprising experimental findings that metallic elements like Os, Ir, and Ru are also good candidates for superhard materials based on their measured low compressibilities. We also present the pressure volume relationships of Ru, Os, and Ir to 70 GPa, in comparison with those of ɛ -Fe, W and C. The results are in a systematic agreement with the change of the bulk moduli and also with the first-principles electronic structure calculations. However, the c/a ratios of the 4,5d-transition metals show a slightly different trend from that of 3d ɛ -Fe at high pressures. Because of the similarity in electronic structure of these metals and Fe, the major constituent of the Earth's core, the EOS's and crystal structural parameters of the Group VIIIA transition metals reported in this paper are central to understanding the Earth's core mineral physics. This work was performed under the auspices of the U.S. Department of Energy by University of California Lawrence Livermore National Laboratory under contract No. W-7405-Eng-48.

  5. 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.

  6. 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. PMID:25982241

  7. 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

    2016-05-01

    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.

  8. 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

    2016-05-01

    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. PMID:27074099

  9. 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.

  10. Electronic, structural and magnetic studies of niobium borides of group 8 transition metals, Nb2MB2 (M=Fe, Ru, Os) from first principles calculations

    NASA Astrophysics Data System (ADS)

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

    2014-03-01

    The Nb2FeB2 phase (U3Si2-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 Nb2OsB2 (space group P4/mnc, no. 128, a twofold superstructure of U3Si2-type) with distorted Nb-layers and Os2-dumbbells was recently achieved, "Nb2RuB2" 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 Nb2FeB2 and Nb2OsB2, but also predict "Nb2RuB2" to crystalize with the Nb2OsB2 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 Nb2FeB2, originating from ferromagnetic interactions within iron chains and antiferromagnetic exchange interactions between them.

  11. 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.

  12. 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. PMID:26523807

  13. 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.

  14. 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.

  15. 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

  16. Spin-State Effects on the Thermal Dihydrogen Release from Solid-State [MH(η(2)-H 2)dppe2](+) (M = Fe, Ru, Os) Organometallic Complexes for Hydrogen Storage Applications.

    PubMed

    Abrecht, David G; Muñoz, Jorge A; Smith, Hillary L; Fultz, Brent

    2014-01-30

    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(η(2)-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.

  17. Can [M(H)2(H2)(PXP)] pincer complexes (M=Fe, Ru, Os; X=N, O, S) serve as catalyst lead structures for NH3 synthesis from N2 and H2?

    PubMed

    Hölscher, Markus; Prechtl, Martin H G; Leitner, Walter

    2007-01-01

    The potential of pincer complexes [M(H)(2)(H(2))(PXP)] (M=Fe, Ru, Os; X=N, O, S) to coordinate, activate, and thus catalyze the reaction of N(2) with classical or nonclassical hydrogen centers present at the metal center, with the aim of forming NH(3) with H(2) as the only other reagent, was explored by means of DF (density functional) calculations. Screening of various complexes for their ability to perform initial hydrogen transfer to coordinated N(2) showed ruthenium pincer complexes to be more promising than the corresponding iron and osmium analogues. The ligand backbone influences the reaction dramatically: the presence of pyridine and thioether groups as backbones in the ligand result in inactive catalysts, whereas ether groups such as gamma-pyran and furan enable the reaction and result in unprecedented low activation barriers (23.7 and 22.1 kcal mol(-1), respectively), low enough to be interesting for practical application. Catalytic cycles were calculated for [Ru(H)(2)(H(2))(POP)] catalysts (POP=2,5-bis(dimethylphosphanylmethyl)furan and 2,6-bis(dimethylphosphanylmethyl)-gamma-pyran). The height of activation barriers for the furan system is somewhat more advantageous. Formation of inactive metal nitrides has not been observed. SCRF calculations were used to introduce solvent (toluene) effects. The Gibbs free energies of activation of the numerous single reaction steps do not change significantly when solvent is included. The reaction steps associated with the formation of the active catalyst from precursors [M(H)(2)(H(2))(PXP)] were also calculated. The otherwise inactive pyridine ligand system allows for the generation of the active catalyst species, whereas the ether ligand systems show activation barriers that could prohibit practical application. Consequently the generation of the active catalyst species needs to be addressed in further studies.

  18. Photoinduced energy- and electron-transfer processes in dinuclear Ru(II)-Os(II), Ru(II)-Os(III), and Ru(III)-Os(II) trisbipyridine complexes containing a shape-persistent macrocyclic spacer.

    PubMed

    Venturi, Margherita; Marchioni, Filippo; Ferrer Ribera, Belén; Balzani, Vincenzo; Opris, Dorina M; Schlüter, A Dieter

    2006-01-16

    The PF6- salt of the dinuclear [(bpy)2Ru(1)Os(bpy)2]4+ complex, where 1 is a phenylacetylene macrocycle which incorporates two 2,2'-bipyridine (bpy) chelating units in opposite sites of its shape-persistent structure, was prepared. In acetonitrile solution, the Ru- and Os-based units display their characteristic absorption spectra and electrochemical properties as in the parent homodinuclear compounds. The luminescence spectrum, however, shows that the emission band of the Ru(II) unit is almost completely quenched with concomitant sensitization of the emission of the Os(II) unit. Electronic energy transfer from the Ru(II) to the Os(II) unit takes place by two distinct processes (k(en) = 2.0x10(8) and 2.2x10(7) s(-1) at 298 K). Oxidation of the Os(II) unit of [(bpy)2Ru(1)Os(bpy)2]4+ by Ce(IV) or nitric acid leads quantitatively to the [(bpy)2Ru(II)(1)Os(III)(bpy)2]5+ complex which exhibits a bpy-to-Os(III) charge-transfer band at 720 nm (epsilon(max) = 250 M(-1) cm(-1)). Light excitation of the Ru(II) unit of [(bpy)2Ru(II)(1)Os(III)(bpy)2]5+ is followed by electron transfer from the Ru(II) to the Os(III) unit (k(el,f) = 1.6x10(8) and 2.7x10(7) s(-1)), resulting in the transient formation of the [(bpy)2Ru(III)(1)Os(II)(bpy)2]5+ complex. The latter species relaxes to the [(bpy)2Ru(II)(1)Os(III)(bpy)2]5+ one by back electron transfer (k(el,b) = 9.1x10(7) and 1.2x10(7) s(-1)). The biexponential decays of the [(bpy)2*Ru(II)(1)Os(II)(bpy)2]4+, [(bpy)2*Ru(II)(1)Os(III)(bpy)2]5+, and [(bpy)2Ru(III)(1)Os(II)(bpy)2]5+ species are related to the presence of two conformers, as expected because of the steric hindrance between hydrogen atoms of the pyridine and phenyl rings. Comparison of the results obtained with those previously reported for other Ru-Os polypyridine complexes shows that the macrocyclic ligand 1 is a relatively poor conducting bridge.

  19. 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

  20. 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.

  1. Can anisotropic exchange be reliably calculated using density functional methods? A case study on trinuclear Mn(III)-M(III)-Mn(III) (M=Fe, Ru, and Os) cyanometalate single-molecule magnets.

    PubMed

    Singh, Saurabh Kumar; Rajaraman, Gopalan

    2014-01-01

    Density functional studies have been performed on a set of trinuclear single-molecule magnets (SMMs) of general formula [{Mn2(5-Br salen)2(MeOH)2}M(CN)6](NEt4) (M=Fe(III) (1), Ru(III) (2) and Os(III) (3); 5-Brsalen=N,N'-ethylenebis(5-bromosalicylidene)iminato anion). We have computed the orbital-dependent exchange interaction for all three complexes for the first time using DFT and complete active space self-consistent field (CASSCF) methods. DFT calculations yield the anisotropic exchange as J(ξξ)=3.5 cm(-1) for 1; J(ξξ)=12.1 cm(-1), J(ζζ)=-6.9 cm(-1) and J(ηη)=-14 cm(-1) for 2; and J(ξξ)=23.7 cm(-1) and J(ζζ) =-11.1 cm(-1) for 3. The computed values are in agreement with the experimental report, and this suggests that the established methodology can be used to compute the anisotropic exchange in larger clusters. Our calculations reiterate the fact that the exchange is described by a three-axis anisotropic exchange for complexes 2 and 3 as evidenced by the experiments. A stronger exchange coupling as we move down the periodic table from 3d to 5d is reproduced by our calculations, and the origin of this enhancement in the exchange interaction has been probed by using molecular orbital analysis. The electronic origin of different types of exchange observed in this series is found to be related to the energy difference between possible degenerate pairs and the nature of orbital interactions. By computing the exchange interaction, the single-ion anisotropy of Mn(III) and zero-field splitting of the S=9/2 ground state of complexes 1-3 using CASSCF and/or DFT methods, we have attempted to shed light on the issue of anisotropic exchange and the barrier height for the magnetisation reversal in SMMs. Comprehensive magneto-structural correlations have been developed to offer clues on how to further enhance the barrier height in this class of SMMs. PMID:24288194

  2. Comparing Ru and Fe-catalyzed olefin metathesis.

    PubMed

    Poater, Albert; Chaitanya Vummaleti, Sai Vikrama; Pump, Eva; Cavallo, Luigi

    2014-08-01

    Density functional theory calculations have been used to explore the potential of Fe-based complexes with an N-heterocyclic carbene ligand, as olefin metathesis catalysts. Apart from a less endothermic reaction energy profile, a small reduction in the predicted upper energy barriers (≈ 2 kcal mol(-1)) is calculated in the Fe catalyzed profile with respect to the Ru catalysed profile. Overall, this study indicates that Fe-based catalysts have the potential to be very effective olefin metathesis catalysts.

  3. 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.

  4. Comparing Ru and Fe-catalyzed olefin metathesis.

    PubMed

    Poater, Albert; Chaitanya Vummaleti, Sai Vikrama; Pump, Eva; Cavallo, Luigi

    2014-08-01

    Density functional theory calculations have been used to explore the potential of Fe-based complexes with an N-heterocyclic carbene ligand, as olefin metathesis catalysts. Apart from a less endothermic reaction energy profile, a small reduction in the predicted upper energy barriers (≈ 2 kcal mol(-1)) is calculated in the Fe catalyzed profile with respect to the Ru catalysed profile. Overall, this study indicates that Fe-based catalysts have the potential to be very effective olefin metathesis catalysts. PMID:24821502

  5. On the mechanisms of degenerate ligand exchange in [M(CH(3))](+)/CH(4) Couples (M=Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt) as explored by mass spectrometric and computational studies: oxidative addition/reductive elimination versus sigma-complex-assisted metathesis.

    PubMed

    Armélin, Marc; Schlangen, Maria; Schwarz, Helmut

    2008-01-01

    The degenerate ligand exchange in [M(CH(3))](+)/CH(4) couples occurs in the gas phase at room temperature for M=Ni, Ru, Rh, Pd, and Pt, whereas the complexes containing Fe and Co are unreactive. Details of hydrogen-atom scrambling versus direct ligand switch have been uncovered by labeling experiments with CD(4) and (13)CH(4), respectively. The reactivity scale ranges from unreactive (M=Fe, Co) or inefficient (M=Ni, Pd) to moderately (M=Ru) and rather reactive (M=Rh, Pt). Quite extensive, but not complete, H/D exchange between the hydrogen atoms of the incoming and outgoing methyl groups is observed for M=Pt, whereas for M=Ni and Pd a predominantly direct ligand switch prevails. DFT calculations performed at the B3LYP level of theory account well for the thermal nonreactivity of the Fe and Co couples. For [Ni[CH(3))](+)/CH(4), a sigma-complex-assisted metathesis (sigma-CAM) is operative such that, in a two-state reactivity (TSR) scenario, two spin flips between the (3)A ground and (1)A excited states take place at the entrance and exit channels of the encounter complexes. For M=Ru and Rh, only oxidative addition/reductive elimination (OA/RE) is favored energetically, and the reaction is confined to the electronic ground states (3)A and (2)A. In contrast, for the [Pd(CH(3))](+)/CH(4) system, on the (1)A ground-state potential-energy surface both the OA/RE and sigma-CAM variants are energetically comparable, and the small reaction efficiency for the ligand switch is reflected in transition states located energetically close to the reactants. For the [M(CH(3))](+)/CH(4) complexes of the 5d elements, the sigma-CAM mechanism does not play a role. For M=Pt, the energetically most favored path proceeds in a spin-conserving manner on the (1)A potential-energy surface, which accounts for the extensive single and double hydrogen-atom exchange preceding ligand exchange. Although for M=Os and Ir the [M(CH(3))](+) complexes could not be generated experimentally, computational

  6. Nature of M-Ga bonds in dihalogallyl complexes (η5-C5H5)(Me3P)2M(GaX2) (M = Fe, Ru, Os) and (η5-C5H5)(OC)2Fe(GaX2) (X = Cl, Br, I): a DFT study.

    PubMed

    Pandey, Krishna K; Patidar, Pankaj; Aldridge, Simon

    2010-11-18

    Density functional theory (DFT) calculations have been performed on the terminal dihalogallyl complexes of iron, ruthenium, and osmium (η(5)-C(5)H(5))(Me(3)P)(2)M(GaX(2)) (M = Fe, Ru, Os; X = Cl, Br, I) and (η(5)-C(5)H(5))(OC)(2)Fe(GaX(2)) (X = Cl, Br, I) at the BP86/TZ2P/ZORA level of theory. On the basis of analyses suggested by Pauling, the M-Ga bonds in all of the dihalogallyl complexes are shorter than M-Ga single bonds; moreover, on going from X = Cl to X = I, the optimized M-Ga bond distances are found to increase. From the perspective of covalent bonding, however, π-symmetry contributions are, in all complexes, significantly smaller than the corresponding σ-bonding contribution, representing only 4-10% of the total orbital interaction. Thus, in these GaX(2) complexes, the gallyl ligand behaves predominantly as a σ donor, and the short M-Ga bond lengths can be attributed to high gallium s-orbital character in the M-Ga σ-bonding orbitals. The natural population analysis (NPA) charge distributions indicate that the group 8 metal atom carries a negative charge (from -1.38 to -1.62) and the gallium atom carries a significant positive charge in all cases (from +0.76 to +1.18). Moreover, the contributions of the electrostatic interaction terms (ΔE(elstat)) are significantly larger in all gallyl complexes than the covalent bonding term (ΔE(orb)); thus, the M-Ga bonds have predominantly ionic character (60-72%). The magnitude of the charge separation is greatest for dichlorogallyl complexes (compared to the corresponding GaBr(2) and GaI(2) systems), leading to a larger attractive ΔE(elstat) term and to M-Ga bonds that are stronger and marginally shorter than in the dibromo and diiodo analogues. PMID:20977253

  7. Site occupation in the Cr-Ru and Cr-Os σ phases

    NASA Astrophysics Data System (ADS)

    Sluiter, Marcel H. F.; Pasturel, Alain

    2009-10-01

    The site occupation in the Cr-Ru and Cr-Os σ phases is computed as a function of temperature. Generally, in σ phases the larger atoms occupy the sites with larger coordinations numbers, as can be explained on the basis of atomic-size and electronic structure. However, for Cr2Ru and Cr2Os the atomic-size argument predicts that Ru and Os occupy the sites with larger coordination numbers, whereas the reasoning based on the approximate degeneracies of electronic levels predicts that Cr occupies those sites. By comparing these predictions with the theoretically computed and the experimentally measured site occupations, the atomic-size and electronic arguments can be judged on their predictive merits.

  8. 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.

  9. Structural investigations in BaFe(2-x)Ru(x)As2 as a function of Ru and temperature.

    PubMed

    Sharma, Shilpam; Bharathi, A; Vinod, K; Sundar, C S; Srihari, V; Sen, Smritijit; Ghosh, Haranath; Sinha, Anil K; Deb, S K

    2015-02-01

    We present the results of synchrotron X-ray diffraction (XRD) measurements on powdered single-crystal samples of BaFe(2-x)Ru(x)As2, as a function of Ru content, and as a function of temperature, across the spin-density wave transition in BaFe(1.9)Ru(0.1)As2. The Rietveld refinements reveal that with Ru substitution, while the a-axis increases, the c-axis decreases. In addition, the variation of positional coordinates of As (z(As)), the Fe-As bond length and the As-Fe-As bond angles have also been determined. In the sample with x = 0.1, temperature-dependent XRD measurements indicate that the orthorhombicity shows the characteristic increase with a decrease in temperature, below the magnetic transition. It is seen that the c-axis, the As-Fe-As bond angles, Fe-As bond length and positional coordinates of the As show definite anomalies close to the structural transition. The observed anomalies in structural parameters are analysed in conjunction with restricted geometric optimization of the structure using ab initio electronic structure calculations.

  10. 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.

  11. 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.

  12. 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.

  13. Giant magnetic anisotropy of Co, Ru, and Os adatoms on MgO (001) surface

    NASA Astrophysics Data System (ADS)

    Wang, Hongbo; Ou, Xuedong; Fan, Fengren; Li, Zhengwei; Wu, Hua

    Large magnetic anisotropy energy (MAE) is desirable and critical for nanoscale magnetic devices. Here, using ligand-field level diagrams and density functional calculations, we well explain the very recent discovery [I.G. Rau et al., Science 344, 988 (2014)] that individual Co adatom on MgO (001) surface has a large MAE of more than 60 meV. More importantly, we predict that a giant MAE up to 110 meV could be realized for Ru adatoms on MgO (001), and even more for the Os adatoms (208 meV). This is a joint effect of the special ligand field, orbital multiplet, and significant spin-orbit interaction, in the intermediate-spin state of the Ru or Os adatoms on top of the surface oxygens. The giant MAE could provide a route to atomic scale memory.

  14. Giant Magnetic Anisotropy of Co, Ru, and Os Adatoms on MgO (001) Surface

    NASA Astrophysics Data System (ADS)

    Ou, Xuedong; Wang, Hongbo; Fan, Fengren; Li, Zhengwei; Wu, Hua

    2015-12-01

    Large magnetic anisotropy energy (MAE) is desirable and critical for nanoscale magnetic devices. Here, using ligand-field level diagrams and density functional calculations, we well explain the very recent discovery [I. G. Rau et al., Science 344, 988 (2014)] that an individual Co adatom on a MgO (001) surface has a large MAE of more than 60 meV. More importantly, we predict that a giant MAE up to 110 meV could be realized for Ru adatoms on MgO (001), and even more for the Os adatoms (208 meV). This is a joint effect of the special ligand field, orbital multiplet, and significant spin-orbit interaction, in the intermediate-spin state of the Ru or Os adatoms on top of the surface oxygens. The giant MAE could provide a route to atomic scale memory.

  15. Ionization and photofragmentation of Ru3(CO)12 and Os3(CO)12

    NASA Astrophysics Data System (ADS)

    Schalk, Oliver; Josefsson, Ida; Richter, Robert; Prince, Kevin C.; Odelius, Michael; Mucke, Melanie

    2015-10-01

    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 M3(CO)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 M3(CO)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 Ru3(CO)12.

  16. 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.

  17. Electronic structure and magnetic properties of RuFe{sub 3}N nitride

    SciTech Connect

    Santos, A.V. dos; Kuhnen, C.A.

    2009-11-15

    Self-consistent band structure calculations were performed on nitride RuFe{sub 3}N in order to investigate its magnetic and ground state properties. The Linear Muffin-Tin Orbital (LMTO) method was employed and calculations were performed at several lattice parameters so as to obtain the RuFe{sub 3}N equilibrium volume. Nonmagnetic and ferromagnetic LMTO calculations have shown that the RuFe{sub 3}N stable stage is ferromagnetic with constant lattice equilibrium of 7.2502 atomic units (a.u.). At equilibrium volume the LMTO calculations have given magnetic moments of 1.25 and 1.63 mu{sub B} at Ru and Fe sites, respectively, and no magnetic moment at N sites. The analysis of states density at equilibrium volume as well as the results for charge transfer illustrates why this ruthenium nitride is ferromagnetic. The LMTO calculations anticipate that the magnetic moment, the hyperfine field (the Fermi contact) and the isomer shift show a strong dependence on the lattice spacing. - Graphical Abstract: Total energy curves, versus lattice spacing for the RuFe{sub 3}N nitride. It is observed an energy difference between ferromagnetic and paramagnetic states, which provides high critic pressure.

  18. Ru substitution effect on the peak effect in superconducting PrOs4Sb12

    NASA Astrophysics Data System (ADS)

    Miyazaki, Ryoichi; Higashinaka, Ryuji; Aoki, Yuji; Sugawara, Hitoshi; Sato, Hideyuki

    2012-12-01

    Ac susceptibility (χac) measurements on Pr(Os1-xRux)4Sb12 single crystals for x = 0.05 and 0.1 were performed by mutual inductance method. A peak structure caused by anomalously enhanced flux pinning force, which is so-called the peak effect, appears in the H dependence of χac. The peak structure shifts to lower fields as T increases and disappears in T > 1 K in both samples, while in PrOs4Sb12 it is observable up to near Tc. This fact indicates that the Ru substitution suppresses the peak effect. We demonstrate that the observed T dependent behavior of the peak structure can be explained roughly by the synchronization model although there remains deviation from the model curve, suggesting some modification may be needed in the model to be applied to Pr(Os1-xRux)4Sb12.

  19. 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.

  20. Topochemical reduction of the Ruddlesden-Popper phases Sr2Fe(0.5)Ru(0.5)O4 and Sr3(Fe(0.5)Ru(0.5))2O7.

    PubMed

    Denis Romero, Fabio; Gianolio, Diego; Cibin, Giannantonio; Bingham, Paul A; d'Hollander, Jeanne-Clotilde; Forder, Susan D; Hayward, Michael A

    2013-10-01

    Reaction of the Ruddlesden-Popper phases Sr2Fe(0.5)Ru(0.5)O4 and Sr3(Fe(0.5)Ru(0.5))2O7 with CaH2 results in the topochemical deintercalation of oxide ions from these materials and the formation of samples with average compositions of Sr2Fe(0.5)Ru(0.5)O(3.35) and Sr3(Fe(0.5)Ru(0.5))2O(5.68), respectively. Diffraction data reveal that both the n = 1 and n = 2 samples consist of two-phase mixtures of reduced phases with subtly different oxygen contents. The separation of samples into two phases upon reduction is discussed on the basis of a short-range inhomogeneous distribution of iron and ruthenium in the starting materials. X-ray absorption data and Mössbauer spectra reveal the reduced samples contain an Fe(3+) and Ru(2+/3+) oxidation state combination, which is unexpected considering the Fe(3+)/Fe(2+) and Ru(3+)/Ru(2+) redox potentials, suggesting that the local coordination geometry of the transition metal sites helps to stabilize the Ru(2+) centers. Fitted Mössbauer spectra of both the n = 1 and n = 2 samples are consistent with the presence of Fe(3+) cations in square planar coordination sites. Magnetization data of both materials are consistent with spin glass-like behavior.

  1. On the dynamical stability of ferromagnetic Ru and Os in the bct structure: a first-principles study

    NASA Astrophysics Data System (ADS)

    Cifuentes-Quintal, M. E.; de Coss, R.

    2015-08-01

    Recent theoretical studies have predicted magnetic states for Ru and Os in the body-centred tetragonal structure (bct) with ?. In this study, we present first principles calculations of the phonon dispersion for ferromagnetic Ru- and Os-bct along the epitaxial and uniaxial Bain paths, to evaluate their dynamical stability. The phonon dispersions were computed using the density functional perturbation theory, including the gradient corrections to the exchange-correlation functional within the plane-waves ultrasoft-pseudopotential approximation. The phonon dispersion for the local minimum in the Bain path with ? as well as the uniaxial and epitaxial strained structures are analysed. We find imaginary frequencies along different directions of the Brillouin zone, which indicates that both systems are dynamically unstable. Consequently, ferromagnetic Ru and Os in the bct with ? are not truly metastable phases.

  2. Crystalline Electric Field Effects in CeT2Al10 (T = Ru, Os)

    NASA Astrophysics Data System (ADS)

    Hanzawa, Katsurou

    2011-02-01

    We address crystalline electric field (CEF) effects in CeT2Al10 (T = Ru, Os) showing novel phase transitions. Because of the absence of inversion symmetry with respect to the b coordinate in the m2m (C2v) site symmetry for Ce ions, there appears the unfamiliar odd-parity term \\mathcal{H}(o) in the CEF, as well as the ordinary even-parity term \\mathcal{H}(e). The latter \\mathcal{H}(e) is used to determine the local 4f electronic structure consistent with the experimental magnetic susceptibility. The former \\mathcal{H}(o) causes 4f--5d on-site mixing, whose effects on the Ruderman--Kittel--Kasuya--Yosida (RKKY) interaction responsible for high transition temperatures and on the peak for the polarization along the b-axis in the optical conductivity are discussed.

  3. Evaluation of Fe and Ru Pincer-Type Complexes as Catalysts for the Racemization of Secondary Benzylic Alcohols.

    PubMed

    Bornschein, Christoph; Gustafson, Karl P J; Verho, Oscar; Beller, Matthias; Bäckvall, Jan-E

    2016-08-01

    Fe and Ru pincer-type catalysts are used for the racemization of benzylic alcohols. Racemization with the Fe catalyst was achieved within 30 minutes under mild reaction conditions, with a catalyst loading as low as 2 mol %. This reaction constitutes the first example of an iron-catalyzed racemization of an alcohol. The efficiency for racemization of the Fe catalyst and its Ru analogue was evaluated for a wide range of sec-benzylic alcohols. The commercially available Ru complex proved to be highly robust and even tolerated the presence of water in the reaction mixture. PMID:27311070

  4. 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.

  5. Highly (110)- and (111)-oriented BiFeO3 films on BaPbO3 electrode with Ru or Pt /Ru barrier layers

    NASA Astrophysics Data System (ADS)

    Lee, Chia-Ching; Wu, Jenn-Ming; Hsiung, Chang-Po

    2007-04-01

    Highly (110)- and (111)-oriented BiFeO3 (BFO) films were fabricated with BaPbO3 (BPO )/Ru and BPO /Pt/Ru as electrode/barrier on Si substrates by rf-magnetron sputtering. The BPO /Ru and BPO /Pt/Ru stacks both induce oriented BFO films and act as diffusion barriers. The (110)- and (111)-oriented BFO films possess excellent ferroelectric properties with only minor leakage. The values of remnant polarization are almost the same, about 42μC/cm2, for (110)- and (111)-oriented BFO films. However, polarization measured under varying pulse widths demonstrates that the switching polarization in (111)-oriented BFO films is higher than in (110)-oriented films. Additionally, (111)-oriented BFO films exhibit better retention properties than (110)-oriented films.

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. Strain-induced topological transition in SrRu2O6 and CaOs2O6

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

    The topological property of SrRu2O6 and isostructural CaOs2O6 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 SrRu2O6 , 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 CaOs2O6 , 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.

  11. Strain-induced topological transition in SrRu2O6 and CaOs2O6

    DOE PAGESBeta

    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 waymore » to realize a topological insulating state in a complex oxide, which has not been experimentally demonstrated so far.« less

  12. Magnetism and electrical transport in Fe 0.9TM 0.1Si, TM=Co, Rh, Ru

    NASA Astrophysics Data System (ADS)

    Paschen, S.; Pushin, D.; Ott, H. R.; Young, D. P.; Fisk, Z.

    1999-01-01

    Our comparative study of magnetic and transport properties of Fe 0.9Co 0.1Si, Fe 0.9Rh 0.1Si, and Fe 0.9Ru 0.1Si indicates that the ferromagnetism previously observed in Fe 0.9Co 0.1Si is not due to localized magnetic moments residing on the Co atoms. It is rather the metallicity of the system which provides the formation of a ferromagnetic state.

  13. Superconductivity in Y3Ru4Ge13 and Lu3Os4Ge13: A comparative study

    NASA Astrophysics Data System (ADS)

    Prakash, Om; Thamizhavel, A.; Ramakrishnan, S.

    2014-12-01

    A variety of unconventional superconductors have low carrier density as a common factor. However, the underlying mechanism of superconductivity in such low carrier density systems is not well understood. Besides, small carrier density is an unfavourable component for conventional superconductivity as described by the Bardeen-Cooper-Schrieffer (BCS) theory. Therefore, studying low carrier density systems can lead to a better understanding in such systems. In this paper, we report superconductivity property studies in low carrier density systems, Y3Ru4Ge13 and Lu3Os4Ge13, using various experimental techniques. Single crystals of Y3Ru4Ge13 and Lu3Os4Ge13 have been grown using the Czochralski crystal pulling method in a tetra-arc furnace. The x-ray diffraction experiment reveals that both compounds crystallize in cubic structure (space group Pm3n, no. 223). The transport, magnetization and heat capacity measurements show that Y3Ru4Ge13 single crystal undergoes a superconducting transition at 2.85 K, whereas, Lu3Os4Ge13 becomes superconductor at 3.1 K.

  14. Energy transfer in hybrids based on a thiophene-substituted ethynylbipyridine dimer decorated with Re(I), Ru(II), and Os(II) units.

    PubMed

    Goeb, Sébastien; De Nicola, Antoinette; Ziessel, Raymond; Sabatini, Cristiana; Barbieri, Andrea; Barigelletti, Francesco

    2006-02-01

    The preparation, structural features, electrochemical behavior, and optical properties (at room temperature and at 77 K) are reported for a series of thiophene-containing hybrids based on the bent conjugated backbone of a rigid ditopic ligand, the dimeric moiety 3,4-dibutyl-2,5-bis{5'-[(3,4-dibutylthien-2-ylethynyl)-2,2'-bipyridin-5-yl]ethynyl}thiophene (TBTBT). Within the dimer, the diethynyl-2,2'-bipyridine units (bpy, the coordination sites) alternate with three 3,4-dibuthylthiophene units and coordination of the [Re(CO)3Cl], [Ru(bpy)2]2+, and [Os(bpy)2]2+ centers results in the mononuclear species RuTBTBT and OsTBTBT and the binuclear species RuTBTBTRu, OsTBTBTOs, RuTBTBTOs, and ReTBTBTOs. At room temperature, the emitting states obtained by photoexcitation are of 3MLCT nature, and vibronic analysis of the emission spectra indicates that they are largely delocalized over the TBTBT ligand. In the binuclear species, the intermetal separation is ca. 17 A, and for RuTBTBTOs, an efficient Ru --> Os excitation transfer takes place, resulting solely in an Os-based emission. The process is ascribed to double-electron transfer (Dexter), as mediated by the TBTBT ligand; a similar conclusion holds for the case of ReTBTBTOs. For RuTBTBTOs, the process is discussed in some detail also with regard to the possibility of disentangling the constituent hole and electron-transfer events.

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

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

    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 (ΔHL) increases with increasing underlayer thickness for all heterostructures. In contrast, the field-like transverse effective field (ΔHT) increases with increasing Ru thickness while it is almost constant or slightly decreases with increasing Cr thickness. The sign of ΔHL observed in the Cr-underlayer devices is opposite from that in the Ru-underlayer devices while ΔHT shows the same sign with a small magnitude. The opposite directions of ΔHL 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.

  16. 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.

  17. Concerto catalysis--harmonising [NiFe]hydrogenase and NiRu model catalysts.

    PubMed

    Ichikawa, Koji; Nonaka, Kyoshiro; Matsumoto, Takahiro; Kure, Bunsho; Yoon, Ki-Seok; Higuchi, Yoshiki; Yagi, Tatsuhiko; Ogo, Seiji

    2010-03-28

    This communication reports the successful merging of the chemical properties of a natural [NiFe]hydrogenase (Desulfovibrio vulgaris Miyazaki F) and our previously reported [NiRu] hydrogenase-mimic. The catalytic activity of both the natural enzyme and the mimic is almost identical, with the exception of working pH ranges, and this allows us to use them simultaneously in the same reaction flask. In such a manner, isotope exchange between D(2) and H(2)O could be conducted over an extended pH range (about 2-10) in one pot under mild conditions at ambient temperature and pressure.

  18. 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.

  19. 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.

  20. Synthesis, crystal structure and properties of the new superconductors TaRuB and NbOsB.

    PubMed

    Zheng, Qiang; Gumeniuk, Roman; Rosner, Helge; Schnelle, Walter; Prots, Yurii; Burkhardt, Ulrich; Grin, Yuri; Leithe-Jasper, Andreas

    2015-10-21

    Two new ternary compounds TaRuB and NbOsB were synthesized by arc-melting and annealing at 1500-1850 °C. They crystallize in orthorhombic primitive structures with space group Pbam. Magnetic susceptibility, electrical resistivity, and specific heat measurements reveal bulk superconductivity for metallic TaRuB with a T(c) ≈ 4 K. Electronic structure calculations by DFT methods show that 4d and 5d transition-metal states dominate the density of states (DOS) at the Fermi level E(F) with a pronounced quasi one-dimensional behaviour along the [0 0 1] direction. Comparison of the calculated DOS at E(F) with specific heat data reveals a moderate electron-phonon coupling. Possible small boron vacancies could significantly reduce the DOS at E(F), hence decrease T(c) for samples annealed at higher temperatures. For NbOsB, the DOS(E(F)) is strongly reduced due to an increase of covalent bonding interactions between Os and B. Accordingly, a lower T(c) ≈ 1 K is observed. PMID:26418029

  1. Synthesis, crystal structure and properties of the new superconductors TaRuB and NbOsB

    NASA Astrophysics Data System (ADS)

    Zheng, Qiang; Gumeniuk, Roman; Rosner, Helge; Schnelle, Walter; Prots, Yurii; Burkhardt, Ulrich; Grin, Yuri; Leithe-Jasper, Andreas

    2015-10-01

    Two new ternary compounds TaRuB and NbOsB were synthesized by arc-melting and annealing at 1500-1850 °C. They crystallize in orthorhombic primitive structures with space group Pbam. Magnetic susceptibility, electrical resistivity, and specific heat measurements reveal bulk superconductivity for metallic TaRuB with a {{T}\\text{c}}≈ 4 K. Electronic structure calculations by DFT methods show that 4d and 5d transition-metal states dominate the density of states (DOS) at the Fermi level {{E}\\text{F}} with a pronounced quasi one-dimensional behaviour along the [0 0 1] direction. Comparison of the calculated DOS at {{E}\\text{F}} with specific heat data reveals a moderate electron-phonon coupling. Possible small boron vacancies could significantly reduce the DOS at {{E}\\text{F}} , hence decrease {{T}\\text{c}} for samples annealed at higher temperatures. For NbOsB, the DOS({{E}\\text{F}} ) is strongly reduced due to an increase of covalent bonding interactions between Os and B. Accordingly, a lower {{T}\\text{c}} ≈ 1 K is observed.

  2. Bond energy and electronic structure in M-bis-terpyridine complexes ( M=Os, Co and Ru)

    NASA Astrophysics Data System (ADS)

    Morari, C.

    2008-03-01

    We investigate the nature of bond energy and electronic structure of M-bis-terpyridine complexes (M = Os, Co and Ru) using Hartree-Fock and DFT calculations. The nature of bond energy is analyzed using a Morokuma-Kitaura decomposition. DFT results are compared with the Hartree-Fock leading to the conclusion that charge transfer and polarization effects are responsible for the bond energy of the complexes. Also we point out the fact that the electronic configuration of the metallic atom plays a dominant role in the charge transfer process.

  3. Gibbs free energies of formation of RuO 2, IrO 2, and OsO 2: A high-temperature electrochemical and calorimetric study

    NASA Astrophysics Data System (ADS)

    O'Neill, Hugh St. C.; Nell, Johan

    1997-12-01

    The Gibbs free energies of formation of RuO 2, OsO 2 and IrO 2 have been determined by measuring the chemical potentials of oxygen (μO 2) defined by the reactions M + O 2 = MO 2, where M = Ru, Os. or Ir, using an electrochemical method with calcia-stabilized zirconia (CSZ) solid electrolytes. Measurements were attempted in the temperature ranges from ˜870 K to 1620, 1270, and 1415 K for the Ru, Os, and Ir equilibria, respectively, but inspection of the results reveals that equilibrium could not be established below ˜930 K for all three reactions. For Ru + RuO 2, the highest temperature data (above 1520 K) may be systematically affected by the onset of significant electronic conduction in the CSZ electrolyte, while the attempted measurements of the Os + OsO 2 equilibrium above 1190 K are obscured by the disproportionation of OsO 2 to gaseous Os oxides. The high temperature heat capacities at constant pressure ( Cp) of RuO 2 and IrO 2 were determined from 370 to 1070 K by differential scanning calorimetry. These data were combined with heat content measurements and low-temperature heat capacities from the literature, and fitted to an extended Maier-Kelley equation. The calorimetric data for RuO 2 and IrO 2, together with assessed data for Ru, Os, and Ir metals and estimated data for OsO 2, were used in a third law analysis of the electrochemical measurements. The values of μO 2 of the three equilibria were smoothed and filtered by the third-law analysis to yield the following equations which can be extrapolated to lower and higher temperatures as indicated: μO 2 ( Ru + RuO 2) = -324563 + 344.151 T-22.1155 T ln T (700 ⩽ T ⩽ 1800) μO 2 ( Os + OsO 2) = -300399 + 307.639 T-17.4819 T ln T (700 ⩽ T ⩽ 1500) μO 2 ( Ir + IrO 2) = -256518 + 295.854 T-15.2368 T ln T (700 ⩽ T ⩽ 1500) where μO 2 is in J mol -1, T is in K, the reference pressure for O 2 is 1 bar (10 5 Pa), and estimated accuracies are approximately 200 to 400 J mol -1. For Ru + RuO 2, the drift

  4. 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.

  5. 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. PMID:24869778

  6. Inverse magnetocaloric effect in Ce(Fe0.96Ru0.04)2: Effect of fast neutron irradiation

    NASA Astrophysics Data System (ADS)

    Dube, V.; Mishra, P. K.; Rajarajan, A. K.; Prajapat, C. L.; Sastry, P. U.; Thakare, S. V.; Singh, M. R.; Ravikumar, G.

    2013-02-01

    We have shown the effect of fast neutron irradiation on the magnetic phase transition and magnetocaloric effect (MCE) in a doped Ce(Fe0.96Ru0.04)2, intermettalic. We show that this leads to suppression of MCE and a to a disordered ferromagnetic phase.

  7. Incongruent transfer in laser deposition of FeSiGaRu thin films

    NASA Astrophysics Data System (ADS)

    van de Riet, E.; Kools, J. C. S.; Dieleman, J.

    1993-06-01

    The laser ablation and deposition of FeSiGaRu is studied. The deposited thin films are analyzed with Auger electron spectroscopy and Rutherford backscattering spectrometry. It is found that the gallium and ruthenium content of the thin films is strongly dependent on the laser fluence. At high laser fluences (6 J/cm2) the thin films are depleted of gallium due to preferential sputtering of the gallium atoms from the thin film. Near the threshold fluence (1.9 J/cm2) the films contain an excess of gallium due to preferential evaporation of gallium from the target. The latter conclusions are based on time-of-flight studies of ablated atoms and ions and on measurements of the atoms that are sputtered from the substrate by the incoming flux.

  8. 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.

  9. Large spin pumping effect in antisymmetric precession of Ni79Fe21/Ru/Ni79Fe21

    NASA Astrophysics Data System (ADS)

    Yang, H.; Li, Y.; Bailey, W. E.

    2016-06-01

    In magnetic trilayer structures, a contribution to the Gilbert damping of ferromagnetic resonance arises from spin currents pumped from one layer to another. This contribution has been demonstrated for layers with weakly coupled, separated resonances, where magnetization dynamics are excited predominantly in one layer and the other layer acts as a spin sink. Here, we show that trilayer structures in which magnetizations are excited simultaneously, antisymmetrically, show a spin-pumping effect roughly twice as large. The antisymmetric (optical) mode of antiferromagnetically coupled Ni79Fe21(8 nm)/Ru/Ni79Fe21(8 nm) trilayers shows a Gilbert damping constant greater than that of the symmetric (acoustic) mode by an amount as large as the intrinsic damping of Py ( Δα≃0.006 ). The effect is shown equally in field-normal and field-parallel to film plane geometries over 3-25 GHz. The results confirm a prediction of the spin pumping model and have implications for the use of synthetic antiferromagnets (SAF)-structures in GHz devices.

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

    DOE PAGESBeta

    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.; et al

    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

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

    NASA Astrophysics Data System (ADS)

    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.

    2015-02-01

    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" Pc h as previously proposed by Kanchanavatee et al. [Phys. Rev. B 84, 245122 (2011), 10.1103/PhysRevB.84.245122] based on bulk measurements on polycrystalline samples. Notably, 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 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 Pc h in URu2 -xFexSi2 as a function of x . The resulting temperature (T )-chemical pressure (Pc h) phase diagram for URu2 -xFexSi2 is in agreement with the established temperature (T )-external pressure (P ) phase diagram of URu2Si2 .

  12. Chemical pressure tuning of URu2 Si2 via isoelectronic substitution of Ru with Fe

    NASA Astrophysics Data System (ADS)

    Janoschek, Marc; Das, Pinaki; Kanchanavatee, Noravee; Helton, Joel S.; Huang, Kevin; Baumbach, Ryan E.; Bauer, Eric D.; Zhao, Yang; Ratcliff, William; White, Ben D.; Maple, M. Brian; Lynn, Jeff W.

    2015-03-01

    We have used specific heat and neutron diffraction measurements on single crystals of URu2-xFexSi2 for Fe concentrations x <= 0.7 to establish that isoelectronic substitution of Ru with Fe acts as ``chemical pressure'' Pch. Neutron diffraction reveals a sharp increase of the uranium magnetic moment at x = 0 . 1 , reminiscent of the ``hidden order'' (HO) to large moment antiferromagnetic (LMAFM) phase transition in URu2Si2. Using the unit cell volume, and the isothermal compressibility κT for URu2Si2, we determine Pch as function of x. The resulting temperature T-chemical pressure Pch phase diagram for URu2-xFexSi2 is in good agreement with the established temperature T-external pressure P phase diagram of URu2Si2. Thus, URu2-xFexSi2 provides a new opportunity to study the close relationship between the HO and LMAFM phases with methods that cannot be used under pressure, and may shed some new light on the on the elusive order parameter of the HO.

  13. 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

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

    NASA Astrophysics Data System (ADS)

    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

    2016-09-01

    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.

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

    PubMed

    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

  16. Anisotropic elastic and vibrational properties of Ru2B3 and Os2B3: a first-principles investigation

    NASA Astrophysics Data System (ADS)

    Ozisik, Haci; Deligoz, Engin; Surucu, Gokhan; Bogaz Ozisik, Havva

    2016-07-01

    The structural, mechanical and lattice dynamical properties of Ru2B3 and Os2B3 have been investigated by using a first-principles method based on the density functional theory within the generalized gradient approximation. The single crystal elastic constants are numerically estimated using strain–stress approach. The polycrystalline aggregate elastic parameters are calculated from the single elastic constants via the Voigt–Reuss–Hill approximations. Subsequently, the ductility and brittleness are characterized with the estimation from Pugh’s rule (B/G) and Cauchy pressure. Additionally, the Debye temperature is calculated from the average elastic wave velocity obtained from bulk and shear moduli. The calculated parameters are consistent with the previous experimental and theoretical data. These borides are both mechanically and dynamically stable in the considered structure.

  17. 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.

  18. Topochemical fluorination of Sr3(M(0.5)Ru(0.5))2O7 (M = Ti, Mn, Fe), n = 2, Ruddlesden-Popper phases.

    PubMed

    Romero, Fabio Denis; Bingham, Paul A; Forder, Susan D; Hayward, Michael A

    2013-03-18

    Reaction of the appropriate Sr3(M(0.5)Ru(0.5))2O7 (M = Ti, Mn, Fe), n = 2, Ruddlesden-Popper oxide with CuF2 under flowing oxygen results in formation of the oxide-fluoride phases Sr3(Ti(0.5)Ru(0.5))2O7F2, Sr3(Mn(0.5)Ru(0.5))2O7F2, and Sr3(Fe(0.5)Ru(0.5))2O(5.5)F(3.5) via a topochemical anion insertion/substitution process. Analysis indicates the titanium and manganese phases have Ti(4+), Ru(6+) and Mn(4+), Ru(6+) oxidation state combinations, respectively, while Mössbauer spectra indicate an Fe(3+), Ru(5.5+) combination for the iron phase. Thus, it can be seen that the soft fluorination conditions employed lead to formation of highly oxidized Ru(6+) centers in all three oxide-fluoride phases, while oxidation states of the other transition metal M cations remain unchanged. Fluorination of Sr3(Ti(0.5)Ru(0.5))2O7 to Sr3(Ti(0.5)Ru(0.5))2O7F2 leads to suppression of magnetic order as the fluorinated material approaches metallic behavior. In contrast, fluorination of Sr3(Mn(0.5)Ru(0.5))2O7 and Sr3(Fe(0.5)Ru(0.5))2O7 lifts the magnetic frustration present in the oxide phases, resulting in observation of long-range antiferromagnetic order at low temperature in Sr3(Mn(0.5)Ru(0.5))2O7F2 and Sr3(Fe(0.5)Ru(0.5))2O(5.5)F(3.5). The influence of the topochemical fluorination on the magnetic behavior of the Sr3(M(0.5)Ru(0.5))2O(x)F(y) phases is discussed on the basis of changes to the ruthenium oxidation state and structural distortions.

  19. 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.

  20. Dihydrogen activation by sulfido-bridged dinuclear Ru/Ge complexes: insight into the [NiFe] hydrogenase unready state.

    PubMed

    Matsumoto, Tsuyoshi; Itakura, Naohisa; Nakaya, Yukiko; Tatsumi, Kazuyuki

    2011-01-21

    A S/SH bridged hetero-dinuclear Ru/Ge complex cation reacted with H(2) to afford the μ-S/μ-H complex. The reaction was considerably slower compared to that of the μ-S/μ-OH complex. Thus, the μ-S/μ-SH and μ-S/μ-OH complexes might provide models for the unready and ready states, respectively, of [NiFe] hydrogenase. PMID:21072402

  1. 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.

  2. Low Temperature Hysteretic Behavior of the Interpenetrating 3-D Network Structured [Ru2(O2CMe)4]3[Fe(CN)6] Magnet

    SciTech Connect

    Haque, F.; Del barco, Enrique; Fishman, Randy Scott; Miller, Joel S.

    2013-01-01

    The low temperature hysteretic behavior between 40 mK and 4.8 K was obtained for [Ru2(O2CMe)4]3[Fe(CN)6]. The unusual constricted hysteretic behavior reported for isomorphous [Ru2(O2CMe)4]3[Cr(CN)6] was not observed. Instead, the [Ru2(O2CMe)4]3-[Fe(CN)6] exhibits a single hysteresis loop and a temperature dependence of the coercivity atypical for a ferrimagnetic ordering transition. The coercive field, constant below ~0.3 K (1.06 kOe), shows a rapid initial decrease below 1 K, to continue decreasing at a slower rate up to at least 4.8 K. In contrast to [Ru2(O2CMe)4]3[Cr(CN)6] which has antiferromagnetic coupling of the ferrimagnetic lattices, due to the reduced spin on the [FeIII(CN)6]3-, [Ru2(O2CMe)4]3[Fe(CN)6] ferromagnetic coupling of the ferrimagnetic lattices dominates for [Ru2(O2CMe)4]3[Fe(CN)6].

  3. 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. PMID:25732233

  4. 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.

  5. 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.

  6. 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.

  7. 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

  8. On the oxidation of EuFe4Sb12 and EuRu4Sb12.

    PubMed

    Peddle, Jessica M; Gaultois, Michael W; Grosvenor, Andrew P

    2011-07-01

    Rare-earth-filled transition-metal pnictides having the skutterudite-type structure have been proposed for use as high-temperature thermoelectric materials to recover waste heat from vehicle exhaust, among other applications. A previous investigation by this research group of one of the most studied skutterudites, CeFe(4)Sb(12), found that, when exposed to air, this material oxidized at temperatures that are considerably below the proposed maximum operating temperature. Here, by the combined use of TGA, powder XRD, and XANES, it has been found that the substitution of Ce(3+) and Fe(2+) for larger rare-earth and transition-metal elements (Eu(2+) and Ru(2+)) results in a significantly higher oxidation temperature compared to that of CeFe(4)Sb(12). This increase can be related to the increased orbital overlap provided by these larger atoms (Eu(2+) and Ru(2+) vs Ce(3+) and Fe(2+)), enabling the development of stronger bonds. These results show how selective substitution of the constituent elements can significantly improve the thermal stability of materials.

  9. 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.

  10. Photocatalytic Hydroxylation of Benzene by Dioxygen to Phenol with a Cyano-Bridged Complex Containing Fe(II) and Ru(II) Incorporated in Mesoporous Silica-Alumina.

    PubMed

    Aratani, Yusuke; Oyama, Kohei; Suenobu, Tomoyoshi; Yamada, Yusuke; Fukuzumi, Shunichi

    2016-06-20

    Photocatalytic hydroxylation of benzene to phenol was achieved by using O2 as an oxidant as well as an oxygen source with a cyano-bridged polynuclear metal complex containing Fe(II) and Ru(II) incorporated in mesoporous silica-alumina ([Fe(H2O)3]2[Ru(CN)6]@sAl-MCM-41). An apparent turnover number (TON) of phenol production per the monomer unit of [Fe(H2O)3]2[Ru(CN)6] was 41 for 59 h. The cyano-bridged polynuclear metal complex, [Fe(H2O)3]2[Ru(CN)6], exhibited catalytic activity for thermal hydroxylation of benzene by H2O2 in acetonitrile (MeCN), where the apparent TON of phenol production reached 393 for 60 h. The apparent TON increased to 2500 for 114 h by incorporating [Fe(H2O)3]2[Ru(CN)6] in sAl-MCM-41. Additionally, [Fe(H2O)3]2[Ru(CN)6] acts as a water oxidation catalyst by using [Ru(bpy)3](2+) (bpy = 2,2'-bipyridine) and Na2S2O8 as a photosensitizer and a sacrificial electron acceptor as evidenced by (18)O-isotope labeling experiments. Photoirradiation of an O2-saturated MeCN solution containing [Fe(H2O)3]2[Ru(CN)6]@sAl-MCM-41 and scandium ion provided H2O2 formation, where photoexcited [Ru(CN)6](4-) moiety reduces O2 as indicated by laser flash photolysis measurements. Thus, hydroxylation of benzene to phenol using molecular oxygen photocatalyzed by [Fe(H2O)3]2[Ru(CN)6] occurred via a two-step route; (1) molecular oxygen was photocatalytically reduced to peroxide by using water as an electron donor, and then (2) peroxide thus formed is used as an oxidant for hydroxylation of benzene. PMID:27265780

  11. Oxidation of methanol on 2nd and 3rd row group VIII transition metals (Pt, Ir, Os, Pd, Rh, and Ru): Application to direct methanol fuel cells

    SciTech Connect

    Kua, J.; Goddard, W.A. III

    1999-12-01

    Using first principles quantum mechanics [nonlocal density functional theory (B3LYP)], the authors calculated the 13 most likely intermediate species for methanol oxidation on clusters of all 2nd and 3rd row Group VIII transition metals for all three likely binding sites (top, bridge, and cap). This comprehensive set of binding energies and structures allows a detailed analysis of possible reaction mechanisms and how they change for different metals. This illustrates the role in which modern quantum chemical methods can be used to provide data for combinatorial strategies for discovering and designing new catalysts. Methanol dehydrogenation is most facile on Pt, with the hydrogens preferentially stripped off the carbon end. However, water dehydrogenation is most facile on Ru. These results support the bifunctional mechanism for methanol oxidation on Pt-Ru alloys in direct methanol fuel cells (DMFCs). Pure Os is capable of performing both functionalities without cocatalyst. It is suggested that pure Os be examined as a potential catalyst for low overpotential, highly dispersed catalyst DMFCs. Pathways to form the second C-O bond differ between the pure metals (Pt and Os) in which (CO){sub ads} is probably activated by (OH){sub ads} and the Pt-Ru binary system in which (COH){sub ads} is probably activated by O{sub ads}. For all cases formation of (COOH){sub ads} is an important precursor to the final dehydrogenation to desorb CO{sub 2} from the surface.

  12. 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.

  13. 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.

  14. 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.

  15. 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}.

  16. Effects of Ru Doping on the Transport Behavior and Superconducting Transition Temperature of NdFeAsO0.89F0.11

    NASA Astrophysics Data System (ADS)

    Lee, Sang Chul; Satomi, Erika; Kobayashi, Yoshiaki; Sato, Masatoshi

    2010-02-01

    The transport behavior and superconducting transition temperature Tc of NdFe1-yRuyAsO0.89F0.11 have been studied for various y values. Because Ru impurities are isoelectronic to host Fe atoms, we basically expect that the number of electrons does not change with y, at least in the region of small y values. The results indicate that the rate of Tc suppression by Ru atoms is too small to be explained by the pair breaking effect of nonmagnetic impurities expected for the S± symmetry, confirming our previous results for Co doping.

  17. 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.

  18. 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. PMID:11284333

  19. 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.

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

    DOE PAGESBeta

    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 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

  1. 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.

  2. Inverse magnetocaloric effect in Ce(Fe{sub 0.96}Ru{sub 0.04}){sub 2}: Effect of fast neutron irradiation

    SciTech Connect

    Dube, V.; Mishra, P. K.; Prajapat, C. L.; Singh, M. R.; Ravikumar, G.; Rajarajan, A. K.; Sastry, P. U.; Thakare, S. V.

    2013-02-05

    We have shown the effect of fast neutron irradiation on the magnetic phase transition and magnetocaloric effect (MCE) in a doped Ce(Fe{sub 0.96}Ru{sub 0.04}){sub 2}, intermettalic. We show that this leads to suppression of MCE and a to a disordered ferromagnetic phase.

  3. Atomic site preferences and its effect on magnetic structure in the intermetallic borides M2Fe(Ru0.8T0.2)5B2 (M=Sc, Ti, Zr; T=Ru, Rh, Ir)

    NASA Astrophysics Data System (ADS)

    Brgoch, Jakoah; Mahmoud, Yassir A.; Miller, Gordon J.

    2012-12-01

    The site preference for a class of intermetallic borides following the general formula M2Fe(Ru0.8T0.2)5B2 (M=Sc, Ti, Zr; T=Ru, Rh, Ir), has been explored using ab initio and semi-empirical electronic structure calculations. This intermetallic boride series contains two potential sites, the Wyckoff 2c and 8j sites, for Rh or Ir to replace Ru atoms. Since the 8j site is a nearest neighbor to the magnetically active Fe atom, whereas the 2c site is a next nearest neighbor, the substitution pattern should play an important role in the magnetic structure of these compounds. The substitution preference is analyzed based on the site energy and bond energy terms, both of which arise from a tight-binding evaluation of the electronic band energy, and are known to influence the locations of atoms in extended solids. According to these calculations, the valence electron-rich Rh and Ir atoms prefer to occupy the 8j site, a result also corroborated by experimental evidence. Additionally, substitution of Rh or Ir at the 8j site results in a modification of the magnetic structure that ultimately results in larger local magnetic moment on the Fe atoms.

  4. Investigation of the binding of cis/trans-[MCl4(1H-indazole)(NO)](-) (M = Ru, Os) complexes to human serum albumin.

    PubMed

    Dömötör, Orsolya; Rathgeb, Anna; Kuhn, Paul-Steffen; Popović-Bijelić, Ana; Bačić, Goran; Enyedy, Eva Anna; Arion, Vladimir B

    2016-06-01

    Overall binding affinity of sodium or indazolium cis/trans-[MCl4(1H-indazole)(NO)] (M = Ru, Os) complexes towards human serum albumin (HSA) and high molecular mass components of the blood serum was monitored by ultrafiltration. HSA was found to be mainly responsible for the binding of the studied ruthenium and osmium complexes. In other words, this protein can provide a depot for the compounds and can affect their biodistribution and transport processes. In order to elucidate the HSA binding sites tryptophan fluorescence quenching studies and displacement reactions with the established site markers warfarin and dansylglycine were performed. Conditional stability constants for the binding to sites I and II on HSA were computed showing that the studied ruthenium and osmium complexes are able to bind into both sites with moderately strong affinity (logK' = 4.4-5.1). Site I is slightly more favored over site II for all complexes. No significant differences in the HSA binding properties were found for these metal complexes demonstrating negligible influence of the type of counterion (sodium vs indazolium), the metal ion center identity (Ru vs. Os) or the position of the nitrosyl group on the binding event. Electron paramagnetic resonance spin labeling of HSA revealed that indazolium trans-[RuCl4(1H-indazole)(NO)] and long-chain fatty acids show competitive binding to HSA. Moreover, this complex has a higher affinity for site I, but when present in excess, it is able to bind to site II as well, and displace fatty acids. PMID:26908285

  5. Unanticipated spin gap measured in the frustrated quasi-FCC d3 double perovskites La2 LiXO6 (X = Ru, Os)

    NASA Astrophysics Data System (ADS)

    Maharaj, Dalini D.; Sala, Gabriele; Marjerrison, Casey A.; Greedan, John; Gaulin, Bruce; Stone, Matthew

    There is much current interest in the influence of strong spin-orbit (SO) interactions on exotic ground state selection in new 4d and 5d magnets, particularly involving 4d5 Ir. Here we consider double perovskites of the form A2 BB'O6 which are based on heavy 4d or 5d magnetic ions, where the SO interaction is expected to be significant as it increases as ~Z4 . The double perovskite structure can accommodate a variety of magnetic ions on the B' site, providing a playground for systematic studies of the exotic ground states stabilized by strong SO coupling. Here, we report inelastic neutron scattering (INS) measurements conducted on the frustrated monoclinic magnets, La2LiXO6 (X = Ru, Os), wherein the magnetic moments decorate a quasi face-centered-cubic lattice. Our results show the development of a spin gap in the spin excitation spectrum of size ΔOs = 8 meV and ΔRu = 2.5meV concomitant with TN, which is unexpected for orbitally quenched d3 systems. We liken these results to INS results obtained for Ba2YXO6 and La2NaXO6, which were also shown to exhibit spin gaps that correlate with TN. We shall discuss trends observed in these three d3 double perovskite families which correlate strong SO coupling, spin gap and TN.

  6. 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

    2014-11-01

    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. PMID:25337807

  7. 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

    2014-11-01

    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.

  8. Structure, bonding, and magnetic response in two complex borides: Zr{sub 2}Fe{sub 1-{delta}}Ru{sub 5+{delta}}B2 and Zr{sub 2}Fe{sub 1-{delta}}(Ru{sub 1-x}Rh{sub x}){sub 5+{delta}}B2

    SciTech Connect

    Brgoch, Jakoah; Yeninas, Steven; Prozorov, Ruslan; Miller, Gordon J.

    2010-12-15

    Polycrystalline samples of two complex intermetallic borides Zr{sub 2}Fe{sub 1-{delta}}Ru{sub 5+{delta}}B2 and Zr{sub 2}Fe{sub 1-{delta}}(Ru{sub 1-x}Rh{sub x}){sub 5+{delta}}B2 ({delta}=ca. 0.10; x=0.20) were synthesized by high-temperature methods and characterized by single-crystal X-ray diffraction, energy dispersive spectroscopy, and magnetization measurements. Both structures are variants of Sc{sub 2}Fe(Ru{sub 1-x}Rh{sub x}){sub 5}B{sub 2} and crystallize in the space group P4/mbm (no. 127) with the Ti{sub 3}Co{sub 5}B{sub 2}-type structure. These structures contain single-atom, Fe-rich Fe/Ru or Fe/Ru/Rh chains along the c-axis with an interatomic metal-metal distance of 3.078(1) A, a feature which makes them viable for possible low-dimensional temperature-dependent magnetic behavior. Magnetization measurements indicated weak ferrimagnetic ordering with ordering temperatures ca. 230 K for both specimens. Tight-binding electronic structure calculations on a model 'Zr{sub 2}FeRu{sub 5}B{sub 2}' using LDA yielded a narrow peak at the Fermi level assigned to Fe-Fe antibonding interactions along the c-axis, a result that indicates an electronic instability toward ferromagnetic coupling along these chains. Spin-polarized calculations of various magnetic models were examined to identify possible magnetic ordering within and between the single-atom, Fe-rich chains. -- Graphical abstract: Zr{sub 2}FeRu{sub 5-x}Rh{sub x}B{sub 2} (x=0, 1) crystallizes with magnetic atoms forming chains which have been shown to order magnetically depending on the total valence electron count. Magnetic measurements and tight-binding electronic structure calculations are employed to investigate the ordering. Display Omitted

  9. 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.

  10. 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.

  11. Ab initio and cluster expansion study of surface alloys of Fe and Au on Ru(0001) and Mo(110): Importance of magnetism

    NASA Astrophysics Data System (ADS)

    Marathe, Madhura; Díaz-Ortiz, Alejandro; Narasimhan, Shobhana

    2013-12-01

    We have performed ab initio density functional theory calculations to study freestanding alloy monolayers of Fe and Au in centered rectangular and hexagonal geometries, as well as Fe-Au surface alloys on Ru(0001) and Mo(110) substrates. Though Fe and Au are bulk immiscible, in all four classes of systems we obtain negative formation energies. While the properties of the two classes of freestanding monolayers are roughly similar, with small differences due to the anisotropy and longer bond lengths of the centered rectangular case, the surface alloys on the two substrates behave quite differently. The formation energies on Mo(110) are markedly smaller; we trace this to the fact that magnetism contributes significantly to mixing on Ru(0001) but not on Mo(110). On Ru(0001), there is a very stable (√3 ×√3 ) FeAu2 phase, in agreement with experiments. By performing cluster expansion calculations, we show that ordering is not favored on Mo(110), again in accordance with experimental data.

  12. Reactivity of Fe sub 3 and Ru sub 3. mu. sub 3 -phenylimido clusters with alkynes, allene, and 1,3-cyclohexadiene

    SciTech Connect

    Song, Jeongsup; Han, Sunghwan; Nguyen, S.T.; Geoffroy, G.L. )

    1990-08-01

    The reactivity of alkynes with the imido clusters Ru{sub 3}({mu}{sub 3}-NPh){sub 2}(CO){sub 9}, H{sub 2}Ru{sub 3}({mu}{sub 3}-NPh)(CO){sub 9}, Fe{sub 3}({mu}{sub 3}-NPh)(CO){sub 10}, Fe{sub 3}({mu}{sub 3}-NPh){sub 2}(CO){sub 9}, and H{sub 2}Fe{sub e}({mu}{sub 3}-NPh)(CO){sub 9} has been examined. The cluster Fe{sub 3}({mu}{sub 3}-NPh)(CO){sub 10} reacts regiospecifically with a series of alkynes to form the binuclear ferrapyrrolinone complexes Fe{sub 2}({mu}{sub 2}-{eta}{sup 3}-RC{double bond}C(R{prime})C(O)NPh)(CO){sub 6}, possessing a metallacycle formed by coupling of the alkyne with CO and the imido ligand. The bis(imido) cluster Ru{sub 3}({mu}{sub 3}-NPh){sub 2}(CO){sub 9} reacts with PhC{triple bond}CPh to form the tetranuclear cluster Ru{sub 4}({mu}{sub 3}-NPh){sub 2}({eta}{sup 2}-{mu}{sub 2}-PhC{triple bond}CPh)(CO){sub 10}, which has been crystallographically shown to possess a butterfly arrangement of the four ruthenium atoms with the alkyne bridging the hinge of the butterfly in a perpendicular fashion and with the imido ligands bridging the open triangular faces of the butterfly.

  13. Ab initio study of low-temperature magnetic properties of double perovskite Sr2FeOsO6

    NASA Astrophysics Data System (ADS)

    Kanungo, Sudipta; Yan, Binghai; Jansen, Martin; Felser, Claudia

    2014-06-01

    Using density-functional theory calculations, we investigated the electronic structure and magnetic exchange interactions of the ordered 3d-5d double perovskite Sr2FeOsO6, which has recently drawn attention for interesting antiferromagnetic transitions. Our study reveals the vital role played by long-range magnetic exchange interactions in this compound. The competition between the ferromagnetic nearest-neighbor Os-O-Fe interaction and antiferromagnetic next-nearest-neighbor Os-O-Fe-O-Os interaction induces strong frustration in this system, which explains the lattice distortion and magnetic phase transitions observed in experiments.

  14. Microstructure and ordering parameter studies in multilayer [FePt(x)/Os]{sub n} films

    SciTech Connect

    Chiang, D. P.; Chen, S. Y.; Chen, Y. Y.; Yao, Y. D.; Ouyang, H.; Yu, C. C.; Lin, H. M.

    2011-04-01

    The microstructure, ordering parameter, and magnetic properties of multilayer [FePt(x)/Os]{sub n} films on glass substrate by dc-magnetron sputtering (with x being thickness in nm; Os with a fixed thickness 5 nm; n being the number of layers) have been studied as a function of the annealing temperatures between 300 and 900 deg. C. The grain size of multilayer films can be controlled by annealing temperature and thickness of the FePt layer with Os space layer. The coercivity as a function of the annealing temperature for samples with n = 1 and pure FePt behaves roughly saturated after annealing above 700 deg. C. However, for samples with n > 4 the value of H{sub c} seems still increasing with increasing annealing temperature between 600 and 900 deg. C, and the ordering parameter decreases with increasing the number of Os layers. Our experimental results are reasonably well to describe the effect of strain-assisted transformation.

  15. Magnetoelectric Coupling in Well-Ordered Epitaxial BiFeO3/CoFe2O4/SrRuO3 Heterostructured Nanodot Array.

    PubMed

    Tian, Guo; Zhang, Fengyuan; Yao, Junxiang; Fan, Hua; Li, Peilian; Li, Zhongwen; Song, Xiao; Zhang, Xiaoyan; Qin, Minghui; Zeng, Min; Zhang, Zhang; Yao, Jianjun; Gao, Xingsen; Liu, Junming

    2016-01-26

    Multiferroic magnetoelectric (ME) composites exhibit sizable ME coupling at room temperature, promising applications in a wide range of novel devices. For high density integrated devices, it is indispensable to achieve a well-ordered nanostructured array with reasonable ME coupling. For this purpose, we explored the well-ordered array of isolated epitaxial BiFeO3/CoFe2O4/SrRuO3 heterostructured nanodots fabricated by nanoporous anodic alumina (AAO) template method. The arrayed heterostructured nanodots demonstrate well-established epitaxial structures and coexistence of piezoelectric and ferromagnetic properties, as revealed by transmission electron microscopy (TEM) and peizoeresponse/magnetic force microscopy (PFM/MFM). It was found that the heterostructured nanodots yield apparent ME coupling, likely due to the effective transfer of interface couplings along with the substantial release of substrate clamping. A noticeable change in piezoelectric response of the nanodots can be triggered by magnetic field, indicating a substantial enhancement of ME coupling. Moreover, an electric field induced magnetization switching in these nanodots can be observed, showing a large reverse ME effect. These results offer good opportunities of the nanodots for applications in high-density ME devices, e.g., high density recording (>100 Gbit/in.(2)) or logic devices. PMID:26651132

  16. Properties of KCo2As2 and alloys with Fe and Ru: density functional calculations

    SciTech Connect

    Singh, David J

    2009-01-01

    Electronic-structure calculations are presented for KCo{sub 2}As{sub 2} and alloys with KFe{sub 2}As{sub 2} and KRu{sub 2}As{sub 2}. These materials show electronic structures characteristic of coherent alloys with a similar Fermi surface structure to that of the Fe-based superconductors when the d-electron count is near 6 per transition metal. However, they are less magnetic than the corresponding Fe compounds. These results are discussed in relation to superconductivity.

  17. Transport properties, upper critical field and anisotropy of Ba(Fe0.75Ru0.25)2As2 single crystals

    NASA Astrophysics Data System (ADS)

    Xing, Jie; Shen, Bing; Zeng, Bin; Liu, JianZhong; Ding, XiaXin; Wang, ZhiHe; Yang, Huan; Wen, HaiHu

    2012-12-01

    The temperature and angle dependent resistivity of Ba(Fe0.75Ru0.25)2As2 single crystals were measured in magnetic fields up to 14 T. The temperature dependent resistivity with the magnetic field aligned parallel to c-axis and ab-planes allow us to derive the slope of d H {/c2 ab }/d T and d H {/c2 c }/d T near T c yielding an anisotropy ratio Γ = d H {/c2 ab }/d T/d H {/c2 c }/d T≈2. By scaling the curves of resistivity vs. angle measured at a fixed temperature but different magnetic fields within the framework of the anisotropic Ginzburg-Landau theory, we obtained the anisotropy in an alternative way. Again we found that the anisotropy ( m c / m ab )1/2 was close to 2. This value is similar to that in Ba0.6K0.4Fe2As2 (K-doped Ba122) and Ba(Fe0.92Co0.08)2As2 (Co-doped Ba122). This suggests that the 3D warping effect of the Fermi surface in Ru-doped samples may not be stronger than that in the K-doped or Co-doped Ba122 samples, therefore the possible nodes appearing in Ru-doped samples cannot be ascribed to the 3D warping effect of the Fermi surface.

  18. 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.

  19. 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.

  20. On the oxidation of EuFe[subscript 4]Sb[subscript 12] and EuRu[subscript 4]Sb[subscript 12

    SciTech Connect

    Peddle, Jessica M.; Gaultois, Michael W.; Grosvenor, Andrew P.

    2011-10-25

    Rare-earth-filled transition-metal pnictides having the skutterudite-type structure have been proposed for use as high-temperature thermoelectric materials to recover waste heat from vehicle exhaust, among other applications. A previous investigation by this research group of one of the most studied skutterudites, CeFe{sub 4}Sb{sub 12}, found that, when exposed to air, this material oxidized at temperatures that are considerably below the proposed maximum operating temperature. Here, by the combined use of TGA, powder XRD, and XANES, it has been found that the substitution of Ce{sup 3+} and Fe{sup 2+} for larger rare-earth and transition-metal elements (Eu{sup 2+} and Ru{sup 2+}) results in a significantly higher oxidation temperature compared to that of CeFe{sub 4}Sb{sub 12}. This increase can be related to the increased orbital overlap provided by these larger atoms (Eu{sup 2+} and Ru{sup 2+} vs Ce{sup 3+} and Fe{sup 2+}), enabling the development of stronger bonds. These results show how selective substitution of the constituent elements can significantly improve the thermal stability of materials.

  1. Structure and properties of ultrathin iron films on Ru(10 overline10) : The formation of metastable surface phases of γ-Fe

    NASA Astrophysics Data System (ADS)

    Harrison, Kevin; Prince, Robert H.; Lambert, Richard M.

    1988-07-01

    The chemisorption and desorption of Fe at the (10 overline10) surface of Ru has been investigated by LEED, Auger spectroscopy, Δφ and thermal desorption measurements over a substrate temperature range of 300-900 K. The growth mode of the iron deposit was found to be strongly dependent on the temperature. At 300 K up to seven iron monolayers could be grown, these adopting the configuration of the fcc (111) plane of bulk γ-iron. The layers were metastable and heating of such films or deposition at elevated temperatures resulted in nucleation and growth of crystallites. Only a single Fe desorption peak ( Ed≈ 250 kJ mol-1) was observed over the whole coverage regime; this is assigned to the evaporation of iron atoms in contact with the ruthenium substrate, either pre-existing in the first monolayer or supplied from the Fe crystallites.

  2. Effect of magnetic field on thermo emf of Pd + Cr + Os/Cu + Fe thermocouple

    SciTech Connect

    Gololobov, E.M.; Petrashko, V.V.; Semenenko, Yu.A.

    1987-06-01

    The effect of a magnetic field with a strength of up to 46.5 kOe on the thermoemf of a thermocouple of Pd + 0.5 at.% Cr + 0.5 at.% Os/Cu + 0.15 at.% Fe in the temperature range of 4.2-85/sup 0/K is studied. The maximum error of the thermocouple due to the magnetic field for a cold-junction (in same field) temperature of 4.2/sup 0/K is less than or equal to 0.38/sup 0/K over the entire temperature range.

  3. 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)].

  4. 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. PMID:24182298

  5. 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.

  6. Anion-cation charge-transfer properties and spectral studies of [M(phen)3][Cd4(SPh)10] (M = Ru, Fe, and Ni).

    PubMed

    Jiang, Jian-Bing; Bian, Guo-Qing; Zhang, Ya-Ping; Luo, Wen; Zhu, Qin-Yu; Dai, Jie

    2011-10-01

    Three anion-cation compounds 1-3 with formula [M(phen)(3)][Cd(4)(SPh)(10)]·Sol (M = Ru(2+), Fe(2+), and Ni(2+), Sol = MeCN and H(2)O) have been synthesized and characterized by single-crystal analysis. Both the cations and anion are well-known ions, but the properties of the co-assembled compounds are interesting. Molecular structures and charge-transfer between the cations and anions in crystal and even in solution are discussed. These compounds are isomorphous and short inter-ion interactions are found in these crystals, such as π···π stacking and C-H···π contacts. Both spectroscopic and theoretical calculated results indicate that there is anion-cation charge-transfer (ACCT) between the Ru-phen complex dye and the Cd-SPh cluster, which plays an important role in their photophysical properties. The intensity of the fluorescent emission of the [Ru(phen)(3)](2+) is enhanced when the cation interacts with the [Cd(4)(SPh)(10)](2-) anion. The mechanism for the enhancement of photoluminescence has been proposed.

  7. Influence of central metalloligand geometry on electronic communication between metals: syntheses, crystal structures, MMCT properties of isomeric cyanido-bridged Fe2Ru complexes, and TDDFT calculations.

    PubMed

    Ma, Xiao; Lin, Chen-Sheng; Hu, Sheng-Min; Tan, Chun-Hong; Wen, Yue-Hong; Sheng, Tian-Lu; Wu, Xin-Tao

    2014-06-01

    To investigate how the central metalloligand geometry influences distant or vicinal metal-to-metal charge-transfer (MMCT) properties of polynuclear complexes, cis- and trans-isomeric heterotrimetallic complexes, and their one- and two-electron oxidation products, cis/trans-[Cp(dppe)Fe(II)NCRu(II)(phen)2CN-Fe(II)(dppe)Cp][PF6]2 (cis/trans-1[PF6]2), cis/trans-[Cp(dppe)Fe(II)NCRu(II)(phen)2CNFe(III)-(dppe)Cp][PF6]3 (cis/trans-1[PF6]3) and cis/trans-[Cp(dppe)Fe(III)NCRu(II)(phen)2CN-Fe(III)(dppe)Cp][PF6]4 (cis/trans-1[PF6]4) have been synthesized and characterized. Electrochemical measurements show the presence of electronic interactions between the two external Fe(II) atoms of the cis- and trans-isomeric complexes cis/trans-1[PF6]2. The electronic properties of all these complexes were studied and compared by spectroscopic techniques and TDDFT//DFT calculations. As expected, both mixed valence complexes cis/trans-1[PF6]3 exhibited different strong absorption signals in the NIR region, which should mainly be attributed to a transition from an MO that is delocalized over the Ru(II)-CN-Fe(II) subunit to a Fe(III) d orbital with some contributions from the co-ligands. Moreover, the NIR transition energy in trans-1[PF6]3 is lower than that in cis-1[PF6]3, which is related to the symmetry of their molecular orbitals on the basis of the molecular orbital analysis. Also, the electronic spectra of the two-electron oxidized complexes show that trans-1[PF6]4 possesses lower vicinal Ru(II) → Fe(III) MMCT transition energy than cis-1[PF6]4. Moreover, the assignment of MMCT transition of the oxidized products and the differences of the electronic properties between the cis and trans complexes can be well rationalized using TDDFT//DFT calculations. PMID:24771667

  8. Spin-glass behavior and pyroelectric anomalies in a new lithium-based oxide, Li3FeRuO5.

    PubMed

    Upadhyay, Sanjay Kumar; Paulose, P L; Iyer, Kartik K; Sampathkumaran, E V

    2016-08-17

    The results of dc and ac magnetization, heat capacity, (57)Fe Mössbauer spectroscopy, dielectric, pyroelectric current and isothermal magneto-capacitance measurements of a recently reported lithium-rich layered oxide, Li3FeRuO5, related to LiCoO2-type (rhombohedral, space group R3[combining macron]m), are presented. The results reveal that the compound undergoes spin-glass freezing at 15 K. There is a peak around 34 K in pyroelectric data, which cannot be attributed to ferroelectricity, but to the phenomenon of thermally stimulated depolarization current. As revealed by magnetocapacitance data above and below the magnetic ordering temperature, magnetic and electric dipoles appear to be coupled, thereby offering evidence for magnetodielectric coupling. PMID:27498689

  9. 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.

  10. 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.

  11. Site preference and vibrational properties of R{sub 3}T{sub 4+x}Al{sub 12-x} (R=Y, Ce, Gd, U, Th; T=Fe, Ru)

    SciTech Connect

    Chen Yi; Shen Jiang; Chen Nanxian

    2010-03-15

    The crystal structures and phase stability of the ternary alloys R{sub 3}T{sub 4+x}Al{sub 12-x} (R=Y, Ce, Gd, U, Th; T=Fe, Ru) have been investigated using the interatomic potentials obtained by the lattice inversion method. These compounds crystallize in the hexagonal Gd{sub 3}Ru{sub 4}Al{sub 12}-type structure and the calculated lattice constants correspond well with the experiments. Among the four different kinds of Al sites in the structure, the most preferential sites for Fe atoms or Ru atoms are 6h sites. The properties related to lattice vibration, such as the phonon density of states (DOS) and Debye temperature of R{sub 3}Fe{sub 4}Al{sub 12,} have been evaluated. A qualitative analysis is carried out with the relevant potentials for the vibrational modes, which makes it possible to predict some thermodynamic properties. - The crystal structure of R{sub 3}T{sub 4}Al{sub 12} could be considered as two kinds of layer stacking up along the hexagonal c axis. Fe and Ru atoms preferentially substitute for Al atoms at 6h site.

  12. 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.

  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

    2015-01-01

    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

  14. 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.

  15. 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

  16. Demonstration of magnetoelectric memory cell in (110) [Pb(Mg1/2Nb2/3)O3]0.68-[PbTiO3]0.32/Ru/FeCo heterostructures

    NASA Astrophysics Data System (ADS)

    Han, Xuemeng; Xi, Li; Li, Yue; Guo, Xiaobin; Li, Dong; Wang, Zhen; Zuo, Yalu; Xue, Desheng

    2014-09-01

    An electric-field pulses driven magnetoelectric memory cell in a single layered ferromagnetic thin film was fabricated by direct-current magnetron sputtering Ru/Fe65Co35 on ferroelectric (110) [Pb(Mg1/2 Nb2/3)O3]0.68-[PbTiO3]0.32 (PMN-PT) substrates. The magnetization in the orthogonal directions can be reset by the positive/negative electric fields pulse in PMN-PT/Ru/FeCo heterostructures due to the strain mediated converse magnetoelectric effect. The high (low) resistance state was realized under the negative (positive) electric fields pulse due to the anisotropy magnetoresistance of FeCo films. Then, a non-volatile magnetic memory cell with resistance and electric field, respectively, as the media and writing field was realized.

  17. Effects of CrRu-SiO{sub x} underlayer with MgO intermediate layer on the microstructure and magnetic properties of FePt-C thin film

    SciTech Connect

    Li, H. H.; Hu, J. F.; Ju, G.; Chow, G. M.; Chen, J. S.

    2011-04-01

    The effect of the CrRu-SiO{sub x} underlayer with different doping concentrations and the thickness of the CrRu underlayer on the microstructure and magnetic properties of FePt-C films were investigated. FePt films exhibited L1{sub 0} (001) texture at various SiO{sub x} doping concentrations. The coercivities were as large as 28 kOe and the slope of M-H loop at coercivity was approximately equal to 1, suggesting that FePt grains were well exchange decoupled. Grain size was only slightly reduced after introducing the CrRu-SiO{sub x} underlayer. But the contact angle between the FePt grains and the MgO intermediate layer around 135 deg. indicated the a MgO intermediate layer was not favored for smaller grains to obtain good L1{sub 0} (001) texture. X-ray photoelectron spectroscopy in-depth profile showed that Si diffused into a whole FePt-C layer and C diffused to the film surface.

  18. Electrical and piezoelectric properties of BiFeO3 thin films grown on SrxCa1-xRuO3-buffered SrTiO3 substrates

    NASA Astrophysics Data System (ADS)

    Yao, Yingbang; Chen, Long; Wang, Zhihong; Alshareef, Husam; Zhang, X. X.

    2012-06-01

    (001)-oriented BiFeO3 (BFO) thin films were grown on SrxCa1-xRuO3- (SCRO; x = 1, 0.67, 0.33, 0) buffered SrTiO3 (001) substrates using pulsed laser deposition. The microstructural, electrical, ferroelectric, and piezoelectric properties of the thin films were considerably affected by the buffer layers. The interface between the BFO films and the SCRO-buffer layer was found to play a dominant role in determining the electrical and piezoelectric behaviors of the films. We found that films grown on SrRuO3-buffer layers exhibited minimal electrical leakage while films grown on Sr0.33Ca0.67RuO3-buffer layers had the largest piezoelectric response. The origin of this difference is discussed.

  19. 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.

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

    DOE PAGESBeta

    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 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

  1. 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.

  2. 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.

  3. 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

  4. Managing magnetization and antiferromagnetic coupling in epitaxially grown magnetic oxide heterostructures of (Ga,Fe)2O3 and SrRuO3

    NASA Astrophysics Data System (ADS)

    Lee, Jihye; Jo, William; Meny, Christian; Roulland, Francois; Viart, Nathalie

    2011-03-01

    We have grown b-axis oriented epitaxial (Ga,Fe)2O3 (GFO) thin films on (111) oriented SrRuO3 (SRO) by pulsed laser deposition to know spin interaction in multilayer system. The easy axis of magnetization of the GFO is located on the plane of the thin films. On the other hand, SRO has unique anisotropic properties on various crystallographic directions in their structure. Magnetic properties of the films were measured as a function of temperature and external magnetic field by a superconducting quantum interference magnetometer. Curie temperature of SRO and GFO was measured at 150K and 370K, respectively. According to the direction of external magnetic field, the magnetic moment value of the GFO/SRO heterostructures show different behavior due to antiferromagnetic coupling. This research was supported by Leading Foreign Research Institute Recruitment Program through the National Research Foundation of Korea(NRF) funded by the Ministry of Education, Science and Technology(MEST) (2010-00453)

  5. Investigation of the synthesis, activation, and isosteric heats of CO2 adsorption of the isostructural series of metal-organic frameworks M3(BTC)2 (M = Cr, Fe, Ni, Cu, Mo, Ru).

    PubMed

    Wade, Casey R; Dincă, Mircea

    2012-07-14

    The synthesis, activation, and heats of CO(2) adsorption for the known members of the M(3)(BTC)(2) (HKUST-1) isostructural series (M = Cr, Fe, Ni, Zn, Ni, Cu, Mo) were investigated to gain insight into the impact of CO(2)-metal interactions for CO(2) storage/separation applications. With the use of modified syntheses and activation procedures, improved BET surface areas were obtained for M = Ni, Mo, and Ru. The zero-coverage isosteric heats of CO(2) adsorption were measured for the Cu, Cr, Ni, Mo, and Ru analogues and gave values consistent with those reported for MOFs containing coordinatively unsaturated metal sites, but lower than for amine functionalized materials. Notably, the Ni and Ru congeners exhibited the highest CO(2) affinities in the studied series. These behaviors were attributed to the presence of residual guest molecules in the case of Ni(3)(BTC)(2)(Me(2)NH)(2)(H(2)O) and the increased charge of the dimetal secondary building unit in [Ru(3)(BTC)(2)][BTC](0.5).

  6. Chalcophile and platinum-group element distribution in the Ultramafic series of the Stillwater Complex, MT, USA—implications for processes enriching chromite layers in Os, Ir, Ru, and Rh

    NASA Astrophysics Data System (ADS)

    Barnes, Sarah-Jane; Pagé, P.; Prichard, H. M.; Zientek, M. L.; Fisher, P. C.

    2016-01-01

    All of the rocks from the Ultramafic series of the Stillwater Complex are enriched in PGE relative to most mafic magmas. Furthermore, the chromite layers are particularly enriched in IPGE (Os, Ir, and Ru) and Rh. This enrichment appears to be a common characteristic of ultramafic rocks from many types of settings, layered intrusions, ophiolites, and zoned complexes. We have carried out a petrological, mineralogical, and geochemical study to assess how the enrichment occurred in the case of the Stillwater Complex and applied our results to the chromite layers of the Bushveld and Great Dyke complexes. The minerals that now host the PGE are laurite and fine-grained intergrowths of pentlandite, millerite, and chalcopyrite. The laurite occurs as inclusions in chromite, and mass balance calculations indicate that it hosts most of the Os, Ir, and Ru. The sulfide minerals occur both as inclusions in chromite and as interstitial grains. The sulfides host much of the Pd and Rh. The IPGE and Rh correlate with Cr but not with S or Se, indicating that these elements were not collected by a sulfide liquid. Palladium, Cu, and Se correlate with each other, but not with S. The low S/Se (<1500) of the whole rock and magnetite rims around the sulfides indicate some S has been lost from the rocks. We conclude that to account for all observations, the IPGE and Rh were originally collected by chromite, and subsequently, small quantities of base metal sulfide liquid was added to the chromite layers from the overlying magma. The IPGE and Rh in the chromite diffused from the chromite into the base metal sulfides and converted some of the sulfides to laurite.

  7. Magnetic properties of the double perovskite Sr2FeOsO6: microscopic insights from ab-initio density-functional theory study

    NASA Astrophysics Data System (ADS)

    Kanungo, Sudipta; Yan, Binghai; Jansen, Martin; Felser, Claudia

    2015-03-01

    Using density-functional theory calculations, we investigated the electronic and magnetic properties of the ordered 3d-5d double perovskite Sr2FeOsO6, which has recently drawn attention for interesting antiferromagnetic (AFM) phase transitions in low temperature observed in experiments. The calculated effective magnetic exchange interactions reveal the importance of long-range super-superexchange interactions in this compound. The competition between the ferromagnetic (FM) Os-O-Fe short-range interaction and AFM Os-O-Fe-O-Os long-range interaction induces strong magnetic frustration along the crystallographic c axis. This strong magnetic frustration is proposed to drive the magnetic phase transition between two AFM phases (AFM1 to AFM2) and related lattice distortion, which were also observed in the experiment.

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

    DOE PAGESBeta

    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 Kmore » was observed. Spin-polarized electronic structure calculations revealed magnetic frustration with dominant antiferromagnetic interactions.« less

  9. 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.

  10. Oxygen trapped by rare earth tetrahedral clusters in Nd{sub 4}FeOS{sub 6}: 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.

    2015-09-15

    Single crystals of Nd{sub 4}FeOS{sub 6} were grown from an Fe–S eutectic solution. Single crystal X-ray diffraction analysis revealed a Nd{sub 4}MnOSe{sub 6}-type structure (P6{sub 3}mc, a=9.2693(1) Å, c=6.6650(1)Å, V=495.94(1) Å{sup 3}, Z=2), featuring parallel chains of face-sharing [FeS{sub 6×1/2}]{sup 4−} trigonal antiprisms and interlinked [Nd{sub 4}OS{sub 3}]{sup 4+} cubane-like clusters. Oxygen atoms were found to be trapped by Nd{sub 4} clusters in the [Nd{sub 4}OS{sub 3}]{sup 4{sub +}} chains. Structural differences among Nd{sub 4}MnOSe{sub 6}-type Nd{sub 4}FeOS{sub 6} and the related La{sub 3}CuSiS{sub 7}− and Pr{sub 8}CoGa{sub 3}-type structures have been described. Magnetic susceptibility measurements on Nd{sub 4}FeOS{sub 6} 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. - Graphical abstract: Trapping of oxygen in Nd{sub 4} tetrahedral clusters results in the formation of the Nd{sub 4}MnOSe{sub 6}-type Nd{sub 4}FeOS{sub 6}, in contrast to the La{sub 3}CuSiS{sub 7}-type oxygen-free Nd{sub 4}FeS{sub 7} and related Pr{sub 8}CoGa{sub 3}-type structures. Complex magnetic frustration inhibits magnetic ordering at low temperature. - Highlights: • Single crystals of Nd{sub 4}FeOS{sub 6} were grown using self-flux method. • Oxygen was found trapped by Nd{sub 4} tetrahedral clusters. • Comparison with two closely related structural types were discussed. • Magnetic measurements revealed antiferromagnetic (AFM) interaction. • VASP calculations confirmed strong magnetic frustration in AFM model.

  11. 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.

  12. Substitution effects of barium and calcium on magnetic properties of AxSr1-x(Fe0.5Ru0.5)O3 double perovskites (x =0.05, A =Ba,Ca)

    NASA Astrophysics Data System (ADS)

    Nomura, K.; Zboril, R.; Tucek, J.; Kosaka, W.; Ohkoshi, S.; Felner, I.

    2007-07-01

    AxSr1-x(Fe0.5Ru0.5)O3 double perovskites (x =0.05 and A =Ba,Ca) were prepared by a sol-gel method and an effect of the cation substitution at the A site of the crystal structure of SrFe0.5Ru0.5O3 on their magnetic properties was monitored by x-ray diffraction (XRD), magnetic measurements, transmission electron microscopy (TEM), scanning electron microscopy (SEM), and temperature-dependent and in-field Fe57 Mössbauer spectroscopy. Both Ca- and Ba-substituted samples reveal the orthorhombic structure similar to the undoped perovskite; however, the cell volume changes with the substituting ion radius. TEM and SEM micrographs manifest agglomerated nanocrystalline samples with particle sizes of about 20-60, 15-50, and 40-70nm for the undoped, Ba-doped, and Ca-doped perovskites, respectively. Generally, the magnetic regime of both substituted and undoped perovskites can be described by a spin-glass behavior caused by a spin frustration. Among other factors, this is manifested by a nonsaturation of the hysteresis loops even at a high field of 50kOe, by a low-temperature divergence of the zero-field-cooled and field-cooled magnetization curves, and by a cusp in the zero-field-cooled magnetization curve. The low-temperature spin-glass state is also supported by the in-field Mössbauer spectra, recorded on these systems. The isomer shift parameters, extracted from the Mössbauer spectra, confirm a high-spin iron(III) state with S =5/2. In contrast to the undoped and Ba-doped samples, the narrower distribution of the hyperfine magnetic fields, observed in the Ca-doped perovskite can be ascribed to the larger particles. Compared to the undoped sample, the field of maximum probability is higher in the Ca-substituted perovskite while it is reduced in the Ba-doped sample because of the effects of the chemical compression and expansion, respectively. In addition, the Ca-doped sample exhibits more negative Weiss temperature (Θ=-105K) than that found for the Ba

  13. Vibronic and magnetic coupling in the radiative deactivation of the lowest excited state of (Os(bpy) sub 3 ) sup 2+ doped into (Ru(bpy) sub 3 )(PF sub 6 ) sub 2

    SciTech Connect

    Braun, D.; Hensler, G.; Gallhuber, E.; Yersin, H. )

    1991-02-07

    Small amounts of (Os(bpy){sub 3}){sup 2+} doped into single-crystal (Ru(bpy){sub 3})(PF{sub 6}){sub 2} exhibit highly resolved MLCT spectra corresponding to the transitions between the ground state and the lowest excited states. The electronic origins as well as the vibronic satellites appear as sharp lines with half-widths of {approx}2 cm{sup {minus}1}. Three distinct spectroscopic sites are identified. For the lowest energy site the lowest excited state {vert bar}I> is located at 14,423 cm{sup {minus}1} and the second excited state {vert bar}II> lies 72 cm{sup {minus}1} above {vert bar}>. Due to the polarization properties of the origins both states are assigned to be doubly degenerate (E representations in the D{sub 3} double group). The emission from {vert bar}I> shows a very weak origin line compared to the intense vibronic satellites which mostly correspond to IR-active vibrations. It is proposed that the vibronic intensity is induced by spin-vibronic and/or spin-orbit-vibronic coupling. The electronic state(s) supplying allowedness to the radiative decay from {vert bar}I> are assigned to doubly degenerate E state(s) of singlet parentage. Further, magnetic fields induce a mixing of the wave functions of {vert bar}I> and {vert bar}II>, which results in an intensity increase of the electronic origin of the perturbed state {vert bar}I{prime}>{sub B} by a factor of about 1,000.

  14. 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.

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

    DOE PAGESBeta

    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 differencesmore » with the more thoroughly studied 3d-3d systems.« less

  16. 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

  17. 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.

  18. 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.

  19. 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.

  20. 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

  1. 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.

  2. 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

    2015-12-01

    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. PMID:26581027

  3. 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.

  4. Structural and physical properties of layered oxy-arsenides LnRuAsO (Ln=La, Nd, Sm, Gd)

    SciTech Connect

    McGuire, Michael A.; May, Andrew F.; Sales, Brian C.

    2012-07-15

    Polycrystalline samples of LaRuAsO, NdRuAsO, SmRuAsO, and GdRuAsO have been synthesized and studied using powder x-ray diffraction, electrical transport, magnetization, and heat capacity measurements. Variations in structural properties across the series reveal a trend toward more ideal tetrahedral coordination around Ru as the size of the rare earth element is reduced. The lattice parameters of these Ru compounds show a more anisotropic response to variation in Ln than their Fe analogs, and significant anisotropy in thermal expansion is also observed. Transport measurements show metallic behavior, and carrier concentrations near 10{sup 21}-10{sup 22} electrons per cm{sup 3} are inferred from simple analysis of Hall effect measurements. Anomalies in resistivity, magnetization, and heat capacity indicate antiferromagnetic ordering of rare earth moments at 5 K for GdRuAsO, 4.5 K for SmRuAsO, and <2K for NdRuAsO. Magnetization measurements on LaRuAsO show no evidence of a magnetic moment on Ru. Observed behaviors are compared to those reported for similar Fe and Ru compounds. - Graphical abstract: Analysis of crystal structure, electrical transport, magnetic susceptibility, and heat capacity of LaRuAsO, NdRuAsO, SmRuAsO, and GdRuAsO. Highlights: Black-Right-Pointing-Pointer Experimental investigation of LaRuAsO, NdRuAsO, SmRuAsO, and GdRuAsO. Black-Right-Pointing-Pointer Anisotropic lattice response to changing Ln radius and temperature. Black-Right-Pointing-Pointer Ru coordination becomes more ideal as Ln radius is reduced. Black-Right-Pointing-Pointer Transport measurements reveal metallic conduction dominated by electrons. Black-Right-Pointing-Pointer Magnetic measurements indicate antiferromagnetic ordering Nd, Sm, and Gd moments.

  5. Effect of arene substituents and temperature on the arene replacement reactions of ((eta/sup 5/-C/sub 5/H/sub 5/)Fe(eta/sup 6/-arene))/sup +/ and ((eta/sup 5/-C/sub 5/H/sub 5/)Ru(eta/sup 6/-arene))/sup +/

    SciTech Connect

    McNair, A.M.; Schrenk, J.L.; Mann, K.R.

    1984-08-15

    Results are reported for investigations to identify the photoactive excited states, delineate substitutent effects, and determine the temperature dependence of the quantum yield for Fe(II)- and Ru(II)-substituted arene complexes. These studies indicate metal-arene bond cleavage for complexes of both metals is nearly complete in the reactive excited state, but nucleophilic interactions of the medium in the transition state ultimately control the quantum yield of arene release for a given complex.

  6. 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.

  7. 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.

  8. Percolation theory and quantum critical systems: A new description of the critical behavior in Ce(Ru{sub 0.24}Fe{sub 0.76}){sub 2}Ge{sub 2}

    SciTech Connect

    Gaddy, John; Heitmann, Tom; Montfrooij, Wouter

    2014-05-07

    The onset of ordering in quantum critical systems is characterized by a competition between the Kondo shielding of magnetic moments and the ordering of these moments. We show how a distribution of Kondo shielding temperatures—resulting from chemical doping—leads to critical behavior whose main characteristics are given by percolation physics. With the aid of Monte Carlo computer simulations, we are able to infer the low temperature part of the distribution of shielding temperatures in heavily doped quantum critical Ce(Ru{sub 0.24}Fe{sub 0.76}){sub 2}Ge{sub 2}. Based on this distribution, we show that the ordering dynamics—such as the growth of the correlation length upon cooling—can be understood by the spawning of magnetic clusters. Our findings explain why the search for universal exponents in quantum critical systems has been unsuccessful: the underlying percolation network associated with the chemical doping of quantum critical systems has to be incorporated in the modeling of these quantum critical systems.

  9. 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.

  10. Reactions of HC triple bond CCMe sub 2 NHCOR alkynes with M sub 3 (CO) sub 12 carbonyls (M = Ru, R = C sub 6 H sub 9 , Ph; M = Os, R = C sub 6 H sub 9 ). Synthesis and crystal structure of Ru sub 4 (CO) sub 11 (HC triple bond CCMe sub 2 NHCOC sub 6 H sub 9 ), a butterfly cluster showing an interaction between a wingtip metal and the amide CO

    SciTech Connect

    Predieri, G.; Tiripicchio, A.; Camellini, M.T.; Costa, M. ); Sappa, E. )

    1990-06-01

    The alkynes HC{triple bond}CCMe{sub 2}NHCOR react with M{sub 3}(CO){sub 12} (M = Ru or Os) giving, upon oxidative addition, the expected hydrides ({mu}-H)M{sub 3}(CO){sub 9}({mu}{sub 3}-{eta}{sup 2}-C{triple bond}CCMe{sub 2}NHCOR) and the unprecedented butterfly clusters M{sub 4}(CO){sub 11}({mu}{sub 4}-{eta}{sup 2}-HC{triple bond}CCME{sub 2}NHCOR). These complexes have been characterized by spectroscopic studies; the structure of the ruthenium butterfly cluster with R = C{sub 6}H{sub 9} has been determined by X-ray diffraction methods. Crystals, containing CHCl{sub 3} as solvation molecules, are triclinic with Z = 2 in a unit cell of dimensions a = 13.521 (6), b = 14.617 (6), c = 9.049 (5) {angstrom}, {alpha} = 79.28 (2), {beta} = 108.79 (2), {gamma} = 111.85 (2){degree}.

  11. All-atom force field for molecular dynamics simulations on organotransition metal solids and liquids. Application to M(CO)(n) (M = Cr, Fe, Ni, Mo, Ru, or W) compounds.

    PubMed

    Bernardes, Carlos E S; Canongia Lopes, José N; Minas da Piedade, Manuel E

    2013-10-31

    A previously developed OPLS-based all-atom force field for organometallic compounds was extended to a series of first-, second-, and third-row transition metals based on the study of M(CO)(n) (M = Cr, Fe, Ni, Mo, Ru, or W) complexes. For materials that are solid at ambient temperature and pressure (M = Cr, Mo, W) the validation of the force field was based on reported structural data and on the standard molar enthalpies of sublimation at 298.15 K, experimentally determined by Calvet-drop microcalorimetry using samples corresponding to a specific and well-characterized crystalline phase: Δ(sub)H(m)° = 72.6 ± 0.3 kJ·mol(–1) for Cr(CO)(6), 73.4 ± 0.3 kJ·mol(–1) for Mo(CO)(6), and 77.8 ± 0.3 kJ·mol(–1) for W(CO)(6). For liquids, where problems of polymorphism or phase mixtures are absent, critically analyzed literature data were used. The force field was able to reproduce the volumetric properties of the test set (density and unit cell volume) with an average deviations smaller than 2% and the experimentally determined enthalpies of sublimation and vaporization with an accuracy better than 2.3 kJ·mol(–1). The Lennard-Jones (12-6) potential function parameters used to calculate the repulsive and dispersion contributions of the metals within the framework of the force field were found to be transferable between chromium, iron, and nickel (first row) and between molybdenum and ruthenium (second row). PMID:24079472

  12. The role of intermolecular interactions in the assemblies of Fe{sup II} and Co{sup II} tetrakis-isothiocyanatometalates with tris(1,10-phenanthroline)-Ru{sup II}: Crystal structures of two dual-metal assemblies featuring octahedral cationic and tetrahedral anionic modules

    SciTech Connect

    Ghazzali, Mohamed Langer, Vratislav; Ohrstroem, Lars

    2008-09-15

    Two new dual-metal assemblies: 2[Ru(phen){sub 3}]{sup 2+}.[Fe(SCN){sub 4}]{sup 2-}.2SCN{sup -}.4H{sub 2}O 1 and [Ru(phen){sub 3}]{sup 2+}.[Co(SCN){sub 4}]{sup 2-}2, (phen:1,10-phenanthroline), have been prepared and their structures were characterized by X-ray diffraction. In 1, the cationic octahedral enantiomers are arranged with a {lambda}{delta}{lambda}{delta}{lambda} sequence supported by {pi}-{pi} stacking and the anionic inorganic tetrahedral units are oriented between these stacks by interacting with the nearby water molecules through strong O-H...O and O-H...S hydrogen bonds. In 2, homochiral double helices in the b-direction are revealed, with tetrakis-isothiocyanate Co{sup II} anions arranged in the crystal to furnish one-dimensional (1D)-helical chains with S...S intermolecular interactions at 3.512(2) and 3.966(2) A supporting [Ru(phen){sub 3}]{sup 2+}{lambda}- and {delta}-helices with Ru...Ru shortest distance of 8.676(7) A. In both 1 and 2, the supramolecular assembly is maintained by C-H...S hydrogen bonds extending between the phenanthroline aromatic carbons in the cationic nodes and the sulphur atoms of the isothiocyanates anions. Analysis of S...S interactions in isothiocyanate containing compounds using Cambridge structural database (CSD) showed an angle dependence categorizing these interactions into 'type-I' and 'type-II'. - Graphical abstract: Side projection in 2 showing the crankshaft caused by S...S interactions in [Co(NCS){sub 4}]{sup 2-} in-between [Ru{sup II}(phen){sub 3}]{sup 2+} helices. Only isothiocyanates arms of [Co(NCS){sub 4}]{sup 2-} that are part of S...S interactions are shown and [Ru{sup II}(phen){sub 3}]{sup 2+} are presented as polyhedra.

  13. A combined experimental and DFT/TD-DFT investigation of structural, electronic, and cation-induced switching of photophysical properties of bimetallic Ru(II) and Os(II) complexes derived from imidazole-4,5-dicarboxylic acid and 2,2'-bipyridine.

    PubMed

    Das, Shyamal; Karmakar, Srikanta; Saha, Debasish; Baitalik, Sujoy

    2013-06-17

    Experimental results coupled with computational studies were utilized to investigate the structural and electronic properties of mixed-ligand bimetallic ruthenium(II) and osmium(II) complexes of composition [(bpy)2M(Imdc)M(bpy)2](+) [M = Ru(II) (1) and M = Os(II) (2)], where H3Imdc = imidazole-4,5-dicarboxylic acid and bpy = 2,2'-bipyridine. The X-ray crystal structures of both the bimetallic complexes were determined which showed that compound 1 crystallizes in monoclinic form with space group P2(1)/c, while 2 is obtained in orthorhombic form with the space group Pca2(1). The optimized geometrical parameters for the complexes computed both in the gas phase and in solution are reported and compared with the single-crystal X-ray data. The absorption spectra, redox behaviors, and luminescence properties of the complexes were thoroughly investigated. The complexes display very intense, ligand-centered absorption bands in the UV and moderately intense MLCT bands in the visible regions. While the Ru(II) complex displays moderately strong luminescence, the corresponding Os(II) complex does not luminesce at room temperature. Both the bimetallic complexes show two successive one-electron reversible metal-centered oxidations. The effect of alkali, alkaline earth, and transition metal cations on the absorption and emission spectral behavior of the complexes has also been studied in detail. As compared to the luminescence intensities and the quantum yields of the free complexes, those of the complexes were enhanced substantially in the presence of selective cations showing cation-induced molecular switching behaviors. Density functional theory (DFT) and time-dependent DFT (TD-DFT) studies provide insight into the nature of the ground and excited states with resulting detailed assignments of the orbitals involved in absorption and emission transitions. In particular, the blue-shifts of the absorption and emission bands in the presence of cations are also reproduced by our

  14. Formation of carbyne complexes in reactions of laser-ablated Os atoms with halomethanes: characterization by C-H(X) and Os-H(X) stretching absorptions and computed structures.

    PubMed

    Cho, Han-Gook; Andrews, Lester

    2009-08-14

    Reactions of laser-ablated Os atoms with halomethanes have been investigated. Small carbyne complexes are produced in reactions of Os atoms with fluoromethanes and identified through matrix infrared spectra and vibrational frequencies computed by density functional theory. The preference for the carbon-osmium triple bond is traced to the low energy of the Os carbyne products. The C-H and C-X stretching absorptions of the carbyne complexes are observed on the high frequency sides of the corresponding precursor bands, which result from the high s character in the C-H bond and interaction between the C-X and C-Os stretching modes, respectively. The calculated Os complex structures show a large variation with the ligands and electronic states, similar to the analogous Ru complex structures. The present report also compares previous Fe, Ru, and Os results and supports the general trend that the higher oxidation state complexes become more stable on going down the family group column. PMID:19623385

  15. Formation of carbyne complexes in reactions of laser-ablated Os atoms with halomethanes: characterization by C-H(X) and Os-H(X) stretching absorptions and computed structures.

    PubMed

    Cho, Han-Gook; Andrews, Lester

    2009-08-14

    Reactions of laser-ablated Os atoms with halomethanes have been investigated. Small carbyne complexes are produced in reactions of Os atoms with fluoromethanes and identified through matrix infrared spectra and vibrational frequencies computed by density functional theory. The preference for the carbon-osmium triple bond is traced to the low energy of the Os carbyne products. The C-H and C-X stretching absorptions of the carbyne complexes are observed on the high frequency sides of the corresponding precursor bands, which result from the high s character in the C-H bond and interaction between the C-X and C-Os stretching modes, respectively. The calculated Os complex structures show a large variation with the ligands and electronic states, similar to the analogous Ru complex structures. The present report also compares previous Fe, Ru, and Os results and supports the general trend that the higher oxidation state complexes become more stable on going down the family group column.

  16. Mediator enhanced water oxidation using Rb4[Ru(II)(bpy)3]5[{Ru(III)4O4(OH)2(H2O)4}(γ-SiW10O36)2] film modified electrodes.

    PubMed

    Guo, Si-Xuan; Lee, Chong-Yong; Zhang, Jie; Bond, Alan M; Geletii, Yurii V; Hill, Craig L

    2014-07-21

    The water insoluble complex Rb4[Ru(II)(bpy)3]5[{Ru(III)4O4(OH)2(H2O)4}(γ-SiW10O36)2], ([Ru(II)bpy]5[Ru(III)4POM]), was synthesized from Rb8K2[{Ru(IV)4O4(OH)2(H2O)4}(γ-SiW10O36)2] and used for electrocatalytic water oxidation under both thin- and thick-film electrode conditions. Results demonstrate that the [Ru(II)bpy]5[Ru(III)4POM] modified electrode enables efficient water oxidation to be achieved at neutral pH using thin-film conditions, with [Ru(bpy)3](3+)([Ru(III)bpy]) acting as the electron transfer mediator and [Ru(V)4POM] as the species releasing O2. The rotating ring disc electrode (RRDE) method was used to quantitatively determine the turnover frequency (TOF) of the catalyst, and a value of 0.35 s(-1) was obtained at a low overpotential of 0.49 V (1.10 V vs Ag/AgCl) at pH 7.0. The postulated mechanism for the mediator enhanced catalytic water process in a pH 7 buffer containing 0.1 M LiClO4 as an additional electrolyte includes the following reactions (ion transfer for maintaining charge neutrality is omitted for simplicity): [Ru(II)bpy]5[Ru(III)4POM] → [Ru(III)bpy]5[Ru(V)4POM] + 13 e(-) and [Ru(III)bpy]5[Ru(V)4POM] + 2H2O → [Ru(III)bpy]5[Ru(IV)4POM] + O2 + 4H(+). The voltammetry of related water insoluble [Ru(II)bpy]2[S2M18O62] (M = W and Mo) and [Fe(II)Phen]x[Ru(III)4POM] materials has also been studied, and the lack of electrocatalytic water oxidation in these cases supports the hypothesis that [Ru(III)bpy] is the electron transfer mediator and [Ru(V)4POM] is the species responsible for oxygen evolution. PMID:25000486

  17. Theoretical study on the electronic and molecular structures of (C sub 5 H sub 5 )M(L) (M = Rh, Ir; L = CO, PH sub 3 ) and M(CO) sub 4 (M = Ru, Os) and their ability to activate the C-H bond in methane

    SciTech Connect

    Ziegler, T.; Tschinke, V.; Fan, L.; Becke, A.D. )

    1989-12-20

    Nonlocal density functional calculations have been carried out on the electronic and molecular structures of (C{sub 5}H{sub 5})M(L) (L = CO, PH{sub 3}; M = Rh, Ir) (a) and M(CO){sub 4} (M = Ru, Os) (b). All systems are found to have a singlet ground state. Optimized geometries are reported for each system on the singlet ground state as well as the first excited triplet state. Calculated dissociation energies are presented for Y = CO, PH{sub 3}, and H{sub 2} in the case of X{sub n}M = a and for Y = CO and H{sub 2} in the case of X{sub n}M = b. Complete reaction profiles have been calculated for the oxidative addition of H{sub 2} and CH{sub 4} to a and b. The addition reactions are found to be more facile for a than for b. It is argued that a is unique as a C-H activating agent in having only empty {sigma}-type d-based orbitals interacting with the incoming C-H bond. Calculations are presented on the reaction enthalpies of the H-H and C-H addition processes along with the M-H and M-CH{sub 3} bond energies.

  18. Synthesis, characterization and use of Ru-Fc intercalation complex as an electrochemical label for the detection of pathogen-DNA

    NASA Astrophysics Data System (ADS)

    Díaz-Serrano, M.; Rosado, A.; Santana, D.; Vega, E. Z.; Guadalupe, A. R.

    2013-03-01

    This report describes the synthesis of [Ru(Fe-Phen)2dppz](PF6)2 (Ru-Fe complex) for a label-free approach to detect DNA hybridization. The Ru-Fe complex showed oxidation signals at +608 mV and +1192 mV corresponding to the RuII/III and FeII/III centers, respectively. We used the Ru-Fe complex and the Ferrocene covalently attached to the target to monitor the hybridization event of a 70-mer oligo immobilized in 10.3KD NHS-PS-NHS. The lowest target detectable concentration for the DNA fragment was around 0.4 μM.

  19. 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.

  20. 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.

  1. 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. PMID:27484222

  2. 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.

  3. Simulating Ru L3-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, N.; Schoenlein, R. W.; Govind, Niranjan; Khalil, Munira

    2013-05-01

    Ruthenium L2,3-edge X-ray absorption (XA) spectroscopy probes transitions from core 2p orbitals to the 4d levels of the atom and is a powerful tool for interrogating the local electronic and molecular structure around the metal atom. However, a molecular-level interpretation of the Ru L2,3-edge spectral lineshapes is often complicated by spin–orbit coupling (SOC) and multiplet effects. In this study, we develop spin-free time-dependent density functional theory (TDDFT) as a viable and predictive tool to simulate the Ru L3-edge spectra. We successfully simulate and analyze the ground state Ru L3-edge XA spectra of a series of RuII and RuIII complexes: [Ru(NH3)6]2+/3+, [Ru(CN)6]4-/3-, [RuCl6]4-/3-, and the ground (1A1) and photoexcited (3MLCT) transient states of [Ru(bpy)3]2+ and Ru(dcbpy)2(NCS)2 (termed N3). The TDDFT simulations reproduce all the experimentally observed features in Ru L3-edge XA spectra. The advantage of using TDDFT to assign complicated Ru L3-edge spectra is illustrated by its ability to identify ligand specific charge transfer features in complex molecules. We conclude that the B3LYP functional is the most reliable functional for accurately predicting the location of charge transfer features in these spectra. Experimental and simulated Ru L3-edge XA spectra are presented for the transition metal mixed-valence dimers [(NC)5MII-CN-RuIII(NH3)5]- (where M = Fe or Ru) dissolved in water. We explore the spectral signatures of electron delocalization in Ru L3-edge XA spectroscopy and our simulations reveal that the inclusion of explicit solvent molecules is crucial for reproducing the experimentally determined valencies, highlighting the importance of the role of the solvent in transition metal charge transfer chemistry.

  4. 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

  5. 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.

  6. 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

  7. Round table on RU486.

    PubMed

    Shallat, L

    1993-01-01

    As a non-invasive means of early abortion, RU-486 has the potential to increase women's reproductive options; at the same time, the "abortion pill" has stimulated debate about the ethics and safety of new medical technologies. When combined with a prostaglandin (PG), the success rate for RU-486 is 96% for pregnancies of up to 9 weeks' gestation. In France, over 120,000 women have used RU-486/PG to terminate pregnancy, and this regimen is now used in about 25% of abortions. Clinical trials of RU-486 are underway in Cuba, China, India, Singapore, and Zambia. The Program for Appropriate Technology has identified four considerations for introducing RU-486 to developing countries: whether abortion or menstrual regulation is legal; whether women find the method acceptable and can comply with the multiple visit treatment regimen; whether the health infrastructure can support safe method use, including prevention of misuse and provision of appropriate medical backup personnel and facilities; and whether the cost of the regimen is affordable to individuals and/or programs --conditions unlikely to be met in most such countries. Ideal would be development of a medical abortifacient that is single dose and the lowest possible dose of each drug, provokes miscarriage within a more predictable time frame with less acute and prolonged bleeding, is safe and effective beyond two months, has minimal side effects, and maximizes short-term safety and minimizes long-term effects. Technological advances are being undermined, however, by political and religious attacks on the method. Even some feminists have expressed concerns about potential long-term effects of RU-486 use. PMID:12179722

  8. 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.

  9. 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.

  10. Effects of SrRuO{sub 3} buffer layer thickness on multiferroic (Bi{sub 0.90}La{sub 0.10})(Fe{sub 0.95}Mn{sub 0.05})O{sub 3} thin films

    SciTech Connect

    Wu Jiagang; Wang, John

    2009-09-01

    Multiferroic (Bi{sub 0.90}La{sub 0.10})(Fe{sub 0.95}Mn{sub 0.05})O{sub 3} (BLFMO) thin films were deposited on SrRuO{sub 3} (SRO) buffered Pt/TiO{sub 2}/SiO{sub 2}/Si(100) substrates with variable buffer layer thicknesses by using off-axis radio frequency sputtering. The orientation of BLFMO thin films is dependent on the SRO buffer layer thickness, which leads to a change in ferroelectric behavior. Due to the low leakage currents arising from the orientation change in association with the variation in SRO buffer layer thickness and the La and Mn codoping, well saturated P-E hysteresis loops (2P{sub r}approx210.0 muC/cm{sup 2} and 2E{sub c}approx525.5 kV/cm) are shown for the (111)-oriented BLFMO thin film at room temperature and 1 kHz. It also demonstrates little ferroelectric fatigue on 10{sup 9} switching cycles. Moreover, the BLFMO thin film exhibits the enhanced magnetic behavior as compared to pure BFO thin films, due to the canting of antiferromagnetically ordered spins.

  11. RU-486: the "abortion pill".

    PubMed

    Herranz, G

    1991-05-23

    A report sent by the Vatican to bishops' conferences throughout the world calls RU-486, the so-called abortion pill currently available in France, "a new, serious threat to human life." The report was developed at the Vatican's request by Gonzalo Herranz, a Spanish bioethicist. A cover letter to bishops' conferences from Cardinal Alfonso Lopez Trujillo, president of the Pontifical Council for the Family, suggested that the report be used "to resist the introduction of the abortion pill RU-486 into your country." Related to TU-486 and to new terminology some use to characterize its non-surgical approach to abortion is an intention "to amoralize and thereby place the transmission of human life into an ethically neutral terrain and reduce it to pure biology," says the report. The report discusses possible future uses of RU-486 as a contraceptive, stating: "Women would no longer have to worry themselves about whether they have conceived or not. Each month they would proceed to clean out their uterus chemically." The report refers to RU-486 as "a technical step forward in an area that did not need it." It says, "The abortion pill favors a woman's privacy and secret, but it condemns her to solitude." The English text from the Vatican follows. PMID:16145821

  12. Simulating Ru L3-Edge X-ray Absorption Spectroscopy with Time-Dependent Density Functional Theory: Model Complexes and Electron Localization in Mixed-Valence Metal Dimers

    SciTech Connect

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

    2013-04-26

    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.

  13. 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.

  14. 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. PMID:12342356

  15. Evolution of supercurrent path in Nb /Ru /Sr2RuO4 dc-SQUIDs

    NASA Astrophysics Data System (ADS)

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

    2016-08-01

    Phase-sensitive measurements of direct-current superconducting quantum interference devices (dc-SQUIDs) composed of Sr2RuO4 -Ru eutectic crystals have been performed to temperatures below a bulk Ru superconducting transition temperature at 0.49 K. A SQUID with Nb /Ru /Sr2RuO4 junctions fabricated on one Ru inclusion exhibits two distinct transitions due to the Ru superconducting transition and competition of proximity-induced superconducting gaps at the junctions. At sufficiently low temperatures, the SQUID interference patterns start to collapse with large phase shifts of the Fraunhofer patterns. This result indicates the influence of magnetic fluxes induced by large bias currents flowing in a strongly asymmetric supercurrent path. Such a large change in supercurrent path suggests superconducting phase mismatch between the s -wave and chiral p -wave states at the Ru /Sr2RuO4 interface.

  16. 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.

  17. 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.

  18. Thermoelectric Properties of Pseudogap Ti10Ru19B8 and Ti9TM2Ru18B8 (TM: Cr-Cu) Compounds

    NASA Astrophysics Data System (ADS)

    Takagiwa, Y.; Yoshida, T.; Yanagihara, D.; Kimura, K.

    2015-06-01

    The thermoelectric properties of ternary Ti10Ru19B8 and quaternary Ti9TM2Ru18B8 (TM: Cr, Mn, Fe, Co, Ni, Cu) compounds were investigated in the temperature range from 373 K to 973 K. They form pseudogaps in the electronic densities of states near the Fermi level, E F, which is suitable for thermoelectric materials. We synthesized crack-free pellet samples using arc-melting followed by spark plasma sintering. A maximum dimensionless figure of merit zT max was 0.09 at 973 K for Ti10Ru19B8 whereas a large power factor of 1.4 mW/m K2 was obtained at that temperature. The phonon thermal conductivity decreased through TM substitutions; however, the power factor also decreased due to an additional electronic density of states originated from TM d-states around E F; that is, excitations of both holes and electrons.

  19. Pattern Growth and Field Emission Characteristics of Flower-Like RuO2 Nanostructures

    NASA Astrophysics Data System (ADS)

    Lee, Kuei-Yi; Chen, Ching-An; Lian, Huan-Bin; Chen, Yi-Min; Huang, Ying-Sheng; Keiser, Gerd

    2010-10-01

    A flower-like RuO2 nanostructure was selectively synthesized on a Si substrate by metal organic chemical vapor deposition (MOCVD). Bis(ethylcyclopentadienyl) ruthenium(II), Ru[(C2H5)C5H4]2, was shower sprayed onto the Si substrate with oxygen gas. Prior to the growth of the flower-like RuO2 nanostructure, patterns of Al and Fe films were deposited on the Si substrate by photolithography and electron beam (e-beam) evaporation deposition. The synthesized flower-like RuO2 nanostructures were examined by scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray (EDX) analysis, X-ray diffraction (XRD), and micro-Raman spectroscopy. The results indicated that the flower-like nanostructures were RuO2 rutile structures with high crystallinity. For the particular synthesized morphology and design pattern, the current density and long-term stability characteristics of electron field-emission characteristics demonstrated that the flower-like RuO2 nanostructure has the potential to be used in a practical field-emission display.

  20. Dipole excitations in 96Ru

    NASA Astrophysics Data System (ADS)

    Linnemann, A.; Fransen, C.; Gorska, M.; Jolie, J.; Kneissl, U.; Knoch, P.; Mücher, D.; Pitz, H. H.; Scheck, M.; Scholl, C.; Brentano, P. Von

    2005-12-01

    Candidates for the two-phonon quadrupole-octupole 1- state and the two-phonon mixed-symmetry 1+ms state have been identified in the N=52 isotope 96Ru using the nuclear resonance fluorescence technique at the bremsstrahlung facility of the Stuttgart Dynamitron accelerator. Detailed information on energies, spins, branching ratios, and transition strengths of four new dipole excitations in 96Ru have been obtained. The observed dipole excitations are nearly at the same energies as in 94Mo, and the transition probabilities are comparable to those for the decay of the (2+1⊗3-1)1- and the (2+1⊗2+ms)1+ms states in 94Mo.

  1. 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.

  2. 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. PMID:27324949

  3. 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

  4. Evolution of superconductivity and magnetism in La1-xYbxRu2P2

    NASA Astrophysics Data System (ADS)

    Roncaioli, Connor; Hodovanets, Halyna; Saha, Shanta; Paglione, Johnpierre

    LaRu2P2, with a 4.1 K transition, is the first known pnictide-based superconductor. Sharing structural and electronic elements similar to those of the unconventional Fe-pnictide superconductors, it is of interest to investigate the parameter space in which a superconducting ground state survives. We present preliminary indications of more interesting magnetic behavior and structural tuning behavior when paramagnetic Yb is substituted for La in La1-xYbxRu2P2, and investigate potential heavy fermion behavior in the Yb end-member of this series.

  5. 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.

  6. Pressure Induced Enhancement of Superconductivity in LaRu2P2.

    PubMed

    Li, Baoxuan; Lu, Pengchao; 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

  7. 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.

  8. 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

  9. 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.

  10. Os trigonum.

    PubMed

    Chao, Wen

    2004-12-01

    There is a wide variation in the nomenclature for the posterior aspect of the talus (eg, os trigonum, trigonal process, Stieda process, posterior process). Injuries to these structures can be caused by chronic, repetitive impingement of the bony prominence or by acute hyperplantar flexion of the foot and ankle. After failing appropriate nonoperative treatment, surgical excision of the bony involvement is recommended. Surgical options include open or arthroscopic excision of the bony structure.

  11. In situ facile synthesis of Ru-based core-shell nanoparticles supported on carbon black and their high catalytic activity in the dehydrogenation of amine-boranes.

    PubMed

    Cao, Nan; Su, Jun; Hong, Xinlin; Luo, Wei; Cheng, Gongzhen

    2014-02-01

    Well-dispersed core-shell Ru@M (M=Co, Ni, Fe) nanoparticles (NPs) supported on carbon black have been synthesized via a facile in situ one-step procedure under ambient condition. Core-shell Ru@Co NPs were synthesized and characterized for the first time. The as-synthesized Ru@Co and Ru@Ni NPs exhibit superior catalytic activity in the hydrolysis of ammonia borane compared with their monometallic and alloy counterparts. The Ru@Co/C NPs are the most reactive, with a turnover frequency (TOF) value of 320 (mol H 2 min(-1)) molRu (-1) and activation energy (Ea) of 21.16 kJ mol(-1). Ru@Ni/C NPs are the next most active, whereas Ru@Fe/C NPs are almost inactive. Additionally, the as-synthesized NPs supported on carbon black exhibit higher catalytic activity than catalysts on other conventional supports, such as SiO2 and γ-Al2O3. PMID:24288206

  12. Effects of Fe cations in ruthenium-complex multilayers fabricated by a layer-by-layer method.

    PubMed

    Oyama, Makiko; Ozawa, Hiroaki; Nagashima, Takumi; Haga, Masa-aki; Ishida, Takao

    2016-04-01

    Molecular multilayers were fabricated using a Ru complex containing Fe cations on an indium tin oxide surface to control the properties of the Ru-complex multilayers such as the multilayer orientation and the electron transport. The Ru-complex multilayer films containing Fe cations were thicker than those containing Zr cations, which have been used previously. The electron transport properties of the multilayers containing Fe cations were evaluated. Solid-state sandwich cell measurements showed that the Ru-complex multilayer films containing Fe cations exhibited increased electron transport with a lower transport coefficient β of 0.01 Å(-1), whereas those that contain Zr cations have β ∼ 0.07 Å(-1). Thus, Fe cations are effective in obtaining thicker Ru-complex layers with increased electron transport abilities.

  13. 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.

  14. 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.

  15. 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.

  16. Thermal stability of spin valves based on a synthetic antiferromagnet and Fe50Mn50 alloy

    NASA Astrophysics Data System (ADS)

    Milyaev, M. A.; Naumova, L. I.; Proglyado, V. V.; Chernyshova, T. A.; Blagodatkov, D. V.; Kamenskii, I. Yu.; Ustinov, V. V.

    2015-11-01

    Magnetron sputtering was used to prepare spin valves with the Ta/Ni80Fe20/Co90Fe10/Cu/Co90Fe10/Ru/Co90Fe10/Fe50Mn50/Ta composition. Changes in the functional characteristics of the spin valves were studied in a temperature range of-180 to +160°C. The maximum temperature at which the functional characteristics of spin valve remain unchanged was shown to depend on the relationship of thicknesses of Co90Fe10 layers separated by the Ru interlayer.

  17. Inner-shell photodetachment from Ru-

    NASA Astrophysics Data System (ADS)

    Dumitriu, I.; Bilodeau, R. C.; Gorczyca, T. W.; Walter, C. W.; Gibson, N. D.; Pešić, Z. D.; Rolles, D.; Berrah, N.

    2010-10-01

    Inner-shell photodetachment from Ru- was studied near and above the 4p excitation region, 29-to-91-eV photon energy range, using a merged ion-photon-beam technique. The absolute photodetachment cross sections of Ru- ([Kr]4d75s2) leading to Ru+, Ru2+, and Ru3+ ion production were measured. In the near-threshold region, a Wigner s-wave law, including estimated postcollision interaction effects, locates the 4p3/2 detachment threshold between 40.10 and 40.27 eV. Additionally, the Ru2+ product spectrum provides evidence for simultaneous two-electron photodetachment (likely to the Ru+ 4p54d65s2 state) located near 49 eV. Resonance effects are observed due to interference between transitions of the 4p electrons to the quasibound 4p54d85s2 states and the 4d→ɛf continuum. Despite the large number of possible terms resulting from the Ru- 4d open shell, the cross section obtained from a 51-state LS-coupled R-matrix calculation agrees qualitatively well with the experimental data.

  18. Polyol-synthesized PtRu/C and PtRu black for direct methanol fuel cells

    NASA Astrophysics Data System (ADS)

    Guo, Junsong; Sun, Gongquan; Shiguo, Sun; Shiyou, Yan; Weiqian, Yang; Jing, Qi; Yushan, Yan; Qin, Xin

    PtRu/C and PtRu black catalysts with nominal Pt:Ru atomic ratio of 1:1 are prepared by a modified polyol process (co-reduction of metal precursor salts) as anode catalysts for direct methanol fuel cells (DMFCs). Without the carbon support, PtRu nanoparticles tend to agglomerate, while the PtRu nanoparticles in PtRu/C have a good dispersion as shown by TEM. Both PtRu black and PtRu/C have the almost same alloy degree indicated by XRD, but PtRu supported on carbon could improve the influence of Ru on Pt toward methanol oxidization as shown by cyclic voltammetry. The microstructure of PtRu/C is further studied by high-resolution transmission electron microscopy (HRTEM), and the results indicate that the lattice constant of Pt in PtRu electrocatalyst has contracted despite a few parts of Pt not alloyed with Ru due to the lattice constant of Pt without contracting, which is further proved by the results of temperature-programmed reduction (TPR). Such parts of unalloyed Ru are further proved to have ability to reduce the methanol oxidation potential on Pt by comparing the catalytic behaviors of Pt/C and Pt + Ru/C prepared by mixing carbon with separately prepared Pt and Ru colloids. Moreover, the catalytic behaviors of PtRu black and PtRu/C are also compared with those of commercial ones.

  19. 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}].

  20. 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.

  1. Quantum Critical Behavior in Heavy-Fermion Iron Oxypnictide Ce(Ru1-xFex) PO

    NASA Astrophysics Data System (ADS)

    Ishida, Kenji

    2014-03-01

    Quantum phase transition in itinerant ferromagnets is one of the major topics in a strongly correlated electron system, since it has been suggested to be always first order when the ferromagnetic (FM) order is suppressed by pressure or chemical doping. In order to obtain universal features of the FM quantum criticality, we have studied the two-dimensional heavy-fermion (HF) system Ce(Ru1-xFex) PO from microscopic 31P-NMR measurements. A HF ferromagnet CeRuPO turns into a HF paramagnet by an isovalent Fe substitution for Ru. We found that Ce(Ru0.15Fe0.85) 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 around x = 0.86, which is a rare example among itinerant ferromagnets. In addition, we point out that the critical behaviors in Ce(Ru0.15Fe0.85) PO share a similarity with those in YbRh2Si2, where the local criticality of f electrons has been discussed. We reveal that Ce(Ru1-xFex) PO is a new system to study FM quantum criticality in HF compound. This work has been done in collaboration with Shunsaku Kitagawa in Kyoto Univ. and T, Nakamura, M. Matoba, and Y. Kamihara, in Department of Applied Physics and Physico-informatics, Keio University.

  2. A comparison of selected Precambrian Brazilian chromitites: Chromite, PGE-PGM, and Re/Os as parental source indicators

    NASA Astrophysics Data System (ADS)

    Girardi, V. A. V.; Ferrario, A.; Correia, C. T.; Diella, V.

    2006-03-01

    Mineralogical and geochemical studies were carried out in chromitites belonging to the mafic-ultramafic bodies of Niquelândia, Luanga, and Campo Formoso, which are, respectively, included in the Goiás Massif and the Amazon and São Francisco cratons. The main platinum-group minerals (PGM) included or associated with chromite grains are laurite in Niquelândia and Campo Formoso and sperrylite and braggite in Luanga. The most common primary base metal sulfides (BMS) are pentlandite, chalcopyrite, and minor pyrrhotite. Also present are base metal alloys (BMA), such as awaruite, and the BMS millerite, pyrite, and copper as secondary mineral phases linked to later alteration process. The Luanga chromites display the lowest Cr 2O 3/Al 2O 3 and Cr 2O 3/FeO t ratios. The chondrite-normalized profiles are strongly enriched in the platinum PGE subgroup (PPGE, Pt, Pd, Rh). The average Pd/Ir ratio (24.2) and 187Os/ 188Os values (0.17869-0.18584) are very high. Niquelândia chromites have higher Cr 2O 3/Al 2O 3 and Cr 2O 3/FeO t ratios than Luanga. Its PGE contents are low and chondrite-normalized profiles depleted, mainly in the PPGE subgroup. The average Pd/Ir ratio (0.45) and 187Os/ 188Os values (0.12598-0.12777) are low. Campo Formoso chromites have the highest Cr 2O 3/Al 2O 3 and Cr 2O 3/FeO t ratios; its average Pd/Ir ratio (0.72) and chondrite-normalized profiles (except the pronounced Ru spike) are closer to those of Niquelândia. The remarkable differences in terms of chromite bulk-composition, PGE contents and patterns, Pd/Ir ratios, and 187Os/ 188Os values associated with probable distinctions in the inferred geochemical compositions of the respective parental magmas indicate that the Luanga and Niquelândia complexes originated from distinct parental sources. Geochemical and isotopic features indicate that Luanga chromitites and associated rocks are consistent with a parental magma, either originated from an enriched mantle reservoir or strongly contaminated

  3. Unoccupied electronic states of Ru(0001)

    NASA Astrophysics Data System (ADS)

    del Campo, Valeria; Correa, Julián-David; Correa-Puerta, Jonathan; Kroeger, Daniel; Häberle, Patricio

    2016-11-01

    This report presents a combined theoretical and experimental description of the unoccupied electronic states of Ru(0001), along the Γ̅M̅ high symmetry direction of the Brillouin zone. A direct comparison between angle-resolved inverse photoemission spectroscopy and ab initio calculations of the 3-dimensional (3D) electronic structure of Ru(0001) have been used to determine the energy dispersion and the identification of different states and surface resonances. Both, measurements and calculations, complement previous reports regarding the electronic structure of Ru.

  4. First identification of excited states in the N=Z+1 nucleus {sup 89}Ru

    SciTech Connect

    Marginean, N.; Rusu, C.; Bucurescu, D.; Ionescu-Bujor, M.; Iordachescu, A.; Alvarez, C. Rossi; Bazzacco, D.; Lunardi, S.; Pavan, P.; Farnea, E.; Lenzi, S.M.; Menegazzo, R.; Ur, C.A.; De Angelis, G.; Axiotis, M.; Gadea, A.; Kroell, Th.; Martinez, T.; Napoli, D.R.; Spolaore, P.

    2004-10-01

    High-spin excited states have been identified for the first time in the N=Z+1 nucleus {sup 89}Ru with the reaction {sup 54}Fe({sup 40}Ca,{alpha}n{gamma}) at 130 MeV, using the GASP array, the ISIS Silicon array, and the n-Ring detector system. The observed structure is discussed within systematics of the N=45 isotones and is compared with shell model calculations.

  5. 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.

  6. [Analgesic properties of morpholinoethylimidazobenzimidazole derivative RU-1205].

    PubMed

    Spasov, A A; Grechko, O Iu; Shtareva, D M; Anisimova, V A

    2013-01-01

    We have studied the analgesic activity of a morpholinoethylimidazobenzimidazole derivative (RU-1205) in comparison to butorphanol. It is established that the test compound exhibits a pronounced analgesic activity, which exceeded that ofbutorphanol six times in the hot-plate test and was comparable to the reference drug effect in the tail-flick and acetic acid-induced writhing tests. It is established that the analgesic action of RU-1205 is based on the kappa-opioidergic mechanism. PMID:24432563

  7. 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.

  8. Synthesis of ruthenium (IV) oxide (RuO2) nanocrystals

    NASA Astrophysics Data System (ADS)

    Nguyen, Nga

    This research concerns the synthesis of well-defined RuO2 nanocrystals. Our hypothesis is RuO2 nanoparticles can be synthesized by oxidation of ruthenium (Ru) nanoparticles with retention of size and shape. Ru nanoparticles were prepared from the decomposition of triruthenium(0)dodecacarbonyl (Ru3(CO)12) or ruthenium(III) trichloride trihydrate (RuCl3.3H2O) in the presence of surfactant, oxidant, and solvent at high temperature. The stabilized nanocrystals were isolated by centrifugation and characterized with transmission electron microscopy (TEM). RuO2 was synthesized by addition Ru nanocrystals and an oxygen atom source to a high temperature solution containing a molecular surfactant. TEM, powder X-ray diffraction, and Raman spectroscopy were used to characterize RuO2 nanoparticles.

  9. Multiple superconducting transitions in the Sr3Ru2O7 region of Sr3Ru2O7-Sr2RuO4 eutectic crystals

    NASA Astrophysics Data System (ADS)

    Kittaka, S.; Fusanobori, S.; Yonezawa, S.; Yaguchi, H.; Maeno, Y.; Fittipaldi, R.; Vecchione, A.

    2008-06-01

    We report the superconducting properties of Sr3Ru2O7-Sr2RuO4 eutectic crystals, which consist of the spin-triplet superconductor Sr2RuO4 with a monolayer stacking of RuO2 planes and the metamagnetic normal metal Sr3Ru2O7 with a bilayer stacking. Although Sr3Ru2O7 so far has not been reported to exhibit superconductivity, our ac susceptibility measurements revealed multiple superconducting transitions that occur in the Sr3Ru2O7 region of the eutectic crystals. The diamagnetic shielding essentially reached the full fraction at low ac fields parallel to the c axis. However, both the shielding fraction and the onset temperature are easily suppressed by ac fields larger than 0.1 mT rms and no anomaly was observed in the specific heat. Moreover, the critical field curves of these transitions have a positive curvature near zero fields, which is different from the upper critical field curve of the bulk Sr2RuO4 . These facts suggest that the superconductivity observed in the Sr3Ru2O7 region is not a bulk property. To explain these experimental results, we propose the scenario that stacking RuO2 planes, which are the building blocks of superconducting Sr2RuO4 , are contained in the Sr3Ru2O7 region as stacking faults.

  10. 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.

  11. Probing terrestrial mantle evolution using Ru isotopes

    NASA Astrophysics Data System (ADS)

    Bermingham, K. R.; Walker, R. J.; Puchtel, I. S.; O'Driscoll, B.

    2013-12-01

    A diversity of materials was likely added to Earth during the late stages of its accretion; however, the specific elemental and isotopic compositions of these contributors are poorly constrained. The efficiency with which these late accreted materials were mixed into the mantle also remains an open question. The highly siderophile element ruthenium (Ru) provides a potentially useful isotopic genetic tracer for late accretionary additions to Earth. Well resolved deficiencies in 100Ru have been reported on the scale of whole-rock samples of meteorites, and are interpreted to stem from the heterogeneous distribution of s-process carrier phases in the solar nebula [1,2]. Isotopically diverse materials are, therefore, likely contributors of late accreted materials to Earth's mantle. Recent isotopic studies have found that major accretionary events (e.g., the Moon-forming giant impact) did not completely homogenize the mantle; thus, long-term preservation of isotopically distinct reservoirs in the mantle might be expected [3]. Identification of isotopically heterogeneous domains in the mantle using Ru isotopic analyses can potentially reveal the nature of different impactors. To investigate the genetics of late accretionary additions and to evaluate the veracity of late accretionary models, we have developed a refined analytical technique for the high-precision measurement of Ru isotopic composition using negative thermal ionization mass spectrometry (N-TIMS). Replicate analyses of an Alfa Aesar Ru standard (n = 56) over the period of several months indicate a current external precision of ×8 ppm (2σ SD) for 100Ru/101Ru. Data are corrected for instrumental mass fractionation using the exponential law and 99Ru/101Ru as the normalizing ratio. Data are also corrected for oxide interferences assuming a natural oxygen isotopic composition. No second order oxygen correction is required [3]. Prior to this study, the highest external precision achieved using standard N-TIMS or

  12. The almost contact system RU Eridani

    NASA Astrophysics Data System (ADS)

    Russo, G.

    1982-01-01

    The Wilson and Devinney (1971) method is used to analyze the V and B light curves of the eclipsing binary RU Eridani, in order to obtain a Roche model solution rather than the Russell and Merrill (1952) model used by Sarma and Sanwal (1981). It is found that the system consists of an evolved K1 secondary component which fills its Roche lobe, and an F0 V primary which seems nearly able to fill its own Roche lobe. An estimate of the absolute elements of RU Eri is made on the assumption of a primary component mass corresponding to its spectral type along the lines suggested by Allen (1973).

  13. 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

  14. 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

  15. The activation mechanism of Fe-based olefin metathesis catalysts

    NASA Astrophysics Data System (ADS)

    Poater, Albert; Pump, Eva; Vummaleti, Sai Vikrama Chaitanya; Cavallo, Luigi

    2014-08-01

    Density functional theory calculations have been used to describe the first turnover for olefin metathesis reaction of a homogenous Fe-based catalyst bearing a N-heterocyclic carbene ligand with methoxyethene as a substrate. Equal to conventional Ru-based catalysts, the activation of its Fe congener occurs through a dissociative mechanism, however with a more exothermic reaction energy profile. Predicted upper energy barriers were calculated to be on average ∼2 kcal/mol more beneficial for Fe catalyzed metathesis. Overall, this present computational study emphasises on advantages of Fe-based metathesis and gives a potential recipe for the design of an efficient Fe-based olefin metathesis catalysts.

  16. 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

  17. Hexadecapolar excitation in sup 100 Ru

    SciTech Connect

    Sirota, S.; Duarte, J.L.M.; Horodynski-Matsushigue, L.B.; Borello-Lewin, T. )

    1989-09-01

    Attention is drawn to the strong collective {ital L}=4 direct excitation of the state at 2.367 MeV in {sup 100}Ru by inelastic scattering of 16 MeV protons characterized by a deformation parameter {beta}{sub 4}=0.10, one of the highest reported for any region of the mass table.

  18. Electroreflectance study of RuSe 2

    NASA Astrophysics Data System (ADS)

    Huang, Y. S.; Lin, S. S.; Sheu, J. S.; Shen, W. M.; Pollak, Fred H.

    1990-12-01

    We report the first electrolyte-electroreflectance (EER) study of a RuSe 2 single crystal in the photon energy region of 0.9-5.5 eV. The EER spectrum exhibits differential like structure in the vicinity of interband transitions. The transition energies are determined accurately. A probable energy-band structure is constructed.

  19. 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.

  20. 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.

  1. Antitubercular activity of Ru (II) isoniazid complexes.

    PubMed

    Aguiar, Inara de; Tavares, Aline; Roveda, Antonio C; da Silva, Augusto C H; Marino, Leonardo B; Lopes, Érica O; Pavan, Fernando R; Lopes, Luiz G F; Franco, Douglas W

    2015-04-01

    Despite the resistance developed by the Mycobacterium tuberculosis (MTb) strains, isoniazid (INH) has been recognized as one of the best drug for treatment of Tuberculosis (Tb). The coordination of INH to ruthenium metal centers was investigated as a strategy to enhance the activity of this drug against the sensitive and resistant strains of MTb. The complexes trans-[Ru(NH3)4(L)(INH)](2+) (L=SO2 or NH3) were isolated and their chemical and antituberculosis properties studied. The minimal inhibitory concentration (MIC) data show that [Ru(NH3)5(INH)](2+) was active in both resistant and sensitive strains, whereas free INH (non-coordinated) showed to be active only against the sensitive strain. The coordination of INH to the metal center in both [Ru(NH3)5(INH)](2+) and trans-[Ru(NH3)4(SO2)(INH)](2+) complexes led to a shift in the INH oxidation potential to less positive values compared to free INH. Despite, the ease of oxidation of INH did not lead to an increase in the in vitro INH activity against MTb, it might have provided sensitivity toward resistant strains. Furthermore, ruthenium complexes with chemical structures analogous to those described above were synthesized using the oxidation products of INH as ligands (namely, isonicotinic acid and isonicotinamide). These last compounds were not active against any strains of MTb. Moreover, according to DFT calculations the formation of the acyl radical, a proposed intermediate in the INH oxidation, is favored in the [Ru(NH3)5(INH)](2+) complex by 50.7kcalmol(-1) with respect to the free INH. This result suggests that the stabilization of the acyl radical promoted by the metal center would be a more important feature than the oxidation potential of the INH for the antituberculosis activity against resistant strains.

  2. Orthometalation of dibenzo[1,2]quinoxaline with ruthenium(II/III), osmium(II/III/IV), and rhodium(III) ions and orthometalated [RuNO](6/7) derivatives.

    PubMed

    Maity, Suvendu; Kundu, Suman; Saha Roy, Amit; Weyhermüller, Thomas; Ghosh, Prasanta

    2015-02-16

    A new family of organometallics of ruthenium(II/III), osmium(II/III/IV), and rhodium(III) ions isolated from C-H activation reactions of dibenzo[1,2]quinoxaline (DBQ) using triphenylphosphine, carbonyl, and halides as coligands is reported. The CN-chelate complexes isolated are trans-[Ru(III)(DBQ)(PPh3)2Cl2] (1), trans-[Ru(II)(DBQ)(CO)(PPh3)2Cl] (2), trans-[Os(III)(DBQ)(PPh3)2Br2] (3), trans-[Os(II)(DBQ)(PPh3)2(CO)Br] (4), and trans-[Rh(III)(DBQ)(PPh3)2Cl2] (5). Reaction of 1 with NO affords trans-[Ru(DBQ)(NO)(PPh3)2Cl]Cl (6(+)Cl(-)), isoelectronic to 2, with a byproduct, [Ru(NO)(PPh3)2Cl3] (7). Complexes 1-5 and 6(+) were characterized by elemental analyses, mass, IR, NMR, and electron paramagnetic resonance (EPR) spectra including the single-crystal X-ray structure determinations of 1-3 and 5. The Ru(III)-C, Ru(II)-C, Os(III)-C, and Rh(III)-C lengths are 2.049(2), 2.074(3), 2.105(16), and 2.012(3) Å in 1, 2, 3, and 5. In cyclic voltammetry, 2, 3, and 4 undergo oxidation at 0.59, 0.39, and 0.46 V, versus Fc(+)/Fc couple, to trans-[Ru(III)(DBQ)(CO)(PPh3)2Cl](+) (2(+)), trans-[Os(IV)(DBQ)(PPh3)2Br2](+) (3(+)), and trans-[Os(III)(DBQ)(CO)(PPh3)2Br](+) (4(+)) ions. Complex 3(+) incorporates an Os(IV)(d(4) ion)-C bond. The 6(+)/trans-[Ru(DBQ)(NO)(PPh3)2Cl] (6) reduction couple at -0.65 V is reversible. 2(+), 3(+), 4(+) and 6 were substantiated by spectroelectrochemical measurements, EPR spectra, and density functional theory (DFT) and time-dependent (TD) DFT calculations. The frozen-glass EPR spectrum of the electrogenerated 6 exhibits hyperfine couplings due to (99,101)Ru and (14)N nuclei. DFT calculations on trans-[Os(III)(DBQ)(PMe3)2Br2] (3(Me)), St = 1/2 and trans-[Os(IV)(DBQ)(PMe3)2Br2](+) (3(Me+)), St = 0, trans-[Ru(DBQ)(NO)(PMe3)2Cl](+) (6(Me+)), St = 0 and trans-[Ru(DBQ)(NO)(PMe3)2Cl] (6(Me)), St = 1/2, authenticated a significant mixing between dOs and πaromatic* orbitals, which stabilizes M(II/III/IV)-C bonds and the [RuNO](6) and [RuNO](7) states

  3. 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

  4. Electrical and magnetic properties of the filled skutterudite Sm(Ru1-xOsx)4P12

    NASA Astrophysics Data System (ADS)

    Sekine, Chihiro; Yoshida, Tomoo; Kimura, Takanori; Namiki, Takahiro; Shirotani, Ichimin; Matsuhira, Kazuyuki; Wakeshima, Makoto; Hinatsu, Yukio

    2007-03-01

    The Os substitution effects on the exotic metal-insulator (M-I) transition in the filled skutterudite compound SmRu4P12 are studied by electrical resistivity and magnetic susceptibility measurements. Sm(Ru1-xOsx)4P12(x=0.05,0.10,0.25,0.50,0.75) has been prepared at high temperature and high pressure. Twenty-five percent Os substitution almost suppresses the M-I transition. A resistivity minimum is observed around 50 K(Tmin) for all alloys and the minimum shifts with x. Furthermore, -logT dependence of resistivity below Tmin is also observed above x=0.25. These facts suggest that the Sm-based filled skutterudite phosphides are Kondo systems.

  5. Designing low thermal conductivity of RuO2 for thermoelectric applications

    NASA Astrophysics Data System (ADS)

    Music, Denis; Kremer, Oliver; Pernot, Gilles; Schneider, Jochen M.

    2015-02-01

    We have applied Umklapp phonon-phonon and phonon-defect scattering to calculate the thermal conductivity of unalloyed as well as Fe- and La-alloyed RuO2 (P42/mnm). These models are computationally efficient and parameter free as they are supported by density functional theory. We predict an order of magnitude drop in the thermal conductivity upon alloying, which is beneficial for thermoelectric applications as it increases the figure of merit. Thermal conductivity data obtained by thermoreflectance on magnetron sputtered thin films are consistent with the calculations. The here employed research strategy may also be beneficial for designing phases that require manipulation of entangled properties.

  6. A redox-active porous coordination network film based on a Ru complex as a building block on an ITO electrode.

    PubMed

    Shinomiya, Takuya; Ozawa, Hiroaki; Mutoh, Yuichiro; Haga, Masa-Aki

    2013-12-01

    The combination of self-assembled monolayer (SAM) and layer-by-layer (LbL) growth methods for the construction of a surface porous film has the potential to incorporate a wide range of chemical functionalities on a solid surface. A novel redox-active Ru complex with 2,6-bis(N-pyridylbenzimidazolyl)-pyridine ligands (Ru complex 1), in which four peripheral pyridine groups act as coordination sites, was used as a building block for a porous coordination network film. By using (4-pyridyl)phenylphosphonic acid as a SAM primer layer on an ITO surface, the Ru complex 1 was immobilized by the successive reaction of PdCl2 on the ITO electrode in the LbL growth method. Multilayer growth was monitored by UV-vis spectra and cyclic voltammetry, in which the linear increases of both absorbance and the peak current were observed. This result indicated that the regular accumulation of Ru complex 1 onto the ITO surface took place. The permselectivity of the present porous coordination network structure was examined using redox-active molecular probes with different sizes and charges such as ferrocene, trimethylaminomethylferrocene, the Os bis(2,6-bis(N-methylbenzimidazolyl)-pyridine) complex, and tetrathiofulvarene (TTF). With the Os complex and cationic ferrocene, only the catalytic peak was observed as a prewave of the adsorbed Ru(II/III) peak at +0.73 V. On the other hand, the oxidation peak of ferrocene was observed around 0 V vs. Fc(+)/Fc even for nine-layered films in addition to the adsorbed Ru(II/III) peak. From these results, not only molecular size but also electrostatic interaction plays an important role in the permeation into the Ru complex 1 porous network film.

  7. 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

    2015-08-01

    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.

  8. 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).

  9. Hydrostatic High-Pressure Studies to 25 GPA on the Model Superconducting Pnictide LaRu2P2

    NASA Astrophysics Data System (ADS)

    Lim, Jinhyuk; Forouzani, Neda; Schilling, James; Fotovat, Roxanna; Zheng, Chong; Hoffmann, Roald

    2014-03-01

    Prior to the discovery of the Fe-pnictides in 2008, the ruthenium phosphide LaRu2P2 possessed the highest value of the su- perconducting transition temperature, Tc ~ 4 K, in the entire pnictide family. Recently, there has been renewed interest in this compound in an effort to better understand why the Fe-pnictides have much higher values of Tc. In related phosphides superconductivity appears to only be present if the separation be- tween the phosphor ions dp-p in neigh- boring Ru2P2 planes is greater than the critical value 2.8 Å, too great for a P-P covalent bond to be formed. For example, in superconducting LaRu2P2, the value of dp-p is 3.0 Å. To test these ideas directly, we have carried out hydro- static high-pressure studies on single-crystalline LaRu2P2 in a diamond-anvil cell using He pressure medium to pres- sures as high as 25 GPa and temperatures as low as 1.5 K. We find that Tc initially increases under pressure, but suddenly disappears above 2.1 GPa. Since dp-p decreases under pressure, the sudden disappearance of superconductivity is likely due to the formation of a covalent P-P bond between adjacent Ru2P2 planes and a possible structural phase transition. Work at Washington University is supported by the NSF through Grant No. DMR-1104742 and by the Carnegie/DOE through NNSA/DOE Grant No. DE-FC52-08NA28554.

  10. 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.

  11. 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

  12. 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.

  13. 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.

  14. 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.

  15. A Small GTPase, OsRab6a, is Involved in the Regulation of Iron Homeostasis in Rice.

    PubMed

    Yang, An; Zhang, Wen-Hao

    2016-06-01

    Plants have evolved two distinct strategies to acquire iron (Fe) from soils. However, the regulatory mechanisms underlying the Fe acquisition remain largely elusive. There is emerging evidence that small GTPases are involved in the responses of plants to environmental cues. Here, we identified a gene encoding a small GTPase, OsRab6a, in rice and characterized its role in Fe acquisition by generating transgenic rice plants with overexpression and knockdown of OsRab6a OsRab6a shared conserved functional domains with other known members of the Rab subfamily and localized ubiquitously in the cytoplasm and nucleus. The expression of OsRab6a was rapidly and transiently up-regulated by Fe deficiency. No differences in growth and development among the OsRab6a-overexpression, OsRab6a-RNAi (RNA interference) and wild-type plants were detected when grown in Fe-sufficient medium. However, overexpression of OsRab6a in rice plants conferred greater tolerance to Fe deficiency than RNAi and wild-type plants, as evidenced by higher seedling height, and greater biomass, Chl contents and Fe concentrations in shoots, roots and grains in the overexpression lines than wild-type and RNAi plants. Moreover, the overexpression lines exhibited larger root systems than wild-type and RNAi plants in Fe-deficient medium. Exposure to Fe-deficient medium led to up-regulation of OsIRO2, OsIRT1, OsNAS1 and OsNAS2 in both wild-type and transgenic rice plants, with the magnitude of up-regulation positively correlated with the expression levels of OsRab6a These results may suggest that OsRab6a plays an important role in the regulation of Fe acquisition in rice plants by modulating physiological processes involved in Fe acquisition and root system architecture in response to Fe-deficient medium. PMID:27257291

  16. Effect of the structural characteristics of binary Pt-Ru and ternary Pt-Ru-M fuel cell catalysts on the activity of ethanol electrooxidation in acid medium.

    PubMed

    Antolini, Ermete

    2013-06-01

    In view of their possible use as anode materials in acid direct ethanol fuel cells, the electrocatalytic activity of Pt-Ru and Pt-Ru-M catalysts for ethanol oxidation has been investigated. This minireview examines the effects of the structural characteristics of Pt-Ru, such as the degree of alloying and Ru oxidation state, on the electrocatalytic activity for ethanol oxidation.

  17. AuRu/AC as an effective catalyst for hydrogenation reactions

    DOE PAGESBeta

    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 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

  18. 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.

  19. Electrocatalytical study of carbon supported Pt, Ru and bimetallic Pt-Ru nanoparticles for oxygen reduction reaction in alkaline media

    NASA Astrophysics Data System (ADS)

    Hosseini, M. G.; Zardari, P.

    2015-08-01

    Carbon supported Pt, Ru and bimetallic Pt-Ru nanoparticles (Pt/C, Ru/C and Pt.Ru/C) have been prepared by the chemical reduction method. Particle morphology, composition and structure of nanoparticles have been investigated by scanning electron microscopy (SEM) and energy dispersive X-ray (EDX) analysis. SEM results showed a uniform dispersion of nanoparticles with rough and porous structure into carbon supports with the average particle size of 30-64 nm. EDX analysis demonstrated the presence of both Pt and Ru nanoparticles in each gas diffusion electrode. The Pt/C, Ru/C and Pt.Ru/C composites were used as electrocatalyst for oxygen reduction reaction (ORR) in alkaline media. The ORR activities of cathodes were characterized using cyclic voltammetry (CV), polarization technique, AC impedance spectroscopy (EIS) and chronoamperometry. CV and polarization curves showed significantly higher activity on Pt.Ru/C electrocatalyst than observed on Pt/C and Ru/C catalysts, which can be related to synergistic effect, which is playing a critical role in ORR activity. The Tafel slope values of 120 mV/dec showed that the first electron transfer is the rate determining step. The EIS results of cathodes under different polarization potentials indicated two different behaviours which depend on the applied dc potentials and reveal different electrochemical processes occurring on the electrodes.

  20. Mantle highly siderophile element concentrations were not established through high-pressure metal-silicate equilibration in a deep magma ocean - New experimental data for Ru, Rh, Pd, Re, Ir, Pt.

    NASA Astrophysics Data System (ADS)

    Mann, Ute; Frost, Daniel J.; Becker, Harry; Audétat, Andreas; Rubie, David C.

    2010-05-01

    The 'highly siderophile' elements (HSE) Ru, Rh, Pd, Os, Ir, Pt, Re, and Au are known to have extremely high metal-silicate partition coefficients of > 104 at 1 bar and they should have consequently been completely removed from the silicate fraction of the Earth during metal-silicate equilibration in a magma ocean. However, they are present in the Earth's mantle in much higher concentrations than these 1 bar partition coefficients would predict and in approximately chondritic proportions. The main theory to explain the HSE inventory of the mantle pictures the late accretion of a highly oxidized, chondritic material after core/mantle differentiation had ceased that mixed a small concentration of these previously strongly depleted elements back into the mantle. Alternatively, it has been discussed, that high pressures and temperatures (e.g. 30-40 GPa, > 3000 K), as expected in a silicate magma ocean, might drastically lower the HSE partition coefficients to levels where metal-silicate partitioning alone would account for their abundances in the Earth's mantle. In this study metal - silicate partitioning data for Ru, Rh, Pd, Re and Pt have been determined by equilibrating liquid HSE-Fe-alloy (40 wt%) and molten peridotite (60 wt%) at 3-25 GPa and 2150 - 2500° C using multianvil technique. In most experiments the HSE's were added as a chip of previously alloyed metal to silicate and Fe-powder mixtures contained in MgO single crystal capsules. The bulk HSE concentration in the Fe-alloy was varied from 50 to 90 wt% which resulted in oxygen fugacities of -1.5 to +2 log units relative to the iron wüstite buffer (?IW). Metal compositions of the run products were determined with the electron microprobe while analyses of the quenched silicate liquid were carried out with laser ablation ICP-MS. Partitioning data were corrected for the fact that large concentrations of HSE were present in the metallic phase of our experiments, i.e. to the level of infinite dilution. Corrected

  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. Mössbauer analysis of the firing process of the sky-green glaze of the imitative ancient Chinese Ru porcelain

    NASA Astrophysics Data System (ADS)

    Songhua, Chen; Zhengyao, Gao; Guoju, Hu; Xiande, Chen

    1994-12-01

    The variation of the Mössbauer parameters of the imitative ancient Ru porcelain skygreen glaze with the firing conditions is studied in detail in the present paper. The Mössbauer spectra show that the sky-green glaze contains three kinds of iron minerals, i.e. the structural iron (Fe2+ and Fe3+); Fe2O3 and Fe3O4. The relative intensity of the paramagnetic peak Fe2+ increases and the magnetic ratio of the magnetic peak decreases with increasing temperature. Based on the variation of the quadrupole splitting ( QS) of the paramagnetic peak Fe2+, the phase transformation characteristics of the sky-green glaze in the firing process is discussed. The coloring mechanism of the sky-green glaze and the variation of its magnetism in the firing process are also investigated in the present paper.

  3. Os trigonum syndrome.

    PubMed

    Figueroa, R T; Dozier, T; Kalmar, J

    2001-08-01

    Os trigonum syndrome refers to a constellation of findings that can result in significant posterior or lateral ankle pain. The diagnosis may be very challenging for the clinician; nonetheless, modern imaging techniques can reliably aid in the diagnosis and in determining the extent of injury. This article explores the anatomy, pathomechanics, imaging findings, and clinical presentation of os trigonum syndrome.

  4. Inner-shell photodetachment from Ru{sup -}

    SciTech Connect

    Dumitriu, I.; Gorczyca, T. W.; Berrah, N.; Bilodeau, R. C.; Pesic, Z. D.; Rolles, D.; Walter, C. W.; Gibson, N. D.

    2010-10-15

    Inner-shell photodetachment from Ru{sup -} was studied near and above the 4p excitation region, 29-to-91-eV photon energy range, using a merged ion-photon-beam technique. The absolute photodetachment cross sections of Ru{sup -} ([Kr]4d{sup 7}5s{sup 2}) leading to Ru{sup +}, Ru{sup 2+}, and Ru{sup 3+} ion production were measured. In the near-threshold region, a Wigner s-wave law, including estimated postcollision interaction effects, locates the 4p{sub 3/2} detachment threshold between 40.10 and 40.27 eV. Additionally, the Ru{sup 2+} product spectrum provides evidence for simultaneous two-electron photodetachment (likely to the Ru{sup +} 4p{sup 5}4d{sup 6}5s{sup 2} state) located near 49 eV. Resonance effects are observed due to interference between transitions of the 4p electrons to the quasibound 4p{sup 5}4d{sup 8}5s{sup 2} states and the 4d{yields}{epsilon}f continuum. Despite the large number of possible terms resulting from the Ru{sup -} 4d open shell, the cross section obtained from a 51-state LS-coupled R-matrix calculation agrees qualitatively well with the experimental data.

  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. 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.

  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. 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.

  9. 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.

  10. Dynamics of formation of Ru, Os, Ir and Au metal nanocrystals on doped graphitic surfaces.

    PubMed

    Pitto-Barry, Anaïs; Sadler, Peter J; Barry, Nicolas P E

    2016-03-11

    The fabrication of precious metal (ruthenium, osmium, gold, and iridium) nanocrystals from single atoms has been studied in real-time. The dynamics of the first stage of the metal nanocrystallisation on a doped (B,S)-graphitic surface are identified, captured, and reported. PMID:26698913

  11. 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.

  12. A beta-D-allopyranoside-grafted Ru(II) complex: synthesis and acid-base and DNA-binding properties.

    PubMed

    Ma, Yan-Zi; Yin, Hong-Ju; Wang, Ke-Zhi

    2009-08-01

    A new ruthenium(II) complex grafted with beta-d-allopyranoside, Ru(bpy)(2)(Happip)(ClO(4))(2) (where bpy = 2,2'-bipyridine; Happip = 2-(4-(beta-d-allopyranoside)phenyl)imidazo[4,5-f][1,10]phenanthroline), has been synthesized and characterized by elemental analysis, (1)H NMR spectroscopy, and mass spectrometry. The acid-base properties of the complex have been studied by UV-visible and luminescence spectrophotometric pH titrations, and ground- and excited-state ionization constants have been derived. The Ru(II) complex functions as a DNA intercalator as revealed by UV-visible and emission titrations, salt effects, steady-state emission quenching by [Fe(CN)(6)](4-), DNA competitive binding with ethidium bromide, DNA melting experiment, and viscosity measurements.

  13. New rock salt-related oxides Li{sub 3}M{sub 2}RuO{sub 6} (M=Co, Ni): Synthesis, structure, magnetism and electrochemistry

    SciTech Connect

    Laha, S.; Morán, E.; Sáez-Puche, R.; Alario-Franco, M.Á.; Dos santos-Garcia, A.J.; Gonzalo, E.; Kuhn, A.; García-Alvarado, F.; Sivakumar, T.; Tamilarasan, S.; Natarajan, S.; Gopalakrishnan, J.

    2013-07-15

    found below 10 K while for the analogous Li{sub 3}Ni{sub 2}RuO{sub 6} , Ru oxidation state is 5+ and a ferrimagnetic (FM) behavior with a Curie temperature of 100 K is found. Electrochemical studies correlate well with both magnetic properties and crystal structure. - Highlights: • New Ruthenium rock salt-related oxides of formula, Li{sub 3}M{sub 2}RuO{sub 6} (M=Co, Ni) were studied. • Structurally different: rhombohedral α-NaFeO{sub 2}-type (Co) and monoclinic Li{sub 2}TiO{sub 3}-type (Ni) • Magnetic behavior is different: the Co sample is AFM while the Ni one is ferrimagnetic. • Ruthenium oxidation states are different: 4+ in the Co sample and 5+ in the Ni one. • Electrochemical studies correlate well with magnetic properties and crystal structures.

  14. 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.

  15. Large in-plane deformation of RuO6 octahedron and ferromagnetism of bulk SrRuO3.

    PubMed

    Lee, Sanghyun; Zhang, J R; Torii, S; Choi, Seongil; Cho, Deok-Yong; Kamiyama, T; Yu, Jaejun; McEwen, K A; Park, Je-Geun

    2013-11-20

    SrRuO3 is a ferromagnetic metal with several unusual physical properties such as zero thermal expansion below Tc, so-called Invar behavior. Another anomalous feature is that the a-axis lattice constant is larger than the b-axis lattice constant, a clear deviation from the predictions of the Glazer structural description with rigid RuO6 octahedron motion. Using high resolution neutron diffraction techniques, we show how these two structural anomalies arise from the irregular in-plane deformation, i.e. plastic behavior of the RuO6 octahedron, a weak band Jahn-Teller distortion. We further demonstrate that the ferromagnetic instability of SrRuO3 is related to the temperature-induced localization of Ru 4d bands. PMID:24136614

  16. 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.

  17. Mechanisms of Reactions of Dihydrogen Complexes: Formation of trans-[RuH(H(2))(dppe)(2)](+) and Substitution of Coordinated Dihydrogen.

    PubMed

    Basallote, Manuel G.; Durán, Joaquín; Fernández-Trujillo, M. Jesús; Máñez, M. Angeles

    1999-11-01

    The reactions between cis-[RuH(2)(DPPE)(2)] and a number of acids in THF solution (DPPE = Ph(2)PCH(2)CH(2)PPh(2)) show biphasic kinetics, with initial formation of trans-[RuH(H(2))(DPPE)(2)](+) followed by slower substitution of coordinated dihydrogen by the anion of the acid. The formation of the dihydrogen complex is a second-order process that occurs with an inverse kinetic isotope effect and rate constants k(HX) strongly dependent on the nature of the acid. There is a linear correlation between the values of log k(HX) for cis-[RuH(2)(DPPE)(2)] and the related cis-[FeH(2)(PP(3))] [PP(3) = P(CH(2)CH(2)PPh(2))(3)] that leads to two parameters, S and R, that can be used as a measure of the selectivity and intrinsic reactivity of the dihydride toward acids. The possible contributions to the values of these parameters are discussed, especially the role of the isomerization of the starting complex and the basicity of the reacting species. The substitution of coordinated dihydrogen in trans-[RuH(H(2))(DPPE)(2)](+) occurs through a simple dissociative mechanism instead of the more complicated one previously proposed for substitutions in the analogous Fe complex; the mechanistic change is associated with the relative strength of the M-H(2) and M-P(chelate) bonds.

  18. 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}.

  19. 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.

  20. Cyclic ethers adsorbed on Ru(001)

    NASA Astrophysics Data System (ADS)

    Walczak, M. M.; Thiel, P. A.

    1990-11-01

    The three cyclic ethers 1,3-dioxane. 1,4-dioxane and 1,3,5-trioxane all exhibit multiple desorption states from Ru(001) between 200 and 310 K, in addition to the multilayer and metastable states at lower temperature. Most distinctive are the two low-temperature α-states. which are similar in shape, position, and relative population for all three compounds. This suggests that these states are associated with configurations which are accessible to all three molecules. The data also indicate that there is some molecular decomposition to gaseous CO and H 2. 1,4-Dioxane yields the largest amounts of these decomposition products, suggesting that this molecule is most susceptible to surface-catalyzed decomposition. The desorption data for the three cyclic ethers are grossly similar to each other, and also to the straight-chain diethers which we have previously studied.

  1. 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.

  2. 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).

  3. 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.

  4. /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.

  5. /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.

  6. Dihydrogen activation by a diruthenium analogue of the Fe-only hydrogenase active site.

    PubMed

    Justice, Aaron K; Linck, Rachel C; Rauchfuss, Thomas B; Wilson, Scott R

    2004-10-20

    The photochemical reaction of Ru2(S2C3H6)(CO)4(PCy3)2 (1) and H2 gives the dihydride Ru2(S2C3H6)(mu-H)(H)(CO)3(PCy3)2 (2). NMR and crystallographic studies reveal mutually trans basal phosphine ligands and both bridging and terminal hydrides. Ru2(S2C2H4)(CO)4(PCy3)2 behaves similarly. Other HX substrates undergo photoaddition to 1, affording Ru2(S2C3H6)(mu-H)(X)(CO)3(PCy3)2 for X = OTs (3a), Cl (3b), and SPh (3c). Treatment of Ru2(S2C3H6)(mu-H)(H)(CO)3(PCy3)2 with [H(OEt2)]BArF4 (ArF = B(C6H3-3,5-(CF3)2) in CD2Cl2 gives [Ru2(S2C3H6)(mu-H)(CO)3(PCy3)2(H2)]+ (4), which catalyzes H2-D2 exchange. The reaction of 2 with [D(OEt2)]BArF4 gave [Ru2(S2C3H6)(mu-H)(CO)3(PCy3)2(HD)]+ (JH-D = 31 Hz). These studies provide the first models for the Fe-only hydrogenases that bear dihydrogen and terminal hydrido ligands. PMID:15479062

  7. 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.

  8. 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.

  9. 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)

  10. Adsorption and diffusion of Ru adatoms on Ru(0001)-supported graphene: Large-scale first-principles calculations

    DOE PAGESBeta

    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

  11. 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).

  12. 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. PMID:25157036

  13. 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.

  14. 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.

  15. Annealing of RuO 2 and Ru Bottom Electrodes and Its Effects on the Electrical Properties of (Ba,Sr)TiO 3 Thin Films

    NASA Astrophysics Data System (ADS)

    Ahn, Joon-Hyung; Choi, Won-Youl; Lee, Won-Jae; Kim, Ho-Gi

    1998-01-01

    Crystalline structures and surface morphologies of annealed RuO2 and Ru thin films were investigated using X-ray diffraction (XRD) and scanning electron microscopy (SEM). The annealing was performed in oxygen and argon ambient and high vacuum in the temperature range of 400 800° C. In oxygen ambient annealing, the surface morphology was drastically changed due to the evaporation of ruthenium dioxides in the form of RuO3 and RuO4. Annealed RuO2 thin film in vacuum was reduced to the Ru metal phase. The actual variation of RuO2 bottom electrodes during the deposition of (Ba,Sr)TiO3 (BST) thin films and the effects of the thermal stability of bottom electrodes on electrical properties of BST thin films deposited on RuO2/SiO2/Si were also investigated.

  16. 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.

  17. Preparation and characterisation of Ru doped MgB2

    NASA Astrophysics Data System (ADS)

    Grivel, J.-C.; Holte, O. J.

    2013-12-01

    Samples with Mg1-xRuxB2 nominal stoichiometry were prepared by sintering at 800 °C. The critical transition temperature decreases up to a substitution level of x ≈ 0.015. A maximum solubility limit slightly in excess of 1 at.% Ru for Mg is confirmed by energy dispersive spectroscopy measurements. From and beyond this limit, an unidentified phase appears in the X-ray diffraction patterns. Interestingly, the lattice parameters of the MgB2 phase are constant up to x = 0.015, but start to decrease for higher Ru contents. This feature could be related to the fact that a Mg-Ru impurity phase results in a Mg-deficient (Mg,Ru)B2 matrix.

  18. 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.

  19. 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.

  20. 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

  1. [Os trigonum syndrome].

    PubMed

    Zeichen, J; Schratt, E; Bosch, U; Thermann, H

    1999-04-01

    The os trigonum syndrome is an entity causing posterior ankle pain and occurs mostly with typical sports activities. Diagnosis and differential diagnosis are presented. Typical complaints and therapeutic procedure are demonstrated in one case. Therapy includes different non-operative methods, resistance to non-operative procedures is an indication for excision of this ossicle.

  2. Highly branched RuO2 Nanorods on Electrospun TiO2 Nanofibers toward Electrochemical Catalysts

    NASA Astrophysics Data System (ADS)

    Cho, Yukyung; Kim, Su-Jin; Lee, Nam-Suk; Kim, Myung Hwa; Lee, Youngmi

    2014-03-01

    We report a facile growth route to synthesize hierarchically grown single crystalline metallic RuO2 nanorods on electrospun TiO2 nanofibers via a combination of a simple vapour phase transport process with an electrospinning process. This synthetic strategy could be very useful to design a variety of highly branched network architectures of the functional hetero-nanostructures for electrochemical applications. Particularly, Ruthenium oxide (RuO2) 1-dimensional nanostructures can be used as the effective catalysts or electrochemical electrode materials. Thus, we first synthesize TiO2 nanofibers from mixture of titanium isopropoxide precursor and polymer and then ruthenium hydroxide precursor on TiO2 nanofibers are transformed into RuO2 nanorods by thermal treatment at 250oC in air. The crystalline structures of products are confirmed using scanning electron microscopy (FE-SEM), X-ray diffraction (XRD) spectrum, Raman spectroscopy, and high resolution electron microscopy (HRTEM). The fundamental electrochemical performances are examined using cyclic voltammetry (CV).

  3. Structurally modulated magnetic properties in the A(3)MnRu(2)O(9) phases (A = Ba, Ca): the role of metal-metal bonding in perovskite-related oxides.

    PubMed

    Gönen, Z S; Gopalakrishnan, J; Eichhorn, B W; Greene, R L

    2001-09-10

    Ca(3)MnRu(2)O(9) and Ba(3)MnRu(2)O(9) were synthesized from transition metal dioxides and alkaline earth metal carbonates at 1100-1300 degrees C. Ca(3)MnRu(2)O(9) adopts the prototypical GdFeO(3)-type perovskite structure with Mn and Ru statistically disordered over the single metal atom site. The susceptibility shows Curie-Weiss behavior above 240 K with mu(eff) = 3.14 micro(B)/metal atom, which is in excellent agreement with the expected spin-only moment of 3.20 micro(B). Below 150 K, the compound shows spin-glass-like short-range ferrimagnetic correlations. The high-temperature region of the electrical resistivity reveals a small activation energy of 17(1) meV whereas the low-temperature region is nonlinear and does not fit a variable range hopping model. Ba(3)MnRu(2)O(9) crystallizes in the 9-layer BaRuO(3)-type structure containing M(3)O(12) face-shared trioctahedral clusters in which Mn and Ru are statistically disordered. Ba(3)MnRu(2)O(9) shows nonlinear reciprocal susceptibility at all temperatures and is described by a variable-spin cluster model with an S = (1)/(2) ground state with thermally populated excited states. The low spin value of this system (S = (1)/(2)) is attributed to direct metal-metal bonding. Below 30 K, the compound shows short-range magnetic correlations and spin-glass-like behavior. The high-temperature region of the electrical resistivity indicates a small activation energy of 8.8(1) meV whereas the low-temperature region is nonlinear. The importance of metal-metal bonding and the relationships to other related compounds are discussed.

  4. Interlayer exchange coupling between [Pd/Co] multilayers and CoFeB/MgO layers with perpendicular magnetic anisotropy

    NASA Astrophysics Data System (ADS)

    Jung, J. H.; Lim, S. H.; Lee, S. R.

    2012-12-01

    Interlayer exchange coupling between [Pd/Co] multilayers and CoFeB/MgO layers with perpendicular magnetic anisotropy (PMA) is investigated as functions of the thicknesses of the Ru spacer and CoFeB layer. The dependence of the coupling behavior on the Ru thickness is similar to that of in-plane anisotropy systems. However, one feature is that the PMA is strengthened through interlayer exchange coupling, as indicated by the fact that PMA of the interface-based CoFeB/MgO structure forms for a thick magnetic layer (1.4 nm). Another observation is the conversion from perpendicular to in-plane anisotropy with thick Ru spacers with almost zero exchange coupling strength.

  5. Clarifying the role of Ru in methanol oxidation at Ru(core)@Pt(shell) nanoparticles.

    PubMed

    El Sawy, Ehab N; El-Sayed, Hany A; Birss, Viola I

    2015-11-01

    The catalytic activity of Rucore@Ptshell nanoparticles (NPs) towards CO oxidation, a strongly adsorbed intermediate that compromises the performance of direct methanol fuel cells, is known to be significantly better than at Pt alone. However, a systematic study aimed at understanding the beneficial effect of Ru on Pt during the methanol oxidation reaction (MOR) has not been carried out as yet. Here, Rucore@Ptshell NPs, having a controlled Ptshell coverage of zero to two monolayers and two different Rucore sizes (2 and 3 nm), were synthesized using the simple polyol method to determine the precise role and impact of Ru on the MOR in 0.5 M H2SO4 + 1 M methanol at RT and 60 °C. Because the structure of our Rucore@Ptshell NPs is known with such certainty, we were able to show here that the rate of methanol adsorption/dehydrogenation can be accelerated either by compression of the Ptshell (by making the Rucore larger) when it is less than one monolayer in thickness, or by decreasing the electronic effect of the Rucore on the Ptshell (achieved by adding a second Pt layer to the Ptshell). At low overpotentials, decreasing the Ptshell thickness also helps in increasing the rate of the MOR by enhancing the rate of oxidation of adsorbed CO. Finally, it is shown that the bi-functional effect of Ru on the Ptshell plays only a minor role in the catalysis of the MOR, especially at large particles where CO surface diffusion is facilitated. PMID:26426281

  6. Solvent-dependent formation of Os(0) complexes by electrochemical reduction of [Os(CO)(2,2'-bipyridine)(L)Cl2]; L = Cl(-), PrCN.

    PubMed

    Tory, Joanne; King, Lisa; Maroulis, Antonios; Haukka, Matti; Calhorda, Maria José; Hartl, František

    2014-02-01

    Cyclic voltammetry and ultraviolet-visible/infrared (UV-vis/IR) spectroelectrochemistry were used to study the cathodic electrochemical behavior of the osmium complexes mer-[Os(III)(CO) (bpy)Cl3] (bpy = 2,2'-bipyridine) and trans(Cl)-[Os(II)(CO) (PrCN)(bpy)Cl2] at variable temperature in different solvents (tetrahydrofuran (THF), butyronitrile (PrCN), acetonitrile (MeCN)) and electrolytes (Bu4NPF6, Bu4NCl). The precursors can be reduced to mer-[Os(II)(CO) (bpy(•-))Cl3](2-) and trans(Cl)-[Os(II)(CO)(PrCN) (bpy(•-))Cl2](-), respectively, which react rapidly at room temperature, losing the chloride ligands and forming Os(0) species. mer-[Os(III)(CO) (bpy)Cl3] is reduced in THF to give ultimately an Os-Os-bonded polymer, probably [Os(0)(CO) (THF)(bpy)]n, whereas in PrCN the well-soluble, probably mononuclear [Os(0)(CO) (PrCN)(bpy)], species is formed. The same products were observed for the 2 electron reduction of trans(Cl)-[Os(II)(CO)(PrCN) (bpy)Cl2] in both solvents. In MeCN, similar to THF, the [Os(0)(CO) (MeCN)(bpy)]n polymer is produced. It is noteworthy that the bpy ligand in mononuclear [Os(0)(CO) (PrCN)(bpy)] is reduced to the corresponding radical anion at a significantly less negative potential than it is in polymeric [Os(0)(CO) (THF)(bpy)]n: ΔE1/2 = 0.67 V. Major differences also exist in the IR spectra of the Os(0) species: the polymer shows a broad ν(CO) band at much smaller wavenumbers compared to the soluble Os(0) monomer that exhibits a characteristic ν(Pr-CN) band below 2200 cm(-1) in addition to the intense and narrow ν(CO) absorption band. For the first time, in this work the M(0)-bpy (M = Ru, Os) mono- and dicarbonyl species soluble in PrCN have been formulated as a mononuclear complex. Density functional theory (DFT) and time-dependent-DFT calculations confirm the Os(0) oxidation state and suggest that [Os(0)(CO) (PrCN)(bpy)] is a square planar moiety. The reversible bpy-based reduction of [Os(0)(CO

  7. Interfacial effects in Fe/4d TM multilayers (abstract)

    SciTech Connect

    Tomaz, M.A.; Antel, W.J., Jr.; Harp, G.R.; OBrien, W.L.

    1997-04-01

    We have studied Fe/TM multilayers (TM=Mo, Nb, Ru, Rh, Pd) using x-ray magnetic circular dischroism, magneto-optical Kerr effect, and x-ray diffraction. A diverse set of magnetic behaviors emerges from the analysis. We focus on the behavior which can be attributed to the existence of a physical interface between different chemical species. In particular, we have measured an enhanced Fe moment in some cases (TM=Ru, Mo, Rh, Pd) yet not in others (TM=Nb). These results will be discussed, including the relative orbital and spin moments and the effects of alloying at the interface. The measured induced moments in the TM layer will be presented as well where applicable. {copyright} {ital 1997 American Institute of Physics.}

  8. 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.

  9. ^99,101Ru NMR Study of Sr_1-xCa_xRuO3 single crytals.

    NASA Astrophysics Data System (ADS)

    Daniel, M.; Budnick, J. I.; Hines, W. A.; Cao, G.

    2000-03-01

    A zero-field spin-echo NMR study of ^99,101Ru has been carried out on 60 mg samples of Sr_1-xCa_xRuO3 (x=0, 0.25, and 0.50) single crystals[1]. The NMR spectrum of SrRuO3 consists of two peaks at 64.4 and 72.2 MHz, corresponding to the ^99Ru and ^101Ru isotopes, respectively, and a hyperfine field of 328 kOe. A clear modulation of the spin-echo amplitude, with a period of τ m = 25 μ s, was observed for the ^99Ru isotope. Measurements of the magnetization indicate that the easy axis lies in the plane perpendicular to the c-axis[1]. Using this result, the electric quadrupole frequency is calculated to be 80 kHz, much less than the centeral peak linewidth which is principally magnetic in orign. With the replacement of Sr by Ca, there is essentially no change in the peak frequencies; however, both peaks show a significant reduction in height with intensity being shifted into the broad wings. The effect of Ca doping on the electric field is observed through the variation of ν _Q. These results will be discussed in terms of structural variation and ferromagnetic exchange coupling. [1] G. Cao, S. McCall, M. Shepard, J. E. Crow, and R. P. Guertin, Phys. Rev. B56, 321(1997).

  10. Atomic hydrogen interaction with Ru(1010).

    PubMed

    Vesselli, E; Comelli, G; Rosei, R

    2004-05-01

    The interaction of atomic hydrogen with clean and deuterium precovered Ru(1010) was studied by means of temperature-programmed desorption (TPD) spectroscopy. Compared to molecular hydrogen experiments, after exposure of the clean surface to gas-phase atomic hydrogen at 90 K, two additional peaks grow in the desorption spectra at 115 and 150 K. The surface saturation coverage, determined by equilibrium between abstraction and adsorption reactions, is 2.5 monolayers. Preadsorbed deuterium abstraction experiments with gas-phase atomic hydrogen show that a pure Eley-Rideal mechanism is not involved in the process, while a hot atom (HA) kinetics describes well the reaction. By least-squares fitting of the experimental data, a simplified HA kinetic model yields an abstraction cross section value of 0.5 +/- 0.2 angstroms2. The atomic hydrogen interaction with an oxygen precovered surface was also studied by means of both TPD and x-ray photoelectron spectroscopy: oxygen hydrogenation and water production take place already at very low temperature (90 K).

  11. 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.

  12. {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}.

  13. [Os trigonum syndrome].

    PubMed

    Bruns, J; Eggers-Ströder, G

    1991-09-01

    The os trigonum is one of the most frequent accessory bones of the foot. It is located dorsal of the talus. Os trigonum syndrome means a typical pain syndrome localized in the back-foot caused by this ossicle. This syndrome occurs mostly in man with sports activities accompanied with intensive stress to different parts of the foot. It can be caused particularly by standing on the toe in the "en-pointe-position" in ballet dancers when the flexor hallucis tendon is under maximal tension or by activities accompanied with maximal plan-tarflexion in soccer players for instance. Typical complaints, findings and different therapeutic procedures are demonstrated in two cases. Therapy includes different non-operative methods. Resistance to non-operative procedures is indication for operative therapy. Excision of this ossicle is surgical therapy of first choice.

  14. RU486 (mifepristone): mechanisms of action and clinical uses.

    PubMed

    Cadepond, F; Ulmann, A; Baulieu, E E

    1997-01-01

    RU486 (mifepristone) has proved to be a remarkably active antiprogesterone and antiglucocorticosteroid agent in human beings. The mechanism of action involves the intracellular receptors of the antagonized hormones (progesterone and glucocorticosteroids). At the molecular level, the most important features are high binding affinity to the receptor, interaction of the phenylaminodimethyl group in the 11 beta-position with a specific region of the receptor binding pocket, and RU486-induced transconformation differences in the ligand-binding domain. These particularities have consequences at different steps of the receptor function as compared with agonists. However, the reasoning cannot be limited to the RU486-receptor interaction, and, for instance, there is the possibility of a switch from antagonistic property to agonist activity, depending on the intervention of other signaling pathways. It would be desirable to have derivatives with only one of the two antagonistic properties (antiprogestin, antiglucocorticosteroid) in spite of similarities between steroid structures, receptors involved, and responsive machineries in target cells. Clinically, the RU486-plus-prostaglandin method is ready to be used on a large scale and is close to being as convenient and safe as any medical method of abortion may be. The early use of RU486 as a contragestive as soon as a woman fears a pregnancy she does not want will help to defuse the abortion issue. Research should now be conducted to define an efficient and convenient contraceptive method with RU486 or other antiprogestins. The usefulness of RU486 for obstetric indications, including facilitation of difficult delivery, has to be assessed rapidly. Gynecologic trials, particularly in leiomyomata, should be systemically continued. The very preliminary results obtained with tumors, including breast cancers, indicate that further studies are necessary. PMID:9046951

  15. Study of the electronic and magnetic properties as a function of isoelectronic substitution in SmFe(1-x)RuxAsO0.85F0.15.

    PubMed

    Simonelli, L; Al-Zein, A; Moretti Sala, M; Joseph, B; Iadecola, A; Bendele, M; Martinelli, A; Palenzona, A; Putti, M; Monaco, G

    2014-02-12

    We have studied the electronic and magnetic properties of SmFe(1-x)RuxAsO0.85F0.15 (x = 0, 0.05, 0.25, 0.33, 0.5) by high-resolution x-ray absorption and x-ray emission spectroscopy. The local Fe magnetic moment (μ) tends to decrease for a small Ru substitution, but it shows a clear increase with further substitution. It appears that impurity scattering prevails in reducing the μ with small Ru substitution due to an extended Ru d-band. A nanoscale phase separation, that decouples the FeAs layers from the spacer layers, drives the increase of μ at higher Ru substitution. The results provide important information on nanoscale phase separation due to isoelectronic substitution in the active layers of iron-based 1111-superconductors and its effect on the local magnetic properties.

  16. Os trigonum syndrome.

    PubMed

    Wenig, J A

    1990-05-01

    The os trigonum is a frequently encountered accessory bone of the foot. It is located at the posterior aspect of the talus, and may appear either as a separate ossicle or fused to the talus. The separate ossicle may represent an accessory bone or a fracture of the posterior process (also called the trigonal process) of the talus. The author reviews the mechanism of injury and the diagnosis and treatment. A case report of a fracture of the trigonal process is presented.

  17. 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

  18. 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.

  19. Field-temperature phase diagram of superconductivity in Sr2RuO4-Ru under out-of-plane uniaxial pressure

    NASA Astrophysics Data System (ADS)

    Taniguchi, H.; Kittaka, S.; Yonezawa, S.; Yaguchi, H.; Maeno, Y.

    2012-12-01

    One of the interesting issues on the spin-triplet superconductor Sr2RuO4 (Tc = 1.5 K) is the origin of the Tc enhancement up to about 3 K in the eutectic system Sr2RuO4-Ru. We have recently revealed a striking fact that Tc of pure Sr2RuO4 is also enhanced up to 3.2 K by uniaxial pressure along the c axis (P||c). When P||c is applied to Sr2RuO4-Ru, there is a crossover at P*||c ~ 0.4 GPa from behavior attributable to interfacial superconductivity (SC) to behavior similar to that in pure Sr2RuO4 under P||c. We focus on the field-temperature phase diagrams of Sr2RuO4-Ru above and below P*||c. We revealed that the H-T curves of Sr2RuO4-Ru both above and below P*||c are concave-up. This fact suggests that the P||c-originated SC above P*||c as well as the interfacial SC below P*||c are granular-like. We also found that the H-T curves of these SCs do not scale with Tc's, which is possibly related to a difference in the spatial distribution of superconducting regions.

  20. Evolution of magnetism in single-crystal Ca2Ru1-xIrxO4(0≤x≤0.65)

    DOE PAGESBeta

    Yuan, S. J.; Terzic, J.; Wang, J. C.; Li, L.; Aswartham, S.; Song, W. H.; Ye, Feng; Cao, Gang

    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

  1. 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.

  2. 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.

  3. 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

    2016-01-01

    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.

  4. 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

  5. Icosahedral phase stabilities in Al-Cu-Ru alloys

    SciTech Connect

    Shield, J.E.; Hoppe, C.; McCallum, R.W.; Goldman, A.I. ); Kelton, K.F.; Gibbons, P.C. )

    1992-02-01

    By examining a wide region of the Al-Cu-Ru phase diagram, a thorough analysis of the compositional and thermal stability of the icosahedral phase has been completed. The primary solidification product of rapid solidification was a topologically and chemically disordered icosahedral phase with an extensive compositional region. Crystallization through exothermic events of the as-solidified materials produced crystalline phases, without the formation of the face-centered-icosahedral (FCI) phase. However, the FCI phase does form at higher temperatures through an endothermic reaction, indicating that it is a stable phase of the system, but only at elevated temperatures. Of the alloys studied, the FCI phase field was found to encompass Al{sub 65}Cu{sub 23}Ru{sub 12}, Al{sub 65}Cu{sub 20}Ru{sub 15}, Al{sub 70}Cu{sub 20}Ru{sub 10}, and Al{sub 70}Cu{sub 15}Ru{sub 15}. The transformation to the FCI phase involves an intermediate approximant phase that is very similar to the FCI structure. Also, a cubic approximant containing atomic arrangements with local icosahedral symmetry similar to {alpha}-Al Mn Si was determined to exist near the FCI phase field.

  6. 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

    2016-01-01

    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

  7. NO-binding in {Ru(NO)₂}⁸-type [Ru(NO)₂(PR₃)₂X]BF₄ compounds.

    PubMed

    Gallien, Anna K E; Schaniel, Dominik; Woike, Theo; Klüfers, Peter

    2014-09-21

    Two different structure types were found for a series of mononuclear dinitrosyl complexes of the general formula [RuL2(NO)2X]BF4 (L = monodentate phosphane, X = Cl, Br, I). The {Ru(NO)2}(8)-type target compounds were prepared by the reduction of the respective {RuNO}(6) precursors and subsequent oxidative addition of (NO)BF4. About one half of the new compounds share their molecular structure with the hitherto only representative of this class of dinitrosyls, Pierpont and Eisenberg's [RuCl(NO)2(PPh3)2]PF6·C6H6 (Inorg. Chem., 1972, 11, 1088-1094). The Cs-symmetric cations exhibit both a linear and a bent Ru-N-O fragment, in line with a formal 6 + 2 split of the {Ru(NO)2}(8) electron sum in the sense of a [Ru(II)(NO(+))((1)NO(-))](2+) bonding. The coordination entity's configuration in this subgroup is described by IUPAC's polyhedral symbol SPY-5. Continuous shape measures (CShM) as defined by Alvarez et al. (Coord. Chem. Rev., 2005, 249, 1693-1708) reveal a uniform deviation from the L-M-L angles expected for SPY-5, in a narrower sense, towards a vacant octahedron (vOC-5). DFT calculations confirmed that Enemark and Feltham's analysis (Coord. Chem. Rev., 1974, 13, 339-406) of the electronic situation of the {Ru(NO)2}(8) group remains adequate. The same holds for the second subclass of new compounds the existence of which had been predicted in the same paper by Enemark and Feltham, namely C(2v)-symmetric, TBPY-5-type cations with two almost equally bonded nitrosyl ligands. In agreement with an 8 + 0 distribution of the relevant electrons, the formal [Ru(0)(NO(+))2](2+) entities are found for L/X couples that donate more electron density on the central metal. Two solid compounds (8a/b, 12a/b) were found in both structures including the special case of the P(i)Pr3/Br couple 12a/b, which led to crystals that contained both structure types in the same solid. Conversely, four compounds showed a single form in the solid but both forms in dichloromethane solution in terms

  8. Anode properties of Ru-coated Si thick film electrodes prepared by gas-deposition

    NASA Astrophysics Data System (ADS)

    Usui, Hiroyuki; Kashiwa, Yuta; Iida, Takahisa; Sakaguchi, Hiroki

    Thick film electrodes consisting of Ru and Ru-coated Si particles were fabricated by a gas-deposition method and their electrochemical properties of anodes for Li rechargeable battery were evaluated. The discharge capacity of the Ru electrode at 1000th cycle is approximately 400 mAh g -1. The result showed that the electrode reaction is based on the redox reaction of RuO 2 which was formed on the Ru surface during the charge-discharge processes. By coating Si particles with Ru using an electroless deposition technique, we obtained an electrode with remarkable discharge capacity of 570 mAh g -1 at 1000th cycle. The reason for the improvement in the electrode performance appears to result from the fact that the Ru electrode exhibits excellent cycleability itself and the Ru coated on Si reduces the stress generated by the immense volumetric changes occurring in the Si particles.

  9. Ru-core/Cu-shell bimetallic nanoparticles with controlled size formed in one-pot synthesis.

    PubMed

    Helgadottir, I; Freychet, G; Arquillière, P; Maret, M; Gergaud, P; Haumesser, P H; Santini, C C

    2014-12-21

    Suspensions of bimetallic nanoparticles (NPs) of Ru and Cu have been synthesized by simultaneous decomposition of two organometallic compounds in an ionic liquid. These suspensions have been characterized by Anomalous Small-Angle X-ray Scattering (ASAXS) at energies slightly below the Ru K-edge. It is found that the NPs adopt a Ru-core, a Cu-shell structure, with a constant Ru core diameter of 1.9 nm for all Ru : Cu compositions, while the Cu shell thickness increases with Cu content up to 0.9 nm. The formation of RuCuNPs thus proceeds through rapid decomposition of the Ru precursor into RuNPs of constant size followed by the reaction of the Cu precursor and agglomeration as a Cu shell. Thus, the different decomposition kinetics of precursors make possible the elaboration of core-shell NPs composed of two metals without chemical affinity.

  10. Bottom-up fabrication of graphene nanostructures on Ru(1010).

    PubMed

    Song, Junjie; Zhang, Han-jie; Cai, Yiliang; Zhang, Yuxi; Bao, Shining; He, Pimo

    2016-02-01

    Investigations on the bottom-up fabrication of graphene nanostructures with 10, 10'-dibromo-9, 9'-bianthryl (DBBA) as a precursor on Ru(1010) were carried out using scanning tunnelling microscopy (STM) and density functional theory (DFT) calculations. Upon annealing the sample at submonolayer DBBA coverage, N = 7 graphene nanoribbons (GNRs) aligned along the [1210] direction form. Higher DBBA coverage and higher annealing temperature lead to the merging of GNRs into ribbon-like graphene nanoflakes with multiple orientations. These nanoflakes show different Moiré patterns, and their structures were determined by DFT simulations. The results showed that GNRs possess growth preference on the Ru(1010) substrate with a rectangular unit cell, and GNRs with armchair and zigzag boundaries are obtainable. Further DFT calculations suggest that the interaction between graphene and the substrate controls the orientations of the graphene overlayer and the growth of graphene on Ru(1010).

  11. 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.

  12. Two Dimensional Antiferromagnetic Chern Insulator: NiRuCl6

    NASA Astrophysics Data System (ADS)

    Zhou, P.; Sun, C. Q.; Sun, L. Z.

    2016-10-01

    Based on DFT and Berry curvature calculations, we predict that quantum anomalous hall effect (QAHE) can be realized in two dimensional anti-ferromagnetic (AFM) NiRuCl6 with zero net magnetic moment. By tuning spin-orbits coupling (SOC), we find that the topological properties of NiRuCl6 come from its energy band reversal. The results indicate that NiRuCl6 behaves as AFM Chern insulator and its spin-polarized electronic structure and strong spin-orbits coupling (SOC) are the origin of QAHE. Considering the compatibility between AFM and insulator, AFM Chern insulator is more suitable to realize high temperature QAHE because generally Neel temperature of AFM systems is more easily improved than Curie temperature of ferromagnetic (FM) systems. Due to the different magnetic coupling mechanism between FM and AFM Chern insulator, AFM Chern insulator provides a new way to archive high temperature QAHE in experiments.

  13. Bimetallic Wiregauze Supported Pt-Ru Nanocatalysts for Hydrogen Mitigation.

    PubMed

    Sanap, Kiran K; Varma, S; Waghmode, S B; Sharma, P; Manoj, N; Vatsa, R K; Bharadwaj, S R

    2015-05-01

    Passive autocatalytic recombiner (PAR) is one of the most suitable devices for mitigation of hydrogen, generated in nuclear power plant under accidental conditions. For this purpose we report development of stainless steel wire gauze supported Pt-Ru nanoparticles as catalysts. Simultaneous electroless deposition has been employed for the synthesis of the catalysts. Pt-Ru based bimetallic catalysts were characterized for their rate of coating kinetics, noble metal loading, phase purity by XRD and surface morphology by SEM, TEM and elemental analysis by SIMS. Developed catalysts were found to be active for efficient recombination of hydrogen and oxygen in air as well as in presence of various prospective poisons like CO2, CH4, CO and relative humidity. Pt-Ru based bimetallic catalyst with 0.9% loading was found to be active for CO poisoning up to 400 ppm of CO. PMID:26504972

  14. Enhanced thermoelectric power and electronic correlations in RuSe₂

    DOE PAGESBeta

    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.

  15. 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.

  16. 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.

  17. Molecularly imprinted Ru complex catalysts integrated on oxide surfaces.

    PubMed

    Muratsugu, Satoshi; Tada, Mizuki

    2013-02-19

    Selective catalysis is critical for the development of green chemical processes, and natural enzymes that possess specialized three-dimensional reaction pockets with catalytically active sites represent the most sophisticated systems for selective catalysis. A reaction space in an enzyme consists of an active metal center, functional groups for molecular recognition (such as amino acids), and a surrounding protein matrix to prepare the reaction pocket. The artificial design of such an integrated catalytic unit in a non-enzymatic system remains challenging. Molecular imprinting of a supported metal complex provides a promising approach for shape-selective catalysis. In this process, an imprinted cavity with a shape matched to a template molecule is created in a polymer matrix with a catalytically active metal site. In this Account, we review our studies on molecularly imprinted metal complex catalysts, focusing on Ru complexes, on oxide surfaces for shape-selective catalysis. Oxide surface-attached transition metal complex catalysts not only improve thermal stability and catalyst dispersion but also provide unique catalytic performance not observed in homogeneous precursors. We designed molecularly imprinted Ru complexes by using surface-attached Ru complexes with template ligands and inorganic/organic surface matrix overlayers to control the chemical environment around the active metal complex catalysts on oxide surfaces. We prepared the designed, molecularly imprinted Ru complexes on SiO(2) surfaces in a step-by-step manner and characterized them with solid-state (SS) NMR, diffuse-reflectance (DR) UV-vis, X-ray photoelectron spectroscopy (XPS), Brunauer-Emmett-Teller isotherm (BET), X-ray fluorescence (XRF), and Ru K-edge extended X-ray absorption fine structure (EXAFS). The catalytic performances of these Ru complexes suggest that this process of molecular imprinting facilitates the artificial integration of catalytic functions at surfaces. Further advances such

  18. 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. PMID:20066185

  19. 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)

  20. The electronic band character of Ru dichalcogenides and its significance for the photoelectrolysis of water

    NASA Astrophysics Data System (ADS)

    Kühne, H.-M.; Jaegermann, W.; Tributsch, H.

    1984-11-01

    Electrodes of Ru dichalcogenides show different electrochemical behavior in contact with aqeuous electrolytes. Whereas RuS 2 is most stable, considerable anodic corrosion occurs at RuSe 2 and RuTe 2. XPS measurements performed to analyse surface species, formed after electrochemical treatment, and to identify the band character of the compounds. A correlation between variations in valence band character and the kinetics of the dissolution reaction is suggested.

  1. Arsenic immobilization in the contaminated soil using poorly crystalline Fe-oxyhydroxy sulfate.

    PubMed

    Yang, Zhihui; Liu, Lin; Chai, Liyuan; Liao, Yingping; Yao, Wenbin; Xiao, Ruiyang

    2015-08-01

    A low crystalline Fe-oxyhydroxy sulfate (FeOS) was used to immobilize arsenic (As) in soils in this study. The effects of FeOS amount, treatment time and soil moisture on As immobilization were investigated. The results showed that water-soluble and NaHCO3-extractable As were immobilized by 53.4-99.8 and 13.8-73.3% respectively, with 1-10% of FeOS addition. The highest immobilization of water-soluble (98.5%) and NaHCO3-extractable arsenic (47.2%) was achieved under condition of 4% of FeOS and 80% of soil moisture. Further, more amounts of FeOS addition resulted in less time requirement for As immobilization. Sequential chemical extraction experiment revealed that easily mobile arsenic phase was transferred to less mobile phase. The FeOS-bonded As may play a significant role in arsenic immobilization. Under leaching with simulated acid rain at 60 times pore volumes, accumulation amount of As release from untreated soil and soil amended with FeOS were 98.4 and 1.2 mg, respectively, which correspond to 7.69 and 0.09% of total As amounts in soil. The result showed that the low crystalline FeOS can be used as a suitable additive for arsenic immobilization in soils.

  2. Arsenic immobilization in the contaminated soil using poorly crystalline Fe-oxyhydroxy sulfate.

    PubMed

    Yang, Zhihui; Liu, Lin; Chai, Liyuan; Liao, Yingping; Yao, Wenbin; Xiao, Ruiyang

    2015-08-01

    A low crystalline Fe-oxyhydroxy sulfate (FeOS) was used to immobilize arsenic (As) in soils in this study. The effects of FeOS amount, treatment time and soil moisture on As immobilization were investigated. The results showed that water-soluble and NaHCO3-extractable As were immobilized by 53.4-99.8 and 13.8-73.3% respectively, with 1-10% of FeOS addition. The highest immobilization of water-soluble (98.5%) and NaHCO3-extractable arsenic (47.2%) was achieved under condition of 4% of FeOS and 80% of soil moisture. Further, more amounts of FeOS addition resulted in less time requirement for As immobilization. Sequential chemical extraction experiment revealed that easily mobile arsenic phase was transferred to less mobile phase. The FeOS-bonded As may play a significant role in arsenic immobilization. Under leaching with simulated acid rain at 60 times pore volumes, accumulation amount of As release from untreated soil and soil amended with FeOS were 98.4 and 1.2 mg, respectively, which correspond to 7.69 and 0.09% of total As amounts in soil. The result showed that the low crystalline FeOS can be used as a suitable additive for arsenic immobilization in soils. PMID:25911284

  3. 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

    2014-10-01

    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.

  4. 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.

  5. Nuclear forward scattering of synchrotron radiation by 99Ru

    DOE PAGESBeta

    Bessas, D.; Merkel, D. G.; Chumakov, A. I.; Ruffer, R.; Hermann, Raphael P.; Sergueev, I.; Mahmoud, A.; Klobes, B.; McGuire, Michael A.; Sougrati, M. T.; et al

    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.

  6. 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. PMID:27072776

  7. [Ethical controversy surrounding RU 486: data and arguments].

    PubMed

    Reiter-Theil, S; Dressel, R

    1992-01-01

    By RU 486 being synthesized (1980) a pharmacological alternative to surgical methods of abortion has been created. Since 1988 Mifepristone is applied for termination of pregnancies under severe control. Major pros and cons in debates about RU 486 in medical publications are analyzed, their relations to central ethical principles being worked out clearly. As consequences of the analysis of arguments the authors formulate four conditions for the use of Mifepristone as method of abortion which should be considered in further research and practice. PMID:1514298

  8. 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

  9. 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.

  10. Three types of condensed cluster phases of rare-earth metal iodides with transition metal interstitials: Pr{sub 4}I{sub 5}Ni, Pr{sub 3}I{sub 3}Os, Pr{sub 2}INi{sub 2}, and La{sub 2}IZ{sub 2}

    SciTech Connect

    Park, Y.; Martin, J.D.; Corbett, J.D.

    1997-03-01

    Syntheses of the title compounds result from appropriate reactions of the elements and RI{sub 3} (R=La, Pr) in sealed Nb containers at, variously, 800-990{degrees}C. The structures of three were detailed by single crystal X-ray diffraction: Pr{sub 4}I{sub 5}Ni, Pmmn, Z = 2, R(F)/R{sub w} = 3.6/5.3%; Pr{sub 3}I{sub 3}Os, P2{sub 1}/m, Z = 2, R/R{sub 2} 2.4/2.8%; Pr{sub 2}INi{sub 2}, P6{sub 3}/mmc, Z = 2, R/R{sub w} = 2.2/3.6. The new compounds La{sub 2}IZ{sub 2}, Z = Fe, Co, Ru, Os, were shown to be isostructural with Pr{sub 2}INi{sub 2}(Gd{sub 2}IFe{sub 2}) by Guinier powder diffraction. Pr{sub 4}I{sub 5}Ni, the first orthorhombic example among the R{sub 4}I{sub 5}Z series, consists of R{sub 6}Z octahedra condensed into chains. The new example contains the most extreme R:Z size proportions and clearly lacks the strong d{pi}-d{pi} bonding between Z and apical R seen within other members. Pr{sub 3}I{sub 3}Os, previously known only with a cubic Gd{sub 3}Cl{sub 3}C-(Ca{sub 3}I{sub 3}P-)-type structure, also occurs as a relatively undistorted member of the monoclinic Pr{sub 3}I{sub 3}Ru (double chain) family. Apical Pr-Os {pi}-bonding appears significant, with Pr-Os distances that are 0.24 {angstrom} shorter than the average within the waist of the parent octahedra. The R{sub 2}IZ{sub 2} phases expand the number of examples of the unusual Gd{sub 2}IFe{sub 2} structure, which contains AlB{sub 2}-like slabs; namely, graphite-like Z{sub 2} nets between eclipsed pairs of R layers that are in turn separated by single iodine layers. Notable distances in Pr{sub 2}INi{sub 2} are Ni-Ni, 2.36 {angstrom}, and Pr-Ni, 2.98 {angstrom}. Charge-consistent, extended Hueckel band calculations in La{sub 2}IFe{sub 2} (in contrast with results reported for Gd{sub 2}IFe{sub 2}) 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.

  11. 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

    2015-02-01

    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

  12. 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.

  13. Diruthenium Tetracarbonate Trianion, [RuII/III2(O2CO)4]3−, Based Molecule-Based Magnets: Three-Dimensional Network Structure and Two-Dimensional Magnetic Ordering

    SciTech Connect

    Novoa, J.; Stephens, P; Weerasekare, M; Shum, W; Miller, J

    2009-01-01

    HxK1-xMII[Ru2(CO3)4](H2O)y(MeOH)z (M = Mn, Fe, Co, Ni, Mg) were synthesized from the reaction of MII and K3[Ru2(CO3)4] in water and are isomorphous with an orthorhombic three-dimensional network structures based on e3-CO32- linkages to Ru2 moieties forming layers and also to trans-MII(OH2)4 sites forming linked chains that connect the layers. They, as well as non-isomorphous M = Cu, magnetically order as canted ferrimagnets with Tc = 4.4 {+-} 1.0 K. The presence of S = 0 MII = Mg(II) has essentially no effect on Tc suggesting that the main magnetic pathway does not occur the through MII-based chains, but only via Ru2{center_dot}...Ru2 linkages that reside in layers. This is a rare example of a magnet based upon a second row transition metal.

  14. 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.

  15. 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.

  16. The effects of grafting of 2-pyridyl to [Ru(bpy)(2)(Hpip)](2+) on acid-base and DNA-binding properties: experimental and DFT studies.

    PubMed

    Zhang, An-Guo; Yang, Huai-Xia; Yang, Ke-Zhi

    2011-06-01

    A new Ru(II) complex of [Ru(bpy)(2)(Hpip)](2+) {bpy = 2,2'bipyridine; Hppip = 2-(4-(pyridin-2-yl)phenyl)-1H-imidazo[4,5-f][1,10]phenanthroline} has been synthesized by grafting of 2-pyridyl to parent complex [Ru(bpy)(2)(Hpip)](2+) {Hppip = 2-(4-phenyl)-1H-imidazo[4,5-f][1,10]phenanthroline}. The acid-base properties of [Ru(bpy)(2)(Hpip)](2+) studied by UV-visible and luminescence spectrophotometric pH titrations, revealed off-on-off luminescence switching of [Ru(bpy)(2)(Hpip)](2+) that was driven by the protonation/deprotonation of the imidazolyl and the pyridyl moieties. The complex was demonstrated to be a DNA intercalator with an intrinsic DNA binding constant of (5.56 ± 0.2) x 10(5) M-1 in buffered 50 mM NaCl, as evidenced by UV-visible and luminescence titrations, reverse salt effect, DNA competitive binding with ethidium bromide, steady-state emission quenching by [Fe(CN)6]4-, DNA melting experiments and viscosity measurements. The density functional theory method was also used to calculate geometric/electronic structures of the complex in an effort to understand the DNA binding properties. All the studies indicated that the introduction of 2-pyridyl onto Hpip ligand is more favorable for extension of conjugate plane of the main ligand than that of phenyl, and for greatly enhanced ct-DNA binding affinity accordingly.

  17. 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.

  18. 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.

  19. 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.

  20. Superconducting and magnetic properties of Sn-doped Ru-1222

    NASA Astrophysics Data System (ADS)

    Balchev, N.; Nenkov, K.; Mihova, G.; Kunev, B.; Pirov, J.

    2007-12-01

    Samples with nominal compositions Ru1-xSnxSr2Gd1.4Ce0.6Cu2Oy (0 ⩽ x ⩽ 0.2) were synthesized and their superconducting and magnetic properties were investigated. A non-monotonic behaviour of the lattice parameters and Tc with the increase of the dopant content was observed. It was established that small doping levels (0Ru-1222 samples, prepared at the same conditions - from 20 K for the undoped sample to 35 K for the x = 0.03 one. The 0.1 ⩽ x ⩽ 0.2 samples are not superconducting, i.e. the Sn-doping more rapidly destroys the superconductivity in Ru-1222 than in the conventional superconductors. The initial increase of Tc was associated with an increase of the hole concentration. The decrease of Tc and suppression of SC at higher doping levels may be explained by an enhanced disorder in the system, due to a possible presence of Sn in both Ru and Cu sites. The latter fact could also explain that the onset of the magnetic transition Tmag weakly depends on the dopant content.

  1. Registration of 'RU9101001'/'Katy' recombinant inbred lines of rice

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The cross of RU9101001/'Katy' rice (Oryza sativa L.) was used to develop a mapping population consisting of 238 F9 generation recombinant inbred lines of rice (Oryza sativa L.) (GSOR100361 to GSOR100600). This population has been used to map major genes that provide resistance to the rice blast pat...

  2. 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.

  3. Photoacoustic characterization of n-RuSe2 semiconductor pellets

    NASA Astrophysics Data System (ADS)

    Bernal-Alvarado, J.; Vargas-Luna, M.; Solorza-Feria, O.; Mondragón, R.; Alonso-Vante, N.

    2000-09-01

    Using the open photoacoustic cell technique, a set of physical properties for a semiconductor (n-RuSe2) in powder form was measured. According to the Dramicanin theoretical model, charge carriers transport parameters (bulk and surface) and the effective thermal diffusivity were obtained.

  4. ELECTRONIC AND TRANSPORT PROPERTIES OF THERMOELECTRIC Ru2Si3

    NASA Astrophysics Data System (ADS)

    Singh, David J.; Parker, David

    2013-10-01

    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.

  5. Evaluation of the (Ba,Sr)RuO3 and (Ba,Sr)RuO3/Ru bilayer as an oxygen diffusion barrier

    NASA Astrophysics Data System (ADS)

    Park, Jeong-Hee; Hong, Duck-Hwa; Kim, Young-Bae; Choi, Duck-Kyun

    2002-06-01

    The (Ba,Sr)RuO3 (BSR) oxide electrode which can enhance electrical properties of (Ba,Sr)TiO3 (BST) dielectric film due to structural and chemical matches with BST, was evaluated as an oxygen diffusion barrier. It was possible to restrain the oxidation of TiN layer under BSR to TiO2 by sequential depositions of amorphous BSR and crystalline BSR, in which the amorphous BSR eventually crystallized into crystalline BSR during the deposition of crystalline BSR. When two-step BSR layers on TiN, however, were annealed in oxygen ambient at 700 degC, oxygen atoms diffused and oxidized TiN layer to TiO2. On the other hand, oxygen could be effectively blocked by the BSR/Ru bilayer. In this system, the Ru sublayer plays a role as an oxygen getter and the bilayer tends to block oxygen diffusion. The blocking effect was more obvious when the thickness of BSR in the bilayer increased. The BST/bilayer showed higher dielectric constant due to the suppression of formation of a low dielectric layer between BST and the bilayer. Although the BST/bilayer showed a slightly higher leakage current density, it was possible to reduce the leakage current density to 10-8 order A/cm2 at 1 V by increasing the BSR thickness in the bilayer.

  6. 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}.

  7. Suppression of ferroelectricity and quantum fluctuations in Ru-doped TbMnO3

    NASA Astrophysics Data System (ADS)

    Guo, Y. Y.; Guo, Y. J.; Zhang, N.; Lin, L.; Liu, J.-M.

    2012-01-01

    We investigate the effects of Ru-doping in polycrystalline TbMn1- x Ru x O3 ( x≤0.10) on the multiferroicity. It is observed that the Ru substitution gradually melts away the dielectric anomaly at the ferroelectric transition point and the ferroelectricity by suppressing the polarization, accompanied with a surprising low-temperature dielectric plateau. While it is reasonable to observe the significant suppression of ferroelectricity, owing to the fact that the Ru-doping disrupts the Mn spiral spin ordering and reduces the Mn-Mn spin angle, quantum fluctuations associated with the Ru substitution, responsible for the low-temperature dielectric plateau, seems to be significant.

  8. Electrochemical design of mesoporous Pt-Ru alloy films with various compositions toward superior electrocatalytic performance.

    PubMed

    Wang, Hongjing; Imura, Masataka; Nemoto, Yoshihiro; Wang, Liang; Jeong, Hu Young; Yokoshima, Tokihiko; Terasaki, Osamu; Yamauchi, Yusuke

    2012-10-01

    Mesoporous Pt-Ru alloy films with various compositions were synthesized by electrochemical plating in an aqueous surfactant solution. After the removal of surfactants, continuous mesoporous Pt-Ru alloy films possessing uniform mesopores with diameter about 7 nm were obtained. The Ru content in the films could be controlled from 0 to 13 at % by changing the precursor compositions. For all the films, the mesostructural periodicities and the mesopore sizes in the films were not changed. Due to the mesoporous structure and the doped Ru content, our mesoporous Pt-Ru films showed superior electrocatalytic activity for methanol oxidation reaction in comparison with the commercially available Pt catalyst.

  9. Monitoring of RU Peg requested for Swift observations

    NASA Astrophysics Data System (ADS)

    Waagen, Elizabeth O.

    2012-06-01

    Dr. Koji Mukai (Universities Space Research Association/NASA Goddard Space Flight Center) has requested AAVSO observers' assistance in monitoring the SS Cyg-type dwarf nova RU Peg in support of target-of-opportunity observations with the NASA Swift satellite during an outburst. His observations will be targeted during the rise to outburst and during late decline from outburst. Thus, your prompt notification to AAVSO Headquarters of activity in RU Peg will be crucial to the success of this campaign. Dr. Mukai writes: "In the famous AAVSO/EUVE/RXTE campaign on SS Cyg (Mattei et al. 2000JAVSO..28..160M), the hard X-ray flux went up (with a delay) during the rise, then suddenly dropped; there was a corresponding flux enhancement episode during the decline. We know that, during the peak of the outburst, many dwarf novae are hard X-ray fainter than in quiescence (with a few exceptions, like U Gem). However, the hard X-ray enhancement episodes seen in SS Cyg have never been obs! erved in other dwarf novae. We have proposed a hypothesis that this is related to the mass of the accreting white dwarf; only dwarf novae with a relatively massive white dwarf show the hard X-ray enhancement. If that's true, we may well see similar enhancement in RU Peg, which is thought to have a massive white dwarf. Even if this hypothesis is completely wrong, RU Peg is a good target for an SS Cyg-like campaign, since it's X-ray bright during quiescence." Visual and CCD observations (filtered preferred to unfiltered) are appropriate for this campaign. Observers are requested to monitor RU Peg duning minimum, throughout the next outburst, and after return to minimym, and report their observations in a timely manner. If RU Peg appears to be brightening from minimum, please report your observations immediately to the AAVSO. If it is brighter than magnitude 12.3, please also send an email report to Elizabeth Waagen (eowaagen@aavso.org) and Matthew Templeton (matthewt@aavso.org). Please be aware that

  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 S.; Hensley, Alyssa; 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. 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).

  12. 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).

  13. Understanding Re-Os systematics and model ages in metamorphosed Archean ultramafic rocks: A single mineral to whole-rock investigation

    NASA Astrophysics Data System (ADS)

    Coggon, Judith A.; Luguet, Ambre; Fonseca, Raúl O. C.; Lorand, Jean-Pierre; Heuser, Alexander; Appel, Peter W. U.

    2015-10-01

    187Rhenium-187Os model ages are used to infer the timing of crust-mantle differentiation events and evolution of lithospheric mantle. However, ancient samples often have long and complex histories of metamorphism, metasomatism and deformation that may be problematic if these processes caused disturbance the Re-Os system. Such processes have been shown to disturb the Re-Os systematics of ophiolitic chromitites, but the effect on stratiform chromitites has not previously been investigated. Here we present a detailed petrographic and Re-Os isotopic study of chromitites, chromite-bearing meta-peridotites and single chromite grains from the Ujaragssuit nunât layered ultramafic intrusion, southwest Greenland, which has experienced intense deformation and at least two episodes of metamorphism up to amphibolite facies. We report the first ever Re-Os isotope and platinum-group element concentration data for single chromite grains achieved by single grain dissolution and isotope dilution. Micrometric Os-, Ir-, Ru - sulphide and sulpharsenide inclusions in chromite occur in the massive chromitites; these accessory phases host a significant portion of the Os, Ir and Ru in these samples. The remaining Os-Ir-Ru budget, along with Pt and Pd, appears to be homogeneously distributed within the chromite, occurring either in the lattice itself, as evenly distributed sub-micrometric alloy inclusions in chromite (unresolvable using the techniques applied in this study) or a combination of both. Rhenium is hosted in silicates, as predicted by previous studies. Both single-grain and whole-rock Re-Os isotope systematics yield unfeasibly young Re-Os model ages due to their radiogenic 187Os/188Os compositions. This could result from country rock contamination of the original melt from which the Ujaragssuit nunât intrusion crystallised, and/or from disturbance of the Re-Os isotope systematics of these rocks during regional metamorphic events at ∼2.8 and/or ∼3.75 Ga. We conclude that it

  14. Hoechst reportedly stalls RU-486 in U.S.

    PubMed

    1994-05-16

    President Clinton's administration would like RU-486 to be widely available in the US, but its manufacturer has been procrastinating about introducing RU-486 in the US. President Clinton lifted the ban on it shortly after ascending to the presidency. After 13 months of negotiations, the parent company of Roussel Uclaf, Hoechst, blocked efforts. It appears to be thwarting Ru-486's manufacture in the US because it fears that antiabortion groups will boycott its other products (textiles, rug fibers, and drugs for diabetics and heart patients). Its annual sales in the US are $7 billion. In April, 1993, Roussel Uclaf said that it would transfer its patent to the Population Council. The Council agreed to perform the clinical trials required to obtain US Food and Drug Administration approval and to find a domestic manufacturer to produce RU-486. Before handing the patent over to the Population Council, Hoechst wants protection from potential product liability or losses from antiabortion protests. US Health and Human Services officials have been trying to promote progress in the negotiations between the Population Council and Hoechst. A US member of Congress has set up a subcommittee hearing to look into the delays, specifically Hoechst's role in the delays. Women's groups want US women to have access to an alternative to surgical abortion. If progress is not made soon, they intend to push the government to revoke Roussel Uclaf's patent or support development of a similar drug. They stress that Hoechst's actions, be they for economic or political reasons, have slowed medical research and have hurt women's well being. RU-486 can also be used to treat breast cancer, some brain tumors, and other diseases. PMID:12318854

  15. Mechanism of RuO2 crystallization in borosilicate glass: an original in situ ESEM approach.

    PubMed

    Boucetta, Hassiba; Podor, Renaud; Stievano, Lorenzo; Ravaux, Johann; Carrier, Xavier; Casale, Sandra; Gossé, Stéphane; Monteiro, Amélie; Schuller, Sophie

    2012-03-19

    Ruthenium, a fission product arising from the reprocessing of spent uranium oxide (UOX) fuel, crystallizes in the form of acicular RuO(2) particles in high-level waste containment glass matrices. These particles are responsible for significant modifications in the physicochemical behavior of the glass in the liquid state, and their formation mechanisms are a subject of investigation. The chemical reactions responsible for the crystallization of RuO(2) particles with acicular or polyhedral shape in simplified radioactive waste containment glass are described. In situ high-temperature environmental scanning electron microscopy (ESEM) is used to follow changes in morphology and composition of the ruthenium compounds formed by reactions at high temperature between a simplified RuO(2)-NaNO(3) precursor and a sodium borosilicate glass (SiO(2)-B(2)O(3)-Na(2)O). The key parameter in the formation of acicular or polyhedral RuO(2) crystals is the chemistry of the ruthenium compound under oxidized conditions (Ru(IV), Ru(V)). The precipitation of needle-shaped RuO(2) crystals in the melt might be associated with the formation of an intermediate Ru compound (Na(3)Ru(V)O(4)) before dissolution in the melt, allowing Ru concentration gradients. The formation of polyhedral crystals is the result of the direct incorporation of RuO(2) crystals in the melt followed by an Ostwald ripening mechanism.

  16. 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.

  17. Magnetic and magnetocaloric properties of Ba and Ti co-doped SrRuO3

    NASA Astrophysics Data System (ADS)

    Sarkar, Babusona; Dalal, Biswajit; Dev Ashok, Vishal; De, S. K.

    2014-12-01

    Temperature evolution of magnetic properties in Ba and Ti doped SrRuO3 has been investigated to observe the effects of larger ionic radius Ba at Sr site and isovalent nonmagnetic impurity Ti at Ru site. Ionic radius mismatch and different electronic configuration in comparison with Ru modify Sr(Ba)-O and Ru(Ti)-O bond lengths and Ru-O-Ru bond angle. The apical and basal Ru-O-Ru bond angles vary significantly with Ti doping. Ferromagnetic Curie temperature decreases from 161 K to 149 K monotonically with Ba (10%) and Ti (10%) substitutions at Sr and Ru sites. The zero field cooled (ZFC) magnetization reveals a prominent peak which shifts towards lower temperature with application of magnetic field. The substitution of tetravalent Ti with localized 3d0 orbitals for Ru with more delocalized 4d4 orbitals leads to a broad peak in ZFC magnetization. A spontaneous ZFC magnetization becomes negative below 160 K for all the compositions. The occurrence of both normal and inverse magnetocaloric effects in Ba and Ti co-doped SrRuO3 makes the system more interesting.

  18. Enhancement of Curie temperature in Mn2RuSn by Co substitution

    NASA Astrophysics Data System (ADS)

    Nelson, A.; Kharel, P.; Huh, Y.; Fuglsby, R.; Guenther, J.; Zhang, W.; Staten, B.; Lukashev, P.; Valloppilly, S.; Sellmyer, D. J.

    2015-04-01

    The Co-substituted Mn2RuSn nanomaterials, namely, Mn2Ru0.5Co0.5Sn and Mn2Ru0.35Co0.65Sn have been synthesized and investigated. The presence of Co in the Mn2RuSn (a = 6.21 Å) decreased the lattice parameter, where a = 6.14 Å and 6.12 Å for the as prepared Mn2Ru0.5Co0.5Sn and Mn2Ru0.35Co0.65Sn, respectively. The samples show a ferrimagnetic spin order with relatively small coercivities, similar to those of soft magnetic materials. There is a substantial increase in the Curie temperature (Tc = 448 K for Mn2Ru0.5Co0.5Sn and 506 K for Mn2Ru0.35Co0.65Sn) of Mn2RuSn (Tc = 272.1 K) due to Co substitution, which is a result of strengthening of the positive exchange interaction in this material. These materials are highly stable against heat treatment of up to 450 °C. The first-principles calculations are consistent with our experimentally observed structural and magnetic properties. They also provide insight on how the magnetic and electronic structures change when Ru is replaced with Co in Mn2RuSn.

  19. Preparation and optimization of RuO 2-impregnated SnO 2 xerogel supercapacitor

    NASA Astrophysics Data System (ADS)

    Wu, Nae-Lih; Kuo, Shin-Liang; Lee, Ming-Hsueh

    A Sb (6 mol%)-doped SnO 2 xerogel impregnated with RuO 2 nanocrystallites is prepared via an incipient-wetness method and is optimized for its electrochemical capacitance in aqueous 1 M KOH electrolyte by adjusting the calcination temperature and the RuO 2 loading. The electrode capacitance does not increase monotonically with increasing RuO 2 loading. A maximum electrode capacitance of 15 F g -1, which represents a three-fold increase compared with the blank xerogel and a specific RuO 2 capacitance of 710 F g -1 RuO 2, is obtained with a RuO 2 loading of 1.4 wt.% and by calcination at 200 °C. Higher loadings presumably result in a homogeneous nucleation upon drying, which causes severe reduction in the total surface area of the RuO 2 crystallites.

  20. 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

    2016-01-01

    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

  1. 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

    2016-01-01

    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

  2. Bulk magnetic measurements and Ru99 and Gd155 Mössbauer spectroscopies of Gd2Ru2O7

    NASA Astrophysics Data System (ADS)

    Gurgul, J.; Rams, M.; Świątkowska, Ż.; Kmieć, R.; Tomala, K.

    2007-02-01

    Bulk magnetic measurements and Ru99 and Gd155 Mössbauer effect investigations were performed to examine magnetic properties of the gadolinium pyrochlore ruthenate Gd2Ru2O7 . A magnetic transition to the antiferromagnetic state at TN=114(1)K is accompanied by a small difference between field-cooled and zero-field-cooled magnetic susceptibilities. Ru99 and Gd155 Mössbauer effect investigations at 4.2K confirmed that both ruthenium and gadolinium sublattices are magnetically ordered. Successful analysis of each spectrum with one set of hyperfine parameters proves that all ruthenium moments have the same magnitude and form the same angle with the local three-fold symmetry axes. The same conclusion concerns Gd magnetic moments. The measured temperature dependence of the hyperfine field at Gd site, together with the molecular-field model, points to the fact that Gd moments also order at TN , with tiny magnetic moments due to Gd-Ru exchange interaction.

  3. The electronic structure and spectra of Ru(II) and Ru(III) complexes with imidazole and its derivatives

    NASA Astrophysics Data System (ADS)

    Rogachevsky, I. V.; Baranovski, V. I.

    2000-12-01

    The calculations of the electronic structure and spectra of [Ru(NH 3) 5L] 2+ (L=imidazole, histidine) and [Ru(NH 3) 5L] 3+ (L=imidazole, N-imidazolate anion, 4-methylimidazole, 4-methyl-1 N-imidazolate anion and 1 N-bound histidine) complexes are performed in the framework of the CI method in the INDO/CNDO approximation. The MO diagram is obtained. The assignment of all transitions with energies of 4-5 eV is made and the nature of corresponding excited states is discussed. For the Ru(II) complexes, the lower energy observable transition is assigned to d→π* type, whereas the higher energy one is assigned to π→π* type. In the spectra of the Ru(III) complexes with charged ligands both transitions are of π→d character, while in the case of uncharged ligands, the higher energy transition mostly incorporates π→π* excitations.

  4. 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.

  5. Synthesis of Pd9Ru@Pt nanoparticles for oxygen reduction reaction in acidic electrolytes

    NASA Astrophysics Data System (ADS)

    Sun, Yu; Hsieh, Yu-Chi; Chang, Li-Chung; Wu, Pu-Wei; Lee, Jyh-Fu

    2015-03-01

    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 successful 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 0.1 M aqueous HClO4 solution. Subsequently, the Pd9Ru/C undergoes 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-1Pt, as compared to that of commercially available Pt nanoparticles (0.107 mA μg-1Pt). 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.

  6. Synthesis of Pd9Ru@Pt nanoparticles for oxygen reduction reaction in acidic electrolytes

    DOE PAGESBeta

    Sun, Yu; Hsieh, Yu -Chi; Chang, Li -Chung; Wu, Pu -Wei; Lee, Jyh -Fu

    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

  7. Photoelectrocatalytic study of water oxidation at n-RuS{sub 2} electrodes

    SciTech Connect

    Salvador, P.; Alonso-Vante, N.; Tributsch, H.

    1998-01-01

    A kinetic study of the photocatalytic oxidation of water at a n-RuS{sub 2} semiconducting single crystal has been undertaken on the basis of photocurrent transients (photocurrent-time behavior as a function of the polarization potential, illumination intensity, and temperature) and electrolyte electroreflectance experiments. The main factor defining the catalytic activity of RuS{sub 2} for water oxidation, both in the dark and under illumination, is a low overpotential ({eta} {approx} 0.3 V), which is comparable to that of the RuO{sub 2} catalyst for oxygen evolution at darkness. Evidence has been given that {eta} is determined by the E{sup o}(Ru{sub s}-OH{sup 0}/Ru{sub s}-H{sub 2}O) redox potential, which strongly depends on the bonding energy of Ru surface species with OH{sup o} radicals generated by direct oxidation of adsorbed water molecules (interfacial Ru-peroxo-type complex formation). This bonding energy increases as the RuS{sub 2} surface becomes oxidized under anodic polarization and reaches its maximum value at the potential of the S{sub 2}RuO{sub 2}/RuS{sub 2} transition (VIII Ru oxidation state). Further oxidation of the Ru-peroxo-type complexes leads to oxygen evolution at a rate which increases with the degree of oxidation of the Ru surface active centers. Although O{sub 2} evolution probably already takes place on Ru(VI) surface sites, high evolution rates (current densities) are only reached under oxidation state VIII. However, in this state (idealized S{sub 2}Ru(VIII)O{sub 2}) Ru-S surface bonds are weakened and occasionally broken, contributing to RuS{sub 2} dissolution with generation of volatile RuO{sub 4} and SO{sub 4}{sup 2{minus}} soluble ions as the main corrosion products. This phenomenon may be attributed to the reaction in acidic medium of H{sub 2}O molecules with Ru(VIII) surface species, giving rise to the formation of unstable intermediate complexes.

  8. Enhanced antiferromagnetic coupling in dual-synthetic antiferromagnet with Co2FeAl electrodes

    NASA Astrophysics Data System (ADS)

    Zhang, D. L.; Xu, X. G.; Wu, Y.; Li, X. Q.; Miao, J.; Jiang, Y.

    2012-05-01

    We study dual-synthetic antiferromagnets (DSyAFs) using Co2FeAl (CFA) Heusler electrodes with a stack structure of Ta/CFA/Ru/CFA/Ru/CFA/Ta. When the thicknesses of the two Ru layers are 0.45 nm, 0.65 nm or 0.45 nm, 1.00 nm, the CFA-based DSyAF has a strong antiferromagnetic coupling between adjacent CFA layers at room temperature with a saturation magnetic field of ∼11,000 Oe, a saturation magnetization of ∼710 emu/cm3 and a coercivity of ∼2.0 Oe. Moreover, the DSyAF has a good thermal stability up to 400 °C, at which CFA films show B2-ordered structure. Therefore, the CFA-based DSyAFs are favorable for applications in future spintronic devices.

  9. A search for FeH in M and S giants

    NASA Technical Reports Server (NTRS)

    Davis-Locanthi, D.

    1980-01-01

    The strongest lines of FeH in the visible spectrum fall in the domain of TiO and ZrO bands. Analysis exists for TiO, but nothing is yet available for the weak but important ZrO lines. Using plate measurements and microphotometer tracings, high dispersion spectra of the following cool stars have been searched for FeH lines: Beta Peg, Mu UMa, Alpha Her, Omicron Cet, Chi Cyg, HR 105, HR 8714, R And, R Cyg, R Cam, T Sgr, R CMi, Cy Cyg, and RU Cam. The strongest FeH lines are unimpressive in R Cyg, where the strong infrared bands of FeH have already been identified. Identification of the blue-green FeH lines in other spectra must be considered inconclusive until a rotational analysis of the FeH spectrum is available.

  10. Multitasking scheduler works without OS

    SciTech Connect

    Howard, D.M.

    1982-09-15

    Z80 control applications requiring parallel execution of multiple software tasks can use the executive routine described and listed in this article when multitasking is not available via an operating system (OS). Although the routine is not as capable or as transparent to software as the multitasking in a full-scale OS, it is simple to understand and use.

  11. First principles studies of the oxygen reduction reaction on Se-Ru nanostructures

    NASA Astrophysics Data System (ADS)

    Zuluaga, Sebastian; Stolbov, Sergey

    2011-03-01

    Experiments show an enhanced rate of the oxygen reduction reaction (ORR) on Se-Ru nanostructures (NS) in hydrogen fuel cell cathodes. We use first principles methods to study Ru and Se-Ru NS of approximate 1.2 nm size and shine some light on how the Se affects the O and OH adsorption, which is the bottle neck of the power delivered by the fuel cell. Experiments shows that the Se-Ru NS have a Ru core but is not clear how the Se is distributed on the surface. Our calculation shows that the Se atom adsorbs on the Ru surface with a binding energies in the range 5.7 to 7.1 eV with electronic charge transfer from the Ru atoms. Due to repulsion between negatively charged Se atoms, they tend to spread uniformly over the the Ru NS rather than form islands on its surface. We have also found that, in contrast to the flat Ru surface, the Se bond to the low coordinated Ru atoms have significant covalent component. Our calculation shows how the presence of Se atoms affects the adsorption of the ORR intermediates on the NS. In particular, we show that the electrostatic repulsion between charged Se and O or OH reduces the binding energy of the latters.

  12. Structures, stabilities, and magnetic properties of CoRu binary clusters

    NASA Astrophysics Data System (ADS)

    Sun, Yue-mei; Yan, Xiao-hong

    2015-01-01

    The geometries, stabilities, and magnetic properties of binary clusters CoN-mRum (N = 2-13, m = 1-5) are explored by density functional theory calculations. The ground-state structures of CoN-mRum alloy clusters are similar to those of corresponding pure CoN or RuN clusters, except for Co3Ru, Co2Ru2, and Co6Ru. Calculations show that when one Co atom is replaced by one Ru atom, the total magnetic moments of the CoN-1Ru (N = 2-13) clusters do not dramatically change and only deviate from those of pure CoN clusters by ±1 μB. On the other hand, when the number of doped Ru atoms is increased to 3, the calculated magnetic moments of CoN-mRum (N = 4-6) clusters sharply decrease. The partial density of states analysis demonstrates that the formation of Ru-Ru bond weakens the spin exchange splitting effect of Ru atoms and thus reduces the magnetism of clusters.

  13. 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.

  14. 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.

  15. Nanoscale variations in 187Os isotopic composition and HSE systematics in a Bultfontein peridotite

    NASA Astrophysics Data System (ADS)

    Wainwright, A. N.; Luguet, A.; Schreiber, A.; Fonseca, R. O. C.; Nowell, G. M.; Lorand, J.-P.; Wirth, R.; Janney, P. E.

    2016-08-01

    Understanding the mineralogical controls on radiogenic chronometers is a fundamental aspect of all geochronological tools. As with other common dating tools, it has become increasingly clear that the Re-Os system can be impacted by multiple mineral formation events. The accessory and micrometric nature of the Re-Os-bearing minerals has made assessing this influence complex. This is especially evident in cratonic peridotites, where long residence times and multiple metasomatic events have created a complex melting and re-enrichment history. Here we investigate a harzburgitic peridotite from the Bultfontein kimberlite (South Africa) which contains sub-micron Pt-Fe-alloy inclusions within base metal sulphides (BMS). Through the combination of the focused ion beam lift-out technique and low blank mass spectrometry we were able to remove and analyse the Pt-Fe-alloy inclusions for their Re-Os composition and highly siderophile element (HSE) systematics. Six repeats of the whole-rock yield 187Os/188Os compositions of 0.10893-0.10965, which correspond to Re depletion model ages (TRD) of 2.69-2.79 Ga. The Os, Ir and Pt concentrations are slightly variable across the different digestions, whilst Pd and Re remain constant. The resulting HSE pattern is typical of cratonic peridotites displaying depleted Pt and Pd. The Pt-Fe-alloys have PUM-like 187Os/188Os compositions of 0.1294 ± 24 (2-s.d.) and 0.1342 ± 38, and exhibit a saw-tooth HSE pattern with enriched Re and Pt. In contrast, their BMS hosts have unradiogenic 187Os/188Os of 0.1084 ± 6 and 0.1066 ± 3, with TRD ages of 2.86 and 3.09 Ga, similar to the whole-rock systematics. The metasomatic origin of the BMS is supported by (i) the highly depleted nature of the mantle peridotite and (ii) their Ni-rich sulphide assemblage. Occurrence of Pt-Fe-alloys as inclusions within BMS grains demonstrates the genetic link between the BMS and Pt-Fe-alloys and argues for formation during a single but continuous event of silicate melt

  16. Nuclear resonant scattering of synchrotron radiation by 187Os

    NASA Astrophysics Data System (ADS)

    Bessas, D.; Sergueev, I.; Merkel, D. G.; Chumakov, A. I.; Rüffer, R.; Jafari, A.; Kishimoto, S.; Wolny, J. A.; Schünemann, V.; Needham, R. J.; Sadler, P. J.; Hermann, R. P.

    2015-06-01

    We performed nuclear forward and inelastic scattering of synchrotron radiation by elemental Os utilizing the nuclear excited state of 187Os which is otherwise inaccessible using any practical radioactive decay process. The lifetime of the excited state, 3.06 (8 )ns , and the energy of the transition, 9.778 (3 )keV , are refined. The nuclear quadrupole moment of the excited state, Q3 /2=1.46 (10 ) b , is determined. The density of phonon states for elemental Os, which is herein experimentally determined, suggests that the Os lattice is a model for the lattice dynamics of hcp-Fe. The combination of the low energy of the nuclear transition and the large nuclear mass leads to a high recoil free fraction, fL M=0.95 (1 ) , at room temperature, a large value that strongly supports the viability of nuclear resonance scattering as a reliable method to study electronic, magnetic, and elastic properties of Os compounds, including Os organometallics.

  17. OsABCB14 functions in auxin transport and iron homeostasis in rice (Oryza sativa L.).

    PubMed

    Xu, Yanxia; Zhang, Saina; Guo, Haipeng; Wang, Suikang; Xu, Ligen; Li, Chuanyou; Qian, Qian; Chen, Fan; Geisler, Markus; Qi, Yanhua; Jiang, De An

    2014-07-01

    Members of the ATP Binding Cassette B/Multidrug-Resistance/P-glyco-protein (ABCB/MDR/PGP) subfamily were shown to function primarily in Oryza sativa (rice) auxin transport; however, none of the rice ABCB transporters have been functionally characterized. Here, we describe that a knock-down of OsABCB14 confers decreased auxin concentrations and polar auxin transport rates, conferring insensitivity to 2,4-dichlorophenoxyacetic acid (2,4-D) and indole-3-acetic acid (IAA). OsABCB14 displays enhanced specific auxin influx activity in yeast and protoplasts prepared from rice knock-down alleles. OsABCB14 is localized at the plasma membrane, pointing to an important directionality under physiological conditions. osabcb14 mutants were surprisingly found to be insensitive to iron deficiency treatment (-Fe). Their Fe concentration is higher and upregulation of Fe deficiency-responsive genes is lower in osabcb14 mutants than in wild-type rice (Nipponbare, NIP). Taken together, our results strongly support the role of OsABCB14 as an auxin influx transporter involved in Fe homeostasis. The functional characterization of OsABCB14 provides insights in monocot auxin transport and its relationship to Fe nutrition.

  18. Evidence for Chiral Doublet Bands in 110,112Ru

    NASA Astrophysics Data System (ADS)

    Luo, Y. X.; Zhu, S. J.; Hamilton, J. H.; Rasmussen, J. O.; Ramayya, A. V.; Goodin, C.; Li, K.; Hwang, J. K.; Che, X. L.; Jang, Z.; Frauendorf, S.; Dimitrov, V.; Zhang, Jing-Ye; Stefanescu, I.; Gelberg, A.; Ter-Akopian, G. M.; Daniel, A. V.; Stoyer, M. A.; Donangelo, R.; Cole, J. D.; Stone, N. J.

    2008-08-01

    From γ-γ-γ coincidence studies of prompt γ rays in the spontaneous fission from 252Cf with Gammasphere, two sets of ΔI = 1 doublet bands assigned odd-parities were identified in 108,110,112Ru. γ-γ (θ) angular correlation data were analyzed to assign multipolarities of the depopulating transitions and spins of the bandheads. The above assignments and the decay pattern of the levels uniquely support the odd-parity assignment of the doublet bands. By checking characteristic conditions for generating chiral symmetry breaking and the fingerprints as expected for observations of chiral doublet bands in the nuclei, and based on the Tilted Axis Cranking calculations, the Δ I = 1 odd-parity doublet bands identified in 110,112Ru are assigned zero and one phonon chiral vibration bands built on υ h11/2 × (d5/2g7/2)-1 configuration.

  19. Superconductivity in Ru-BASED Cuprate Ru(Sr1.5Ca0.5)PbCu2O8 Prepared by Sol-Gel Route

    NASA Astrophysics Data System (ADS)

    Yeoh, L. M.; Ahmad, M.; Abd-Shukor, R.

    Pb containing ruthenium-based superconducting cuprates Ru(Sr1.5Ca0.5)PbCu2O8 (Ru-1212 type) have been successfully synthesized through the sol-gel route. The optimum annealing temperature for the ruthenium-based cuprate superconductor was found to be 890°C. The crystal structure determined by X-ray powder diffraction method showed a single Ru-1212 type phase with tetragonal symmetry with lattice parameters a = b = 3.920 Å, and c = 11.76 Å. The Ru(Sr1.5Ca0.5)PbCu2O8 material showed onset temperature, Tc-onset at 35 K and zero resistant temperature, Tc-zero at 20 K. Pb together with the partial substitution of Sr with Ca lowered the formation temperature of the Ru-1212 type phase.

  20. Was photosynthetic RuBisCO recruited by acquisitive evolution from RuBisCO-like proteins involved in sulfur metabolism?

    PubMed

    Ashida, Hiroki; Danchin, Antoine; Yokota, Akiho

    2005-01-01

    Genome analyses have revealed that the genomes of non-photosynthetic bacteria including Bacillus subtilis code for proteins similar to the large subunit of RuBisCO (called RuBisCO-like protein (RLP)). This raises a fundamental question as to their functional relationship to photosynthetic RuBisCO. Recently, we identified the RLP of B. subtilis as the 2,3-diketo-5-methylthiopentyl-1-phosphate enolase in the methionine salvage pathway. In this mini-review, we suggest functional and evolutionary links between B. subtilis RLP and photosynthetic RuBisCO. Furthermore, we propose that photosynthetic RuBisCOs evolved from RLPs similar to that found in B. subtilis.

  1. RU-486 hits snags in U.K.

    PubMed

    Diconsiglio, J M

    1992-01-01

    With over 2 years in clinical trials and 1500 uses of RU-486, family planning leaders have claimed that RU-486 is not going to be as popular as it has promised. In France, 25% of the women who are eligible to use it do. The problem is that the public perception of the abortion bill is that you take and call the doctor in the morning. However, in actual use, it is more expensive and requires more time in the clinic than a vacuum abortion. There are also restrictions on its use. Women over 35 or who smoke heavily are not recommended to use it. It is also illegal to use after the 63rd day of pregnancy because of diminished effectiveness and increased risk of complication. Its complication rate is 1-2% which is equal to vacuum abortions. When polled women have said that they like RU-486 because it is not invasive, does not require anesthesia, and feels more natural. The pill requires 4 visits and about 9 hours of time in the clinic compared to 2 visits and 6 hours for a vacuum abortion. The 1st visits is to determine if a women qualifies to use it. Then she returns a 2nd time to have the drug administered, after which she must remain at the clinic for 2 hours to be monitored for side effects like nausea. 48 hours later she must return to have a dosage of prostaglandins which cause the uterus to contract. The women will then miscarry in 4 to 6 hours. The 4th visit is compulsory because up to 30% of women will not miscarry, although they are confident that this figure will decrease as physicians acquire more experience using it. The cost will be between 40-70L higher than vacuum abortions. It is predicted that when the extra time and money are factored into the decision, most women will choose vacuum abortion over RU-486. PMID:12317119

  2. {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.

  3. Thermal fragmentation of acyl thiolato complexes to reactive metal sulfido intermediates. Structure of Ru([eta][sup 6]-SC[sub 3]Me[sub 3]COMe)(PPh[sub 3])[sub 2

    SciTech Connect

    Feng, Q.; Krautscheid, H.; Rauchfuss, T.B.; Skaugset, A.E.; Venturelli, A. )

    1995-01-01

    In this study we have examined the thermal fragmentation of acyl thiolate complexes of the type (ring)M(SC[sub 3]Me[sub 3]COMe). While the (cymene)Ru derivative only gave insoluble materials, the thermolysis of the corresponding osmium compound, (cymene)Os(SC[sub 3]Me[sub 3]COMe) (2), proved very informative. Here it was established that the tetramethylfuran is indeed released prior to formation of the free cymene. Furthermore, two intermediates were observed, the second of which was identified as (cymene)[sub 3]Os[sub 3]S[sub 2]. This species is more stable with respect to loss of cymene than the corresponding (cymene)[sub 3]Ru[sub 3]S[sub 2]. Attempts were made to intercept intermediates in these fragmentation processes by employing PPh[sub 3] as a trapping agent. For the Ru case, PPh[sub 3] completely changed the course of the reaction and no tetramethylfuran was generated. Instead we obtained the structurally unusual [eta][sup 6]-acyl thiolate complex (5). We propose that this unimolecular step involves the formation of ([eta][sup 4]-cymene)Ru([eta][sup 6]-SC[sub 3]Me[sub 3]COMe). The forward rate for this equilibration is far slower than the rate of isomerization of the acyl thiolate and far faster than that for the unassisted thermal decomposition of (cymene)Ru(SC[sub 3]MesCOMe). This result leads to a more global assessment of the reactivity of the acyl thiolates: the orientation of the carbonyl center determines the decomposition pathway. 21 refs., 7 figs., 1 tab.

  4. Aluminum thin film growth on a Ru(0001) surface

    NASA Astrophysics Data System (ADS)

    Ceballos, G.; Theis, M.; Pelzer, Th.; Schick, M.; Rangelov, G.; Wandelt, K.

    1995-07-01

    The growth of thin Al films on a Ru(0001) substrate has been investigated by means of AES, LEED, TDS, and PAX measurements. A plot of the Ru and Al AES intensities versus evaporation time for a deposition temperature of 300 K reveals a distinct break at θAl = 1, while for higher coverages the Ru intensity decays exponentially indicating a three-dimensional growth of Al clusters. From this behavior we deduce a Stranski-Krastanov growth mechanism. This behavior persists up to 650 K. For higher deposition temperatures a diffusion of Al into the substrate and a partial desorption of the Al film is found. At low Al coverage the LEED pattern reveals an initial film growth with Al(111) structure and an expansion of the interatomic spacing of 2% compared to the Al(111) bulk plane. This superstructure persisted up to ˜ 2.5 ML. In the submonolayer regime CO and Xe TD-spectra as well as Xe 4d PAX-spectra suggest together with LEED an island growth.

  5. OsWRKY74, a WRKY transcription factor, modulates tolerance to phosphate starvation in rice

    PubMed Central

    Dai, Xiaoyan; Wang, Yuanyuan; Zhang, Wen-Hao

    2016-01-01

    The WRKY transcription factor family has 109 members in the rice genome, and has been reported to be involved in the regulation of biotic and abiotic stress in plants. Here, we demonstrated that a rice OsWRKY74 belonging to group III of the WRKY transcription factor family was involved in tolerance to phosphate (Pi) starvation. OsWRKY74 was localized in the nucleus and mainly expressed in roots and leaves. Overexpression of OsWRKY74 significantly enhanced tolerance to Pi starvation, whereas transgenic lines with down-regulation of OsWRKY74 were sensitive to Pi starvation. Root and shoot biomass, and phosphorus (P) concentration in rice OsWRKY74-overexpressing plants were ~16% higher than those of wild-type (WT) plants in Pi-deficient hydroponic solution. In soil pot experiments, >24% increases in tiller number, grain weight and P concentration were observed in rice OsWRKY74-overexpressing plants compared to WT plants when grown in P-deficient medium. Furthermore, Pi starvation-induced changes in root system architecture were more profound in OsWRKY74-overexpressing plants than in WT plants. Expression patterns of a number of Pi-responsive genes were altered in the OsWRKY74-overexpressing and RNA interference lines. In addition, OsWRKY74 may also be involved in the response to deficiencies in iron (Fe) and nitrogen (N) as well as cold stress in rice. In Pi-deficient conditions, OsWRKY74-overexpressing plants exhibited greater accumulation of Fe and up-regulation of the cold-responsive genes than WT plants. These findings highlight the role of OsWRKY74 in modulation of Pi homeostasis and potential crosstalk between P starvation and Fe starvation, and cold stress in rice. PMID:26663563

  6. Ruthenocuprates RuSr2(Eu,Ce)2Cu2O10-y: Intrinsic magnetic multilayers

    NASA Astrophysics Data System (ADS)

    Živković, I.; Hirai, Y.; Frazer, B. H.; Prester, M.; Drobac, D.; Ariosa, D.; Berger, H.; Pavuna, D.; Margaritondo, G.; Felner, I.; Onellion, M.

    2002-04-01

    We report ac susceptibility data on RuSr2(Eu,Ce)2Cu2O10-y (Ru-1222, Ce content x=0.5 and 1.0), RuSr2GdCu2O8 (Ru-1212), and SrRuO3. Both Ru-1222 (x=0.5, 1.0) sample types exhibit unexpected magnetic dynamics in low magnetic fields: logarithmic time relaxation, switching behavior, and ``inverted'' hysteresis loops. Neither Ru-1212 nor SrRuO3 exhibit such magnetic dynamics. The results are interpreted as evidence of the complex magnetic order in Ru-1222. We propose a specific multilayer model to explain the data, and note that superconductivity in the ruthenocuprate is compatible with both the presence and absence of the magnetic dynamics.

  7. Size-controlled synthesis of thermal stable single-cored Ru@H-SiO2 core-shell nanoparticles

    NASA Astrophysics Data System (ADS)

    Yu, Xiaolong; Yu, Hongbo; Lim, Zi-Yian; Yang, Guangming; Xie, Zhaohui; Zhou, Shenghu; Yin, Hongfeng

    2016-06-01

    Single-cored Ru@H-SiO2 (H: hollow) core-shell nanoparticles (NPs) with around 4.3 nm Ru cores and hollow SiO2 shells were prepared successfully. In this synthetic process, we obtained multi-cored Ru@SiO2 NPs initially, single-cored RuO2@H-SiO2 NPs during treatment, and single-cored Ru@H-SiO2 NPs in the end. The Ru@SiO2 NPs were prepared by water-in-oil microemulsion method, and the size and core number of Ru@SiO2 NPs can be controlled. Single-cored RuO2@H-SiO2 NPs and Ru@H-SiO2 NPs were successively obtained by calcination and reduction. The structure showed promising aggregate-resistant performance and potential application in catalysis.

  8. New-Type Phase Transition of Li2RuO3 with Honeycomb Structure

    NASA Astrophysics Data System (ADS)

    Miura, Yoko; Yasui, Yukio; Sato, Masatoshi; Igawa, Naoki; Kakurai, Kazuhisa

    2007-03-01

    A new-type structural transition has been found in Li2RuO3 with a honeycomb lattice of edge-sharing RuO6 octahedra. With decreasing temperature T, the electrical resistivity exhibits an anomalous increase at T=Tc ˜ 540 K, suggesting the (metal-to-insulator)-like transition, and the magnetic susceptibility also shows a sharp decrease. Detailed structure analyses have revealed that the high-temperature space group C2/m changes to P21/m at Tc. The most striking fact is that a significant reduction of the bond lengths is found between two of the six Ru-Ru pairs of the hexagon in the low-temperature phase, indicating a new-type phase transition driven by the formation of the molecular orbits of these Ru-Ru pairs.

  9. Dimerization Induced Deprotonation of Water on RuO2(110)

    SciTech Connect

    Mu, Rentao; Cantu Cantu, David; Lin, Xiao; Glezakou, Vassiliki Alexandra; Wang, Zhitao; Lyubinetsky, Igor; Rousseau, Roger J.; Dohnalek, Zdenek

    2014-10-02

    RuO2 has proven to be indispensable as a co-catalyst in numerous systems designed for photocatalytic water splitting. In this study we have carried out a detailed mechanistic study of water behavior on the most stable RuO2 face, RuO2(110), by employing variable temperature scanning tunneling microscopy and density functional theory calculations. We show that water monomers adsorb molecularly on Ru sites, become mobile above 238 K, diffuse along the Ru rows and form water dimers. The onset for dimer diffusion is observed at ~277 K indicating significantly higher diffusion barrier than that for monomers. More importantly, we find that water dimers deprotonate readily to form Ru-bound H3O2 and bridging OH species. The observed behavior is compared and contrasted with that observed for water on isostructural rutile TiO2(110).

  10. Fractionation of Highly Siderophile Elements in Refertilized Mantle: Implications for the Os Isotope Composition of Basalts

    NASA Astrophysics Data System (ADS)

    Marchesi, C.; Dale, C. W.; Garrido, C. J.; Pearson, D. G.; Bosch, D.; Bodinier, J. L.; Gervilla, F.; Hidas, K.

    2014-12-01

    Highly fertile lherzolite and spinel websterite in the Ronda peridotite massif are enriched in Pt and Pd compared to Os, Ir, Ru and Re. The fractionation of the highly siderophile elements (HSE) in these rocks was produced by reaction of melt with their peridotite and pyroxenite precursors. Modelling indicates that upon reaction primary HSE hosts were dissolved and magmatic sulphides precipitated, largely erasing the original HSE signature of reacting protoliths. The budget of HSE in the melt was controlled by sulphide-silicate partitioning or entrainment of molten sulphide in silicate melt. Rhenium was likely removed from precursor peridotite and pyroxenite by previous melt extraction. Refertilization of peridotite by melts increased Al2O3, CaO, Pt, Pd contents and 187Os/188Os beyond typical values for mantle peridotite and the primitive upper mantle. The interaction of melts with residual peridotite and pyroxenite, as illustrated in the Ronda massif, can generate radiogenic-Os-enriched domains in the mantle with high melt productivity, higher Pt/Os and Pt/Re than common peridotite, and lower Re/Os than typical pyroxenite. As also previously proposed for pyroxenites, these "hybrid" domains can account for the difference in Os isotope compositions between many basalts (e.g., MORB and OIB) and common depleted mantle peridotites. Moreover, the presence of these enriched hybrid components in the mantle, evolved over sufficient timescales and in geologically reasonable proportions, may account for the 186Os-187Os enrichment of plume lavas without requiring a chemical contribution from the core.

  11. Fractionation of highly siderophile elements in refertilized mantle: Implications for the Os isotope composition of basalts

    NASA Astrophysics Data System (ADS)

    Marchesi, Claudio; Dale, Christopher W.; Garrido, Carlos J.; Pearson, D. Graham; Bosch, Delphine; Bodinier, Jean-Louis; Gervilla, Fernando; Hidas, Károly

    2014-08-01

    Highly fertile lherzolite and spinel websterite in the Ronda peridotite massif are enriched in Pt and Pd compared to Os, Ir, Ru and Re. The fractionation of the highly siderophile elements (HSE) in these rocks was produced by reaction of melt with their peridotite and pyroxenite precursors. Modeling indicates that upon reaction primary HSE hosts were dissolved and magmatic sulphides precipitated, largely erasing the original HSE signature of reacting protoliths. The budget of HSE in the melt was controlled by sulphide-silicate partitioning or entrainment of molten sulphide in silicate melt. Rhenium was likely removed from precursor peridotite and pyroxenite by previous melt extraction. Refertilization of peridotite by melts increased Al2O3, CaO, Pt, Pd contents and 187Os/188Os beyond typical values for mantle peridotite and the primitive upper mantle. The interaction of melts with residual peridotite and pyroxenite, as illustrated in the Ronda massif, can generate radiogenic-Os-enriched domains in the mantle with high melt productivity, higher Pt/Os and Pt/Re than common peridotite, and lower Re/Os than typical pyroxenite. As also previously proposed for pyroxenites, these “hybrid” domains can account for the difference in Os isotope compositions between many basalts (e.g., MORB and OIB) and common depleted mantle peridotites. Moreover, the presence of these enriched hybrid components in the mantle, evolved over sufficient timescales and in geologically reasonable proportions, may account for the 186Os-187Os enrichment of plume lavas without requiring a chemical contribution from the core.

  12. Anomalous switching in Nb/Ru/Sr2RuO4 topological junctions by chiral domain wall motion

    NASA Astrophysics Data System (ADS)

    Anwar, M. S.; Nakamura, Taketomo; Yonezawa, S.; Yakabe, M.; Ishiguro, R.; Takayanagi, H.; Maeno, Y.

    2013-08-01

    A spontaneous symmetry breaking in a system often results in domain wall formation. The motion of such domain walls is utilized to realize novel devices like racetrack-memories, in which moving ferromagnetic domain walls store and carry information. Superconductors breaking time reversal symmetry can also form domains with degenerate chirality of their superconducting order parameter. Sr2RuO4 is the leading candidate of a chiral p-wave superconductor, expected to be accompanied by chiral domain structure. Here, we present that Nb/Ru/Sr2RuO4 topological superconducting-junctions, with which the phase winding of order parameter can be effectively probed by making use of real-space topology, exhibit unusual switching between higher and lower critical current states. This switching is well explained by chiral-domain-wall dynamics. The switching can be partly controlled by external parameters such as temperature, magnetic field and current. These results open up a possibility to utilize the superconducting chiral domain wall motion for future novel superconducting devices.

  13. [sup 187]Os-[sup 186]Os and [sup 187]Os-[sup 188]Os method of dating: An introduction

    SciTech Connect

    Yin, Q.Z.; Jagoutz, E.; Waenke, H. ); Verkhovskiy, A.B. )

    1993-08-01

    A Re-containing sample is irradiated with thermal neutrons in a nuclear reactor. The following reactions occur with high cross sections: [sup 185]Re(n, [gamma])[sup 186]Re and [sup 187]Re(n, [gamma])[sup 188]Re. Both [sup 186]Re (half-life 90.6 h) and [sup 188]Re (16.7 h) [beta]-decay to the stable isotopes [sup 186]Os and [sup 188]Os. Thus [sup 186]Os and [sup 188]Os are enriched in proportion to the neutron fluence and R/Os ratio of the sample being irradiated. Analyzing merely the isotopic composition of the sample, the authors get two ages that should be consistent. In one irradiated molybdenite sample from Kingsgate molybdenum mine in New South Wales, Australia, the measured [sup 186]Os/[sup 192]Os and [sup 188]Os/[sup 192]Os are 0.3284 and 0.6299, whereas in an unirradiated sample they are assumed to be 0.0390 and 0.3248. These ratios are measurable with negative thermal ionization mass spectrometry (N-TIMS) to a precision of 1[per thousand]. The derived ages for this sample are t[sub 186] = 220.5 [+-] 8.6 Ma and t[sub 188] = 214.9 [+-] 8.9 Ma, respectively (or [+-] 1.4 Ma and [+-] 1.7 Ma, respectively, when excluding the uncertainty of [sup 187]Re half-life). These values are in close agreement with the 221--238 Ma K-Ar ages of the leucogranites emplacement that causes the Mo mineralization at Kingsgate. The major limiting factor on the precision of this age determination is the uncertainty in the half-life of [sup 187]Re. The errors associated with the irradiation parameters are greatly reduced by choosing an appropriate neutron flux monitor. The advantage of this method is that the Re/Os ratio is determined on the same sample and that only one measurement of the isotope composition of osmium is required, thus overcoming some of the experimental difficulties of the conventional Re-Os analysis. The problem of sample inhomogeneity and the need to measure the absolute concentrations of rhenium and osmium are thus eliminated. 30 refs., 3 figs., 1 tab.

  14. Triaxial shapes in the ground states of even-even neutron-rich Ru isotopes

    SciTech Connect

    Ahmad, I.; Lister, C.J.; Morss, L.R.

    1995-08-01

    Partial level schemes for {sup 108,110,112}Ru, and {sup 114}Ru about which nothing was previously known, were determined from the measurement of prompt, triple-gamma coincidences in {sup 248}Cm fission fragments. A 5-mg {sup 249}Cm source, mixed with 65-mg KCl and pressed in the form of a 7-mm diameter pellet, was used for the experiment. Prompt {gamma} rays emitted from the fission fragments were detected with the Eurogam array at Daresbury, which at that time consisted of 45 Compton suppressed Ge detectors and 5 LEPS spectrometers. Transitions in Ru were identified by gating on {gamma} rays in the complementary Te fragments. Figure I-25 shows the technique used to identify the previously unknown transitions in {sup 114}Ru and its partial level scheme. High spin states up to spin 10 h were observed and the {gamma}-ray branching ratios were determined. The ratios of electric quadrupole transition probabilities deduced from the experimental branching ratios were found to be in good agreement with the predictions of a simple model of rigid triaxial rotor. Our analysis shows that gamma deformation in Ru isotopes is increasing with the neutron number and the gamma value for {sup 112}Ru and {sup 114}Ru is {approximately} 25 degrees. This is one of the highest gamma values encountered in nuclei, suggesting soft triaxial shapes for {sup 112}Ru and {sup 114}Ru. The results of this investigation were published.

  15. Mössbauer study of the Ru porcelain of Chinese Song Dynasty and Yuan Dynasty

    NASA Astrophysics Data System (ADS)

    Zhengyao, Gao; Songhua, Chen; Xiande, Chen

    1994-12-01

    The Mössbauer spectra from the glazes of the Song Dynasty and the Yuan Dynasty Ru porcelains and the imitative ancient Ru porcelain are compared and analyzed. It is determined that the original firing atmosphere of the Yuan Dynasty Ru porcelain was reductive. The firing temperature was 1250±20 ‡C. The original firing atmosphere of the Song Dynasty Ru porcelain was also reductive; the firing temperature was above 1200 ‡C. The coloring mechanism of these glazes is discussed.

  16. Active Site Dependent Reaction Mechanism over Ru/CeO2 Catalyst toward CO2 Methanation.

    PubMed

    Wang, Fei; He, Shan; Chen, Hao; Wang, Bin; Zheng, Lirong; Wei, Min; Evans, David G; Duan, Xue

    2016-05-18

    Oxygen vacancy on the surface of metal oxides is one of the most important defects which acts as the reactive site in a variety of catalytic reactions. In this work, operando spectroscopy methodology was employed to study the CO2 methanation reaction catalyzed by Ru/CeO2 (with oxygen vacancy in CeO2) and Ru/α-Al2O3 (without oxygen vacancy), respectively, so as to give a thorough understanding on active site dependent reaction mechanism. In Ru/CeO2 catalyst, operando XANES, IR, and Raman were used to reveal the generation process of Ce(3+), surface hydroxyl, and oxygen vacancy as well as their structural evolvements under practical reaction conditions. The steady-state isotope transient kinetic analysis (SSITKA)-type in situ DRIFT infrared spectroscopy undoubtedly substantiates that CO2 methanation undergoes formate route over Ru/CeO2 catalyst, and the formate dissociation to methanol catalyzed by oxygen vacancy is the rate-determining step. In contrast, CO2 methanation undergoes CO route over Ru surface in Ru/α-Al2O3 with the absence of oxygen vacancy, demonstrating active site dependent catalytic mechanism toward CO2 methanation. In addition, the catalytic activity evaluation and the oscillating reaction over Ru/CeO2 catalyst further prove that the oxygen vacancy catalyzes the rate-determining step with a much lower activation temperature compared with Ru surface in Ru/α-Al2O3 (125 vs 250 °C).

  17. Site activities of zeolite-support Ru for CO hydrogenation. Final report

    SciTech Connect

    Goodwin, J.G. Jr.

    1983-10-01

    The work supported by this grant can be grouped under three headings: a comprehensive study of RuY, Ru supported on zeolites having a range of Si/Al values, and alkali promotion of Ru. NaY-supported Ru catalysts have been prepared by incipient-wetness (I.W.) (using RuCl/sub 3/), ion-exchange (I.E.) (using Ru(NH/sub 3/)/sub 6/Cl/sub 3/), and vapor-impregnation (V.I.) (using Ru/sub 3/(CO)/sub 12/). The resulting catalysts were extensively studied by chemisorption, atomic absorption, IR, ESCA, and catalytic reaction (especially F-T). Significant differences were found depending on the method of preparation. These differences were exhibited in both the physical and chemical characteristics of the catalysts. By variation of the preparation method and Si/Al ratio of the zeolite it is possible to develop a better understanding of how metal particle size and location, metal-zeolite interactions, neutralizing cation type and concentration, and the presence of zeolite acid sites can influence the catalytic properties of the supported metal. Ten papers are included in this final report and are grouped under the following headings: (1) chemisorption characteristics; (2) electronic state of Ru; (3) hydrogenolysis properties of NaY-supported Ru; and (4) Fischer-Tropsch synthesis. All papers have been processed for inclusion in the Energy Data Base.

  18. Activity and stability of the oxygen evolution reaction on electrodeposited Ru and its thermal oxides

    NASA Astrophysics Data System (ADS)

    Kim, Jin Yeong; Choi, Jihui; Kim, Ho Young; Hwang, Eunkyoung; Kim, Hyoung-Juhn; Ahn, Sang Hyun; Kim, Soo-Kil

    2015-12-01

    The activity and stability of Ru metal and its thermal oxide films for the oxygen evolution reaction (OER) were investigated. The metallic Ru films were prepared by electrodeposition on a Ti substrate and then thermally oxidized at various temperatures under atmospheric conditions. During long-term operation of the OER with cyclic voltammetry (CV) in H2SO4 electrolyte, changes in the properties of the Ru and its thermal oxides were monitored in terms of their morphology, crystal structure, and electronic structure. In the initial stages of the OER, all of the Ru thermal oxide films underwent an activation process that was related to the continuous removal of low-activity Ru oxides from the surface. With further cycling, the OER activity decreased. The rate of decrease was different for each Ru film and was related to the annealing temperatures. Monitoring of material properties indicates that the amount of stable anhydrous RuO2 is important for OER stability because it prevents both the severe dissolution of metallic Ru beneath the oxide surface and the formation of a less active hydrous RuO2 at the surface.

  19. Magnetic properties and spin polarization of Ru doped half metallic CrO{sub 2}

    SciTech Connect

    West, Kevin G.; Dao, Nam N. H.; Lu, Jiwei; Osofsky, Michael; Mazin, I. I.; Wolf, Stuart A.

    2015-07-06

    Chromium dioxide (CrO{sub 2}) is a half metal that is of interest for spintronic devices. It has not been synthesized through traditional physical vapor deposition (PVD) techniques because of its thermodynamic instability in low oxygen pressures. Epitaxial thin films of Ru doped tetragonal rutile CrO{sub 2} were synthesized by a PVD technique. The as-deposited Ru{sub x}Cr{sub 1−x}O{sub 2} was ferrimagnetic with the saturation magnetization moment showing a strong dependence on the Ru concentration. Curie temperature as high as 241 K has been obtained for ∼23 at. % Ru. The Ru substitution increased the electrical conductivity by increasing the minority spin concentration. The spin polarization was found to be as high as 70% for 9 at. % Ru and decreased to ∼60% with Ru concentrations up to ∼44 at. %, which is determined by the Fermi velocities of the majority and minority spins. First principle calculations were performed to understand the effect of Ru content on the properties of CrO{sub 2}. The PVD processes of Ru doped CrO{sub 2} could lead to the practical applications of the high spin polarization of CrO{sub 2} in spintronic devices.

  20. Effect of delithiation on the dimer transition of the honeycomb-lattice ruthenate Li2 -xRuO3

    NASA Astrophysics Data System (ADS)

    Jimenez-Segura, Marco-Polo; Ikeda, Atsutoshi; Kimber, Simon A. J.; Giacobbe, Carlotta; Yonezawa, Shingo; Maeno, Yoshiteru

    2016-09-01

    The honeycomb-lattice ruthenate Li2RuO3 is made heavily Li deficient by chemical oxidation by iodine. The delithiation induces a different phase Li2 -xRuO3 , the "D phase," with superlattice. For the first time we disclose the magnetic and structural properties of the D phase in the dimer-solid state. The low-temperature magnetic susceptibility and the bond lengths indicate a bonding configuration consisting of both Ru4 +-Ru4 + and Ru5 +-Ru5 + dimers.

  1. Characterization of a trinuclear ruthenium species in catalytic water oxidation by Ru(bda)(pic)2 in neutral media.

    PubMed

    Zhang, Biaobiao; Li, Fei; Zhang, Rong; Ma, Chengbing; Chen, Lin; Sun, Licheng

    2016-06-30

    A Ru(III)-O-Ru(IV)-O-Ru(III) type trinuclear species was crystallographically characterized in water oxidation by Ru(bda)(pic)2 (H2bda = 2,2'-bipyridine-6,6'-dicarboxylic acid; pic = 4-picoline) under neutral conditions. The formation of a ruthenium trimer due to the reaction of Ru(IV)[double bond, length as m-dash]O with Ru(II)-OH2 was fully confirmed by chemical, electrochemical and photochemical methods. Since the oxidation of the trimer was proposed to lead to catalyst decomposition, the photocatalytic water oxidation activity was rationally improved by the suppression of the formation of the trimer.

  2. Atomic Layer Deposition of Ru Thin Films Using a New Beta-Diketonate Ru Precursor and NH3 Plasma as a Reactant.

    PubMed

    Jung, Jae-Hun; Lee, Seung-Joon; Lee, Hyun-Jung; Lee, Min Young; Cheon, Taehoon; Bae, So Ik; Saito, Masayuki; Suzuki, Kazuharu; Nabeya, Shunichi; Lee, Jeongyeop; Kim, Sangdeok; Yeom, Seungjin; Seo, Jong Hyun; Kim, Soo-Hyun

    2015-11-01

    Ruthenium (Ru) thin films were grown on thermally-grown SiO2 substrates by plasma enhanced atomic layer deposition (PEALD) using a sequential supply of a new betadiketonate Ru metallorganic precursor, dicarbonyl-bis(5-methyl-2,4-hexanediketonato) Ru(II) (C16H22O6Ru) with a high vapor pressure and NH3 plasma as a reactant at the substrate temperature ranging from 175 and 310 degrees C. A self-limited film growth was confirmed at the deposition temperature of 225 degrees C and the growth rate was 0.063 nm/cycle on the SiO2 substrate with very short number of incubation cycles (approximately 10 cycles). The resistivity of PEALD-Ru films was dependent on the microstructural features characterized by grain size and crystallinity, which could be controlled by varying the deposition temperature. Ru film with the resistivity of -20 μΩ-cm and high density of 11.5 g/cm3 was obtained at the deposition temperature as low as 225 degrees C. It formed polycrystalline structure with hexagonal-close-packed phase that was confirmed by X-ray diffractometry and transmission electronic microscopy analysis. Step coverage of PEALD-Ru film deposited with the optimum condition was good (-75%) at the very small-sized trench (aspect ratio: -4.5 and the top opening size of 25 nm).

  3. Targeting Human Telomeric G-Quadruplex DNA and Inhibition of Telomerase Activity With [(dmb)2Ru(obip)Ru(dmb)2]4+

    PubMed Central

    Cao, Tongcheng; Liu, Jie; Gao, Xing; Hao, Jian; Lv, Chunyan; Huang, Hailiang; Xu, Jun; Yao, Tianming

    2013-01-01

    Inhibition of telomerase by inducing/stabilizing G-quadruplex formation is a promising strategy to design new anticancer drugs. We synthesized and characterized a new dinuclear complex [(dmb)2Ru(obip)Ru(dmb)2]4+ (dmb = 4,4’-dimethyl-2,2’-bipyridine, obip = (2-(2-pyridyl)imidazo[4,5-f][1,10]phenanthroline) with high affinity for both antiparallel and mixed parallel / antiparallel G-quadruplex DNA. This complex can promote the formation and stabilize G-quadruplex DNA. Dialysis and TRAP experiments indicated that [(dmb)2Ru(obip)Ru(dmb)2]4+ acted as an excellent telomerase inhibitor due to its obvious selectivity for G-quadruplex DNA rather than double stranded DNA. In vitro co-culture experiments implied that [(dmb)2Ru(obip)Ru(dmb)2]4+ inhibited telomerase activity and hindered cancer cell proliferation without side effects to normal fibroblast cells. TUNEL assay indicated that inhibition of telomerase activity induced DNA cleavage further apoptosis in cancer cells. Therefore, RuII complex represents an exciting opportunity for anticancer drug design by specifically targeting cancer cell G-quadruplexes DNA. PMID:24386376

  4. Magnetic and orbital orders coupled to negative thermal expansion in Mott insulators, Ca2Ru1--xM xO4 (M = 3d transition metal ion)

    NASA Astrophysics Data System (ADS)

    Qi, Tongfei

    Ca2RuO4 is a structurally-driven Mott insulator with a metal-insulator (MI) transition at TMI = 357K, followed by a well-separated antiferromagnetic order at T N = 110 K. Slightly substituting Ru with a 3d transition metal ion M effectively shifts TMI and induces exotic magnetic behavior below TN. Moreover, M doping for Ru produces negative thermal expansion in Ca2Ru1-- xMxO4 (M = Cr, Mn, Fe or Cu); the lattice volume expands on cooling with a total volume expansion ratio, DeltaV/V, reaching as high as 1%. The onset of the negative thermal expansion closely tracks TMI and TN, sharply contrasting classic negative thermal expansion that shows no relevance to electronic properties. In addition, the observed negative thermal expansion occurs near room temperature and extends over a wide temperature interval. These findings underscores new physics driven by a complex interplay between orbital, spin and lattice degrees of freedom. These materials constitute a new class of Negative Thermal Expansion (NTE) materials with novel electronic and magnetic functions. KEYWORDS: Transition Metal Oxide, Ruthenate, Negative Thermal Expansion, Single crystal XRD, Invar Effect, Orbital Ordering, Magnetic Ordering, Jahn-Teller Effect.

  5. Neutron capture by Ru: Neutron cross sections of {sup 96,102,104}Ru and gamma-ray spectroscopy in the decays of {sup 97,103,105}Ru

    SciTech Connect

    Krane, K. S.

    2010-04-15

    Cross sections for radiative capture of neutrons have been measured for stable isotopes of Ru with mass numbers 96,102, and 104. From separate irradiations using thermal and epithermal neutrons, independent values for the thermal cross section and effective resonance integral have been determined. Spectroscopic studies of the gamma rays emitted in the decays of {sup 97,103,105}Ru have enabled improvements in the precision of the energies and intensities of the radiations along with corresponding improvements in the beta-decay feeding intensities and the energies of the levels in the respective daughter nuclei. Similar spectroscopic measurements of the decays of {sup 105}Rh (daughter of {sup 105}Ru) and {sup 96}Tc (produced from n,p reactions on {sup 96}Ru) have resulted in improved gamma-ray energies and intensities in those decays.

  6. Structural and electrical properties of ternary Ru-AlN thin films prepared by plasma-enhanced atomic layer deposition

    SciTech Connect

    Shin, Yu-Ri; Kwack, Won-Sub; Park, Yun Chang; Kim, Jin-Hyock; Shin, Seung-Yong; Moon, Kyoung Il; Lee, Hyung-Woo; Kwon, Se-Hun

    2012-03-15

    Highlights: Black-Right-Pointing-Pointer Ru-AlN thin films were grown by plasma-enhanced atomic layer deposition (PEALD). Black-Right-Pointing-Pointer Structural properties were systematically investigated by XRD, BF-STEM and EDX. Black-Right-Pointing-Pointer A drastic decrease in resistivity was due to the microstructural change of the films. -- Abstract: Ruthenium-aluminum-nitride (Ru-AlN) thin films were grown by plasma-enhanced atomic layer deposition (PEALD) at 300 Degree-Sign C. The Ru intermixing ratio of Ru-AlN thin films was controlled by the number of Ru unit cycles, while the number of AlN unit cycles was fixed to one cycle. The electrical resistivity of Ru-AlN thin film decreased with increasing the Ru intermixing ratio, but a drastic decrease in electrical resistivity was observed when the Ru intermixing ratio was around 0.58-0.78. Bright-field scanning transmission electron microscope (BF-STEM) and energy-dispersive X-ray spectroscopy (EDX) element mapping analysis revealed that the electrical resistivity of Ru-AlN thin film was strongly dependent on the microstructures as well as on the Ru intermixing ratio. Although the electrical resistivity of Ru-AlN thin films decreased with increasing the Ru intermixing ratio, a drastic decrease in electrical resistivity occurred where the electrical paths formed as a result of the coalescence of Ru nanocrystals.

  7. PtRu nanofilm formation by electrochemical atomic layer deposition (E-ALD).

    PubMed

    Jayaraju, Nagarajan; Banga, Dhego; Thambidurai, Chandru; Liang, Xuehai; Kim, Youn-Guen; Stickney, John L

    2014-03-25

    The high CO tolerance of PtRu electrocatalysis, compared with pure Pt and other Pt-based alloys, makes it interesting as an anode material in proton exchange membrane fuel cells (PEMFC) and direct methanol fuel cells (DMFC). This report describes the formation of bimetallic PtRu nanofilms using the electrochemical form of atomic layer deposition (E-ALD). Metal nanofilm formation using E-ALD is facilitated by use of surface-limited redox replacement (SLRR), where an atomic layer (AL) of a sacrificial metal is first formed by UPD. The AL is then spontaneously exchanged for a more noble metal at the open-circuit potential (OCP). In the present study, PtRu nanofilms were formed using SLRR for Pt and Ru, and Pb UPD was used to form the sacrificial layers. The PtRu E-ALD cycle consisted of Pb UPD at -0.19 V, followed by replacement using Pt(IV) ions at OCP, rinsing with blank, then Pb UPD at -0.19 V, followed by replacement using Ru(III) ions at OCP. PtRu nanofilm thickness was controlled by the number of times the cycle was repeated. PtRu nanofilms with atomic proportions of 70/30, 82/18, and 50/50 Pt/Ru were formed on Au on glass slides using related E-ALD cycles. The charge for Pb UPD and changes in the OCP during replacement were monitored during the deposition process. The PtRu films were then characterized by CO adsorption and electrooxidation to determine their overpotentials. The 50/50 PtRu nanofilms displayed the lowest CO electrooxidation overpotentials as well as the highest currents, compared with the other alloy compositions, pure Pt, and pure Ru. In addition, CO electrooxidation studies of the terminating AL on the 50/50 PtRu nanostructured alloy were investigated by deposition of one or two SLRR of Pt, Ru, or PtRu on top.

  8. Ternary Pt-Ru-Ni catalytic layers for methanol electrooxidation prepared by electrodeposition and galvanic replacement

    PubMed Central

    Papaderakis, Athanasios; Pliatsikas, Nikolaos; Prochaska, Chara; Papazisi, Kalliopi M.; Balomenou, Stella P.; Tsiplakides, Dimitrios; Patsalas, Panagiotis; Sotiropoulos, Sotiris

    2014-01-01

    Ternary Pt-Ru-Ni deposits on glassy carbon substrates, Pt-Ru(Ni)/GC, have been formed by initial electrodeposition of Ni layers onto glassy carbon electrodes, followed by their partial exchange for Pt and Ru, upon their immersion into equimolar solutions containing complex ions of the precious metals. The overall morphology and composition of the deposits has been studied by SEM microscopy and EDS spectroscopy. Continuous but nodular films have been confirmed, with a Pt ÷ Ru ÷ Ni % bulk atomic composition ratio of 37 ÷ 12 ÷ 51 (and for binary Pt-Ni control systems of 47 ÷ 53). Fine topographical details as well as film thickness have been directly recorded using AFM microscopy. The composition of the outer layers as well as the interactions of the three metals present have been studied by XPS spectroscopy and a Pt ÷ Ru ÷ Ni % surface atomic composition ratio of 61 ÷ 12 ÷ 27 (and for binary Pt-Ni control systems of 85 ÷ 15) has been found, indicating the enrichment of the outer layers in Pt; a shift of the Pt binding energy peaks to higher values was only observed in the presence of Ru and points to an electronic effect of Ru on Pt. The surface electrochemistry of the thus prepared Pt-Ru(Ni)/GC and Pt(Ni)/GC electrodes in deaerated acid solutions (studied by cyclic voltammetry) proves the existence of a shell consisting exclusively of Pt-Ru or Pt. The activity of the Pt-Ru(Ni) deposits toward methanol oxidation (studied by slow potential sweep voltammetry) is higher from that of the Pt(Ni) deposit and of pure Pt; this enhancement is attributed both to the well-known Ru synergistic effect due to the presence of its oxides but also (based on the XPS findings) to a modification effect of Pt electronic properties. PMID:24959530

  9. Enhancement of Curie temperature in Mn{sub 2}RuSn by Co substitution

    SciTech Connect

    Nelson, A.; Huh, Y.; Fuglsby, R.; Guenther, J.; Kharel, P.; Zhang, W.; Sellmyer, D. J.; Staten, B.; Lukashev, P.; Valloppilly, S.

    2015-04-21

    The Co-substituted Mn{sub 2}RuSn nanomaterials, namely, Mn{sub 2}Ru{sub 0.5}Co{sub 0.5}Sn and Mn{sub 2}Ru{sub 0.35}Co{sub 0.65}Sn have been synthesized and investigated. The presence of Co in the Mn{sub 2}RuSn (a = 6.21 Å) decreased the lattice parameter, where a = 6.14 Å and 6.12 Å for the as prepared Mn{sub 2}Ru{sub 0.5}Co{sub 0.5}Sn and Mn{sub 2}Ru{sub 0.35}Co{sub 0.65}Sn, respectively. The samples show a ferrimagnetic spin order with relatively small coercivities, similar to those of soft magnetic materials. There is a substantial increase in the Curie temperature (T{sub c} = 448 K for Mn{sub 2}Ru{sub 0.5}Co{sub 0.5}Sn and 506 K for Mn{sub 2}Ru{sub 0.35}Co{sub 0.65}Sn) of Mn{sub 2}RuSn (T{sub c} = 272.1 K) due to Co substitution, which is a result of strengthening of the positive exchange interaction in this material. These materials are highly stable against heat treatment of up to 450 °C. The first-principles calculations are consistent with our experimentally observed structural and magnetic properties. They also provide insight on how the magnetic and electronic structures change when Ru is replaced with Co in Mn{sub 2}RuSn.

  10. Magnetic and Crystal Structure of α-RuCl3

    NASA Astrophysics Data System (ADS)

    Sears, Jennifer

    The layered honeycomb material α-RuCl3 has been proposed as a candidate material to show significant bond-dependent Kitaev type interactions. This has prompted several recent studies of magnetism in this material that have found evidence for multiple magnetic transitions in the temperature range of 8-14 K. We will present elastic neutron scattering measurements collected using a co-aligned array of α-RuCl3 crystals, identifying zigzag magnetic order within the honeycomb planes with an ordering temperature of ~8 K. It has been reported that the ordering temperature depends on the c axis periodicity of the layered structure, with ordering temperatures of 8 and 14 K for three and two-layer periodicity respectively. While the in-plane magnetic order has been identified, it is clear that a complete understanding of magnetic ordering and interactions will depend on the three dimensional structure of the crystal. Evidence of a structural transition at ~150 K has been reported and questions remain about the structural details, in particular the stacking of the honeycomb layers. We will present x-ray diffraction measurements investigating the low and high temperature structures and stacking disorder in α-RuCl3. Finally, we will present inelastic neutron scattering measurements of magnetic excitations in this material. Work done in collaboration with K. W. Plumb (Johns Hopkins University), J. P. Clancy, Young-June Kim (University of Toronto), J. Britten (McMaster University), Yu-Sheng Chen (Argonne National Laboratory), Y. Qiu, Y. Zhao, D. Parshall, and J. W. Lynn (NCNR).

  11. Highly siderophile element geochemistry of 187Os-enriched 2.8 Ga Kostomuksha komatiites, Baltic Shield

    NASA Astrophysics Data System (ADS)

    Puchtel, Igor S.; Humayun, Munir

    2005-03-01

    New analyses of highly siderophile elements (HSE; Re, Os, Ir, Ru, Pt, and Pd) obtained by Carius tube digestion isotope dilution inductively coupled plasma mass-spectrometry (ID-ICPMS) technique are reported for 187Os-enriched 2.8 Ga komatiites from the Kostomuksha greenstone belt. As a result of a significant improvement in the yield over our previous digestions by the NiS fire-assay technique, these komatiites have now been shown to contain 22 to 25% more Os, Ir, and Pt and 34% more Ru. The emplaced komatiite lavas at Kostomuksha thus had siderophile element abundances comparable to those of the Abitibi belt. The discrepancies observed between the two techniques are interpreted to be the result of incomplete digestion of HSE carriers (particularly chromite) during the NiS fire-assay procedure. Our results for UB-N peridotite reference material agree well with those obtained by the high-pressure ashing digestion ID-ICPMS technique reported in the literature. Two types of komatiite lavas have been distinguished in this study based on the IPGE (Os, Ir, and Ru) behavior during lava differentiation. The Kostomuksha type is unique and is characterized by an incompatible behavior of IPGEs, with bulk solid-liquid partition coefficients for IPGEs being close to those for olivine. Cumulate zones in this type of komatiite lava occupy <20% of the total thickness of the flows. The Munro type exhibits a compatible behavior of IPGEs during lava differentiation. The cumulate zone in this type of komatiite occupies >20% of the total thickness of the flows. The calculated bulk partition coefficients indicate that, as with the other Munro-type komatiite lavas, the bulk cumulate contained an IPGE-rich minor phase(s) in addition to olivine. The non-CI chondritic HSE pattern for the source of the Kostomuksha komatiites calculated here is similar to that of Abitibi komatiites and to average depleted spinel lherzolite (ADSL) and supports the hypothesis of a non-CI chondritic HSE

  12. Fe N-Heterocyclic Carbene Complexes as Promising Photosensitizers.

    PubMed

    Liu, Yizhu; Persson, Petter; Sundström, Villy; Wärnmark, Kenneth

    2016-08-16

    The photophysics and photochemistry of transition metal complexes (TMCs) has long been a hot field of interdisciplinary research. Rich metal-based redox processes, together with a high variety in electronic configurations and excited-state dynamics, have rendered TMCs excellent candidates for interconversion between light, chemical, and electrical energies in intramolecular, supramolecular, and interfacial arrangements. In specific applications such as photocatalytic organic synthesis, photoelectrochemical cells, and light-driven supramolecular motors, light absorption by a TMC-based photosensitizer and subsequent excited-state energy or electron transfer constitute essential steps. In this context, TMCs based on rare and expensive metals, such as ruthenium and iridium, are frequently employed as photosensitizers, which is obviously not ideal for large-scale implementation. In the search for abundant and environmentally benign solutions, six-coordinate Fe(II) complexes (Fe(II)L6) have been widely considered as highly desirable alternatives. However, not much success has been achieved due to the extremely short-lived triplet metal-to-ligand charge transfer ((3)MLCT) excited state that is deactivated by low-lying metal-centered (MC) states on a 100 fs time scale. A fundamental strategy to design useful Fe-based photosensitizers is thus to destabilize the MC states relative to the (3)MLCT state by increasing the ligand field strength, with special focus on making eg σ* orbitals on the Fe center energetically less accessible. Previous efforts to directly transplant successful strategies from Ru(II)L6 complexes unfortunately met with limited success in this regard, despite their close chemical kinship. In this Account, we summarize recent promising results from our and other groups in utilizing strongly σ-donating N-heterocyclic carbene (NHC) ligands to make strong-field Fe(II)L6 complexes with significantly extended (3)MLCT lifetimes. Already some of the first

  13. RuO2 Non-isothermal Thermometry

    NASA Astrophysics Data System (ADS)

    Ventura, Guglielmo; Giomi, Silvia

    2016-08-01

    The use of a RuO2 resistor in non-isothermal measuring setup is proposed. A calculation is presented to explain the principle for a resistor obeying variable-range-hopping theory and the results are compared to measurements in the range of 11.2-30 mK for a commercial resistor. The thermometer, which measures the electron temperature, does not show overheating effects at 11.2 mK with a measuring power of 10^{-12} W.

  14. Adsorption of RuSex (x =1-5) cluster on Se-doped graphene: First principle calculations

    NASA Astrophysics Data System (ADS)

    Üzengi Aktürk, O.; Tomak, M.

    2015-08-01

    We have investigated the adsorption of RuSex (x =1-5) cluster on Se-doped graphene. The change of the adsorption energy with the number of Se atoms and magnetization values are investigated. Electronic properties of adsorption of RuSex (x =1-5) cluster on Se-doped graphene are investigated. The highest adsorption energy belongs to RuSe adsorbate. The biggest magnetization value belongs to RuSe2 adsorbate. This adsorbate makes the substrate half metallic. This property is important in electronic device applications. It is observed that substitutional Se atom changes the electronic properties of graphene. This substitution makes graphene metallic. While RuSe, RuSe4,RuSe5 adsorbate make substrate metallic, RuSe3 makes it semiconducting. Generally, it is found that there is a charge transfer from the substrate to clusters within the Löwdin analysis. This is in line with the charge difference results.

  15. Low leakage Ru-strontium titanate-Ru metal-insulator-metal capacitors for sub-20 nm technology node in dynamic random access memory

    SciTech Connect

    Popovici, M. Swerts, J.; Redolfi, A.; Kaczer, B.; Aoulaiche, M.; Radu, I.; Clima, S.; Everaert, J.-L.; Van Elshocht, S.; Jurczak, M.

    2014-02-24

    Improved metal-insulator-metal capacitor (MIMCAP) stacks with strontium titanate (STO) as dielectric sandwiched between Ru as top and bottom electrode are shown. The Ru/STO/Ru stack demonstrates clearly its potential to reach sub-20 nm technology nodes for dynamic random access memory. Downscaling of the equivalent oxide thickness, leakage current density (J{sub g}) of the MIMCAPs, and physical thickness of the STO have been realized by control of the Sr/Ti ratio and grain size using a heterogeneous TiO{sub 2}/STO based nanolaminate stack deposition and a two-step crystallization anneal. Replacement of TiN with Ru as both top and bottom electrodes reduces the amount of electrically active defects and is essential to achieve a low leakage current in the MIM capacitor.

  16. First principles study of oxygen adsorption on Se-modified Ru nanoparticles

    NASA Astrophysics Data System (ADS)

    Zuluaga, Sebastian; Stolbov, Sergey

    2012-08-01

    We present here the results of our density-functional-theory-based calculations of the electronic and geometric structures and energetics of Se and O adsorption on Ru 93- and 105-atom nanoparticles. These studies have been inspired by the fact that Se/Ru nanoparticles are considered promising electrocatalysts for the oxygen reduction reaction (ORR) on direct methanol fuel cell cathodes and the oxygen binding energy is a descriptor for the catalyst activity toward this reaction. We find the character of chemical bonding of Se on a flat nanoparticle facet to be ionic, similar to that obtained earlier for the Se/Ru(0001) surface, while in the case of a low-coordinated Ru configuration there is an indication of some covalent contribution to the bonding leading to an increase in Se binding energy. Se and O co-adsorbed on the flat facet both accept electronic charge from Ru, whereas the adsorption on low-coordinated sites causes more complicated valence charge redistribution. The Se modification of the Ru particles leads to weakening of the oxygen bonding to the particles. However, overall, O binding energies are found to be higher for the particles than for Se/Ru(0001). The high reactivity of the Se/Ru nanoparticles found in this work is not favorable for ORR. We thus expect that larger particles with well-developed flat facets will be more efficient ORR catalysts than small nanoparticles with a large fraction of under-coordinated adsorption sites.

  17. Photoluminescence quenching of [Ru(bpy)2(atatp)](2+) bound to a condensed DNA matrix.

    PubMed

    Chen, Linlin; Chao, Hui; Zhao, Qianwen; Zheng, Xuling; Li, Hong

    2016-01-01

    A novel [Ru(bpy)2(atatp)](2+) (bpy=2,2'-bipyridine and atatp=acenaphtheno[1,2-b]-1,4,8,9-tetraazatriphenylene) can induce the condensation of herring sperm DNA to form an orange-red cast film via intercalation and electrostatic attraction. The thus-prepared cast film shows microsecond emission lifetimes and reversible luminescence tuning characteristics by oxygen and nitrogen with an on-off emission intensity ratio of 4.3. The photoluminescence of [Ru(bpy)2(atatp)](2+) bound to a DNA condensed matrix can be quenched by water, dissolved oxygen, copper(II) and ferrocyanide ions. The DNA binding is found to hardly alter the dynamic quenching of [Ru(bpy)2(atatp)](2+) by oxygen at a low DNA-to-Ru(II) molar ratio (r=0.83), allowing [Ru(bpy)2(atatp)](2+) to keep a basically unchanged oxygen quenching constant, as well as endow the photo-induced electron transfer between [Ru(bpy)2(atatp)](2+) and copper(II) cations, and weaken the electrostatic attraction of [Ru(bpy)2(atatp)](2+) with ferrocyanide anions. In addition, the DNA condensation induced by [Ru(bpy)2(atatp)](2+) can protect the DNA oxidative damage against superoxide anion and hydroxyl radical toxicity. The present results could provide a versatile platform for better fabrication of optoelectronic devices.

  18. Direct evidence for catalase activity of [Ru(V)(edta)(O)](-).

    PubMed

    Chatterjee, Debabrata; Jaiswal, Namita; Franke, Alicja; van Eldik, Rudi

    2014-12-01

    Reported is the first example of a ruthenium(III) complex, Ru(III)(edta) (edta(4-) = ethylenediaminetetraacetate), that catalyzes the disproportion of H2O2 to O2 and water in resemblance to catalase activity, and shedding light on the possible mechanism of action of the [Ru(V)(edta)(O)](-) formed in the reacting system. PMID:25307989

  19. The effect of the surface composition of Ru-Pt bimetallic catalysts for methanol oxidation

    DOE PAGESBeta

    Garrick, Taylor R.; Diao, Weijian; Tengco, John M.; Stach, Eric A.; Senanayake, Sanjaya D.; Chen, Donna A.; Monnier, John R.; Weidner, John W.

    2016-02-23

    Here, a series of Ru-Pt bimetallic catalysts prepared by the electroless deposition of controlled and variable amounts of Ru on the Pt surface of a commercially-available 20 wt% Pt/C catalyst has been characterized and evaluated for the oxidation of methanol. The activity of each Ru-Pt catalyst was determined as a function of surface composition via cyclic voltammetry. For the Ru-Pt bimetallic catalysts, activity passed through a maximum at approximately 50% monodisperse Ru surface coverage. However, due to the monolayer coverage of Ru on Pt, the amount of metal in the catalyst is minimized compared to a bulk 1:1 atomic ratiomore » of Ru:Pt seen in commercial bimetallic catalysts. Chemisorption and temperature programmed reduction experiments confirmed that the surface had characteristics of a true bimetallic catalyst. On a mass of Pt basis, the activity of this composition for methanol oxidation was 7 times higher than pure Pt and 3.5 times higher than a commercial catalyst with a 1:1 Pt:Ru bulk atomic ratio.« less

  20. The steroid hormone antagonist RU486. Mechanism at the cellular level and clinical applications.

    PubMed

    Baulieu, E E

    1991-12-01

    The cellular and molecular mechanism of RU486, a steroid hormone antagonist, is discussed in detail. Principally, RU486 opposes the action of two types of hormones: progesterone and glucocorticosteroids. The clinical applications are also described, as well as the future outlook.

  1. Ru alkylidene compounds bearing tridentate, dianionic ligands: Lewis acid activation and olefin metathesis.

    PubMed

    McKinty, Adam M; Stephan, Douglas W

    2016-03-01

    The series of tridentate complexes of Ru-alkylidenes (L)Ru(CHPh)(SCH2CH2)2E (E = O, L = SIMes 1, PCy3 2, E = S, L = SIMes 3, PCy3 4; E = PPh 7, L = PCy3), (L)Ru(CHPh)(SC6H4)2S (L = SIMes 5, PCy3 6), (L)Ru(CHPh) (OCH2CH2)2O (L = SIMes 8, PCy3 9) were prepared and shown to react with one equivalent of BCl3 to give the complexes (L)Ru(CHPh)Cl[E(CH2CH2S)2BCl2] (E = O, L = SIMes 10, PCy3 11, E = S, L = SIMes 12a/b, PCy3 13, E = PPh, L = PCy3 16) and (L)Ru(CHPh)(SC6H4)2O (L = SIMes 14, PCy3 15). In the case of 1 and 2 reaction with two equivalents of BCl3 affording the corresponding cation via chloride abstraction. These cations coordinate MeCN to give the six coordinate Ru cation salts [(L)Ru(CHPh)- (NCMe)(O(CH2CH2S)2BCl2)][BCl4] L = SIMes 17, PCy3 18). The generated five coordinate cations derived from 2-9 via addition of two equivalents of BCl3 were evaluated in standard preliminary tests for olefin metathesis catalysis.

  2. Ru alkylidene compounds bearing tridentate, dianionic ligands: Lewis acid activation and olefin metathesis.

    PubMed

    McKinty, Adam M; Stephan, Douglas W

    2016-03-01

    The series of tridentate complexes of Ru-alkylidenes (L)Ru(CHPh)(SCH2CH2)2E (E = O, L = SIMes 1, PCy3 2, E = S, L = SIMes 3, PCy3 4; E = PPh 7, L = PCy3), (L)Ru(CHPh)(SC6H4)2S (L = SIMes 5, PCy3 6), (L)Ru(CHPh) (OCH2CH2)2O (L = SIMes 8, PCy3 9) were prepared and shown to react with one equivalent of BCl3 to give the complexes (L)Ru(CHPh)Cl[E(CH2CH2S)2BCl2] (E = O, L = SIMes 10, PCy3 11, E = S, L = SIMes 12a/b, PCy3 13, E = PPh, L = PCy3 16) and (L)Ru(CHPh)(SC6H4)2O (L = SIMes 14, PCy3 15). In the case of 1 and 2 reaction with two equivalents of BCl3 affording the corresponding cation via chloride abstraction. These cations coordinate MeCN to give the six coordinate Ru cation salts [(L)Ru(CHPh)- (NCMe)(O(CH2CH2S)2BCl2)][BCl4] L = SIMes 17, PCy3 18). The generated five coordinate cations derived from 2-9 via addition of two equivalents of BCl3 were evaluated in standard preliminary tests for olefin metathesis catalysis. PMID:26822161

  3. Factors controlling the CO intercalation of h-BN overlayers on Ru(0001).

    PubMed

    Dong, Aiyi; Fu, Qiang; Wu, Hao; Wei, Mingming; Bao, Xinhe

    2016-09-21

    The space between a two-dimensional (2D) material overlayer and a metal surface can be regarded as a nanoreactor, in which molecule adsorption and surface reaction may occur. In this work, we present CO intercalation under a hexagonal boron nitride (h-BN) overlayer on Ru(0001) at room temperature, observed using X-ray photoelectron spectroscopy, ultraviolet photoelectron spectroscopy, and scanning tunneling microscopy. Critical factors influencing the interfacial process have been investigated, including CO partial pressure, h-BN coverage, and oxygen pre-adsorption on the Ru surface. It has been identified that CO adsorption on the bare Ru surface region plays an important role in CO intercalation. Comparative studies of CO intercalation at h-BN/Ru(0001) and graphene/Ru(0001) interfaces indicate that CO starts to intercalate h-BN overlayers more easily than graphene. Temperature-programmed CO desorption experiments from h-BN/CO/Ru(0001) and graphene/CO/Ru(0001) surfaces reveal a similar confinement effect of the 2D cover on CO adsorption, which results in a more abrupt and quick CO desorption in comparison with the CO/Ru(0001) surface. PMID:27530273

  4. 187Os/186Os in Lunar and Meteoritic Materials

    NASA Astrophysics Data System (ADS)

    Birck, J. L.; Allegre, C. J.

    1993-07-01

    The unique potentiallity of the ^187Re-^1870s radiochronometer stems from the chemical properties of the 2 elements. Their siderophilic nature has made the dating of the metal phase of iron meteorites and chondrites possible [1,2]. In silicate crystallization or melting, Os behaves as a strongly compatible element [3]. For Re the results hereunder show that its behavior is highly variable, depending on context. The development of the highly sensitive negative thermal ionization mass spectrometry [4,5] made possible the extensive analysis of silicate materials. We developed a chemical separation method allowing the analysis of 0,5 g of silicate with an Os blank of 0.3 pg (1pg=10^-12 g). The isotopic measurement of Os has a typical precision of a few permil for 1 pg of Os. A variety of samples has been investigated. Iron Meteorites: The main purpose of this study was to shed some light on the history of Kodaikanal. The silicate inclusions of this meteorite were reset at 3.7 Ga for both the Rb-Sr and the U-Pb chronometers [6,7]. The data from Coahuila, Canyon Diablo, Tlacotepec, and North Chile plot within 1% on the same isochron along with 3 samples from 2 locations inside the meteorite of Kodaikanal. As a consequence the Kodaikanal parent body did not form at 3.7 Ga but at about the same time as the parent bodies of the the majority of the other iron meteorites (~4.5 Ga). The only difference is that Kodaikanal suffered a strong secondary event at 3.7 Ga, which reset Rb/Sr and U-Pb chronometers but did not fractionate the Re/Os ratio. This result has already been suggested by our earlier work [8]. The St Severin Chondrite: A bulk sample and several batches of the metal separated from this chondrite were analysed. They plot on the iron meteorite isochron. However this metal is heterogeneous in Re/Os by a factor of at least 2 and indicates an uncomplete homogeinization of Re/Os between metal grains during parent body metamorphism. Basaltic Materials: Basaltic

  5. Anatomy of the os trigonum.

    PubMed

    Grogan, D P; Walling, A K; Ogden, J A

    1990-01-01

    Three anatomic specimens of os trigonum from skeletally immature patients demonstrated anatomic continuity of the cartilage containing the ossicle with the body of the talus, with a synchondrosis being present between the two ossifying regions. The os trigonum may be considered a developmental analogue of a secondary ossification center similar to the posterior calcaneal apophysis (although there are obvious histologic differences). The chondro-osseous border of the synchondrosis may be injured either as a chronic stress fracture or, less frequently, as an acute fracture, comparable to the injury patterns involving the accessory navicular.

  6. Enhanced thermoelectric power and electronic correlations in RuSe{sub 2}

    SciTech Connect

    Wang, Kefeng Wang, Aifeng; Tomic, A.; Wang, Limin; Petrovic, C.; Abeykoon, A. M. Milinda; Dooryhee, E.; Billinge, S. J. L.

    2015-04-01

    We report the electronic structure, electric and thermal transport properties of Ru{sub 1−x}Ir{sub x}Se{sub 2} (x ≤ 0.2). RuSe{sub 2} is a semiconductor that crystallizes in a cubic pyrite unit cell. The Seebeck coefficient of RuSe{sub 2} 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. Ru{sub 0.8}Ir{sub 0.2}Se{sub 2} 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 RuSb{sub 2}.

  7. A density functional theory study of propylene epoxidation on RuO2(110) surface

    NASA Astrophysics Data System (ADS)

    Atmaca, Deniz Onay; Düzenli, Derya; Ozbek, M. Olus; Onal, Isik

    2016-11-01

    Propylene epoxidation is investigated on RuO2(110) and oxygen added RuO2-Oot(110) surfaces by periodic DFT computational method. The desired product propylene oxide (PO) as well as the undesired products acetone (AC) or propionaldehyde (PA) form on both surfaces through either surface intermediate oxometallopropylene (OMMP) or direct oxygen insertion mechanisms. On RuO2(110) surface, nucleophilic lattice oxygen at bridge position (Obr) favors the stable surface intermediate mechanism where high energy requirements for forward reactions are demonstrated in our calculations. On RuO2-Oot(110) surface, however, higher reactivity of the electrophilic oxygen (Oot) species lowers the reaction barriers and enables an exothermic reaction path to the direct oxygen insertion for PO production. Therefore, RuO2-Oot surface is expected to show a higher PO rate.

  8. High-performance PdRu bimetallic catalyst supported on mesoporous silica nanoparticles for phenol hydrogenation

    NASA Astrophysics Data System (ADS)

    Huang, Chao; Yang, Xu; Yang, Hui; Huang, Peiyan; Song, Huiyu; Liao, Shijun

    2014-10-01

    A high-performance PdRu bimetallic catalyst supported on mesoporous silica nanoparticles (MSN), PdRu/MSN, was prepared by a facile impregnation-hydrogen reduction method. It was found that PdRu/MSN showed 5 times higher activity than that of Pd/MSN towards the liquid-phase hydrogenation of phenol. The catalysts were characterized comprehensively by multiple techniques, X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and hydrogen temperature program reduction (TPR). It was revealed that adding Ru could effectively improve the Pd dispersion and promote the electronic interaction between the Pd and Ru, both of which contribute to enhancing the catalytic activity.

  9. Triaxial and Triaxial Softness in Neutron Rich ru and pd Nuclei

    NASA Astrophysics Data System (ADS)

    Luo, Y. X.; Hamilton, J. H.; Ramaya, A. V.; Hwang, J. K.; Liu, S. H.; Rasmussen, J. O.; Frauendorf, S.; Ter-Akopian, G. M.; Daniel, A. V.; Oganessian, Yu. Ts.; Zhu, S. J.

    2013-06-01

    The level structures of 108,110,112Ru (Z=44) and 112,114,115,116,117,118Pd (Z=46) have been significantly expanded through studies of prompt γ-γ-γ coincidences observed with Gammasphere following the spontaneous fission of 252Cf. The softness to triaxiality perturbs the band structures of 108Ru and even-N Pd isotopes. Two sets of odd-parity bands are identified in 112,114,116Pd similar to but different from those in 110,112Ru. These differences can be accounted for by interferences of the chiral doubling and softness to triaxiality. Also in 112Ru, evidence for wobbling motion is found in the behavior of the γ vibrational band. Similar evidence for wobbling motion is found in 114Pd, the N = 68 isotone of 112Ru.

  10. Enhanced thermoelectric power and electronic correlations in RuSe2

    NASA Astrophysics Data System (ADS)

    Wang, Kefeng; Wang, Aifeng; Tomic, A.; Wang, Limin; Abeykoon, A. M. Milinda; Dooryhee, E.; Billinge, S. J. L.; Petrovic, C.

    2015-04-01

    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.

  11. Decoupled CuO2 and RuO2 layers in superconducting and magnetically ordered RuSr2GdCu2O8

    NASA Astrophysics Data System (ADS)

    Požek, M.; Dulčić, A.; Paar, D.; Hamzić, A.; Basletić, M.; Tafra, E.; Williams, G. V.; Krämer, S.

    2002-05-01

    Comprehensive measurements of dc and ac susceptibility, dc resistance, magnetoresistance, Hall resistivity, and microwave absorption and dispersion in fields up to 8 T have been carried out on RuSr2GdCu2O8 with the aim to establish the properties of RuO2 and CuO2 planes. At ~130 K, where the magnetic order develops in the RuO2 planes, one observes a change in the slope of dc resistance, change in the sign of magnetoresistance, and the appearance of an extraordinary Hall effect. These features indicate that the RuO2 planes are conducting. A detailed analysis of the ac susceptibility and microwave data on both ceramic and powder samples show that the penetration depth remains frequency dependent and larger than the London penetration depth even at low temperatures. We conclude that the conductivity in the RuO2 planes remains normal even when superconducting order is developed in the CuO2 planes below ~45 K. Thus, experimental evidence is provided in support of theoretical models which base the coexistence of superconductivity and magnetic order on decoupled CuO2 and RuO2 planes.

  12. The Ruthenostannylene Complex [Cp*(IXy)H2 Ru-Sn-Trip]: Providing Access to Unusual Ru-Sn Bonded Stanna-imine, Stannene, and Ketenylstannyl Complexes.

    PubMed

    Liu, Hsueh-Ju; Ziegler, Micah S; Tilley, T Don

    2015-05-26

    Reactivity studies of the thermally stable ruthenostannylene complex [Cp*(IXy)(H)2 Ru-Sn-Trip] (1; IXy=1,3-bis(2,6-dimethylphenyl)imidazol-2-ylidene; Cp*=η(5) -C5 Me5 ; Trip=2,4,6-iPr3 C6 H2 ) with a variety of organic substrates are described. Complex 1 reacts with benzoin and an α,β-unsaturated ketone to undergo [1+4] cycloaddition reactions and afford [Cp*(IXy)(H)2 RuSn(κ(2) -O,O-OCPhCPhO)Trip] (2) and [Cp*(IXy)(H)2 RuSn(κ(2) -O,C-OCPhCHCHPh)Trip] (3), respectively. The reaction of 1 with ethyl diazoacetate resulted in a tin-substituted ketene complex [Cp*(IXy)(H)2 RuSn(OC2 H5 )(CHCO)Trip] (4), which is most likely a decomposition product from the putative ruthenium-substituted stannene complex. The isolation of a ruthenium-substituted stannene [Cp*(IXy)(H)2 RuSn(=Flu)Trip] (5) and stanna-imine [Cp*(IXy)(H)2 RuSn(κ(2) -N,O-NSO2 C6 H4 Me)Trip] (6) complexes was achieved by treatment of 1 with 9-diazofluorene and tosyl azide, respectively.

  13. The Thermal Behavior of Pd on Graphene/Ru(0001)

    SciTech Connect

    Yi, Cheol-Woo W.; Szanyi, Janos

    2015-11-01

    The thermal behavior of various amounts of palladium deposited onto graphene/Ru(0001) at room temperature was investigated by x-ray photoelectron spectroscopy (XPS) and infrared reflection absorption spectroscopy (IRAS) of adsorbed CO. IRAS spectra of adsorbed CO on palladium deposited onto the graphene layer reveal the formation of defect-rich, highly-stepped and/or nanoparticle-typed palladium clusters. Annealing to temperatures below ~900 K, palladium clusters mainly experience agglomeration on the graphene layer, but at higher temperatures intercalation of palladium between the graphene layer and Ru substrate takes place. Eventually, palladium completely desorbs and the graphene layer dissolves into the ruthenium substrate at 1400 K. Even though the annealing induces the intercalation and desorption of palladium, the topmost graphene layer stays intact without any physical damage at and below 1300 K. We gratefully acknowledge the US Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division for the support of this work. The research described in this article was performed at the Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by the DOE Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory (PNNL). PNNL is operated for the US DOE by Battelle Memorial Institute under contract number DE-AC05-76RL01830. CWY also acknowledges the support of this work by Sungshin Women’s University Research Grant of 2014.

  14. Ruthenium (Ru) peeling and predicting robustness of the capping layer using finite element method (FEM) modeling

    NASA Astrophysics Data System (ADS)

    Jang, Il-Yong; John, Arun; Goodwin, Frank; Lee, Su-Young; Kim, Byung-Gook; Kim, Seong-Sue; Jeon, Chan-Uk; Kim, Jae Hyung; Jang, Yong Hoon

    2014-07-01

    Ruthenium (Ru) film used as capping layer in extreme ultraviolet (EUV) mask peeled off after annealing and in-situ UV (IUV) cleaning. We investigated Ru peeling and found out that the mechanical stress caused by the formation of Si oxide due to the penetration of oxygen atoms from ambient or cleaning media to top-Si of ML is the root cause for the problem. To support our experimental results, we developed a numerical model of finite element method (FEM) using commercial software (ABAQUS™) to calculate the stress and displacement forced on the capping layer. By using this model, we could observe that the displacement agrees well with the actual results measured from the transmission electron microscopy (TEM) image. Using the ion beam deposition (IBD) tool at SEMATECH, we developed four new types of alternative capping materials (RuA, RuB, B4C, B4C-buffered Ru). The durability of each new alternative capping layer observed by experiment was better than that of conventional Ru. The stress and displacement calculated from each new alternative capping layer, using modeling, also agreed well with the experimental results. A new EUV mask structure is proposed, inserting a layer of B4C (B4C-buffered Ru) at the interface between the capping layer (Ru) and the top-Si layer. The modeling results showed that the maximum displacement and bending stress observed from the B4C-buffered Ru are significantly lower than that of single capping layer cases. The durability investigated from the experiment also showed that the B4C-buffered structure is at least 3X stronger than that of conventional Ru.

  15. Removal of emerging pollutants by Ru/TiO2-catalyzed permanganate oxidation.

    PubMed

    Zhang, Jing; Sun, Bo; Xiong, Xinmei; Gao, Naiyun; Song, Weihua; Du, Erdeng; Guan, Xiaohong; Zhou, Gongming

    2014-10-15

    TiO2 supported ruthenium nanoparticles, Ru/TiO2 (0.94‰ as Ru), was synthesized to catalyze permanganate oxidation for degrading emerging pollutants (EPs) with diverse organic moieties. The presence of 1.0 g L(-1) Ru/TiO2 increased the second order reaction rate constants of bisphenol A, diclofenac, acetaminophen, sulfamethoxazole, benzotriazole, carbamazepine, butylparaben, diclofenac, ciprofloxacin and aniline at mg L(-1) level (5.0 μM) by permanganate oxidation at pH 7.0 by 0.3-119 times. The second order reaction rate constants of EPs with permanganate or Ru/TiO2-catalyzed permanganate oxidation obtained at EPs concentration of mg L(-1) level (5.0 μM) underestimated those obtained at EPs concentration of μg L(-1) level (0.050 μM). Ru/TiO2-catalyzed permanganate could decompose a mixture of nine EPs at μg L(-1) level efficiently and the second order rate constant for each EP was not decreased due to the competition of other EPs. The toxicity tests revealed that Ru/TiO2-catalyzed permanganate oxidation was effective not only for elimination of EPs but also for detoxification. The removal rates of sulfamethoxazole by Ru/TiO2-catalyzed permanganate oxidation in ten successive cycles remained almost constant in ultrapure water and slightly decreased in Songhua river water since the sixth run, indicating the satisfactory stability of Ru/TiO2. Ru/TiO2-catalyzed permanganate oxidation was selective and could remove selected EPs spiked in real waters more efficiently than chlorination. Therefore, Ru/TiO2-catalyzed permanganate oxidation is promising for removing EPs with electron-rich moieties. PMID:25016299

  16. FePtC magnetic recording media with (200) textured MoC intermediate layer

    SciTech Connect

    Tsai, Jai-Lin Tseng, Yun-Ting; Li, Chia-Ru; Fu, Sheng-Chun

    2015-05-07

    The FePt films with thickness of 4–10 nm were deposited on MoC/CrRu/glass at 425 °C by using magnetron sputtering. The Mo{sub 40}C{sub 60} target was used to form the MoC and C two phases after deposition. The MoC intermediate layer was epitaxially grown on the (200) textured CrRu seed layer at 425 °C and the MoC (200) diffraction peak was not clearly indexed below 10 nm but observed at 25 nm. Finally, the FePt film was prepared on (200) textured MoC at 425 °C and shown the strong (001) texture. Perpendicular anisotropy of 1.7 × 10{sup 7} erg/cm{sup 3} and out-of-plane coercivity of 7.5 kOe has been demonstrated in 10 nm thick FePt film. From microstructure, the FePt grains were distributed in- or between-islands like structure and further separated by excess carbon from MoC intermediate layer. Thinner FePt film was more separated by excess carbon and shown higher coercivity.

  17. Determination of (187)Os in molybdenite by ICP-MS with neutron-induced (186)Os and (188)Os spikes.

    PubMed

    Qu, W; Du, A; Zhao, D

    2001-10-31

    The article describes a method for the determination of (187)Os in molybdenite by isotope dilution inductively coupled plasma-mass spectrometry (ID-ICP-MS) with neutron-induced (186)Os and (188)Os spike. The spike used in the present work was prepared in line with the principle by which artificial nuclides are produced in a nuclear reaction. The concentration and isotopic composition of osmium in the prepared spike were evaluated accurately with the isotope dilution method, using negative thermal ion mass spectrometry (N-TIMS). The advantage of this method is that using (186)Os and (188)Os double spikes can effectively compensate for the mass discrimination effects of ICP-MS. Thus, the common correction practice for mass bias in the isotope dilution method with a single spike is unnecessary. In addition, the method enables one to reduce the determined error arising from instrumental instability. The precision for the (187)Os/((186)Os+(188)Os) ratio was approximately 2% (2sigma, RSD), but in the case of (187)Os/(186)Os, (187)Os/(188)Os and (186)Os/(188)Os, precision ranged from 2.0 to 8% (2sigma, RSD). The results for (187)Os concentration in a molybdenite sample determined with this method showed good agreement with reference values.

  18. Os and HSE of the hot upper mantle beneath southern Tibet: Indian mantle affinity?

    NASA Astrophysics Data System (ADS)

    Zhao, Z.; Dale, C. W.; Pearson, D. G.; Niu, Y.; Zhu, D.; Mo, X.

    2011-12-01

    The subduction of the Indian plate (including cratonic continental crust and/or upper mantle) beneath southern Tibet is widely accepted from both geological and geophysical studies. Mantle-derived xenoliths from this region provide a means of directly investigating the mantle underlying the southern part of the plateau. Studies of xenoliths hosted in the Sailipu ultrapotassic volcanic rocks, erupted at ~17 Ma, have indicated that the subcontinental mantle of southern Tibetan Plateau is hot and strongly influenced by metasomatism (Zhao et al., 2008a, b; Liu et al., 2011). Here we report comprehensive EPMA and LA-ICP-MS major and trace element data for the Sailipu xenoliths and also whole rock Os isotope and HSE data in order to constrain the depletion history of the mantle and to identify the presence of any potential Indian cratonic mantle. The xenoliths, ranging in size from 0.5cm to 1.5cm in diameter, are mostly peridotites. The calculated temperatures are 1010-1230°C at the given pressures of ~1.6-2.0 GPa (n=47). These P-T conditions are similar to rift-related upper mantle regimes (e.g. Kenya), indicating the influence of regional extension beneath southern Tibet in the Miocene. A series of compositional discriminations for minerals (Cpx, Opx, Ol, and Phl), e.g. Fo<90, suggest that the xenoliths are non-cratonic spinel-peridotite (cratonic peridotite olivine Fo> ~91), with a clear metasomatic signature We obtained Os isotope data and abundances of highly siderophile elements (HSE, including Os, Ir, Ru, Pt, Pd and Re) on a set of six olivine-dominated peridotite samples from Sailipu volcanics, less than 1 cm in dimension. They allow us to further constrain the nature and state of the upper mantle beneath the southern Tibet. Sailipu samples display low total HSE abundances (Os+Ir+Ru+Pt+Pd+Re) ranging from 8.7 to 25 ppb, with nearly constant Os, Ir , and Ru, but rather varied Pt (2-13), Pd (0.4-5.2), and Re (0.01-0.5). Chondrite-normalised Pd/Ir ratios range from

  19. Estimation of continental 187Os/186Os values by using 187Os/186Os and 143Nd/144Nd ratios in marine manganese nodules

    PubMed Central

    Turekian, Karl K.; Luck, Jean-Marc

    1984-01-01

    The relationship between 187Os/186Os and 143Nd/144Nd in different manganese nodule fields is used to determine the 187Os/186Os ratio of the continental terrains bounding the major ocean basins. The Atlantic Ocean drainages yield 187Os/186Os of about 11; the Pacific Ocean, between 25 and 36; and the western Indian Ocean, 20. By assuming a two-component continental crust composed of “ultramafic rocks” (high Os concentration, low 187Os/186Os) and “granite” with only radiogenic 187Os produced in accessory Re-bearing molybdenite, the ultramafic contribution to weathering is about 0.2%. Some or most of this may come from the alteration of oceanic ultramafics. PMID:16578780

  20. Estimation of continental Os/Os values by using Os/Os and Nd/Nd ratios in marine manganese nodules.

    PubMed

    Turekian, K K; Luck, J M

    1984-12-01

    The relationship between (187)Os/(186)Os and (143)Nd/(144)Nd in different manganese nodule fields is used to determine the (187)Os/(186)Os ratio of the continental terrains bounding the major ocean basins. The Atlantic Ocean drainages yield (187)Os/(186)Os of about 11; the Pacific Ocean, between 25 and 36; and the western Indian Ocean, 20. By assuming a two-component continental crust composed of "ultramafic rocks" (high Os concentration, low (187)Os/(186)Os) and "granite" with only radiogenic (187)Os produced in accessory Re-bearing molybdenite, the ultramafic contribution to weathering is about 0.2%. Some or most of this may come from the alteration of oceanic ultramafics.

  1. Syntrophic Effects in a Subsurface Clostridial Consortium on Fe(III)-(Oxyhydr)oxide Reduction and Secondary Mineralization

    SciTech Connect

    Shah, Madhavi; Lin, Chu-Ching; Kukkadapu, Ravi K.; Engelhard, Mark H.; Zhao, Xiuhong; Wang, Yangping; Barkay, Tamar; Yee, Nathan

    2013-07-09

    In this study, we cultivated from subsurface sediments an anaerobic Clostridia 25 consortium that was composed of a fermentative Fe-reducer Clostridium species (designated as 26 strain FGH) and a novel sulfate-reducing bacterium belonging to the Clostridia family 27 Vellionellaceae (designated as strain RU4). In pure culture, Clostridium sp. strain FGH mediated 28 the reductive dissolution/transformation of iron oxides during growth on peptone. When 29 Clostridium sp. FGH was grown with strain RU4 on peptone, the rates of iron oxide reduction 30 were significantly higher. Iron reduction by the consortium was mediated by multiple 31 mechanisms, including biotic reduction by Clostridium sp. FGH and biotic/abiotic reactions 32 involving biogenic sulfide by strain RU4. The Clostridium sp. FGH produced hydrogen during 33 fermentation, and the presence of hydrogen inhibited growth and iron reduction activity. The 34 sulfate-reducing partner strain RU4 was stimulated by the presence of H2 gas and generated 35 reactive sulfide which promoted the chemical reduction of the iron oxides. Characterization of 36 Fe(II) mineral products showed the formation of magnetite during ferrihydrite reduction, and 37 the precipitation of iron sulfides during goethite and hematite reduction. The results suggest an 38 important pathway for iron reduction and secondary mineralization by fermentative sulfate-39 reducing microbial consortia is through syntrophy-driven biotic/abiotic reactions with biogenic 40 sulfide.

  2. Photoluminescence quenching/recovery kinetics of [Ru(bpy)2(tatp)]2+ and [Ru(bpy)2(dmtatp)]2+ intercalated within DNA by copper(II) ions and EDTA

    NASA Astrophysics Data System (ADS)

    Ji, Shibo; Chen, Miaojing; Gan, Guilian; Li, Hong; Li, Weishan

    2012-03-01

    The quenching and recovery kinetics of photoluminescence of [Ru(bpy)2(tatp)]2+ (Ru1) and [Ru(bpy)2(dmtatp)]2+ (Ru2) intercalated within DNA (where bpy = 2,2'-bipyridine, tatp = 1,4,8,9-tetra-aza-triphenylene and dmtatp = 2,3-dimethyl-1,4,8,9-tetra-aza-triphenylene) have been investigated by steady-state and time-resolved methods performed at various temperatures (293-333 K). Two complexes Ru1 and Ru2 show a single-exponential luminescence decay with τRu1 = 246.0 ns and τRu2 = 513.5 ns, whose luminescence upon intercalating into DNA exhibits very consistent bi-exponential decay changes. The addition of Cu2+ ions is found to dynamically quench the luminescence of both DNA-bound Ru(II) complexes, involving a spontaneous exothermic process. The sequential addition of EDTA can partially recover the luminescence quenched by Cu2+, however depending on methyl substituents of the intercalative ligand. The chemical conversion and luminescence control mechanism of the two DNA-bound Ru(II) complexes is discussed in detail. The present results should be of value for better understanding chemical modulation of DNA-bound Ru(II) complexes as luminescence probes.

  3. Photoluminescence quenching/recovery kinetics of [Ru(bpy)2(tatp)]2+ and [Ru(bpy)2(dmtatp)]2+ intercalated within DNA by copper(II) ions and EDTA.

    PubMed

    Ji, Shibo; Chen, Miaojing; Gan, Guilian; Li, Hong; Li, Weishan

    2012-03-01

    The quenching and recovery kinetics of photoluminescence of [Ru(bpy)(2)(tatp)](2+) (Ru1) and [Ru(bpy)(2)(dmtatp)](2+) (Ru2) intercalated within DNA (where bpy=2,2'-bipyridine, tatp=1,4,8,9-tetra-aza-triphenylene and dmtatp=2,3-dimethyl-1,4,8,9-tetra-aza-triphenylene) have been investigated by steady-state and time-resolved methods performed at various temperatures (293-333K). Two complexes Ru1 and Ru2 show a single-exponential luminescence decay with τ(Ru1)=246.0 ns and τ(Ru2)=513.5 ns, whose luminescence upon intercalating into DNA exhibits very consistent bi-exponential decay changes. The addition of Cu(2+) ions is found to dynamically quench the luminescence of both DNA-bound Ru(II) complexes, involving a spontaneous exothermic process. The sequential addition of EDTA can partially recover the luminescence quenched by Cu(2+), however depending on methyl substituents of the intercalative ligand. The chemical conversion and luminescence control mechanism of the two DNA-bound Ru(II) complexes is discussed in detail. The present results should be of value for better understanding chemical modulation of DNA-bound Ru(II) complexes as luminescence probes. PMID:22208960

  4. Distribution of 103Ru-chloride in tumor-bearing animals and the mechanism for accumulation in tumor and liver.

    PubMed

    Ando, A; Ando, I; Hiraki, T; Hisada, K

    1988-01-01

    Tumor uptake rates of 103Ru-chloride were smaller than those for 67Ga-citrate. In three tumors and liver, 103Ru in the mitochondrial fraction containing lysosome increased with time after the administration of 103Ru-chloride. The concentration of 103Ru was more dominant in connective tissue (especially inflammatory tissue) than in viable tumor tissue or in necrotic tissue. Quite large amounts of 103Ru in the tumor and liver were bound to the acid mucopolysaccharide whose molecular masses exceeded 40,000. Behavior of this nuclide was essentially similar to that of 67Ga. PMID:3366616

  5. Experimentally tuning the ground state of BaFe2As2 by orbital differentiation

    NASA Astrophysics Data System (ADS)

    Rosa, Priscila; Adriano, Cris; Garitezi, Thales; Grant, Ted; Fisk, Zachary; Urbano, Ricardo; Pagliuso, Pascoal

    2015-03-01

    The role of structural parameters in layered systems, such as iron pnictides/chalcogenides (Fe-Pn/Ch), cuprates and heavy fermions, has become crucial for the understanding of their properties. In this talk, I will discuss this subject using a combination of macroscopic and microscopic techniques to study Ba1-xEuxFe2-yMy As2 single crystals (M = Co, Cu, Mn, Ni, and Ru). Interestingly, a close connection arises between the spin-density wave (SDW) phase suppression and local distortions in the structure. Furthermore, these changes are reflected at the Fermi surface by an increase of anisotropy and localization of the Fe 3 d bands at the FeAs plane. Our results suggest that such increase in the planar (xy /x2 -y2) orbital symmetry seems to be a favorable ingredient for the emergence of superconductivity in this class of materials. This work was supported by FAPESP, CNPq, CAPES-Brazi and AFOSR MURI.

  6. Evolution of superconductivity in SrFe2As2 with Ni and Pt substitution

    NASA Astrophysics Data System (ADS)

    Saha, S. R.; Drye, T.; Kirshenbaum, K.; Butch, N. P.; Zhang, X.; Greene, R.; Paglione, J.

    2010-03-01

    The superconducting state in the iron pnictide compounds with tetragonal ThCr2Si2 crystal structure has attracted much interest. Transition metal substitution is known to suppress the antiferromagnetic phase of the parent compounds, yielding superconductivity with maximum Tc values approaching ˜20-25 K when Co, Ni, Ru, Rh, Pd, or Ir are used to replace Fe. However, this trend is known to be broken in the case of SrFe2-xNixAs2 and SrFe2-xPdxAs2, which both exhibit reduced maximum Tc values of order 10 K. We will present the effects of Ni and Pt substitution in single crystalline SrFe2As2 as measured by resistivity, magnetic susceptibility and specific heat, and discuss how our results relate to the isoelectronic case of Pd substitution as well as other neighboring transition metal substitution series.

  7. Mac OS X for Astronomy

    NASA Astrophysics Data System (ADS)

    Pierfederici, F.; Pirzkal, N.; Hook, R. N.

    Mac OS X is the new Unix based version of the Macintosh operating system. It combines a high performance DisplayPDF user interface with a standard BSD UNIX subsystem and provides users with simultaneous access to a broad range of applications which were not previously available on a single system such as Microsoft Office and Adobe Photoshop, as well as legacy X11-based scientific tools and packages like IRAF, SuperMongo, MIDAS, etc. The combination of a modern GUI layered on top of a familiar UNIX environment paves the way for new, more flexible and powerful astronomical tools to be developed while assuring compatibility with already existing, older programs. In this paper, we outline the strengths of the Mac OS X platform in a scientific environment, astronomy in particular, and point to the numerous astronomical software packages available for this platform; most notably the Scisoft collection which we have compiled.

  8. Properties of Ru-doped near-stoichiometric lithium niobate crystals produced by vapor transport equilibration

    NASA Astrophysics Data System (ADS)

    Chiang, Chang-Hung; Chen, Jyh-Chen; Huang, Tzu-Ming; Hu, Chieh

    2008-05-01

    Ruthenium (Ru)-doped near-stoichiometric lithium niobate crystals (Ru:SLN) were prepared by the vapor transport equilibration (VTE) technique from Ru-doped congruent lithium niobate (CLN) grown using the Czochralski method. Increasing the duration time of the VTE treatment caused the ratio of [Li]/[Nb] in the crystal to increase, which in turn caused the absorption edges to shift to violet. The absorption coefficient in the UV/VIS absorption spectra at 530 nm decreased because of the change in the valence of the Ru ions cause by the VTE treatment. The OH - absorption spectra showed that the broad band located at 3482 cm -1 gradually decreased while another band located at 3466 cm -1 gradually increased and the shape became sharper as the VTE treatment time increased. When the VTE treatment time reached 200 h, Ru-doped near-stoichiometric lithium niobate crystals were obtained. Two-beam coupling examination with a 532 nm laser showed that the Ru-doped near-stoichiometric lithium niobate crystals had a larger exponential gain coefficient, lower diffraction efficiency, faster response time, and higher sensitivity than did the Ru-doped CLN crystals.

  9. Gluing together metallic and covalent layers to form Ru2C under ambient conditions.

    PubMed

    Sun, Weiwei; Li, Yunguo; Zhu, Li; Ma, Yanming; Di Marco, Igor; Johansson, Börje; Korzhavyi, Pavel

    2015-04-21

    Ru2C has recently been synthesised at high pressure and high temperature, and was assumed to have a structure with space group P3̅m1. However, subsequent theoretical work has revealed that this structure is unstable under ambient conditions, which motivated us to look for the stable structure. In this work, we explore the structures of Ru2C by using an unbiased swarm structure searching algorithm. The structures with R3m and R3̅m symmetries have been found to be lower in energy than the P3̅m1 structure, at the same time being dynamically stable under ambient conditions. These layered structures consist of alternating Ru bilayers and C monolayers in the R3m structure, and alternating Ru tetra-layers and C bilayers in the R3̅m structure. The C layers are more evenly distributed and more covalently bound to the Ru layers in the R3m structure than in the R3̅m structure. Instead, in the R3̅m structure there exists more Ru-Ru metallic bonding, which has a crucial role in diminishing the hardness of this material. Our findings should stimulate further explorations of the structures and properties of the heavy transition metal carbides and nitrides, potentially leading to industrial applications.

  10. The search for meaning: RU 486 and the law of abortion.

    PubMed Central

    Banwell, S S; Paxman, J M

    1992-01-01

    The advent of RU 486 (mifepristone), a steroid analogue capable of inducing menses within 8 to 10 weeks of a missed menstrual period, has provoked a firestorm of concern and controversy. When used in conjunction with prostaglandin (RU 486/PG), it is at least 95% effective. Used in France principally to terminate confirmed pregnancies very early in the process of gestation, RU 486 raises many interesting legal questions. This article focuses on whether and how RU 486/PG can be accommodated within the framework of the world's current abortion laws. Four avenues are explored and conclusions drawn. First, it is clear that RU 486/PG can be used readily, if approved, within the regimens established by liberal abortion laws, as has been the experience in France, the United Kingdom, and even China. Second, although unlikely, the introduction of this new technology may inspire a reexamination of restrictive abortion statutes themselves. Third, some of the presently restrictive laws may be interpreted to permit RU 486/PG use as a legal procedure, for a very narrow range of reasons. Finally, in some settings the early use of RU 486/PG (before pregnancy can be confirmed) may fall outside the reach of abortion legislation and hence be acceptable from a legal point of view. PMID:1415870

  11. High antiferromagnetic transition temperature of a honeycomb compound SrRu2O6

    DOE PAGESBeta

    Tian, Wei; Svoboda, Chris; Ochi, M.; Matsuda, M.; Cao, Huibo; Cheng, J. -G.; Sales, B. C.; Mandrus, D.; Arita, R.; Trivedi, Nandini; et al

    2015-09-14

    We study the high-temperature magnetic order in a quasi-two-dimensional honeycomb compound SrRu2O6 by measuring magnetization and neutron powder diffraction with both polarized and unpolarized neutrons. SrRu2O6 crystallizes into the hexagonal lead antimonate (PbSb2O6, space group P31m) structure with layers of edge-sharing RuO6 octahedra separated by Sr2+ ions. SrRu2O6 is found to order at TN = 565 K with Ru moments coupled antiferromagnetically both in plane and out of plane. The magnetic moment is 1.30(2) μB/Ru at room temperature and is along the crystallographic c axis in the G-type magnetic structure. We perform density functional calculations with constrained random-phase approximation (RPA)more » to obtain the electronic structure and effective intra- and interorbital interaction parameters. The projected density of states shows strong hybridization between Ru 4d and O 2p. By downfolding to the target t2g bands we extract the effective magnetic Hamiltonian and perform Monte Carlo simulations to determine the transition temperature as a function of interand intraplane couplings. We find a weak interplane coupling, 3% of the strong intraplane coupling, permits three-dimensional magnetic order at the observed TN .« less

  12. Unconventional Magnetic Domains in Triple-layered Sr4Ru3O10

    NASA Astrophysics Data System (ADS)

    Du, Kai; Lim, Seong Joon; Kim, Jae Wook; Cao, Gang; Cheong, Sang Wook; Rutgers Center for Emergent Material Team; Center for Advanced Materials, University of Kentucky Collaboration

    A plethora of fascinating phenomena including p-wave superconductivity in Sr2RuO4 (n=1) and hybrid improper ferroelectricity in Ca3Ru2O7 (n=2) have been observed in Ruddlesden-Popper ruthenates (Ca, Sr)n+1RunO3n+1. The triple-layered Sr4Ru3O10 (n=3) is believed to have an intriguing complex magnetic state, compared with its neighboring bi-layered meta-magnetic Sr3Ru2O7(n=2) and ferromagnetic SrRuO3 (n= ∞). The phase competition nature associated with this complexity is considered to be responsible for its novel properties such as coupled anisotropic magnetism and transport, low frequency quantum oscillations and sharp magneto-resistivity steps, which are still not well understood yet. To better understand its microscopic mechanism, we studied the magnetic domain structure on Sr4Ru3O10 using low-temperature magnetic force microscopy. The observed unique domain structures in Sr4Ru3O10 may shed lights on its microscopic phase competition nature and lead to a deeper understanding on its relations with other layered ruthenates. This work is funded by the Gordon and Betty Moore Foundation's EPiQS Initiative through Grant GBMF4413 to the Rutgers Center for Emergent Materials.

  13. [CuO-Ru/Al2O3 catalytic ozonation of acetophenone in water].

    PubMed

    Zhang, Hua; Shi, Rui; Zang, Xing-jie; Tong, Shao-ping; Ma, Chun-an

    2010-03-01

    Two-component CuO-Ru based on active Al2O3 (CuO-Ru/Al2O3) catalyst was prepared by incipient wetness impregnation and used to catalytic ozonation of acetophenone (AP). The results showed that doping Ru could significantly improve the catalytic activity of CuO/Al2O3. For example, the COD removal rates of AP solution after 30 min by ozonation alone, CuO/Al2O3/O3, and CuO-Ru/Al2O3/O3 were 6.3%, 20.0% and 54.0%, respectively. The change of pH almost had no affect on degradation efficiency of AP. However, a comparison of COD removal between ozonation alone and catalytic ozonation indicated that CuO-Ru/Al2O3 catalyst was more suitable for application in neutral or acidic condition. CuO-Ru/Al2O3 catalyst could accelerate decomposition rate of ozone in water, and its decomposition rate constant reached 2.58 x 10(-3) s(-1) while that of ozone alone in double-water was 1.19 x 10(-3) s(-1). The experimental result of t-butanol indicated that CuO-Ru/Al2O3 catalytic ozonation of AP followed a radical-type mechanism. PMID:20358832

  14. Stable monolayer honeycomb-like structures of RuX2 (X =S,Se)

    NASA Astrophysics Data System (ADS)

    Ersan, Fatih; Cahangirov, Seymur; Gökoǧlu, Gökhan; Rubio, Angel; Aktürk, Ethem

    2016-10-01

    Recent studies show that several metal oxides and dichalcogenides (M X2) , which exist in nature, can be stable in two-dimensional (2D) form and each year several new M X2 structures are explored. The unstable structures in H (hexagonal) or T (octahedral) forms can be stabilized through Peierls distortion. In this paper, we propose new 2D forms of RuS2 and RuSe2 materials. We investigate in detail the stability, electronic, magnetic, optical, and thermodynamic properties of 2D Ru X2 (X =S,Se) structures from first principles. While their H and T structures are unstable, the distorted T structures (T'-Ru X2) are stable and have a nonmagnetic semiconducting ground state. The molecular dynamic simulations also confirm that T'-Ru X2 systems are stable even at 500 K without any structural deformation. T'-RuS2 and T'-RuSe2 have indirect band gaps with 0.745 eV (1.694 eV with HSE) and 0.798 eV (1.675 eV with HSE) gap values, respectively. We also examine their bilayer and trilayer forms and find direct and smaller band gaps. We find that AA stacking is more favorable than the AB configuration. The new 2D materials obtained can be good candidates with striking properties for applications in semiconductor electronic, optoelectronic devices, and sensor technology.

  15. Formation of a Cu@RhRu core-shell concave nanooctahedron via Ru-assisted extraction of Rh from the Cu matrix and its excellent electrocatalytic activity toward the oxygen evolution reaction

    NASA Astrophysics Data System (ADS)

    Park, Suhyun; Yoon, Donghwan; Bang, Sulgi; Kim, Jongchan; Baik, Hionsuck; Yang, Haesik; Lee, Kwangyeol

    2015-09-01

    A facile one step route has been developed for the synthesis of trimetallic Cu@RhRu core-shell concave nanooctahedra by co-decomposition of Ru, Rh and Cu precursors. A mechanistic study reveals that nanoparticles with a CuRh alloy core and a Ru shell are initially formed and a subsequent migration of Rh to the shell results in the Cu@RhRu core-shell concave nanooctahedron. The shell exhibits atomically mixed Ru and Rh phases with an fcc atomic structure, although the hcp atomic structure is commonly found for the bulk Ru. We also report an unusually high catalytic activity of the Cu@RhRu octahedral nanocrystals toward the oxygen evolution reaction in alkaline solution.A facile one step route has been developed for the synthesis of trimetallic Cu@RhRu core-shell concave nanooctahedra by co-decomposition of Ru, Rh and Cu precursors. A mechanistic study reveals that nanoparticles with a CuRh alloy core and a Ru shell are initially formed and a subsequent migration of Rh to the shell results in the Cu@RhRu core-shell concave nanooctahedron. The shell exhibits atomically mixed Ru and Rh phases with an fcc atomic structure, although the hcp atomic structure is commonly found for the bulk Ru. We also report an unusually high catalytic activity of the Cu@RhRu octahedral nanocrystals toward the oxygen evolution reaction in alkaline solution. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr03942h

  16. Capacitive behavior of amorphous and crystalline RuO 2 composite electrode fabricated by spark plasma sintering technique

    NASA Astrophysics Data System (ADS)

    Bharali, P.; Kuratani, K.; Takeuchi, T.; Kiyobayashi, T.; Kuriyama, N.

    This study is intended to determine if the capacitive properties are improved when a specific amount of crystalline ruthenium oxide (c-RuO 2) is added to an amorphous hydrous ruthenium oxide (a-RuO 2) electrode fabricated by the spark plasma sintering technique. For at the cyclic voltammetry scan rates higher than 10 mV s -1, the capacitance of a highly pseudo-capacitive, but less electron-conductive a-RuO 2 electrode is augmented by adding 5-20 wt.% of c-RuO 2 which is less capacitive, but more electron-conductive than a-RuO 2. The capacitance fades when more than 20 wt.% of c-RuO 2 is added because the less capacitive nature of c-RuO 2 prevails. The proximate cause of this phenomenon is the electronic conductivity, σ, of the composite electrode as we observe a maximum in σ at around a 5-20 wt.% c-RuO 2 content. The fact that c-RuO 2 is composed of smaller particles than a-RuO 2 seems to be related to the maximum σ value for a certain c-RuO 2 content of the composite electrode.

  17. Magnetic and magnetocaloric properties of Ba and Ti co-doped SrRuO{sub 3}

    SciTech Connect

    Sarkar, Babusona; Dalal, Biswajit; Dev Ashok, Vishal; De, S. K.

    2014-12-28

    Temperature evolution of magnetic properties in Ba and Ti doped SrRuO{sub 3} has been investigated to observe the effects of larger ionic radius Ba at Sr site and isovalent nonmagnetic impurity Ti at Ru site. Ionic radius mismatch and different electronic configuration in comparison with Ru modify Sr(Ba)-O and Ru(Ti)-O bond lengths and Ru-O-Ru bond angle. The apical and basal Ru-O-Ru bond angles vary significantly with Ti doping. Ferromagnetic Curie temperature decreases from 161 K to 149 K monotonically with Ba (10%) and Ti (10%) substitutions at Sr and Ru sites. The zero field cooled (ZFC) magnetization reveals a prominent peak which shifts towards lower temperature with application of magnetic field. The substitution of tetravalent Ti with localized 3d{sup 0} orbitals for Ru with more delocalized 4d{sup 4} orbitals leads to a broad peak in ZFC magnetization. A spontaneous ZFC magnetization becomes negative below 160 K for all the compositions. The occurrence of both normal and inverse magnetocaloric effects in Ba and Ti co-doped SrRuO{sub 3} makes the system more interesting.

  18. Is the semi-regular variable RU Vulpeculae undergoing a helium-shell flash?

    NASA Astrophysics Data System (ADS)

    Uttenthaler, S.; Greimel, R.; Templeton, M.

    2016-03-01

    The semi-regular variable star RU Vulpeculae (RU Vul) is being observed visually since 1935. Its pulsation period and amplitude are declining since ˜ 1954. A leading hypothesis to explain the period decrease in asymptotic giant branch (AGB) stars such as RU Vul is an ongoing flash of the He-burning shell, also called a thermal pulse (TP), inside the star. In this paper, we present a CCD photometric light curve of RU Vul, derive its fundamental parameters, and test if the TP hypothesis can describe the observed period decline. We use CCD photometry to determine the present-day pulsation period and amplitude in three photometric bands, and high-resolution optical spectroscopy to derive the fundamental parameters. The period evolution of RU Vul is compared to predictions by evolutionary models of the AGB phase. We find that RU Vul is a metal-poor star with a metallicity [M/H]=-1.59±0.05 and an effective surface temperature of T_eff=3634±20 K. The low metallicity of RU Vul and its kinematics indicate that it is an old, low-mass member of the thick disc or the halo population. The present day pulsation period determined from our photometry is ˜ 108 d, the semi-amplitude in the V-band is 0.39±0.03 mag. The observed period decline is found to be well matched by an evolutionary AGB model with stellar parameters comparable to those of RU Vul. We conclude that the TP hypothesis is in good agreement with the observed period evolution of RU Vul. Based on observations made with the Mercator Telescope, operated on the island of La Palma by the Flemish Community, at the Spanish Observatorio del Roque de los Muchachos of the Instituto de Astrofísica de Canarias.

  19. The chemistry of (ring)Ru sup 2+ (ring = tetramethylthiophene, p-cymene)

    SciTech Connect

    Ganja, E.A.; Rauchfuss, T.B.; Stern, C.L. )

    1991-01-01

    Described are the compounds ((ring)Ru(OTf){sub 2}){sub x}, where ring = 2,3,4,5-tetramethylthiophene (TMT, 1), and p-cymene (2). These electrophilic reagents serve as precursors to ((ring)RuL{sub 3}){sup 2+}, where L{sub 3} = (H{sub 2}O){sub 3}, (NH{sub 3}){sub 3}, and (PH{sub 3}){sub 3}. Solutions of 1 and 2 react with carbon monoxide to give (ring)Ru(CO)(OTf){sub 2}. The addition of thiophenes to CH{sub 2}Cl{sub 2} solutions of 1 or 2 leads to the precipitation of the sandwich compounds ((ring)(SC{sub 4}R{sub 4})Ru)(OTf){sub 2}, where SC{sub 4}R{sub 4} = thiophene, 2,5-dimethylthiophene, and TMT. ((TMT)Ru(H{sub 2}O){sub 3})(OTf){sub 2} was characterized by single-crystal X-ray crystallography, which established a piano-stool geometry with a planar TMT ligand. ((TMT)Ru(D{sub 2}O){sub 3})(OTf){sub 2} decomposes in D{sub 2}O solution at 150C to give ((TMT){sub 2}Ru){sup 2+}, which undergoes selective deuteration at the 2,5-methyl groups. D{sub 2}O solutions of ((TMT){sub 2}Ru){sup 2+} undergo photochemical loss of one TMT ligand in water to give ((TMT)Ru(H{sub 2}O){sub 3}){sup 2+}. A procedure is described for the reversible loading of 1 onto {gamma}-alumina, which in turn was characterized by {sup 13}C CP-MAS NMR spectroscopy.

  20. Active Site Dependent Reaction Mechanism over Ru/CeO2 Catalyst toward CO2 Methanation.

    PubMed

    Wang, Fei; He, Shan; Chen, Hao; Wang, Bin; Zheng, Lirong; Wei, Min; Evans, David G; Duan, Xue

    2016-05-18

    Oxygen vacancy on the surface of metal oxides is one of the most important defects which acts as the reactive site in a variety of catalytic reactions. In this work, operando spectroscopy methodology was employed to study the CO2 methanation reaction catalyzed by Ru/CeO2 (with oxygen vacancy in CeO2) and Ru/α-Al2O3 (without oxygen vacancy), respectively, so as to give a thorough understanding on active site dependent reaction mechanism. In Ru/CeO2 catalyst, operando XANES, IR, and Raman were used to reveal the generation process of Ce(3+), surface hydroxyl, and oxygen vacancy as well as their structural evolvements under practical reaction conditions. The steady-state isotope transient kinetic analysis (SSITKA)-type in situ DRIFT infrared spectroscopy undoubtedly substantiates that CO2 methanation undergoes formate route over Ru/CeO2 catalyst, and the formate dissociation to methanol catalyzed by oxygen vacancy is the rate-determining step. In contrast, CO2 methanation undergoes CO route over Ru surface in Ru/α-Al2O3 with the absence of oxygen vacancy, demonstrating active site dependent catalytic mechanism toward CO2 methanation. In addition, the catalytic activity evaluation and the oscillating reaction over Ru/CeO2 catalyst further prove that the oxygen vacancy catalyzes the rate-determining step with a much lower activation temperature compared with Ru surface in Ru/α-Al2O3 (125 vs 250 °C). PMID:27135417

  1. OsFRDL1 expressed in nodes is required for distribution of iron to grains in rice

    PubMed Central

    Yokosho, Kengo; Yamaji, Naoki; Ma, Jian Feng

    2016-01-01

    Iron (Fe) is essential for plant growth and development, but the molecular mechanisms underlying its distribution to different organs are poorly understood. We found that OsFRDL1 (FERRIC REDUCTASE DEFECTIVE LIKE 1), a plasma membrane-localized transporter for citrate, was highly expressed in the upper nodes of rice at the reproductive growth stage. OsFRDL1 was expressed in most cells of enlarged vascular bundles, diffuse vascular bundles, and the interjacent parenchyma cell bridges of uppermost node I, as well as vascular tissues of the leaf blade, leaf sheath, peduncle, rachis, husk, and stamen. Knockout of OsFRDL1 decreased pollen viability and grain fertility when grown in a paddy field. Iron was deposited in the parenchyma cell bridges, a few of the cell layers of the parenchyma tissues outside of the bundle sheath of enlarged vascular bundles in node I in both the wild-type rice and osfrdl1 mutant, but the mutant accumulated more Fe than the wild-type rice in this area. A stem-fed experiment with stable isotope 57Fe showed that the distribution of Fe in the anther and panicle decreased in the knockout line, but that in the flag leaf it increased compared with the wild-type rice. Taken together, our results show that OsFRDL1 expressed in the upper nodes is required for the distribution of Fe in the panicles through solubilizing Fe deposited in the apoplastic part of nodes in rice. PMID:27555544

  2. Electrocatalytic activity of Rh-Ru alloys in electroreduction process

    SciTech Connect

    Bukherissa, S.; Belik, V.V.; Kudryashov, I.V.; Meretskii, A.M.

    1986-04-01

    The authors study the kinetics of cathodic hydrogen evolution in 1 N H/sub 2/SO/sub 4/ and of maleic acid electroreduction in C/sub 4/H/sub 4/O/sub 4/ solutions of different concentrations in 1 N H/sub 2/SO/sub 4/ as a base electrolyte at Rh-Ru alloy ingots prepared by vacuum arc melting. The results of polarization measurements for cathodic hydrogen evolution were analyzed in semilogarithmic plots of overvoltage against the logarithm of current density. Over the range of current densities from 10/sup -5/ to 10/sup -3/ A/cm/sup 2/, the polarization curves exhibit distinctly linear sections and can be described by the Tafel equation.

  3. Photon upconversion sensitized by a Ru(II)-pyrenyl chromophore

    PubMed Central

    Deng, Fan; Lazorski, Megan S.; Castellano, Felix N.

    2015-01-01

    The near-visible-to-blue singlet fluorescence of anthracene sensitized by a ruthenium chromophore with a long-lived triplet-excited state, [Ru(5-pyrenyl-1,10-phenanthroline)3](PF6)2, in acetonitrile was investigated. Low intensity non-coherent green light was used to selectively excite the sensitizer in the presence of micromolar concentrations of anthracene generating anti-Stokes, singlet fluorescence in the latter, even with incident power densities below 500 μW cm−2. The resultant data are consistent with photon upconversion proceeding from sensitized triplet–triplet annihilation (TTA) of the anthracene acceptor molecules, confirmed through transient absorption spectroscopy as well as static and dynamic photoluminescence experiments. Additionally, quadratic-to-linear incident power regimes for the upconversion process were identified for this composition under monochromatic 488 nm excitation, consistent with a sensitized TTA mechanism ultimately producing the anti-Stokes emission characteristic of anthracene singlet fluorescence. PMID:25987571

  4. Magnetic structure of the quasi-one-dimensional La3OsO7 as determined by neutron powder diffraction

    DOE PAGESBeta

    Morrow, Ryan; Susner, Michael A.; Sumption, Michael D.; Woodward, Patrick M.

    2015-10-05

    Insulating 5d3 La3OsO7 and the isostructural hole-doped analog La2.8Ca0.2OsO7 that feature pseudo-one-dimensional zigzag chains of corner-sharing OsO6 octahedra were synthesized and their magnetic and electrical transport properties characterized. Both of these compounds are insulating antiferromagnets. Moreover, for long range magnetic order between the antiferromagnetic chains we determined with a propagation vector k = 1/2,1/2,1 and TN = 45 and 33 K the parent and doped materials. An Os5+ moment of 1.7(1)μB for La3OsO7 and 1.2(2)μB for La2.8Ca0.2OsO7 is refined. The long range magnetic structure is compared to the isostructural compounds La3RuO7 and La3MoO7, both of which adopt different magnetic structures.

  5. The control of Pt and Ru nanoparticle size on high surface area supports.

    PubMed

    Liu, Qiuli; Joshi, Upendra A; Über, Kevin; Regalbuto, John R

    2014-12-28

    Supported Ru and Pt nanoparticles are synthesized by the method of strong electrostatic adsorption and subsequently treated under different steaming-reduction conditions to achieve a series of catalysts with controlled particle sizes, ranging from 1 to 8 nm. While in the case of oxidation-reduction conditions, only Pt yielded particles ranging from 2.5 to 8 nm in size and a loss of Ru was observed. Both Ru and Pt sinter faster in air than in hydrogen. This methodology allows the control of particle size using a "production-scalable" catalyst synthesis method which can be applied to high surface area supports with common metal precursors.

  6. The control of Pt and Ru nanoparticle size on high surface area supports.

    PubMed

    Liu, Qiuli; Joshi, Upendra A; Über, Kevin; Regalbuto, John R

    2014-12-28

    Supported Ru and Pt nanoparticles are synthesized by the method of strong electrostatic adsorption and subsequently treated under different steaming-reduction conditions to achieve a series of catalysts with controlled particle sizes, ranging from 1 to 8 nm. While in the case of oxidation-reduction conditions, only Pt yielded particles ranging from 2.5 to 8 nm in size and a loss of Ru was observed. Both Ru and Pt sinter faster in air than in hydrogen. This methodology allows the control of particle size using a "production-scalable" catalyst synthesis method which can be applied to high surface area supports with common metal precursors. PMID:25200960

  7. Oxidation resistance and microstructure of Ru-capped extreme ultraviolet lithography multilayers

    SciTech Connect

    Bajt, S; Dai, Z; Nelson, E J; Wall, M A; Alameda, J B; Nguyen, N; Baker, S L; Robinson, J C; Taylor, J S; Aquila, A; Edwards, N V

    2005-06-15

    The oxidation resistance of protective capping layers for extreme ultraviolet lithography (EUVL) multilayers depends on their microstructure. Differently prepared Ru-capping layers, deposited on Mo/Si EUVL multilayers, were investigated to establish their baseline structural, optical, and surface properties in as-deposited state. The same capping layer structures were then tested for their thermal stability and oxidation resistance. The best performing Ru-capping layer structure was analyzed in detail with transmission electron microscopy (TEM). As compared to other Ru capping layers preparations studied here it is the only one that shows grains with preferential orientation. This information is essential for modeling and performance optimization of EUVL multilayers.

  8. Spin-lozenge thermodynamics and magnetic excitations in Na3RuO4

    NASA Astrophysics Data System (ADS)

    Haraldsen, J. T.; Stone, M. B.; Lumsden, M. D.; Barnes, T.; Jin, R.; Taylor, J. W.; Fernandez-Alonso, F.

    2009-12-01

    We report inelastic and elastic neutron scattering, magnetic susceptibility, and heat capacity measurements for polycrystalline sodium ruthenate (Na3RuO4). Previous work suggests that this material consists of isolated tetramers of S = 3/2 Ru5+ ions in a so-called lozenge configuration. Comparisons of magnetic susceptibility and inelastic and elastic neutron scattering results with analytic calculations for several cluster models show that although there may be significant spin-spin correlations within the lozenge cluster, a simple isolated lozenge model is not appropriate for Na3RuO4.

  9. Spin-lozenge thermodynamics and magnetic excitations in Na(3)RuO(4).

    PubMed

    Haraldsen, J T; Stone, M B; Lumsden, M D; Barnes, T; Jin, R; Taylor, J W; Fernandez-Alonso, F

    2009-12-16

    We report inelastic and elastic neutron scattering, magnetic susceptibility, and heat capacity measurements for polycrystalline sodium ruthenate (Na(3)RuO(4)). Previous work suggests that this material consists of isolated tetramers of S = 3/2  Ru(5+) ions in a so-called lozenge configuration. Comparisons of magnetic susceptibility and inelastic and elastic neutron scattering results with analytic calculations for several cluster models show that although there may be significant spin-spin correlations within the lozenge cluster, a simple isolated lozenge model is not appropriate for Na(3)RuO(4). PMID:21836228

  10. Synthesis of Pd9Ru@Pt nanoparticles for oxygen reduction reaction in acidic electrolytes

    SciTech Connect

    Sun, Yu; Hsieh, Yu -Chi; Chang, Li -Chung; Wu, Pu -Wei; Lee, Jyh -Fu

    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 0.1 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.

  11. X-ray absorption spectroscopy of Ru-doped relaxor ferroelectrics with a perovskite-type structure

    NASA Astrophysics Data System (ADS)

    Vitova, T.; Mangold, S.; Paulmann, C.; Gospodinov, M.; Marinova, V.; Mihailova, B.

    2014-04-01

    X-ray absorption near-edge structure and extended x-ray absorption fine structure spectroscopy at the Ru K edge of Ru-doped PbSc0.5Ta0.5O3 (PST-Ru), PbSc0.5Nb0.5O3 (PSN-Ru), and 0.9PbZn1/3Nb2/3O3-0.1PbTiO3 (PZN-0.1PT-Ru) as well as at the Ta L3 edge of PST-Ru and the Nb K edge of PSN-Ru was applied to study the short- and intermediate-range atomic arrangements in perovskite-type (ABO3) relaxor ferroelectrics. The compounds were also analyzed by complementary Raman scattering, visible/near-visible absorption spectroscopy, and synchrotron x-ray single-crystal diffraction. The results show that Ru is octahedrally coordinated in all three relaxor host matrices but the average oxidation state of Ru in PST-Ru and PSN-Ru is ˜4.4, whereas it is ˜3.8 in PZN-0.1PT-Ru. In PbSc0.5B''0.5O3 (B'' = Ta, Nb) Ru substitutes for the B'' cations in the form of isolated point defects, while in PZN-0.1PT-Ru Ru replaces adjacent A and B sites, forming a chainlike structural species of face-sharing elongated octahedra. Chemical 1:1 B-site order as well as dynamic BO6 tilting is observed around both the Ru dopant and the major B'' cation in PST-Ru and PSN-Ru regardless of the fact that according to x-ray diffraction at ambient conditions, the average structure is cubic with weak or no long-range chemical order. Pb cations are off-center displaced from the prototypic cubic A site for all three compounds and in Ru-doped PbSc0.5B''0.5O3 the BO6 tilt angle correlates with the degree of coherent B-Pb distances.

  12. Epitaxial growth of multiferroic BiFeO3 thin films with (101) and (111) orientations on (100) Si substrates

    NASA Astrophysics Data System (ADS)

    Kyun Lee, Sung; Ho Choi, Bum; Hesse, Dietrich

    2013-06-01

    Multiferroic (101)- and (111)-oriented BiFeO3 thin films were grown on heteroepitaxial substrates of (110) SrRuO3/(100) YSZ/(100) Si and (111) SrRuO3/(111) Pt/(100) YSZ/(100) Si, respectively, by pulsed laser deposition. X-ray diffraction θ-2θ scans, ϕ scans, and pole figures showed the well-developed out-of-plane and in-plane orientations of the epitaxial BiFeO3 films. The (111) BiFeO3 films showed ˜√3 /√2 times higher remanent polarization (58.9 μC/cm2) than that of the (101) BiFeO3 films (44.3 μC/cm2), thus revealing the ferroelectric anisotropy. The (101) BiFeO3 films exhibited a good fatigue resistance up to 4.6 × 107 cycles, whereas the (111) BiFeO3 films proved to be vulnerable to fatigue, which is associated with the polarization switching path.

  13. Thermodynamic investigations of [(phen)2Ru(tatpp)Ru(phen)2](4+) interactions with B-DNA.

    PubMed

    Le, Vu H; McGuire, Matthew R; Ahuja, Pooja; MacDonnell, Frederick M; Lewis, Edwin A

    2015-01-01

    While the antitumor activity of P(4+) is relatively well understood, the binding mechanism and thermodynamics for formation of (P(4+)·DNA) complexes remain in question. The thermodynamic parameters (Ka, ΔG, ΔH, and -TΔS) for formation of DNA complexes of the ruthenium dimer, [(phen)2Ru(tatpp)Ru(phen)2](4+) (abbreviated as P(4+)), where phen is 1,10-phenanthroline and tatpp is 9,11,20,22-tetraazatetrapyrido[3,2-a:2',3'-c:3″,2″-1:2‴,3‴-n]-pentacene, were determined using isothermal titration calorimetry. Calorimetric and spectroscopic titration experiments were performed in which P(4+) was added to three duplex DNAs of different lengths. We determined that P(4+) binds to duplex DNA at 298 K with modest affinity (Ka ≈ 3.8 × 10(5) M(-1), ΔG ≈ -7.6 kcal/mol), that the enthalpy change is unfavorable (ΔH ≈ +2.1 kcal/mol), and that complex formation is driven by a large favorable change in entropy (-TΔS ≈ -9.7 kcal/mol). These thermodynamic values were found to be approximately independent of the length of the DNA, and the stoichiometry of the (P(4+)·DNA) complexes was determined to be 1 P(4+)/2 DNA bp, at least for the two shorter DNAs. On the basis of the thermodynamic parameters, and the binding stoichiometry (verified in ESI-MS experiments), we conclude that P(4+) is intercalating between two adjacent DNA base pairs and that the neighbor sites on either side of the bound ligand are excluded from binding additional P(4+).

  14. Synthesis and thermoelectric properties of RuO{sub 2} nanorods

    SciTech Connect

    Music, Denis; Basse, Felix H.-U.; Schneider, Jochen M.; Hassdorf, Ralf

    2010-07-15

    We have explored the effect of the O/Ru ratio on the morphology and the Seebeck coefficient of RuO{sub 2} nanorods (space group P4{sub 2}/mnm) synthesized by reactive sputtering. At an O/Ru ratio of 1.69, a faceted surface is observed, while nanorod formation occurs at O/Ru ratios of 2.03 and 2.24. Using classical molecular dynamics with the potential parameters derived in this work, we show that volatile species enable nanorod formation. Based on ab initio calculations, two effects of the nanorod formation on the Seebeck coefficient are observed: (i) increase due to additional states in the vicinity of the Fermi level and (ii) decrease due to oxygen point defects (volatile species). These two competing effects give rise to a moderate increase in the Seebeck coefficient upon nanorod formation.

  15. Optical-absorption study of RuS2 - xSex single crystals

    NASA Astrophysics Data System (ADS)

    Huang, Jeng-Kuang; Huang, Ying-Sheng; Yang, Tzuen-Rong

    1995-08-01

    An optical-absorption study of synthetic RuS2-xSex single crystals is reported over a temperature range from 80 to 300 K. The data are fitted to several expressions for the shape of the absorption edge, with the best fit being to that expected for indirect allowed transitions. The band gaps at any temperature varies smoothly with the Se composition x, indicating that the nature of the band edges are similar for RuS2, RuSe2, and the compounds of intermediate compositions. The indirect band gaps of various temperatures are determined and their temperature dependence are analyzed by the Varshni equation [Physica 34, 149 (1967)] and an empirical expression proposed by O'Donnell and Chen [Appl. Phys. Lett. 58, 2924 (1991)]. The parameters that describe the temperature dependence of energy gap of RuS2-xSex are evaluated and discussed.

  16. Formation of Ru nanocrystals by plasma enhanced atomic layer deposition for nonvolatile memory applications

    SciTech Connect

    Yim, Sung-Soo; Lee, Moon-Sang; Kim, Ki-Su; Kim, Ki-Bum

    2006-08-28

    The formation of Ru nanocrystals is demonstrated on a SiO{sub 2} substrate by plasma enhanced atomic layer deposition using diethylcyclopentadienyl ruthenium and NH{sub 3} plasma. The island growth of Ru was observed at the initial stages of the film formation up to a nominal thickness of 11.1 nm. A maximum Ru nanocrystal spatial density of 9.7x10{sup 11} /cm{sup 2} was achieved with an average size of 3.5 nm and standard deviation of the size of 20%. Electron charging/discharging effect in the Ru nanocrystals is demonstrated by measuring the flatband voltage shift in the capacitance-voltage measurement of metal-oxide-semiconductor memory capacitor structure.

  17. Constructing molecular structures on periodic superstructure of graphene/Ru(0001)

    PubMed Central

    Li, Geng; Huang, Li; Xu, Wenyan; Que, Yande; Zhang, Yi; Lu, Jianchen; Du, Shixuan; Liu, Yunqi; Gao, Hong-Jun

    2014-01-01

    We review the way to fabricate large-scale, high-quality and single crystalline graphene epitaxially grown on Ru(0001) substrate. A moiré pattern of the graphene/Ru(0001) is formed due to the lattice mismatch between graphene and Ru(0001). This superstructure gives rise to surface charge redistribution and could behave as an ordered quantum dot array, which results in a perfect template to guide the assembly of organic molecular structures. Molecules, for example iron phthalocyanine and C60, on this template show how the molecule–substrate interaction makes different superstructures. These results show the possibility of constructing ordered molecular structures on graphene/Ru(0001), which is helpful for practical applications in the future. PMID:24615151

  18. JeffDescription of the Honeycomb Mott Insulatorα‑RuCl3

    NASA Astrophysics Data System (ADS)

    Koitzsch, A.; Habenicht, C.; Müller, E.; Knupfer, M.; Büchner, B.; Kandpal, H. C.; van den Brink, J.; Nowak, D.; Isaeva, A.; Doert, Th.

    2016-09-01

    Novel ground states might be realized in honeycomb lattices with strong spin-orbit coupling. Here we study the electronic structure of {\\alpha}-RuCl_3, in which the Ru ions are in a d5 configuration and form a honeycomb lattice, by angle-resolved photoemission, x-ray photoemission and electron energy loss spectroscopy supported by density functional theory and multiplet calculations. We find that {\\alpha}-RuCl_3 is a Mott insulator with significant spin-orbit coupling, whose low energy electronic structure is naturally mapped onto Jeff states. This makes {\\alpha}-RuCl_3 a promising candidate for the realization of Kitaev physics. Relevant electronic parameters such as the Hubbard energy U, the crystal field splitting 10Dq and the charge transfer energy are evaluated. Furthermore, we observe significant Cl photodesorption with time, which must be taken into account when interpreting photoemission and other surface sensitive experiments.

  19. Photoluminescence and electrochemiluminescence of a Ru(II)(bpy)3-quencher dual-labeled oligonucleotide probe.

    PubMed

    Wilson, Robert; Johansson, Mary Katherine

    2003-11-01

    A molecular beacon oligonucleotide probe covalently labeled with Ru(II)(bpy)3 and Black Hole Quencher-2 is synthesized, and hybridization assays are performed using photoluminescence and electrochemiluminescence methods of excitation.

  20. Aqueous chemistry and antiproliferative activity of a pyrone-based phosphoramidate Ru(arene) anticancer agent.

    PubMed

    Meier, Samuel M; Novak, Maria S; Kandioller, Wolfgang; Jakupec, Michael A; Roller, Alexander; Keppler, Bernhard K; Hartinger, Christian G

    2014-07-14

    A water-stable phosphoramidate Ru(arene) metallodrug shows antiproliferative activity comparable to KP1019 in human cancer cell lines. This novel compound can cross-link the peptide backbone of cytochrome c, but features low apoptosis inducing properties.